WO2024043194A1 - 強化ガラス板、強化ガラス板の製造方法及び強化用ガラス板 - Google Patents

強化ガラス板、強化ガラス板の製造方法及び強化用ガラス板 Download PDF

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WO2024043194A1
WO2024043194A1 PCT/JP2023/029900 JP2023029900W WO2024043194A1 WO 2024043194 A1 WO2024043194 A1 WO 2024043194A1 JP 2023029900 W JP2023029900 W JP 2023029900W WO 2024043194 A1 WO2024043194 A1 WO 2024043194A1
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glass plate
tempered glass
mgo
glass
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English (en)
French (fr)
Japanese (ja)
Inventor
雄太 永野
健 結城
光 池田
智 新井
雄介 清水
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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Priority to CN202380055826.5A priority Critical patent/CN119522198A/zh
Priority to JP2024542800A priority patent/JPWO2024043194A1/ja
Priority to KR1020257008450A priority patent/KR20250054228A/ko
Publication of WO2024043194A1 publication Critical patent/WO2024043194A1/ja
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a tempered glass plate and a method for manufacturing the same, and in particular, a tempered glass plate suitable for cover glass of touch panel displays such as mobile phones, digital cameras, PDAs (portable terminals), etc., a method for manufacturing a tempered glass plate, and a glass plate for tempering. Regarding.
  • tempered glass plates subjected to ion exchange treatment are used as cover glasses for touch panel displays (see Patent Document 1).
  • properties required of a cover glass include, for example, (1) high mechanical strength, (2) high transparency, and (3) low manufacturing cost.
  • mechanical strength refers to the strength characteristics of glass determined by the mechanical characteristics and reinforcement characteristics of glass.
  • mechanical properties refer to properties related to the strength of glass, which are determined mainly due to the glass composition, and include, for example, fracture toughness values.
  • the reinforcing property refers to a property related to the strength of the glass that is subsequently imparted to the glass after molding by an ion exchange treatment, and is, for example, a compressive stress value on the glass surface.
  • a tempered glass plate that has been subjected to ion exchange treatment has a compressive stress layer on its surface, so it has the characteristic of easily suppressing the formation and propagation of cracks on the surface (see Patent Document 1).
  • crystallized glass contains crystals, its transmittance tends to be lower than that of amorphous glass, and when used as a cover glass, there is a risk that the visibility and color expressiveness of the display will be reduced.
  • the present invention has been made in view of the above circumstances, and its technical problem is to achieve higher mechanical strength than conventional amorphous tempered glass sheets without crystallization treatment, that is, without crystallization.
  • a method for producing the tempered glass plate and a tempering glass plate that can be obtained at low cost is to provide a tempered glass plate having a higher transmittance than a crystallized chemically strengthened glass plate.
  • the tempered glass plate of the present invention is a tempered glass plate having a compressive stress layer on the surface, and the glass composition includes, in mol%, SiO 2 50-80%, Al 2 O 3 1-25%, B 2 O 3 0. ⁇ 15%, Li 2 O 0-20%, Na 2 O 0-25%, K 2 O 0-20%, ZnO 0-10%, P 2 O 5 0-15%, ZrO 2 0-10%, SnO 2 0-0.30%, [Li 2 O] + [Na 2 O] 1-30%, [Li 2 O] + [MgO] 1-25%, [MgO] + [CaO] + [SrO] +[BaO] It is characterized by containing 0.5 to 30%.
  • [Li 2 O] + [Na 2 O] is the total amount of Li 2 O and Na 2 O
  • [Li 2 O] + [MgO] is the total amount of Li 2 O and MgO
  • [MgO] + [ CaO]+[SrO]+[BaO] refers to the total content of MgO, CaO, SrO, and BaO.
  • the tempered glass plate of the present invention is a tempered glass plate having a compressive stress layer on the surface, and the glass composition includes, in mol%, SiO 2 52-80%, Al 2 O 3 11.5-25%, B 2 O. 3 0-15%, Li 2 O 7-20%, Na 2 O 0.5-25%, K 2 O 0-20%, MgO 0-20%, CaO 0-10%, SrO 0-10%, BaO 0-10%, ZnO 0-10%, P 2 O 5 0-15%, ZrO 2 0-10%, SnO 2 0-0.30%, [MgO] + [CaO] + [SrO] + [ BaO] It is preferable to contain 6.5 to 30%.
  • the tempered glass plate of the present invention preferably contains MgO as a glass composition, and the content of MgO is preferably 6.5 to 20 mol%.
  • the high-temperature viscosity is lowered, the meltability and moldability are increased, and the strain point, Vickers hardness, Young's modulus, and fracture toughness are easily increased.
  • the tempered glass plate of the present invention preferably has a molar ratio [RO]/[R 2 O] of 0.5 to 1.5.
  • [RO] is the total amount of alkaline earth metal oxides ([MgO] + [CaO] + [SrO] + [BaO])
  • [R 2 O] is the total amount of alkaline earth metal oxides ([MgO] + [CaO] + [SrO] + [BaO]).
  • the total amount of oxides is ([Li 2 O] + [Na 2 O] + [K 2 O]). Therefore, "[RO]/[R 2 O]” is the value obtained by dividing the total amount of alkaline earth metal oxides by the total amount of alkali metal oxides.
  • the tempered glass plate of the present invention preferably does not substantially contain crystals and has a transmittance of 85% or more at a wavelength of 400 nm when converted to a thickness of 0.6 mm.
  • substantially not containing refers to the content of crystals in the tempered glass plate being 0.01% by mass or less.
  • the tempered glass plate of the present invention preferably has a Young's modulus of 76 GPa or more.
  • the tempered glass plate of the present invention has a fracture toughness K1c of 0.78 MPa ⁇ m 0.5 or more.
  • a tempered glass plate that is unlikely to cause self-destruction or that is unlikely to be explosively shattered when broken is obtained.
  • the tempered glass plate of the present invention has a plate shape with a thickness of 0.01 to 2.0 mm, the compressive stress value CS of the outermost surface of the compressive stress layer is 200 to 1200 MPa, and the stress depth of the compressive stress layer is Preferably, the DOC is 3 to 200 ⁇ m.
  • the "compressive stress value of the outermost surface” and the “stress depth” are, for example, when the compressive stress is caused by Na ions introduced by ion exchange, the scattered light photoelastic stress meter SLP-2000 (Co., Ltd.
  • a value measured from a phase difference distribution curve observed using a surface stress meter FSM-6000 refers to the value measured from the phase difference distribution curve observed using The stress depth refers to the depth at which the stress value becomes zero.
  • the refractive index and photoelastic constant were used to calculate the stress characteristics of each sample. For the refractive index, a value measured by the V block method was used. For the photoelastic constant, the value measured by optical heterodyne measurement method was used.
  • the tempered glass plate of the present invention has a plate shape with a thickness of 0.35 to 2.0 mm, the stress depth DOC of the compressive stress layer is 50 to 170 ⁇ m, and the compressive stress at a depth of 30 ⁇ m from the outermost surface
  • the value CS30 is between 25 and 400 MPa.
  • the tempered glass plate of the present invention has a temperature of 1680° C. or lower at a high temperature viscosity of 10 2.5 dPa ⁇ s.
  • the "temperature at a high temperature viscosity of 10 2.5 dPa ⁇ s" can be measured, for example, by a platinum ball pulling method.
  • the molten glass can be easily formed into a plate shape.
  • the tempered glass plate of the present invention preferably contains Cl as a glass composition, and the content of Cl is 0.02 mol% or more.
  • the diameter of bubbles in the molten glass can be easily expanded, and a high clarification effect can be obtained.
  • the tempered glass plate of this invention contains MoO3 as a glass composition, and content of MoO3 is 0.0001 mol% or more.
  • the tempered glass plate easily absorbs ultraviolet rays, and it is possible to suppress deterioration of elements inside the device due to ultraviolet rays.
  • the tempered glass plate of the present invention is a tempered glass plate having a compressive stress layer on the surface, and the glass composition includes, in mol%, SiO 2 60 to 70%, Al 2 O 3 3 to 20%, B 2 O. 3 0-1%, Li 2 O 0-10%, Na 2 O 10-25%, K 2 O 0-5%, MgO 5-20%, CaO 0-1%, SrO 0-10%, BaO 0 It is preferable to contain ZnO 0-10%, P 2 O 5 0-4.7%, and [MgO]+[CaO]+[SrO]+[BaO] 5-30%.
