WO2020138062A1 - 強化ガラス板及びその製造方法 - Google Patents

強化ガラス板及びその製造方法 Download PDF

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Publication number
WO2020138062A1
WO2020138062A1 PCT/JP2019/050571 JP2019050571W WO2020138062A1 WO 2020138062 A1 WO2020138062 A1 WO 2020138062A1 JP 2019050571 W JP2019050571 W JP 2019050571W WO 2020138062 A1 WO2020138062 A1 WO 2020138062A1
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Prior art keywords
tempered glass
less
mol
glass
glass plate
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PCT/JP2019/050571
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English (en)
French (fr)
Japanese (ja)
Inventor
結城　健
鈴木　良太
智憲 市丸
清貴 木下
雄太 永野
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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Publication date
Application filed by Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Priority to CN201980086095.4A priority Critical patent/CN113227005A/zh
Priority to US17/417,523 priority patent/US11964908B2/en
Priority to KR1020217022729A priority patent/KR20210106515A/ko
Priority to CN202311377838.8A priority patent/CN117534320A/zh
Priority to JP2020563298A priority patent/JP7651862B2/ja
Publication of WO2020138062A1 publication Critical patent/WO2020138062A1/ja
Anticipated expiration legal-status Critical
Priority to US18/221,661 priority patent/US20240010545A1/en
Ceased legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—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
    • 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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/18—Compositions for glass with special properties for ion-sensitive glass
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00—Glasses, glazes or enamels with special properties

Definitions

  • the present invention relates to a tempered glass plate and a method for manufacturing the same, and particularly relates to a tempered glass plate suitable for a cover glass for a touch panel display such as a mobile phone, a digital camera, a PDA (mobile terminal) and a method for manufacturing the same.
  • Patent Document 1 For applications such as mobile phones, digital cameras, and PDAs (mobile terminals), ion-exchange treated tempered glass plates are used as cover glass for touch panel displays (see Patent Document 1 and Non-Patent Document 1).
  • JP, 2006-83045 A Japanese Patent Publication No. 2016-524581 Japanese Patent Publication No. 2011-510903
  • the cover glass may be damaged and the smartphone may become unusable. Therefore, in order to avoid such a situation, it is important to increase the strength of the tempered glass sheet.
  • Deepening the stress depth is a useful way to increase the strength of a tempered glass sheet. More specifically, when the cover glass collides with the road surface when the smartphone is dropped, protrusions and sand grains on the road surface penetrate the cover glass and reach the tensile stress layer, resulting in damage. Therefore, if the stress depth of the compressive stress layer is increased, it becomes difficult for projections and sand grains on the road surface to reach the tensile stress layer, and the probability of breakage of the cover glass can be reduced.
  • Lithium aluminosilicate glass is advantageous in obtaining a deep stress depth.
  • a strengthening glass plate made of lithium aluminosilicate glass is immersed in a molten salt containing NaNO 3 and Li ions in the glass are exchanged with Na ions in the molten salt, a strengthened glass having a deep stress depth is obtained.
  • the board can be obtained.
  • the compressive stress value of the compressive stress layer may be too small.
  • the glass composition is designed so that the compressive stress value of the compressive stress layer is increased, the chemical stability may be reduced. Further, in the lithium aluminosilicate glass, the balance of the glass composition is lost, and devitrification lumps are likely to occur during molding, so that it is difficult to form a plate.
  • the present invention has been made in view of the above circumstances, and its technical problem is to provide a tempered glass plate that can be formed into a plate shape, has excellent chemical stability, and is not easily damaged when dropped. Is.
  • the tempered glass sheet of the present invention is a tempered glass having a compressive stress layer on the surface, and has a glass composition of mol% of SiO 2 of 50 to 80%, Al 2 O 3 of 8 to 25%, and B 2 O 3 of 0. -10%, Li 2 O 3-15%, Na 2 O 3-21%, K 2 O 0-10%, MgO 0-10%, ZnO 0-10%, P 2 O 5 0-15% It is characterized by doing.
  • the tempered glass plate of the present invention has a molar ratio of [[Na 2 O]-[Li 2 O])/([Al 2 O 3 ]+[B 2 O 3 ]+[P 2 O 5 ]) ⁇ 0. It is preferable to satisfy the relationship of 0.29.
  • [Na 2 O] refers to the mol% content of Na 2 O.
  • Li 2 O] refers to the mol% content of Li 2 O.
  • Al 2 O 3 ] refers to the mol% content of Al 2 O 3 .
  • [B 2 O 3 ] refers to a mol% content of B 2 O 3 .
  • [P 2 O 5 ] refers to the mol% content of P 2 O 5 .
  • the tempered glass plate of the present invention has a molar ratio ([B 2 O 3 ]+[Na 2 O]-[P 2 O 5 ])/([Al 2 O 3 ]+[Li 2 O]) ⁇ 0. It is preferable to satisfy the relationship of 0.30.
  • ([B 2 O 3 ]+[Na 2 O] ⁇ [P 2 O 5 ])/([Al 2 O 3 ]+[Li 2 O]) is the sum of B 2 O 3 and Na 2 O. It indicates a value obtained by dividing the amount obtained by subtracting the content of P 2 O 5 from the total amount by the total amount of Al 2 O 3 and Li 2 O.
  • the tempered glass plate of the present invention contains ([Li 2 O]+[Na 2 O]+[K 2 O]) in an amount of 12 mol% or more, and [SiO 2 ]+1.2 ⁇ [P 2 O 5 ]-3 ⁇ [Al 2 O 3 ]-2 ⁇ [Li 2 O]-1.5 ⁇ [Na 2 O]-[K 2 O]-[B 2 O 3 ] ⁇ -22 mol%
  • [K 2 O] refers to the mol% content of K 2 O.
  • [SiO 2 ] refers to the mol% content of SiO 2 .
  • the tempered glass sheet of the present invention preferably has a P 2 O 5 content of 0.1 to 2.3 mol %.
  • the tempered glass plate of the present invention preferably has a B 2 O 3 content of 0.1 to 4 mol %.
  • the compressive stress value of the outermost surface of the compressive stress layer is 200 to 1000 MPa.
  • the “compressive stress value on the outermost surface” and the “stress depth” are measured from a phase difference distribution curve observed using, for example, a scattered light photoelastic stress meter SLP-1000 (manufactured by Orihara Manufacturing Co., Ltd.). Refers to a value.
  • the stress depth indicates the depth at which the stress value becomes zero.
  • the refractive index of each measurement sample is 1.51 and the photoelastic constant is 30.1 [(nm/cm)/MPa].
  • the stress depth of the compression stress layer is 50 to 200 ⁇ m.
  • the temperature at a high temperature viscosity of 10 2.5 dPa ⁇ s is less than 1650°C.
  • the “temperature at a high temperature viscosity of 10 2.5 dPa ⁇ s” can be measured by, for example, a platinum ball pulling method.
  • the tempered glass sheet of the present invention preferably has an overflow merging surface in the central portion in the sheet thickness direction, that is, formed by the overflow downdraw method.
  • the "overflow down draw method” is to overflow the molten glass from both sides of the molded body refractory, while the overflowed molten glass is merged at the lower end of the molded body refractory, stretch forming downward to form a glass plate. It is a manufacturing method.
  • the tempered glass plate of the present invention is preferably used as a cover glass for a touch panel display.
  • the tempered glass sheet of the present invention is a tempered glass having a compressive stress layer on the surface, and as a glass composition, Al 2 O 3 is 17 mol% or more, P 2 O 5 is 1 mol% or more, ([Li 2 O ]+[Na 2 O]+[K 2 O]) in an amount of 12 mol% or more, and [SiO 2 ]+1.2 ⁇ [P 2 O 5 ]-3 ⁇ [Al 2 O 3 ]-2 ⁇ [Li 2 O]-1.5 ⁇ [Na 2 O]-[K 2 O]-[B 2 O 3 ] ⁇ -22 mol% is satisfied.
  • This makes it possible to form a plate while improving the ion exchange performance, and it becomes easier to obtain a glass having high acid resistance.
  • the tempered glass sheet of the present invention preferably has a Fe 2 O 3 content of 0.001 to 0.1 mol %.
  • the tempered glass plate of the present invention preferably has a TiO 2 content of 0.001 to 0.1 mol %.
  • the tempered glass plate of the present invention preferably has a SnO 2 content of 0.01 to 1 mol %.
  • the tempered glass plate of the present invention preferably has a Cl content of 0.001 to 0.1 mol %.
  • the tempered glass plate of the present invention preferably has a stress profile in the thickness direction having at least a first peak, a second peak, a first bottom and a second bottom.
  • the glass plate for strengthening of the present invention has a glass composition of, in mol %, SiO 2 50 to 80%, Al 2 O 3 8 to 25%, B 2 O 3 0 to 10%, Li 2 O 3 to 15%, It is characterized by containing Na 2 O 3 to 21%, K 2 O 0 to 10%, MgO 0 to 10%, ZnO 0 to 10%, and P 2 O 5 0 to 15%.
  • the method for producing a tempered glass sheet of the present invention is such that the glass composition is, in mol %, SiO 2 50 to 80%, Al 2 O 3 8 to 25%, B 2 O 3 0 to 10%, Li 2 O 3 to 15%. %, Na 2 O 3 to 21%, K 2 O 0 to 10%, MgO 0 to 10%, ZnO 0 to 10%, P 2 O 5 0 to 15%, a preparatory step for preparing a strengthening glass plate. And an ion exchange step of performing an ion exchange treatment a plurality of times on the tempering glass plate to obtain a tempered glass plate having a compressive stress layer on the surface.
  • Tempered glass plate of the present invention (reinforced glass plate), as a glass composition, in mol%, SiO 2 50 ⁇ 80% , Al 2 O 3 8 ⁇ 25%, B 2 O 3 0 ⁇ 10%, Li 2 O 3 to 15%, Na 2 O 3 to 21%, K 2 O 0 to 10%, MgO 0 to 10%, ZnO 0 to 10%, P 2 O 5 to 0 to 15%.
  • the reasons for limiting the content range of each component are shown below. In the description of the content range of each component, “%” indicates mol% unless otherwise specified.
  • SiO 2 is a component that forms a glass network. If the content of SiO 2 is too small, vitrification becomes difficult, and the thermal expansion coefficient becomes too high, and the thermal shock resistance tends to decrease. Therefore, a suitable lower limit of SiO 2 is 50% or more, 55% or more, 57% or more, 59% or more, and particularly 61% or more. On the other hand, if the content of SiO 2 is too large, the meltability and moldability are likely to be lowered, and the thermal expansion coefficient is too low, making it difficult to match the thermal expansion coefficient of the peripheral materials. Therefore, the preferred upper limit range of SiO 2 is 80% or less, 70% or less, 68% or less, 66% or less, 65% or less, and particularly 64.5% or less.