  • the tempered glass plate of the present invention is a tempered glass plate having a compressive stress layer on the surface, and the glass composition includes, in mol%, SiO 2 65-82%, Al 2 O 3 5-16%, B 2 O. 3 0-10%, Li 2 O 0-10%, Na 2 O 5-25%, K 2 O 0-5%, MgO 0-10%, CaO 0-6%, SrO 0-5%, BaO 0 -5%, ZnO 0-10%, P 2 O 5 0-4.7%, [Li 2 O] + [Na 2 O] 5-20%, [MgO] + [CaO] + [SrO] + [ It is preferable to contain 1 to 10% of BaO].
  • a reinforced glass plate with high acid resistance particularly hydrofluoric acid resistance
  • the surface of the strengthened glass plate can be made to have fewer minute irregularities. As a result, the strength of the tempered glass plate can be increased.
  • the method for manufacturing a tempered glass plate of the present invention includes, in terms of glass composition, SiO 2 50-80%, Al 2 O 3 1-25%, B 2 O 3 0-15%, Li 2 O 0 ⁇ 20%, Na 2 O 0-25%, K 2 O 0-20%, ZnO 0-10%, P 2 O 5 0-15%, ZrO 2 0-10%, SnO 2 0-0.30% , [Li 2 O] + [Na 2 O] 1 to 30%, [Li 2 O] + [MgO] 1 to 25%, [MgO] + [CaO] + [SrO] + [BaO] 0.5 to A preparation step of preparing a tempering glass plate containing 30%, and an ion exchange step of performing ion exchange treatment on the tempering glass plate to obtain a tempered glass plate having a compressive stress layer on the surface. It is characterized by
  • the glass composition for strengthening of the present invention includes, in mol%, SiO 2 50-80%, Al 2 O 3 1-25%, B 2 O 3 0-15%, Li 2 O 0-20%. %, Na 2 O 0-25%, K 2 O 0-20%, ZnO 0-10%, P 2 O 5 0-15%, ZrO 2 0-10%, SnO 2 0-0.30%, [ Li 2 O] + [Na 2 O] 1 to 30%, [Li 2 O] + [MgO] 1 to 25%, [MgO] + [CaO] + [SrO] + [BaO] 0.5 to 30% It is characterized by containing.
  • a tempered glass plate having mechanical strength and transmittance suitable for a cover glass, a method for manufacturing a tempered glass plate, and a glass plate for tempering.
  • FIG. 2 is a schematic diagram illustrating a stress profile (stress distribution in the thickness direction of the glass plate) of a strengthened glass plate in which Li ions and Na ions in a molten salt have been ion-exchanged.
  • the tempered glass plate and glass plate for tempering of the present invention have a glass composition, in mol%, of SiO 2 50 to 80%, Al 2 O 3 1 to 25%, B 2 O 3 0 to 15%, Li 2 O 0 ⁇ 20%, Na 2 O 0-25%, K 2 O 0-20%, ZnO 0-10%, P 2 O 5 0-15%, ZrO 2 0-10%, SnO 2 0-0.30% , [Li 2 O] + [Na 2 O] 1 to 30%, [Li 2 O] + [MgO] 1 to 25%, [MgO] + [CaO] + [SrO] + [BaO] 0.5 to Contains 30%.
  • the reason for limiting the content range of each component is shown below.
  • % indication refers to mol% unless otherwise specified.
  • SiO 2 is a component that forms the glass network. If the content of SiO 2 is too low, it becomes difficult to vitrify, and the coefficient of thermal expansion becomes too high, making it easy to reduce thermal shock resistance. Furthermore, there is a possibility that hydrofluoric acid resistance may be reduced. Therefore, the preferred lower limit ranges for SiO 2 are 50% or more, 52% or more, 55% or more, 57% or more, 58% or more, 58.5% or more, 59% or more, 60% or more, 61% or more, 62%. 62.5% or more, 63% or more, 63.5% or more, 64.0% or more, 64.5% or more, especially 65% or more. On the other hand, if the content of SiO 2 is too large, meltability and moldability tend to decrease.
  • the preferable upper limit ranges of SiO 2 are 85% or less, 82% or less, 80% or less, 75% or less, 73% or less, 72% or less, 71% or less, 70.5% or less, 70% or less, 69. 5% or less, 69% or less, 68.5% or less, 68% or less, 67.8% or less, 67.5% or less, 67.2% or less, especially 67% or less.
  • Al 2 O 3 is a component that improves ion exchange performance, and is also a component that increases strain point, Young's modulus, fracture toughness, and Vickers hardness. Therefore, the preferred lower limit ranges for Al 2 O 3 are 1% or more, 3% or more, 5% or more, 7% or more, 7.2% or more, 7.5% or more, 7.8% or more, 8% or more, 8.2% or more, 8.5% or more, 9% or more, 9.2% or more, 9.4% or more, 9.5% or more, 9.8% or more, 10.0% or more, 10.3% 10.5% or more, 10.8% or more, 11% or more, 11.2% or more, 11.4% or more, 11.5% or more, 11.6% or more, 11.7% or more, 11.
  • the preferable upper limit ranges of Al 2 O 3 are 25% or less, 23% or less, 21% or less, 20.5% or less, 20% or less, 19.8% or less, 19.5% or less, 19.0%. 18.5% or less, 18% or less, 17.5% or less, 17% or less, 16.5% or less, 16% or less, 15.5% or less, 15.2% or less, 15% or less, 14. 9% or less, 14.7% or less, 14.5% or less, 14.3% or less, 14% or less, 13.5 or less, especially 13% or less.
  • B 2 O 3 is a component that lowers high-temperature viscosity and density, stabilizes glass, makes it difficult to deposit crystals, and lowers liquidus temperature. Furthermore, it is a component that increases the binding force of oxygen electrons by cations and lowers the basicity of glass. If the content of B 2 O 3 is too small, the stress depth DOC during ion exchange between Li ions contained in the glass and Na ions in the molten salt will become too deep, resulting in a predetermined depth ( 5 to 50 ⁇ m), the compressive stress value tends to be small. Further, there is a possibility that the glass becomes unstable and the devitrification resistance decreases.
  • the preferred lower limit ranges for B 2 O 3 are 0% or more, 0.10% or more, 0.15% or more, 0.20% or more, 0.30% or more, 0.4% or more, and 0.5%. 0.6% or more, 0.7% or more, 0.8% or more, 0.9% or more, 1% or more, 1.5% or more, 2% or more, 2.5% or more, 3% or more, It is 3.5% or more, 4% or more, especially 4.5% or more.
  • the preferred upper limit ranges of B 2 O 3 are 15% or less, 14.5% or less, 14% or less, 13.5% or less, 13% or less, 12.5% or less, 12% or less, 11.5%.
  • a suitable content is 0 to 1%, 0 to 0.8%, particularly 0 to 0.5%.
  • Li 2 O is an ion exchange component, and is particularly effective for ion exchange between Li ions contained in the glass and Na ions in the molten salt to obtain a deep stress depth. Furthermore, Li 2 O is a component that lowers high temperature viscosity and increases meltability and moldability, as well as a component that increases Young's modulus. Therefore, the preferred lower limit ranges for Li 2 O are 0% or more, 1% or more, 1.5% or more, 2% or more, 2.5% or more, 3% or more, 3.5% or more, 4% or more, 4% or more.
  • the preferred upper limit ranges of Li 2 O are 20% or less, 18% or less, 17% or less, 15% or less, 13% or less, 12% or less, 11.5% or less, 11% or less, 10.5% or less , 10% or less, 9.8% or less, 9.5% or less, 9.3% or less, 9% or less, 8.8% or less, especially 8.5% or less.
  • Na 2 O is an ion exchange component, and also a component that lowers high temperature viscosity and improves meltability and moldability. Moreover, Na 2 O is a component that improves devitrification resistance, and is a component that particularly suppresses devitrification caused by reaction with an alumina-based refractory. Therefore, the preferred lower limit ranges for Na 2 O are 0% or more, 0.1% or more, 0.2% or more, 0.3% or more, 0.5% or more, 0.7% or more, and 0.8% or more.
  • the preferred upper limit ranges of Na 2 O are 25% or less, 21% or less, 20% or less, 19% or less, 18% or less, 15% or less, 13% or less, 11% or less, 10% or less, and 9% or less. , 8% or less, 7.5% or less, 7% or less, 6.5% or less, 6% or less, 5.8% or less, 5.5% or less, 5.2% or less, especially 5% or less.
  • the preferred lower limit ranges for Na 2 O are 5% or more, 6% or more, 7% or more, 8% or more, and 9%. or more, especially 10% or more.
  • K 2 O is a component that lowers high temperature viscosity and improves meltability and moldability. Furthermore, it is a component that increases stress depth. Therefore, the preferred lower limit ranges for K 2 O are 0% or more, 0.01% or more, 0.02% or more, 0.03% or more, 0.05% or more, 0.08% or more, and 0.1% or more. , 0.2% or more, 0.3% or more, 0.4% or more, especially 0.5% or more.
  • the content of K 2 O is too large, the coefficient of thermal expansion will increase, and there is a possibility that the thermal shock resistance will decrease. Moreover, the compressive stress value at the outermost surface tends to decrease.
  • the preferred upper limit ranges of K 2 O are 20% or less, 18% or less, 15% or less, 12% or less, 10% or less, 7% or less, 6% or less, 5% or less, 4% or less, and 3% or less. , 2% or less, 1.5% or less, 1% or less, especially less than 1%.
  • MgO is a component that lowers high-temperature viscosity, increases meltability and moldability, and also increases strain point, Vickers hardness, Young's modulus, and fracture toughness.
  • MgO has the highest ion exchange performance. It is an ingredient that has a great effect on increasing the Therefore, the preferable lower limit ranges for MgO are 0% or more, 0.1% or more, 0.5% or more, 1% or more, 1.5% or more, 2% or more, 2.5% or more, 3% or more, 3.5% or more, 4% or more, 4.5% or more, 5% or more, 5.2% or more, 5.5% or more, 5.8% or more, 6% or more, 6.1% or more, 6.
  • the preferable upper limit ranges of MgO are 20% or less, 19% or less, 18% or less, 17% or less, 16% or less, 15% or less, 14% or less, 13% or less, 12% or less, 11% or less, 10.8% or less, 10.5% or less, 10.4% or less, 10.3% or less, 10.2% or less, 10.1% or less, especially 10% or less.
  • CaO is a component that lowers high-temperature viscosity, increases meltability and moldability, and increases strain point and Vickers hardness without reducing devitrification resistance.
  • the content of CaO is 0-12%, 0-10%, 0-9%, 0-8%, 0-7%, 0-6%, 0-5.5%, 0-5%, It is preferably 0 to 4.5%, 0 to 4%, 0 to 3.5%, 0 to 3%, 0 to 2%, particularly 0 to 1%.
  • SrO is a component that lowers high-temperature viscosity, increases meltability and moldability, and increases strain point and Young's modulus, but if its content is too large, ion exchange reactions are likely to be inhibited. In addition, the density and coefficient of thermal expansion become unduly high, and the glass tends to devitrify. Therefore, the SrO content is 0-12%, 0-10%, 0-9%, 0-8%, 0-7%, 0-6%, 0-5%, 0-4%, 0-3 %, 0-2%, 0-1.5%, particularly 0-1%.
  • BaO is a component that lowers high-temperature viscosity, improves meltability and moldability, and increases strain point and Young's modulus, but if its content is too large, ion exchange reactions are likely to be inhibited. In addition, the density and thermal expansion coefficient become unduly high, and the glass tends to devitrify. Therefore, the content of BaO is 0-12%, 0-10%, 0-9%, 0-8%, 0-7%, 0-6%, 0-5%, 0-4%, 0- It is preferably 3%, 0-2%, 0-1.5%, particularly 0-1%.
  • ZnO is a component that improves ion exchange performance, and is particularly effective in increasing the compressive stress value on the outermost surface of the compressive stress layer. It is also a component that reduces high temperature viscosity without significantly reducing low temperature viscosity. On the other hand, if the content of ZnO is too large, the glass tends to undergo phase separation, decrease in devitrification resistance, increase in density, and decrease in stress depth. Therefore, the preferred upper limit range of ZnO is 10% or less, 8% or less, 7% or less, 6% or less, 5.5% or less, 5.2% or less, 5% or less, 4.5% or less, especially 4%. It is as follows.
  • the preferred lower limit range of ZnO is 0% or more, 0.1% or more, 0.2% or more, 0.3% or more, 0.4% or more, 0.5% or more, 0.7% or more, 1% or more. , 1.1% or more, 1.2% or more, 1.5% or more, 1.8% or more, 2.0% or more, 2.1% or more, 2.2% or more, 2.5% or more, 2 .8% or more, 3.0% or more, 3.1% or more, 3.2% or more, especially 3.5% or more.
  • P 2 O 5 is a component that enhances ion exchange performance, and particularly increases stress depth. Furthermore, it is a component that also improves acid resistance. Furthermore, it is a component that increases the binding force of oxygen electrons by cations and lowers the basicity of glass. However, if the content of P 2 O 5 is too large, the glass will undergo phase separation and water resistance will tend to decrease. In addition, the stress depth DOC during ion exchange between Li ions contained in the glass and Na ions in the molten salt becomes too deep, resulting in a small compressive stress value at a predetermined depth (5 to 50 ⁇ m) from the outermost surface. easy.
  • the preferred upper limit ranges of P 2 O 5 are 15% or less, 12% or less, 10% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4.7% or less, 4.5%. Below, it is 4% or less, especially 3.5% or less.
  • the content of P 2 O 5 is too small, there is a possibility that the ion exchange performance cannot be fully exhibited. Further, there is a possibility that the glass becomes unstable and the devitrification resistance decreases. Furthermore, if the basicity of the glass becomes too high, the amount of O 2 released by the reaction of the fining agent will decrease, the foamability will decrease, and there is a risk that bubbles will remain in the glass when it is molded into a plate. Therefore, the preferable lower limit range of P 2 O 5 is 0% or more, 0.01% or more, 0.02% or more, 0.03% or more, 0.05% or more, especially 0.1% or more.
  • the preferable lower limit range of SnO2 is 0% or more, 0.001% or more, 0.002% or more, 0.005% or more, 0.007% or more, especially 0.010% or more
  • the preferable upper limit is The range is 0.30% or less, 0.27% or less, 0.25% or less, 0.20% or less, 0.18% or less, 0.15% or less, 0.12% or less, 0.10% or less , 0.09% or less, 0.08% or less, 0.07% or less, 0.06% or less, 0.05% or less, 0.047% or less, 0.045% or less, 0.042% or less, 0 0.040% or less, 0.038% or less, 0.035% or less, 0.032% or less, 0.030% or less, 0.025% or less, 0.020% or less, especially 0.015% or less.
  • Cl is a clarifying agent.
  • the bubble diameter in the glass tends to expand, making it easier to exhibit the clarification effect.
  • the preferred lower limit ranges for Cl are 0.001% or more, 0.005% or more, 0.008% or more, 0.010% or more, 0.015% or more, 0.018% or more, 0.019% or more.
  • the content of Cl is too small, it is necessary to increase the amount of SnO 2 in order to ensure the desired clarity, and there is a possibility that the devitrification resistance will decrease.
  • MoO 3 is a component that absorbs ultraviolet light (light with a wavelength of 200 to 300 nm). By containing MoO 3 in the glass, it is possible to suppress deterioration of internal elements of a device using the tempered glass plate of the present invention as a cover glass due to ultraviolet rays. Further, MoO 3 can be introduced by adding a small amount to the raw material batch, but it may also be introduced by elution from the Mo electrode when the raw material batch is melted by electric melting heating. By using electric melting, the amount of water in the glass can be reduced. When the water content in the glass decreases, the liquidus viscosity and softening point increase, and the devitrification resistance and heat resistance of the glass can be improved.
  • the preferable lower limit range of the content of MoO 3 is 0% or more, 0.0001% or more, 0.0003% or more, 0.0005% or more, 0.0008% or more, 0.001% in mol%.
  • the content is 0.0012% or more, 0.0015% or more, particularly 0.002% or more.
  • the content of MoO 3 is too large, the transmittance of the cover glass tends to decrease.
  • the preferable upper limit range of the content of MoO 3 is 0.02% or less, 0.018% or less, 0.015% or less, 0.012% or less, 0.01% or less, 0.02% or less, 0.018% or less, 0.01% or less, and 0. 0.008% or less, 0.007% or less, 0.006% or less, 0.005% or less, especially less than 0.004%.
  • the preferred lower limit range of [Li 2 O] + [Na 2 O], which is the total content of Li 2 O and Na 2 O, is 1% or more, 3% or more, 5% or more, 6% or more, 7% or more. % or more, 7.5% or more, 8% or more, 8.5% or more, 8.8% or more, 9% or more, 9.5% or more, 9.7% or more, especially 10% or more. If [Li 2 O] + [Na 2 O] is too small, ion exchange becomes difficult. On the other hand, if there is too much [Li 2 O] + [Na 2 O], there is a risk that the chemical resistance will decrease.