  • Al 2 O 3 is a component that enhances ion exchange performance, and also a component that enhances strain point, Young's modulus, fracture toughness, and Vickers hardness. Therefore, a suitable lower limit range of Al 2 O 3 is 8% or more, 10% or more, 12% or more, 13% or more, 14% or more, 14.4% or more, 15% or more, 15.3% or more, 15. 6% or more, 16% or more, 16.5% or more, 17% or more, 17.2% or more, 17.5% or more, 17.8% or more, 18% or more, more than 18%, 18.3% or more, Particularly, they are 18.5% or more, 18.6% or more, 18.7% or more, and 18.8% or more.
  • the preferable upper limit range of Al 2 O 3 is 25% or less, 21% or less, 20.5% or less, 20% or less, 19.9% or less, 19.5% or less, 19.0% or less, particularly 18% or less. It is below 9%.
  • B 2 O 3 is a component that lowers the viscosity and density at high temperatures, stabilizes the glass, makes it difficult to deposit crystals, and lowers the liquidus temperature.
  • the stress depth in the ion exchange between Li ions contained in the glass and Na ions in the molten salt becomes too deep, resulting in the compression stress value (CS) of the compression stress layer. Na ) tends to be small. Further, the glass may become unstable, and the devitrification resistance may decrease. Therefore, the preferred lower limit range of B 2 O 3 is 0% or more, 0.1% or more, 0.2% or more, 0.5% or more, 0.6% or more, 0.7% or more, 0.8%.
  • the preferable upper limit range of B 2 O 3 is 10% or less, 5% or less, 4% or less, 3.8% or less, 3.5% or less, 3.3% or less, 3.2% or less, 3. It is 1% or less, 3% or less, and particularly 2.9% or less.
  • Li 2 O is an ion exchange component, and in particular, is an essential component for ion exchange between Li ions contained in the glass and Na ions in the molten salt to obtain a deep stress depth.
  • Li 2 O is a component that lowers the high temperature viscosity to enhance the meltability and moldability, and also enhances the Young's modulus. Therefore, the preferred lower limit of Li 2 O is 3% or more, 4% or more, 5% or more, 5.5% or more, 6.5% or more, 7% or more, 7.3% or more, 7.5% or more. , 7.8% or more, particularly 8% or more.
  • the preferable upper limit range of Li 2 O is 15% or less, 13% or less, 12% or less, 11.5% or less, 11% or less, 10.5% or less, less than 10%, particularly 9.9% or less, It is 9% or less and 8.9% or less.
  • Na 2 O is an ion-exchange component and also a component that lowers the high temperature viscosity and improves the meltability and moldability. Further, Na 2 O is a component that enhances devitrification resistance, and is particularly a component that suppresses devitrification caused by a reaction with an alumina refractory. Therefore, the preferable lower limit range of Na 2 O is 3% or more, 4% or more, 5% or more, 6% or more, 7% or more, 7.5% or more, 8% or more, 8.5% or more, 8.8. % Or more, especially 9% or more. On the other hand, if the content of Na 2 O is too large, the thermal expansion coefficient becomes too high, and the thermal shock resistance tends to decrease.
  • the preferred upper limit of Na 2 O is 21% or less, 20% or less, 19% or less, particularly 18% or less, 15% or less, 13% or less, 11% or less, particularly 10% or less.
  • K 2 O is a component that lowers the high temperature viscosity and improves the meltability and moldability.
  • the preferable upper limit of K 2 O is 10% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, 1.5% or less, 1% or less, 1% or less. %, 0.5% or less, particularly less than 0.1%.
  • the preferable lower limit of K 2 O is 0% or more, 0.1% or more, 0.3% or more, and particularly 0.5% or more.
  • the molar ratio [Li 2 O]/([Na 2 O]+[K 2 O]) is preferably 0.4 to 1.0, 0.5 to 0.9, especially 0.6 to 0.8. is there. If the molar ratio [Li 2 O]/([Na 2 O]+[K 2 O]) is too small, the ion exchange performance may not be sufficiently exhibited. In particular, the efficiency of ion exchange between Li ions contained in the glass and Na ions in the molten salt tends to decrease.
  • MgO is a component that lowers the high temperature viscosity to improve the meltability and moldability, and also increases the strain point and Vickers hardness.
  • MgO is a component that has a large effect of enhancing the ion exchange performance. is there.
  • the preferable content of MgO is 0 to 10%, 0 to 5%, 0.1 to 4%, 0.2 to 3.5%, and particularly 0.5 to less than 3%.
  • ZnO is a component that enhances the ion exchange performance, and is a component that has a particularly large effect of increasing the compressive stress value on the outermost surface. It is also a component that reduces high temperature viscosity without reducing low temperature viscosity.
  • the preferred lower limit of ZnO is 0% or more, 0.1% or more, 0.3% or more, 0.5% or more, 0.7% or more, and particularly 1% or more.
  • the content of ZnO is too large, the glass tends to undergo phase separation, devitrification resistance decreases, the density increases, and the stress depth tends to become shallow.
  • the preferable upper limit of ZnO is 10% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, 1.5% or less, 1.3% or less, 1.2% or less. , Especially 1.1% or less.
  • P 2 O 5 is a component that enhances the ion exchange performance, and particularly a component that deepens the stress depth. Furthermore, it is a component that also improves acid resistance. If the content of P 2 O 5 is too small, the ion exchange performance may not be sufficiently exhibited. In particular, the efficiency of ion exchange between Na ions contained in the glass and K ions in the molten salt tends to decrease, and the stress depth (DOL_ZERO K ) of the compression stress layer tends to decrease. Further, the glass may become unstable, and the devitrification resistance may decrease.