  • the preferable upper limit range of [Li 2 O] + [Na 2 O] is 30% or less, 28% or less, 25% or less, 23% or less, particularly 20% or less.
  • the preferred lower limit range of [Li 2 O] + [MgO], which is the total content of Li 2 O and MgO, is 1% or more, 3% or more, 5% or more, 6% or more, 7% or more, 7% or more. .5% or more, 8% or more, 8.5% or more, 8.8% or more, 9% or more, 9.5% or more, 9.7% or more, especially 10% or more. If [Li 2 O] + [MgO] is too small, it is difficult to improve mechanical properties such as Young's modulus and fracture toughness. Furthermore, there is a risk that the high temperature viscosity will increase and the meltability and moldability will decrease.
  • [Li 2 O] + [MgO] is too large, the devitrification resistance may be reduced.
  • the preferred upper limit range of [Li 2 O] + [MgO] is 25% or less, 23% or less, 20% or less, particularly 18% or less.
  • the preferred lower limit range of [MgO] + [CaO] + [SrO] + [BaO], which is the total content of MgO, CaO, SrO and BaO, is 0.5% or more, 0.6% or more, 0. .7% or more, 0.8% or more, 0.9% or more, 1% or more, 1.5% or more, 2% or more, 3% or more, 3.5% or more, 4% or more, 4.5% or more , 5% or more, 6% or more, 6.5% or more, 7% or more, 7.5% or more, especially 8% or more.
  • the preferred upper limit ranges of [MgO] + [CaO] + [SrO] + [BaO] are 30% or less, 28% or less, 25% or less, 24% or less, 22% or less, 20% or less, and 18%. Below, it is 15% or less, 12% or less, especially 10% or less.
  • the preferred lower limit range of [B 2 O 3 ] + [MgO] + [CaO], which is the total content of B 2 O 3 , MgO, and CaO, is 0.1% or more, 0.5% or more, 0.8% or more, 1% or more, 2% or more, 3% or more, 3.5% or more, 4% or more, 5% or more, 6% or more, 6.5% or more, especially 7% or more. If [B 2 O 3 ] + [MgO] + [CaO] is too small, it will be difficult to lower the softening point. On the other hand, if there is too much [B 2 O 3 ] + [MgO] + [CaO], the glass may become unstable and the devitrification resistance may decrease.
  • the preferable upper limit range of [B 2 O 3 ] + [MgO] + [CaO] is 30% or less, 28% or less, 25% or less, 24% or less, 22% or less, 20% or less, especially 18%. It is as follows.
  • the preferred lower limit range of [Li 2 O ] + [Na 2 O] + [K 2 O], which is the total content of Li 2 O, Na 2 O and K 2 O, is 7% or more, 7.5%. % or more, 8% or more, 8.5% or more, 8.8% or more, 9% or more, 9.5% or more, 9.7% or more, especially 10% or more. If [Li 2 O] + [Na 2 O] + [K 2 O] is too small, the efficiency of ion exchange tends to decrease and it is difficult to lower the softening point. On the other hand, if there is too much [Li 2 O] + [Na 2 O] + [K 2 O], there is a possibility that the chemical resistance will decrease.
  • the preferable upper limit range of [Li 2 O] + [Na 2 O] + [K 2 O] is 30% or less, 28% or less, 25% or less, 23% or less, 20% or less, especially 18% or less .
  • the preferred lower limit range of the molar ratio [R 2 O]/[Al 2 O 3 ] is 0.6 or more, 0.65 or more, 0.7 or more, 0.75 or more, 0.8 or more, especially 0.85. That's all. If the molar ratio [R 2 O]/[Al 2 O 3 ] is too small, the efficiency of ion exchange tends to decrease. On the other hand, if the molar ratio [R 2 O]/[Al 2 O 3 ] is too large, the efficiency of ion exchange tends to decrease.
  • the preferable upper limit ranges of the molar ratio [R 2 O]/[Al 2 O 3 ] are 2 or less, 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, and 1.5 or less. , 1.4 or less, especially 1.3 or less.
  • “[R 2 O] / [Al 2 O 3 ]” represents the total content of Li 2 O, Na 2 O and K 2 O. Refers to the value divided by the amount.
  • Suitable lower limit ranges of the molar ratio [RO]/[R 2 O] are 0.5 or more, 0.52 or more, 0.55 or more, 0.58 or more, 0.6 or more, 0.62 or more, 0. 65 or more, 0.68 or more, 0.70 or more, 0.72 or more, 0.75 or more, 0.78 or more, especially 0.8 or more. If [RO]/[R 2 O] is too small, the strain point, Vickers hardness, Young's modulus, and fracture toughness may decrease. On the other hand, if the molar ratio [RO]/[R 2 O] is too large, devitrification resistance and ion exchange efficiency tend to decrease, making it difficult to lower the softening point. Therefore, the preferable upper limit range of the molar ratio [RO]/[R 2 O] is 1.5 or less, 1.3 or less, 1.2 or less, 1.1 or less, particularly 1 or less.
  • Suitable upper limit ranges of the molar ratio [Al 2 O 3 ]/([R 2 O] + [RO]) are 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, 1.1 Below, it is 1 or less, especially 0.9 or less. If [Al 2 O 3 ]/([R 2 O] + [RO]) is too large, the high temperature viscosity will increase and the meltability and moldability will tend to decrease. On the other hand, if [Al 2 O 3 ]/([R 2 O] + [RO]) is too small, the liquidus temperature and liquidus viscosity may decrease.
  • the preferable lower limit range of [Al 2 O 3 ]/([R 2 O] + [RO]) is 0.2 or more, 0.25 or more, 0.3 or more, 0.35 or more, especially 0. It is 4 or more.
  • the molar ratio [Al 2 O 3 ]/([R 2 O] + [RO]) represents the content of Al 2 O 3 and the total amount of the content of MgO, CaO, SrO, and BaO. ] and [R 2 O], which represents the total content of Li 2 O, Na 2 O, and K 2 O.
  • Suitable upper limit ranges of the molar ratio [Na 2 O]/[Li 2 O] are 1.0 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.65 or less, 0.6 or less, 0.58 or less, 0.55 or less, 0.52 or less, 0.5 or less, 0.48 or less, 0.45 or less, 0.43 or less, especially 0.4 or less. If the molar ratio [Na 2 O]/[Li 2 O] is too large, the efficiency of ion exchange between Li ions contained in the glass and Na ions in the molten salt tends to decrease.
  • the molar ratio [Na 2 O]/[Li 2 O] is too small, the high temperature viscosity may increase and the meltability and moldability may decrease. Moreover, devitrification resistance tends to decrease. Preferably it is 0 or more, 0.03 or more, 0.05 or more, 0.07 or more, 0.10 or more, 0.15 or more, 0.18 or more, especially 0.2 or more. Note that the molar ratio [Na 2 O]/[Li 2 O] refers to the value obtained by dividing the content of Na 2 O by the content of Li 2 O.
  • the preferred lower limit range of the molar ratio ([ZnO] + [Li 2 O] + [Na 2 O] + [K 2 O]) / [Al 2 O 3 ] is 0.5 or more, 0.55 or more, 0 .60 or more, 0.7 or more, 0.75 or more, 0.8 or more, especially 0.85 or more. If the molar ratio ([ZnO] + [Li 2 O] + [Na 2 O] + [K 2 O]) / [Al 2 O 3 ] is too small, the efficiency of ion exchange tends to decrease, lowering the softening point. It's hard to let go.
  • the preferable upper limit range of the molar ratio ([ZnO] + [Li 2 O] + [Na 2 O] + [K 2 O]) / [Al 2 O 3 ] is 2 or less, 1.8 or less, 1 .9 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.35 or less, 1.3 or less, especially 1.25 or less.
  • the molar ratio ([ZnO] + [Li 2 O] + [Na 2 O] + [K 2 O]) / [Al 2 O 3 ] is the ratio of ZnO, Li 2 O, Na 2 O and K 2 O. It is the value obtained by dividing the total content by Al 2 O 3 .
  • the molar ratio [MgO]/[Al 2 O 3 ] is preferably 1.2 or less, 1.1 or less, 1.05 or less, 1.0 or less, 0.95 or less, 0.9 or less, 0.85 or less , 0.8 or less, 0.75 or less, 0.7 or less, 0.6 or less, especially 0.5 or less. If [MgO]/[Al 2 O 3 ] is too large, reaction lumps are likely to occur when it comes into contact with a molded body (particularly an alumina molded body) at a high temperature, and there is a risk that the quality of the glass formed into a plate shape will deteriorate.