  • the preferred lower limit of P 2 O 5 is 0% or more, 0.1% or more, 0.4% or more, 0.7% or more, 1% or more, 1.2% or more, 1.4% or more, It is 1.6% or more, 2% or more, 2.3% or more, 2.5% or more, and particularly 3% or more.
  • the content of P 2 O 5 is too large, the glass is likely to undergo phase separation and the water resistance tends to be lowered.
  • the stress depth in the ion exchange between Li ions contained in the glass and Na ions in the molten salt becomes too deep, and as a result, the compressive stress value (CS Na ) of the compressive stress layer tends to be small.
  • the preferred upper limit range of P 2 O 5 is 15% or less, 10% or less, 5% or less, 4.5% or less, or 4% or less.
  • the content of P 2 O 5 is set in a suitable range, it becomes easy to form a non-monotonic profile.
  • the alkali metal oxide is an ion-exchange component, which is a component that lowers the high temperature viscosity and enhances the meltability and moldability. If the content of the alkali metal oxide ([Li 2 O]+[Na 2 O]+[K 2 O]) is too large, the coefficient of thermal expansion may increase. In addition, the acid resistance may decrease. Therefore, the preferred lower limit of the alkali metal oxide ([Li 2 O]+[Na 2 O]+[K 2 O]) is 10% or more, 11% or more, 12% or more, 13% or more, 14% or more. , 15% or more. Therefore, the preferable upper limit range of the alkali metal oxide ([Li 2 O]+[Na 2 O]+[K 2 O]) is 25% or less, 23% or less, 20% or less, 19% or less, 18% or less. Is.
  • the molar ratio [Li 2 O]/[P 2 O 5 ] is preferably 4-30, 10-25, in particular 15-20. If the molar ratio [Li 2 O]/[P 2 O 5 ] is too small, the efficiency of ion exchange between Li ions contained in the glass and Na ions in the molten salt tends to decrease. On the other hand, if the molar ratio [Li 2 O]/[P 2 O 5 ] is too large, devitrified crystals tend to precipitate in the glass, making it difficult to form a plate by the overflow downdraw method or the like. Note that “[Li 2 O]/[P 2 O 5 ]” refers to a value obtained by dividing the content of Li 2 O by the content of P 2 O 5 .
  • the molar ratio ([Na 2 O]?[Li 2 O])/([Al 2 O 3 ]+[B 2 O 3 ]+[P 2 O 5 ]) is preferably 0.29 or less, 0.27. The following values are 0.26 or less, 0.25 or less, 0.23 or less, 0.20 or less, and particularly 0.15 or less. If the molar ratio ([Na 2 O]?[Li 2 O])/([Al 2 O 3 ]+[B 2 O 3 ]+[P 2 O 5 ]) is too large, the ion exchange performance will be sufficiently demonstrated. There is a risk that it will not be possible. In particular, the Li ion contained in the glass and the Na ion in the molten salt are likely to reduce the efficiency of ion exchange.
  • the molar ratio ([B 2 O 3 ]+[Na 2 O]?[P 2 O 5 ])/([Al 2 O 3 ]+[Li 2 O]) is preferably 0.30 or more and 0.35. As described above, 0.40 or more, 0.42 or more, 0.43 or more, and particularly 0.45 or more. When the molar ratio ([B 2 O 3 ]+[Na 2 O]?[P 2 O 5 ])/([Al 2 O 3 ]+[Li 2 O]) is too small, devitrified crystals precipitate on the glass. It becomes difficult to form into a plate shape by the overflow down draw method or the like.
  • ([SiO 2 ]+1.2 ⁇ [P 2 O 5 ]-3 ⁇ [Al 2 O 3 ]-2 ⁇ [Li 2 O]-1.5 ⁇ [Na 2 O]-[K 2 O] -[B 2 O 3 ]) is preferably 30 mol% or less, 20 mol% or less, 15 mol% or less, 10 mol% or less, 5 mol% or less, and particularly 0 mol% or less.
  • ingredients for example, the following ingredients may be added.
  • CaO is a component that lowers the high temperature viscosity, improves the meltability and moldability, and increases the strain point and Vickers hardness, without lowering the devitrification resistance as compared with other components.
  • the preferable upper limit range of CaO is 6% or less, 5% or less, 4% or less, 3.5% or less, 3% or less, 2% or less, 1% or less, 1% or less, 0.5% or less, particularly It is less than 0.1%.
  • SrO and BaO are components that lower the viscosity at high temperature to improve the meltability and moldability, and increase the strain point and Young's modulus, but if their contents are too large, the ion exchange reaction is likely to be inhibited. In addition, the density and the thermal expansion coefficient become unreasonably high, and the glass tends to devitrify. Therefore, the preferable contents of SrO and BaO are 0 to 2%, 0 to 1.5%, 0 to 1%, 0 to 0.5%, 0 to 0.1%, and especially 0 to 0.1%. It is less than %.
  • ZrO 2 is a component that increases the Vickers hardness and also a component that increases the viscosity and the strain point near the liquidus viscosity, but if its content is too large, the devitrification resistance may significantly decrease. Therefore, the preferable content of ZrO 2 is 0 to 3%, 0 to 1.5%, 0 to 1%, and particularly 0 to 0.1%.
  • TiO 2 is a component that enhances the ion exchange performance and a component that lowers the high temperature viscosity. However, if the content is too large, the transparency and devitrification resistance tend to lower. Therefore, the preferable content of TiO 2 is 0 to 3%, 0 to 1.5%, 0 to 1%, 0 to 0.1%, and particularly 0.001 to 0.1 mol%.
  • SnO 2 is a component that enhances the ion exchange performance, but if the content thereof is too large, the devitrification resistance tends to decrease. Therefore, SnO 2 has a preferable lower limit of 0.005% or more, 0.01% or more, particularly 0.1% or more, and a preferable upper limit of 3% or less, 2% or less, particularly 1% or less. ..
  • Cl is a fining agent, but if its content is too large, it has a negative effect on the environment and equipment. Therefore, a preferable lower limit range of Cl is 0.001% or more, particularly 0.01% or more, and a preferable upper limit range is 0.3% or less, 0.2% or less, and particularly 0.1% or less.
  • 0.001 to 1% of one or more selected from the group of SO 3 and CeO 2 (preferably the group of SO 3 ) may be added.
  • Fe 2 O 3 is an impurity that is inevitably mixed from the raw materials. Suitable contents of Fe 2 O 3 are less than 1000 ppm (less than 0.1%), less than 800 ppm, less than 600 ppm, less than 400 ppm, especially less than 300 ppm. 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 lower limit range is 10 ppm or more, 20 ppm or more, 30 ppm or more, 50 ppm or more, 80 ppm or more, 100 ppm or more. If the content of Fe 2 O 3 is too small, a high-purity raw material is used, so that the raw material cost rises and the product cannot be manufactured at low cost.
  • 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 the Young's modulus.
  • the raw material cost is high, and when added in a large amount, the devitrification resistance is likely to decrease. Therefore, the preferable content of the rare earth oxide is 5% or less, 3% or less, 2% or less, 1% or less, 0.5% or less, and particularly 0.1% or less.
  • the tempered glass plate (glass plate for tempering) of the present invention does not substantially contain As 2 O 3 , Sb 2 O 3 , PbO, and F as a glass composition from the environmental consideration. Further, it is also preferable that substantially no Bi 2 O 3 is contained in consideration of the environment. “Substantially does not contain” means that the explicit component is not added as a glass component, but the impurity level is allowed to be added. Specifically, the content of the explicit component is 0. It refers to the case of less than 0.05%.
  • the tempered glass plate (tempered glass plate) of the present invention preferably has the following characteristics.
  • Density is preferably 2.55 g / cm 3 or less, 2.53 g / cm 3 or less, 2.50 g / cm 3 or less, 2.49 g / cm 3 or less, 2.45 g / cm 3 or less, particularly 2.35 ⁇ It is 2.44 g/cm 3 .
  • the coefficient of thermal expansion at 30 to 380° C. is preferably 150 ⁇ 10 ⁇ 7 /° C. or less, 100 ⁇ 10 ⁇ 7 /° C. or less, and particularly 50 to 95 ⁇ 10 ⁇ 7 /° C.
  • the “coefficient of thermal expansion at 30 to 380° C.” refers to the value obtained by measuring the average coefficient of thermal expansion using a dilatometer.
  • the softening point is preferably 950°C or lower, 930°C or lower, 900°C or lower, 880°C or lower, 860°C or lower, particularly 850 to 700°C.
  • the "softening point” refers to the value measured based on the method of ASTM C338.
  • the temperature at a high temperature viscosity of 10 2.5 dPa ⁇ s is preferably 1660° C. or lower, less than 1620° C., 1600° C. or lower, and particularly preferably 1400 to 1590° C. If the temperature at the high temperature viscosity of 10 2.5 dPa ⁇ s is too high, the meltability and moldability are deteriorated, and it becomes difficult to mold the molten glass into a plate shape.
  • the “temperature at high temperature viscosity of 10 2.5 dPa ⁇ s” refers to a value measured by a platinum ball pulling method.
  • the liquidus viscosity is preferably 10 3.74 dPa ⁇ s or more, 10 4.5 dPa ⁇ s or more, 10 4.8 dPa ⁇ s or more, 10 4.9 dPa ⁇ s or more, 10 5.0 dPa ⁇ s or more.
  • the above is 10 5.1 dPa ⁇ s or more, 10 5.2 dPa ⁇ s or more, 10 5.3 dPa ⁇ s or more, 10 5.4 dPa ⁇ s or more, and particularly 10 5.5 dPa ⁇ s or more.
  • liquidus viscosity refers to a value obtained by measuring the viscosity at a liquidus temperature by a platinum ball pulling method.
  • “Liquid phase temperature” means that the glass powder that has passed through a standard sieve 30 mesh (500 ⁇ m) and remains at 50 mesh (300 ⁇ m) is put in a platinum boat and kept 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 recognized inside the glass by microscopic observation.
  • the Young's modulus is preferably 70 GPa or more, 74 GPa or more, 75 to 100 GPa, and particularly 76 to 90 GPa. When the Young's modulus is low, the cover glass easily bends when the plate thickness is thin.
  • the "Young's modulus" can be calculated by a known resonance method.
  • the tempered glass sheet of the present invention has a compressive stress layer on the surface.
  • the compressive stress value of the outermost surface is preferably 165 MPa or more, 200 MPa or more, 220 MPa or more, 250 MPa or more, 280 MPa or more, 300 MPa or more, 310 MPa or more, and particularly 320 MPa or more.
  • the higher the compressive stress value on the outermost surface the higher the Vickers hardness.
  • the tensile stress inherent in the tempered glass becomes extremely high, and the dimensional change before and after the ion exchange treatment may become large.