  • the lower limit of [MgO]/[Al 2 O 3 ] is not particularly limited, but is, for example, 0 or more, 0.01 or more, 0.03 or more, or 0.05 or more. Note that [MgO]/[Al 2 O 3 ] refers to the value obtained by dividing the MgO content by the Al 2 O 3 content.
  • the preferred lower limit range is 0.30 or more, 0.33 or more, 0.35 0.37 or more, 0.38 or more, 0.39 or more, 0.40 or more, 0.41 or more, 0.42 or more, 0.43 or more, 0.44 or more, 0.45 or more, 0.48 0.50 or more, 0.51 or more, 0.52 or more, 0.53 or more, 0.54 or more, especially 0.55 or more.
  • ([SiO 2 ]+1.2 ⁇ [P 2 O 5 ] ⁇ 3 ⁇ [Al 2 O 3 ] ⁇ [B 2 O 3 ] ⁇ 2 ⁇ [Li 2 O] ⁇ 1.5 ⁇ [Na 2 O ]-[K 2 O]) is too large, there is a risk that the ion exchange performance cannot be fully exhibited. Therefore, ([SiO 2 ]+1.2 ⁇ [P 2 O 5 ] ⁇ 3 ⁇ [Al 2 O 3 ] ⁇ [B 2 O 3 ] ⁇ 2 ⁇ [Li 2 O] ⁇ 1.5 ⁇ [Na 2 O ]-[K 2 O]) is preferably 50 or less, 45 or less, 40 or less, 35 or less, 30 or less, 25 or less, particularly 20 or less.
  • ([SiO 2 ]+1.2 ⁇ [P 2 O 5 ] ⁇ 3 ⁇ [Al 2 O 3 ] ⁇ [B 2 O 3 ] ⁇ 2 ⁇ [Li 2 O] ⁇ 1.5 ⁇ [Na 2 O ]-[K 2 O]) is the sum of the SiO 2 content and 1.2 times the P 2 O 5 content, 3 times the Al 2 O 3 content, and the B 2 O 3 content.
  • the content is twice the Li 2 O content, 1.5 times the Na 2 O content, and the total of the K 2 O content is reduced.
  • the value of X in the following formula is a factor that correlates with the exchange rate of Li ions and Na ions. If the X value is too small, the efficiency of ion exchange between Li ions and Na ions in the molten salt will decrease, making it difficult to apply compressive stress. In particular, the depth of stress (DOC) of the compressive stress layer during ion exchange between Li ions contained in the glass and Na ions in the molten salt may become small. Therefore, the preferable lower limit range of the X value is 300 or more, 320 or more, 330 or more, 340 or more, 350 or more, 400 or more, 450 or more, 460 or more, 480 or more, 500 or more, 520 or more, especially 550 or more.
  • the upper limit range of X is not particularly limited, but is, for example, 850 or less and 800 or less.
  • X -1.49 ⁇ [SiO 2 ]+26.98 ⁇ [Al 2 O 3 ]-3.23 ⁇ [B 2 O 3 ]+48.56 ⁇ [Li 2 O]-24.31 ⁇ [Na 2 O ]-0.28 ⁇ [MgO]+2.74 ⁇ [CaO]
  • the W value in the following formula is a factor that correlates with Young's modulus. If the W value is too small, the Young's modulus will be low and the glass will be easily damaged. Therefore, the preferable lower limit range of the W value is 250 or more, 300 or more, 330 or more, 340 or more, 350 or more, 360 or more, 370 or more, 400 or more, 430 or more, 450 or more, 480 or more, especially 500 or more.
  • the upper limit range of the W value is not particularly limited, but is, for example, 750 or less and 700 or less.
  • TiO 2 is a component that enhances ion exchange performance and lowers high-temperature viscosity, but if its content is too large, transparency and devitrification resistance tend to decrease. Therefore, the preferred content of TiO 2 is 0 to 10%, 0 to 5%, 0 to 3%, 0 to 1.5%, 0 to 1%, 0 to 0.1%, especially 0.001 to 0. .1 mol%.
  • ZrO 2 is a component that increases Vickers hardness and also increases viscosity near the liquid phase viscosity and strain point, but if its content is too large, there is a risk that devitrification resistance will be significantly reduced. Therefore, the preferred content of ZrO 2 is 0-10%, 0-5%, 0-3%, 0-1.5%, 0-1%, 0-0.5%, 0-0.4%. , 0-0.3%, 0-0.2%, especially 0-0.1%.
  • Fe 2 O 3 is an impurity mixed in from raw materials. Suitable upper limit ranges of Fe 2 O 3 are 0.1% or less, 0.08% or less, 0.05% or less, 0.02% or less, less than 0.015%, and less than 0.01% in mol%. , less than 0.008%, especially less than 0.005%. If the content of Fe 2 O 3 is too large, the transmittance of the cover glass tends to decrease. On the other hand, the preferable lower limit range is 0.001% or more, 0.002% or more, and 0.003% or more in mol%. If the content of Fe 2 O 3 is too low, the cost of raw materials will rise due to the use of high-purity raw materials, making it impossible to manufacture products at low cost.
  • SO 3 and/or CeO 2 may be added in an amount of 0.001 to 1%.
  • Rare earth oxides such as Nd 2 O 3 , La 2 O 3 , Y 2 O 3 , Nb 2 O 5 , Ta 2 O 5 and Hf 2 O 3 are components that increase Young's modulus.
  • the raw material cost is high, and when added in a large amount, devitrification resistance tends to decrease. Therefore, the preferable content of the rare earth oxide is 5% or less, 4% or less, 3% or less, 2% or less, 1% or less, 0.5% or less, particularly 0 to 0.1%.
  • the tempered glass plate (glass plate for tempering) of the present invention preferably does not substantially contain As 2 O 3 , Sb 2 O 3 , PbO, and F as a glass composition from environmental considerations. Furthermore, from environmental considerations, it is also preferable that substantially no Bi 2 O 3 be contained.
  • substantially not containing means that no specified component is actively added as a glass component, but the addition of impurity level is allowed. Specifically, it refers to a case where the content of the specified component is less than 0.05 mol%.
  • the tempered glass plate (strengthening glass plate) of the present invention preferably has the following characteristics.
  • the density ( ⁇ ) is preferably 2.9 g/cm 3 or less, 2.85 g/cm 3 or less, 2.83 g/cm 3 or less, 2.8 g/cm 3 or less, 2.75 g/cm 3 or less, 2. 7 g/cm 3 or less, 2.35 to 2.65 g/cm 3 , especially 2.25 to 2.6 g/cm 3 .
  • the thermal expansion coefficient at 30 to 380°C is preferably 150 x 10 -7 /°C or less, 100 x 10 -7 /°C or less, 50 to 95 x 10 -7 /°C, particularly 40 to 85 x 10 -7 /°C. It is. Note that the "thermal expansion coefficient at 30 to 380° C.” refers to the value of the average thermal expansion coefficient measured using a dilatometer.
  • the softening point (Ts) is preferably 920°C or lower, 910°C or lower, 900°C or lower, 890°C or lower, 880°C or lower, 870°C or lower, 860°C or lower, 850°C or lower, 840°C or lower, 830°C or lower, especially
  • the temperature is 700-820°C. If the softening point is too high, there is a risk that thermal workability will be reduced.
  • the temperature at high temperature viscosity of 10 2.5 dPa ⁇ s is preferably 1680°C or lower, 1670°C or lower, 1660°C or lower, 1650°C or lower, 1640°C or lower, 1630°C or lower, 1620°C or lower, 1600°C or lower, 1550°C or lower, 1520°C or lower °C or lower, 1500°C or lower, especially 1300 to 1490°C. If the temperature at a high-temperature viscosity of 10 2.5 dPa ⁇ s is too high, the meltability and formability will decrease, making it difficult to form the molten glass into a plate shape.
  • the liquidus viscosity ( ⁇ ) is preferably 10 2.8 dPa ⁇ s or more, 10 2.9 dPa ⁇ s or more, 10 3.0 dPa ⁇ s or more, 10 3.1 dPa ⁇ s or more, 10 3.2 dPa ⁇ s or more, 10 3.3 dPa ⁇ s Above, 10 3.4 dPa ⁇ s or above, 10 3 . It is 5 dPa ⁇ s or more, 10 3.55 dPa ⁇ s or more, especially 10 3.58 dPa ⁇ s or more. Note that the higher the liquidus viscosity, the better the devitrification resistance improves, and the less likely devitrification lumps will occur during molding.