  • the compressive stress value of the outermost surface is preferably 1000 MPa or less, 900 MPa or less, 700 MPa or less, 680 MPa or less, 650 MPa or less, and particularly 600 MPa or less. If the ion exchange time is shortened or the temperature of the ion exchange solution is lowered, the compressive stress value on the outermost surface tends to increase.
  • the stress depth is preferably 50 ⁇ m or more, 60 ⁇ m or more, 80 ⁇ m or more, 100 ⁇ m or more, and particularly 120 ⁇ m or more.
  • the deeper the stress depth the more difficult it becomes for the road surface projections and sand grains to reach the tensile stress layer when the smartphone is dropped, and the probability of damage to the cover glass can be reduced.
  • the stress depth is too deep, there is a possibility that the dimensional change will be large before and after the ion exchange treatment. Further, the compressive stress value on the outermost surface tends to decrease. Therefore, the stress depth is preferably 200 ⁇ m or less, 180 ⁇ m or less, 150 ⁇ m or less, and particularly 140 ⁇ m or less. The stress depth tends to increase as the ion exchange time increases or the temperature of the ion exchange solution increases.
  • 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, and particularly 0.8 mm or less. is there. As the plate thickness is smaller, the mass of the tempered glass plate can be reduced. On the other hand, if the plate thickness is too thin, it becomes difficult to obtain the desired mechanical strength. Therefore, the plate thickness is preferably 0.3 mm or more, 0.4 mm or more, 0.5 mm or more, 0.6 mm or more, and particularly 0.7 mm or more.
  • the method for producing a tempered glass sheet of the present invention is such that the glass composition is, in mol %, SiO 2 50 to 80%, Al 2 O 3 8 to 25%, B 2 O 3 0 to 10%, Li 2 O 3 to 15%. %, Na 2 O 3 to 21%, K 2 O 0 to 10%, MgO 0 to 10%, ZnO 0 to 10%, P 2 O 5 0 to 15%, a preparatory step for preparing a strengthening glass plate. And an ion exchange step of performing an ion exchange treatment a plurality of times on the tempering glass plate to obtain a tempered glass plate having a compressive stress layer on the surface.
  • the method for producing a tempered glass plate of the present invention is characterized by performing ion exchange treatment a plurality of times, but the tempered glass plate of the present invention is only used when a plurality of ion exchange treatments are performed. However, the case where the ion exchange treatment is performed only once is also included.
  • the method of manufacturing tempering glass is as follows, for example. First, a glass raw material prepared to have a desired glass composition is charged into a continuous melting furnace, heated and melted at 1400 to 1700° C., clarified, and then the molten glass is supplied to a molding apparatus and molded into a plate shape. It is preferable to cool. A well-known method can be adopted as a method of cutting into a predetermined size after forming into a plate shape.
  • Overflow down draw method is preferable as a method for forming molten glass into a plate shape.
  • the surface of the glass plate that is to be the surface does not come into contact with the surface of the molded refractory material, but is molded into a plate shape with a free surface. Therefore, it is possible to inexpensively manufacture a glass plate which is not polished and has a good surface quality.
  • an alumina refractory or a zirconia refractory is used as a molded refractory.
  • the tempered glass plate of the present invention (tempered glass plate) has good compatibility with alumina-based refractory materials and zirconia-based refractory materials (especially alumina-based refractory materials), it reacts with these refractory materials It has a property that it is difficult to generate bubbles and lumps.
  • a molding method such as a float method, a down draw method (a slot down draw method, a redraw method, etc.), a roll out method, a press method or the like can be adopted.
  • the temperature range between the slow cooling point and the strain point of the molten glass at a cooling rate of 3° C./minute or more and less than 1000° C./minute, 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, particularly 300. It is less than °C/min. If the cooling rate is too fast, the glass structure becomes rough, and it becomes difficult to increase the Vickers hardness after the ion exchange treatment. On the other hand, if the cooling rate is too slow, the production efficiency of the glass sheet will decrease.
  • ion exchange treatment is performed a plurality of times.
  • the compressive stress value on the outermost surface can be increased while ensuring a deep stress depth.
  • first ion exchange step KNO 3 and LiNO 3
  • second ion exchange step the non-monotonic stress profile shown in FIGS. 1 and 2, that is, the stress profile having at least the first peak, the second peak, the first bottom, and the second bottom can be formed.
  • Li ions contained in the glass and Na ions in the molten salt are ion-exchanged.
  • a mixed molten salt of NaNO 3 and KNO 3 is used, the Na ions contained in the glass and the molten salt are further added.
  • the ion exchange between the Li ions contained in the glass and the Na ions in the molten salt is faster than the ion exchange between the Na ions contained in the glass and the K ions in the molten salt, and the ion exchange efficiency is high. high.
  • the second ion exchange step Na ions in the vicinity of the glass surface (a shallow region from the outermost surface to 20% of the plate thickness) and Li ions in the molten salt are ion-exchanged, and in addition, near the glass surface (from the outermost surface to the plate Na ions in a shallow region (up to 20% of the thickness) and K ions in the molten salt are ion-exchanged. That is, in the second ion exchange step, K ions having a large ionic radius can be introduced while desorbing Na ions near the glass surface. As a result, the compressive stress value of the outermost surface can be increased while maintaining a deep stress depth.
  • the molten salt temperature is preferably 360 to 400° C., and the ion exchange time is preferably 30 minutes to 6 hours.
  • the temperature of the ion exchange solution is preferably 370 to 400° C., and the ion exchange time is preferably 15 minutes to 3 hours.