  • liquidus viscosity refers to a value of viscosity at liquidus temperature measured by a platinum ball pulling method.
  • Liquidus temperature refers to the glass powder that passes through a standard sieve of 30 mesh (500 ⁇ m) and remains on 50 mesh (300 ⁇ m), is placed in a platinum boat, held in a temperature gradient furnace for 24 hours, and then the platinum boat is taken out. , the highest temperature at which devitrification (devitrification spots) was observed inside the glass by microscopic observation.
  • the transmittance at a wavelength of 400 nm when converted to a thickness of 0.6 mm is preferably 85% or more, 88% or more, particularly 90% or more. If the transmittance is low, there is a risk that the visibility and color expression of the display will be reduced when used for a cover glass. Although the upper limit range of transmittance is not particularly limited, it is realistically 100% or less.
  • mechanical properties refer to properties related to the strength of glass, which are mainly determined by the glass composition, and specifically include properties such as Young's modulus and fracture toughness value.
  • Young's modulus (E) is preferably 76 GPa or more, 77 GPa or more, 78 GPa or more, 79 GPa or more, 80 GPa or more, especially 82 GPa or more.
  • Young's modulus is preferably 76 GPa or more, 77 GPa or more, 78 GPa or more, 79 GPa or more, 80 GPa or more, especially 82 GPa or more.
  • the cover glass becomes easy to bend when the plate thickness is thin.
  • the upper limit range of Young's modulus is not particularly limited, but is substantially 150 GPa or less. Note that "Young's modulus" can be calculated using a well-known resonance method.
  • the fracture toughness K1c is preferably 0.78 MPa ⁇ m 0.5 or more, 0.79 MPa ⁇ m 0.5 or more, 0.80 MPa ⁇ m 0.5 or more, 0.81 MPa ⁇ m 0.5 or more, particularly 0.82 MPa ⁇ m 0.5 or more. If the fracture toughness K1c is low, the tempered glass plate will be easily damaged. Although the upper limit of the fracture toughness K1c is not particularly limited, it is substantially 3 MPa ⁇ m 0.5 or less.
  • the reinforcing property refers to a property related to the strength of the glass that is subsequently imparted to the glass after molding by ion exchange treatment, and specifically refers to the compressive stress value (CS) of the outermost surface of the glass, Properties such as compressive stress value (CS30), stress depth (DOC), and internal tensile stress value (CTcv) at a depth of 30 ⁇ m from the outermost surface are included.
  • the compressive stress value (CS) of the outermost surface in ion exchange between Li ions contained in the glass and Na ions in the molten salt is preferably 240 MPa or more, 260 MPa or more, 280 MPa or more, or 300 MPa or more. , 320 MPa or more, 340 MPa or more, 350 MPa or more, 380 MPa or more, 400 MPa or more, 420 MPa or more, especially 450 MPa or more.
  • the larger the compressive stress value (CS) of the outermost surface the higher the strength.
  • the compressive stress value (CS) of the outermost surface is preferably 1200 MPa or less, 1000 MPa or less, 900 MPa or less, 850 MPa or less, 800 MPa or less, 780 MPa or less, 750 MPa or less, particularly 740 MPa or less.
  • the compressive stress value (CS30) at a depth of 30 ⁇ m from the outermost surface in ion exchange of Li ions contained in the glass and Na ions in the molten salt is preferably 25 MPa or more, 30 MPa or more, 35 MPa or more, 40 MPa or more, 50 MPa or more. , 60 MPa or more, 70 MPa or more, 80 MPa or more, 90 MPa or more, 100 MPa or more, 105 MPa or more, 110 MPa or more, 115 MPa or more, especially 120 MPa or more.
  • CS30 has a characteristic that can effectively improve the four-point bending strength during damage.
  • the compressive stress value (CS30) at a depth of 30 ⁇ m is preferably 400 MPa or less, 350 MPa or less, 330 MPa or less, 300 MPa or less, 280 MPa or less, 270 MPa or less, 260 MPa or less, particularly 250 MPa or less.
  • the depth of stress (DOC) in ion exchange between Li ions contained in the glass and Na ions in the molten salt is preferably 3 ⁇ m or more, 5 ⁇ m or more, 10 ⁇ m or more, 20 ⁇ m or more, 25 ⁇ m or more, 30 ⁇ m or more, 35 ⁇ m or more, 40 ⁇ m.
  • the thickness is 45 ⁇ m or more, particularly 50 ⁇ m or more. The deeper the stress depth, the harder it is for road surface protrusions and sand grains to reach the tensile stress layer when the smartphone is dropped, making it possible to reduce the probability of damage to the cover glass. On the other hand, if the stress depth is too deep, there is a risk that dimensional changes will become large before and after the ion exchange treatment.
  • the depth of stress (DOC) is preferably 200 ⁇ m or less, 180 ⁇ m or less, 170 ⁇ m or less, 150 ⁇ m or less, 140 ⁇ m or less, 130 ⁇ m or less, 120 ⁇ m or less, 110 ⁇ m or less, especially 100 ⁇ m or less. Note that if the ion exchange time is increased or the temperature of the ion exchange solution is increased, the stress depth tends to increase.
  • the internal tensile stress value (CTcv) in ion exchange between Li ions contained in the glass and Na ions in the molten salt is preferably 88 MPa or less, 85 MPa or less, 80 MPa or less, 75 MPa or less, 73 MPa or less, 70 MPa or less, 68 MPa or less , 65 MPa or less, 62 MPa or less, especially 60 MPa or less. If the internal tensile stress value is too large, there is a risk that the tempered glass plate will self-destruct due to a point collision, or that the glass will shatter explosively at the time of destruction.
  • the lower limit range of the internal tensile stress value (CTcv) is not particularly limited, but is substantially 5 MPa or more.
  • the mass loss per unit surface area when immersed in a 5% by mass HCl aqueous solution heated to 80°C for 24 hours is 2.0 mg/cm 2 or less, 1.5 mg/cm 2 or less , 1.0 mg/cm 2 or less, 0.9 mg/cm 2 or less, 0.8 mg/cm 2 or less, 0.7 mg/cm 2 or less, 0.6 mg/cm 2 or less, 0.5 mg/cm 2 or less, 0 It is preferably at most .4 mg/cm 2 , at most 0.3 mg/cm 2 , at most 0.2 mg/cm 2 , particularly at most 0.1 mg/cm 2 .
  • the tempered glass plate may come into contact with acidic chemicals depending on the environment in which the device is used, so it is preferable to have high acid resistance from the viewpoint of preventing device malfunctions.
  • the mass loss per unit surface area when immersed in a 5% by mass NaOH aqueous solution heated to 80°C for 6 hours was 5.0 mg/cm 2 or less, 4.5 mg/cm 2 or less, 4.0 mg/cm 2 or less, 3.5 mg/cm 2 or less, 3.0 mg/cm 2 or less, 2.5 mg/cm 2 or less, 2.0 mg/cm 2 or less, 1.5 mg/cm 2 or less, especially 1.0 mg/cm 2 It is preferable that it is below. Tempered glass plates are required to have high alkali resistance, as they may come into contact with alkaline chemicals and detergents depending on the environment in which the device is used.
  • the mass loss per unit surface area when immersed in a 10% by mass HF aqueous solution maintained at 20°C for 20 minutes is 30 mg/cm 2 or less, 25 mg/cm 2 or less, 20 mg/cm 2 or less, 15 mg/cm 2 14 mg/cm 2 or less, 13 mg/cm 2 or less, 12 mg/cm 2 or less, 11 mg/cm 2 or less, 10.5 mg/cm 2 or less, 10 mg/cm 2 or less, 9.5 mg/cm 2 or less, 9.
  • Tempered glass plates may be chemically etched to adjust the thickness or modify the surface condition, but even in such cases it is preferable that the tempered glass plates have high hydrofluoric acid resistance. . If the tempered glass plate has high hydrofluoric acid resistance, the glass surface after chemical etching treatment can be made into a state with few minute irregularities, and high strength can be obtained.
  • mechanical strength refers to the strength properties of glass determined by the mechanical properties and reinforcement properties of glass, and specifically includes the four-point bending strength.
  • the tempered glass plate of the present invention preferably has a four-point bending strength of 150 MPa or more, 160 MPa or more, 1170 MPa or more, 180 MPa or more, 190 MPa or more, 200 MPa or more, 220 MPa or more, 240 MPa or more, particularly 265 MPa or more. If the four-point bending strength is too low, when used as a cover glass for a smartphone, it will easily break when dropped. Although the upper limit of the four-point bending strength is not particularly limited, it is realistically 1500 MPa or less.
  • the plate thickness is preferably 2.0 mm or less, 1.5 mm or less, 1.3 mm or less, 1.1 mm or less, 1.0 mm or less, 0.9 mm or less, particularly 0.85 mm or less. be.
  • the plate thickness is preferably 0.01 mm or more, 0.02 mm or more, 0.03 mm or more, 0.05 mm or more, 0.1 mm or more, 0.2 mm or more, 0.3 mm or more, 0.35 mm or more, 0.
  • strengthening can also be made into the same range.
  • the thickness of the tempered glass plate can be selected depending on the application. For example, for display applications that do not fold, the plate thickness is preferably 0.35 to 0.85 mm, more preferably 0.45 to 0.75 mm, and 0.51 to 0.71 mm. On the other hand, for foldable display applications, the thickness is preferably 0.01 to 0.10 mm, more preferably 0.02 to 0.05 mm, and 0.025 to 0.04 mm.
  • crystals are not substantially included.
  • substantially not containing refers to the content of crystals in the glass being 0.01% by mass or less.
  • crystals may be included.
  • the method for producing a tempered glass plate of the present invention includes, in terms of glass composition, SiO 2 50-80%, Al 2 O 3 1-25%, B 2 O 3 0-15%, Li 2 O 1-20%. %, Na 2 O 0-25%, K 2 O 0-20%, ZnO 0-10%, P 2 O 5 0-15%, ZrO 2 0-10%, SnO 2 0-0.30%, [ Li 2 O] + [Na 2 O] 1 to 30%, [Li 2 O] + [MgO] 1 to 25%, [MgO] + [CaO] + [SrO] + [BaO] 0.1 to 30% a preparation step of preparing a tempering glass plate containing the above-mentioned material; and an ion exchange step of performing an ion exchange treatment on the tempering glass plate to obtain a tempered glass plate having a compressive stress layer on the surface.
  • the method for manufacturing a tempered glass plate of the present invention includes not only the case where the
  • a method for manufacturing a glass sheet for reinforcement is as follows. First, glass raw materials prepared to have the desired glass composition are put into a continuous melting furnace, heated and melted at 1400 to 1700°C, and after being clarified, the molten glass is fed to a forming device and formed into a plate shape. , preferably cooled. After forming into a plate shape, a well-known method can be used to cut the plate into a predetermined size.
  • an overflow down-draw method is preferable.
  • the overflow merging surface is formed in the center of the glass plate in the thickness direction, and the surface that should become the surface of the glass plate does not contact the surface of the molded refractory and is formed into a plate shape as a free surface. Ru. Therefore, an unpolished glass plate with good surface quality can be manufactured at low cost.
  • an alumina-based refractory or a zirconia-based refractory is used as the molded refractory.
  • the tempered glass plate (strengthening glass plate) of the present invention has good compatibility with alumina-based refractories and zirconia-based refractories (particularly alumina-based refractories), so it does not react with these refractories. It has the property of not easily generating bubbles or lumps.
  • a molding method such as a float method, a down-draw method (slot down-draw method, redraw method, etc.), a roll-out method, a press method, etc. can be adopted.
  • tempering glass plate and tempered glass plate of the present invention include not only flat plate shapes but also forms in which a three-dimensional shape is given by bending or the like after being formed into a plate shape.
  • the temperature range between the annealing point and strain point of the molten glass it is preferable to cool the temperature range between the annealing point and strain point of the molten glass at a cooling rate of 3°C/min or more and less than 1000°C/min, and the lower limit range of the cooling rate is , preferably 10°C/min or more, 20°C/min or more, 30°C/min or more, especially 50°C/min or more, and the upper limit range is preferably less than 1000°C/min, less than 500°C/min, especially 300°C/min or more. less than °C/min. If the cooling rate is too fast, the structure of the glass will become coarse, making it difficult to increase the Vickers hardness after ion exchange treatment. On the other hand, if the cooling rate is too slow, the production efficiency of glass plates will decrease.
  • the glass plate for reinforcement may be crystallized by heat treatment.
  • a tempered glass plate of the present invention from the viewpoint of suppressing explosive destruction, it is preferable to use an ion exchange treatment in which the glass plate is immersed once in a mixed molten salt of NaNO 3 and KNO 3 .
  • the compressive stress value (CS) at the outermost surface and the compressive stress value (CS30) at a depth of 30 ⁇ m from the outermost surface can be efficiently controlled. Therefore, the tensile stress value ( CTCV ) inside the tempered glass plate is prevented from becoming too high, and a safe tempered glass plate with a small number of fragments when dropped is easily obtained.
  • Figure 1 is a schematic diagram of the stress profile (stress distribution in the thickness direction of the glass plate) of a strengthened glass plate after ion exchange of Li ions and Na ions in the molten salt.
  • the broken line represents the stress profile of a tempered glass plate strengthened with a mixed molten salt containing 10% by mass of NaNO 3 and 90% of KNO 3 .
  • the tempered glass plate strengthened with 100% by mass of NaNO 3 shown by the solid line has a CS of 498 MPa, a CS30 of 265 MPa, and a CT CV of 91 MPa, whereas the NaNO 3 shown by the broken line
  • CS is suppressed to 425 MPa and CS30 is suppressed to 241 MPa, and as a result, CT CV is also reduced to 87 MPa.
  • the concentration of NaNO 3 is preferably 0.5% by mass or more, 1% by mass or more, 5% by mass or more, 7% by mass or more, 10% by mass or more, In particular, it is 12 to 20% by mass. If the concentration of NaNO 3 is too low, it may become difficult to measure stress using the surface stress meter SLP-2000. Furthermore, if the concentration of NaNO 3 is too high, there is a risk that the compressive stress value formed when Li ions contained in the glass and Na ions in the molten salt undergo ion exchange will become too high.
  • ion exchange may be performed by immersing it in a molten salt containing 100% by mass of NaNO 3 .
  • the glass plate for strengthening contains Na 2 O
  • ion exchange of Na ions in the glass and K ions in the molten salt may be performed by immersing it in a molten salt containing 100% by mass of KNO 3 .
  • the temperature of the molten salt is preferably 360 to 430°C, and the ion exchange time is preferably 30 minutes to 6 hours.
  • Example 1 Tables 1 to 50 show the glass compositions and glass properties of Examples of the present invention (Samples Nos. 1 to 23, 26 to 320) and Comparative Examples (Samples Nos. 24 and 25). Also, N. A. indicates not measured. Further, R 2 O represents the total amount of Li 2 O, Na 2 O and K 2 O, and RO represents the total amount of MgO, CaO, SrO and BaO.
  • Sample Nos. 1 to 50 in Tables 1 to 50 were prepared as follows. 1 to 320 were produced. First, sample No. listed in Tables 1 to 25. Glass raw materials were prepared to have a glass composition of 1 to 320, and melted at 1600° C. for 21 hours using a platinum pot. Next, the obtained molten glass was poured onto a carbon plate and formed into a flat plate shape, and then cooled at a rate of 3°C/min in the temperature range between the annealing point and the strain point. A glass plate) was obtained. The obtained glass plates were evaluated for various properties listed in Tables 26 to 50.
  • the density ( ⁇ ) is a value measured by the well-known Archimedes method.
  • the coefficient of thermal expansion at 30-380°C ( ⁇ 30-380 °C) is a value obtained by measuring the average coefficient of thermal expansion using a dilatometer.
  • the softening point (Ts) is a value measured based on the method of ASTM C338.
  • the temperature at a high temperature viscosity of 10 2.5 dPa ⁇ s (10 2.5 dPa ⁇ s) is a value measured by the platinum ball pulling method.
  • Young's modulus (E) was calculated by a method based on JIS R1602-1995 "Testing method for elastic modulus of fine ceramics".
  • the transmittance at a wavelength of 400 nm is the value obtained by measuring the linear transmittance in the thickness direction of a tempered glass plate with a thickness of 0.6 mm using an ultraviolet-visible near-infrared spectrophotometer (UH4150 manufactured by Hitachi High-Tech Science). It is.
  • the obtained sample No. Ion exchange treatment was performed by immersing the tempering glass plates Nos. 1 to 24 in NaNO 3 molten salt at 380° C. for 1 hour. After the ion exchange treatment, the surface of each sample was washed. Next, the compressive stress value (CS) at the outermost surface and the compressive stress value (CS30) at a depth of 30 ⁇ m were determined from the phase difference distribution curve observed using a scattered light photoelastic stress meter SLP-2000 (manufactured by Orihara Seisakusho Co., Ltd.). The depth of stress (DOC) and internal tensile stress value (CTcv) were calculated. Here, DOC is the depth at which the stress value becomes zero. In addition, the obtained sample No.