  • the NaNO 3 and KNO 3 mixed molten salt used in the first ion exchange step has a NaNO 3 concentration higher than that of KNO 3 and a second ion exchange step.
  • the concentration of KNO 3 is preferably higher than the concentration of LiNO 3 .
  • the concentration of KNO 3 is preferably 0% by mass or more, 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, 15% by mass or more, and particularly 20 to 90% by mass. If the concentration of KNO 3 is too high, the compressive stress value formed when the Li ions contained in the glass and the Na ions in the molten salt are ion-exchanged may be too low. On the other hand, if the concentration of KNO 3 is too low, stress measurement by the surface stress meter FSM-6000 may become difficult.
  • the concentration of LiNO 3 is preferably more than 0 to 5% by mass, more than 0 to 3% by mass, and more than 0 to 2% by mass, and more preferably 0. It is 1 to 1% by mass. If the concentration of LiNO 3 is too low, Na ions in the vicinity of the glass surface will not easily desorb. On the other hand, if the concentration of LiNO 3 is too high, the compressive stress value formed by ion exchange between Na ions and K ions in the molten salt near the glass surface may be too low.
  • Tables 1 to 22 show the glass compositions and glass characteristics of the examples (Sample Nos. 1 to 35 and 38 to 215) of the present invention and the comparative examples (Samples No. 36 and 37).
  • NA means unmeasured
  • (Na ⁇ Li)/(Al+B+P)” means the molar ratio ([Na 2 O]?[Li 2 O])/( [Al 2 O 3 ]+[B 2 O 3 ]+[P 2 O 5 ])
  • (B+Na-P)/(Al+Li) means a molar ratio ([B 2 O 3 ]+ [Na 2 O]?[P 2 O 5 ])/([Al 2 O 3 ]+[Li 2 O]), which means “Si+1.2P-3Al-2Li-1.5Na-KB.
  • Each sample in the table was prepared as follows. First, glass raw materials were prepared so as to have the glass composition shown in the table, and melted at 1600° C. for 21 hours using a platinum pot. Subsequently, the obtained molten glass was poured onto a carbon plate and formed into a flat plate shape, and then the temperature range between the slow cooling point and the strain point was cooled at 3° C./min to obtain a glass plate (for tempering). A glass plate) was obtained. The surface of the obtained glass plate was optically polished so that the plate thickness was 1.5 mm, and then various characteristics were evaluated.
  • the density ( ⁇ ) is a value measured by the well-known Archimedes method.
  • the coefficient of thermal expansion ( ⁇ 30-380° C. ) at 30 to 380° C. is a value obtained by measuring the average coefficient of thermal expansion using a dilatometer.
  • 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.
  • the softening point (Ts) is a value measured based on the method of ASTM C338.
  • the liquidus temperature (TL) passed through a standard sieve 30 mesh (500 ⁇ m), and the glass powder remaining at 50 mesh (300 ⁇ m) was put into a platinum boat and kept in a temperature gradient furnace for 24 hours, and then the platinum boat was taken out. The highest temperature at which devitrification (devitrification spots) was observed inside the glass by microscopic observation was used.
  • the liquidus viscosity (log ⁇ TL) is the value measured by the platinum sphere pull-up method at the liquidus temperature, and is logarithmically shown as log ⁇ .
  • the Young's modulus (E) is calculated by a method according to JIS R1602-1995 “Fine Ceramics Elastic Modulus Test Method”.
  • a glass sample having a size of 50 ⁇ 10 ⁇ 1.0 mm double-sided mirror-polished was used as a measurement sample, thoroughly washed with a neutral detergent and pure water, and then heated to 80° C. to 5% by mass. It is evaluated by immersing in a HCl aqueous solution for 24 hours and calculating the mass loss (mg/cm 2 ) per unit surface area before and after the immersion.
  • the alkali resistance test uses a glass sample having a size of 50 ⁇ 10 ⁇ 1.0 mm and mirror-polished double-sided as a measurement sample, thoroughly washed with a neutral detergent and pure water, and then heated to 80° C. to 5% by mass. It was evaluated by immersing in a NaOH aqueous solution for 6 hours and calculating the mass loss (mg/cm 2 ) per unit surface area before and after the immersion.
  • each glass plate was immersed in KNO 3 molten salt at 430° C. for 4 hours for ion exchange treatment to obtain a tempered glass plate having a compressive stress layer on the surface, and then the glass surface was washed. From the number of interference fringes observed using a surface stress meter FSM-6000 (manufactured by Orihara Seisakusho Co., Ltd.) and their intervals, the compressive stress value (CS K ) and the stress depth (DOL_ZERO) of the outermost compressive stress layer are measured. K ) was calculated.
  • DOL_ZERO K is the depth at which the compressive stress value becomes zero.
  • the refractive index of each sample was 1.51 and the photoelastic constant was 30.1 [(nm/cm)/MPa].
  • each glass plate was immersed in NaNO 3 molten salt at 380° C. for 1 hour for ion exchange treatment to obtain a tempered glass plate, and then the glass surface was washed, and then scattered light photoelastic stress was applied.
  • the compressive stress value (CS Na ) and the stress depth (DOL_ZERO Na ) on the outermost surface were calculated from the phase difference distribution curve observed using a total SLP-1000 (manufactured by Orihara Manufacturing Co., Ltd.).
  • DOL_ZERO Na is the depth at which the stress value becomes zero.
  • the refractive index of each sample was 1.51 and the photoelastic constant was 30.1 [(nm/cm)/MPa].