  • Ion exchange treatment was performed by immersing a glass plate for tempering No. 26 to 320 in KNO 3 molten salt at 380° C. for 4 hours. After the ion exchange treatment, the surface of each sample was washed. Next, the compressive stress value (CS) at the outermost surface, the compressive stress value (CS30) at a depth of 30 ⁇ m, and the stress depth were determined from the phase difference distribution curve observed using a surface stress meter FSM-6000 (manufactured by Orihara Seisakusho Co., Ltd.). (DOC) and internal tensile stress value (CTcv) were calculated. Here, DOC is the depth at which the stress value becomes zero.
  • the refractive index of each sample was set to 1.53, and the optical elastic constant was set to 29.0 [(nm/cm)/MPa]. Note that although the glass composition in the surface layer of the glass differs microscopically before and after the ion exchange treatment, when viewed as a whole, the glass composition does not substantially differ.
  • sample No. In No. 25 both surfaces were optically polished to a plate thickness of 0.6 mm, and then heat treated at 615° C. for 12 hours and at 850° C. for 3 hours to precipitate crystals to obtain crystallized glass.
  • the Young's modulus and transmittance of the obtained crystallized glass were measured under the conditions described above.
  • ion exchange treatment was performed by immersing it in NaNO 3 molten salt at 430° C. for 6 hours. After the ion exchange treatment, the surface of each sample was washed.
  • the fracture toughness value (K1c) was measured by the SEPB method based on JIS R1607 "Fracture toughness testing method for fine ceramics.” The fracture toughness value of each sample was determined from the average value of three points.
  • sample No. Nos. 1 to 23 and 26 to 65 have high Young's modulus, especially No. No. 1 had a fracture toughness value of 0.82 MPa ⁇ m 0.5 , and a glass with high mechanical properties was obtained.
  • sample No. which is a comparative example.
  • Sample No. 24 had a low Young's modulus of 74 GPa and a low fracture toughness value of 0.76 MPa ⁇ m 0.5 due to low RO.
  • sample No. Nos. 1 to 23 had a high transmittance of 91.2% or more.
  • sample No., which is a crystallized strengthened glass plate, No. 25 had a low transmittance of 72.5% after crystallization.
  • Example 2 Table 51 shows the glass properties of Example A of the present invention and Comparative Example B.
  • SPP-4PB represents the 4-point bending strength due to damage
  • N.A represents not measured.
  • Example A and Comparative Example B (strengthened glass plates) shown in Table 51 were produced in the following manner.
  • Glass raw materials were prepared to have glass compositions 1 and 24, and melted at 1600° C. for 21 hours using a platinum pot. Thereafter, the obtained molten glass was poured onto a carbon plate, formed into a flat plate shape, and slowly cooled. The Young's modulus of the obtained glass plate was evaluated in the same manner as in Example 1. Thereafter, the resulting flat glass was ground and polished to obtain a reinforcing glass plate with a thickness of 0.6 mm. Next, each of the obtained tempering glass plates was cut into a predetermined size.
  • the tempering glass plate of Example A was immersed at 430°C in a mixed molten salt containing 15% by mass of NaNO 3 and 85% by mass of KNO 3 for 1 hour to perform ion exchange treatment and strengthen it. It was made of glass plate.
  • the tempering glass plate of Comparative Example B was subjected to ion exchange treatment by immersing it in molten NaNO 3 at 380°C for 3 hours, and then 95% by mass of KNO 3 and 5% by mass of NaNO 3 at 380°C. % of the mixed molten salt for 45 minutes to perform an ion exchange treatment to obtain a tempered glass plate.
  • the fracture toughness value and 4-point bending strength of the obtained tempered glass plate were measured.
  • the fracture toughness value (K1c) was evaluated in the same manner as in Example 1.
  • the four-point bending strength was measured using the following procedure.
  • the glass was damaged using the following procedure.
  • a 35mm x 35mm tempered glass plate processed to a thickness of 0.6mm was fixed vertically to a 1.5mm thick SUS plate, and the tip of the pendulum-shaped arm was attached to it through P180 sandpaper. They collided and caused injuries.
  • the tip of the arm is an iron cylinder with a diameter of 5 mm, and the weight of the arm is 550 g.
  • the height at which the arm was swung down was 100 mm from the collision point.
  • the damaged sample was subjected to a 4-point bending test according to JIS R1601 (1995), and the "damaged 4-point bending strength" was measured. The test was conducted on six samples for each example, and the average value of the measured values was used as the evaluation result.
  • Example A has high mechanical properties such as a Young's modulus of 87 GPa and a fracture toughness value of 0.82 MPa ⁇ m 0.5 , and has compressive stress at a depth of 30 ⁇ m from the outermost surface of the compressive stress layer. Since the value (CS30) was also high at 244 MPa, the 4-point bending strength was high at 290 MPa. On the other hand, Comparative Example B had a Young's modulus of 74 GPa and a fracture toughness value of 0.76 MPa ⁇ m 0.5 , which were lower than those of Example A, and also had a low CS30 of 120 MPa, so the four-point bending strength was also low at 172 MPa.
  • Example 3 Sample No. listed in the table. 73 and no. Glass raw materials were prepared to have a glass composition of 304 and melted at 1600° C. for 21 hours using a platinum pot. Thereafter, the obtained molten glass was poured onto a carbon plate, formed into a flat plate shape, and slowly cooled. The resulting flat glass was ground and polished to obtain a glass plate with a thickness of 0.3 mm, and then slimmed by an etching process using hydrofluoric acid to obtain a reinforcing glass plate with a thickness of 31 ⁇ m. Next, each of the obtained tempering glass plates was cut into a size of 50 mm x 50 mm. Furthermore, sample No. The tempering glass plate No.
  • sample No. The tempering glass plate No. 304 was subjected to ion exchange treatment by immersing it in a KNO 3 molten salt at 380° C. for 1 hour and 45 minutes to obtain a strengthened glass plate. Further, the obtained tempered glass plate was slimmed by an etching process using hydrofluoric acid to obtain a measurement sample having a thickness of 30 ⁇ m. Sample No. of the measurement sample The compressive stress value of Sample No. 73 was 698 MPa, and the compressive stress layer depth was 5.5 ⁇ m. The compressive stress value of No. 304 was 418 MPa, and the compressive stress layer depth was 4.8 ⁇ m.
  • the surface roughness and impact strength of the measurement samples were measured.
  • the surface roughness is the "arithmetic mean height" measured using a scanning white interferometer (New View 7300 manufactured by Zygo) and calculated in accordance with ISO 25178.
  • the detailed measurement conditions are as follows.
  • the impact resistance strength was measured by the following impact resistance test.
  • the obtained measurement sample (planar view dimensions: 50 mm x 50 mm) was placed on a stone surface plate, and a ball-point impactor with a spherical rod tip (a ballpoint pen with a ball tip diameter of 0.7 mm and a total mass of 5.4 g: manufactured by BIC)
  • the test was conducted by dropping the tip of an orange EG0.7) onto a glass sample.
  • the impactor was dropped to the glass sample through the inner hole of the guide tube held vertically so that the tip of the impactor fell perpendicularly to the glass sample.
  • the height of the tip of the colliding object before falling was taken as the falling height, and the initial value was set to 1.0 cm, and the object was dropped. If the glass sample was not damaged by the drop, the height was raised by 0.5 cm and the sample was dropped again. In this way, trials of increasing the drop height and dropping were repeated until the glass sample broke, and the drop height at which the glass sample broke was determined as the fracture height.
  • Sample No. No. 73 had a surface roughness of 0.24 nm and a fracture height of 10.5 cm.
  • sample No. No. 304 had a surface roughness of 0.31 nm and a fracture height of 10.7 cm.
  • the tempered glass plate of the present invention is suitable as a cover glass for touch panel displays such as mobile phones, digital cameras, and PDAs (portable terminals).
  • touch panel displays such as mobile phones, digital cameras, and PDAs (portable terminals).
  • the tempered glass sheet of the present invention can also be used for uses that require high mechanical strength, such as window glass, magnetic disk substrates, flat panel display substrates, flexible display substrates, and solar cells. It is expected to be applied to cover glasses, solid-state image sensor cover glasses, and automotive cover glasses.

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JP2010059038A (ja) * 2008-08-04 2010-03-18 Nippon Electric Glass Co Ltd 強化ガラスおよびその製造方法
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