  • the sample No. Nos. 1 to 35 and 38 to 215 had a compressive stress value (CS K ) of the outermost compressive stress layer of 473 MPa or more when subjected to ion exchange treatment with KNO 3 molten salt, and were subjected to ion exchange treatment with NaNO 3 molten salt.
  • CS K compressive stress value of the outermost compressive stress layer of 473 MPa or more when subjected to ion exchange treatment with KNO 3 molten salt, and were subjected to ion exchange treatment with NaNO 3 molten salt.
  • the compressive stress value (CS Na ) of the compressive stress layer on the outermost surface is 165 MPa or more, it is considered that any molten salt can be subjected to ion exchange treatment and is less likely to be damaged when dropped.
  • the sample No. 37 to 215 are ([SiO 2 ]+1.2 ⁇ [P 2 O 5 ]-3 ⁇ [Al 2 O 3 ]-2 ⁇ [Li 2 O]-1.5 ⁇ [Na 2 O]-[K Since 2 O]-[B 2 O 3 ]) is -36 mol% or more, the acid resistance is high, so that it is easily applied to the acid treatment step and is considered to be suitable as a cover glass.
  • Glass raw materials were prepared so as to have a glass composition of 35, and melted at 1600° C. for 21 hours using a platinum pot.
  • the obtained molten glass was poured onto a carbon plate and formed into a flat plate shape, and then the temperature range between the slow cooling point and the strain point was cooled at 3° C./min to obtain a glass plate (for tempering).
  • a glass plate) was obtained.
  • No. No. 2 has a plate thickness of 0.7 mm and No.
  • the surface of No. 35 was optically polished to a plate thickness of 0.8 mm.
  • the obtained glass plate for strengthening was subjected to an ion exchange treatment by immersing it in a molten salt of NaNO 3 at 380° C. (concentration of NaNO 3 was 100% by mass) for 3 hours, and then was mixed and melted at 380° C. with KNO 3 and LiNO 3.
  • the ion exchange treatment was performed by immersing in salt (concentration of LiNO 3 2.5% by mass) for 75 minutes.
  • the surface of the obtained tempered glass plate is washed, it is strengthened by using a scattered light photoelastic stress meter SLP-1000 (manufactured by Orihara Manufacturing Co., Ltd.) and a surface stress meter FSM-6000 (manufactured by Orihara Manufacturing Co., Ltd.).
  • SLP-1000 scattered light photoelastic stress meter
  • FSM-6000 surface stress meter
  • sample No. in Table 12 109 and the sample No. of Table 15. A glass raw material was prepared so as to have a glass composition of 146, and melted at 1600° C. for 21 hours using a platinum pot. Subsequently, the obtained molten glass was poured onto a carbon plate and formed into a flat plate shape, and then the temperature range between the slow cooling point and the strain point was cooled at 3° C./min to obtain a glass plate (for tempering). A glass plate) was obtained. The surface of the obtained glass plate was optically polished to a plate thickness of 0.7 mm.
  • the obtained glass plate for strengthening was subjected to an ion exchange treatment by immersing it in a molten salt of NaNO 3 at 380° C. (concentration of NaNO 3 was 100% by mass) for 3 hours, and then was mixed and melted at 380° C. with KNO 3 and LiNO 3.
  • the ion exchange treatment was performed by immersing in salt (concentration of LiNO 3 1.5% by mass) for 45 minutes. Further, after the surface of the obtained tempered glass plate is washed, it is strengthened by using a scattered light photoelastic stress meter SLP-1000 (manufactured by Orihara Manufacturing Co., Ltd.) and a surface stress meter FSM-6000 (manufactured by Orihara Manufacturing Co., Ltd.).
  • sample No. in Table 15 A glass raw material was prepared so as to have a glass composition of 147, and melted at 1600° C. for 21 hours using a platinum pot. Subsequently, the obtained molten glass was poured onto a carbon plate and formed into a flat plate shape, and then the temperature range between the slow cooling point and the strain point was cooled at 3° C./minute to obtain a glass plate (for tempering). A glass plate) was obtained. The surface of the obtained glass plate was optically polished to a plate thickness of 0.7 mm.
  • the obtained glass plate for strengthening was subjected to an ion exchange treatment by immersing it in a molten salt of NaNO 3 at 380° C. (concentration of NaNO 3 was 100% by mass) for 3 hours, and then was mixed and melted at 380° C. with KNO 3 and LiNO 3.
  • the ion exchange treatment was performed by immersing in salt (concentration of LiNO 3 1.5% by mass) for 45 minutes. Further, after the surface of the obtained tempered glass plate is washed, it is strengthened by using a scattered light photoelastic stress meter SLP-1000 (manufactured by Orihara Manufacturing Co., Ltd.) and a surface stress meter FSM-6000 (manufactured by Orihara Manufacturing Co., Ltd.).
  • the tempered glass plate of the present invention is suitable as a cover glass for a touch panel display of a mobile phone, a digital camera, a PDA (mobile terminal), etc.
  • the tempered glass sheet of the present invention is also used in applications requiring high mechanical strength, such as window glass, substrates for magnetic disks, substrates for flat panel displays, substrates for flexible displays, and solar cells. It is expected to be applied to cover glass, cover glass for solid-state imaging devices, and cover glass for vehicles.

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KR20210106515A (ko) * 2018-12-25 2021-08-30 니폰 덴키 가라스 가부시키가이샤 강화 유리판 및 그 제조 방법
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CN112110644B (zh) * 2020-09-23 2022-04-12 成都光明光电股份有限公司 玻璃组合物和化学强化玻璃
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