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WO2018199046A1 - Verre chimiquement renforcé et verre destiné à un renforcement chimique - Google Patents

Verre chimiquement renforcé et verre destiné à un renforcement chimique Download PDF

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Publication number
WO2018199046A1
WO2018199046A1 PCT/JP2018/016505 JP2018016505W WO2018199046A1 WO 2018199046 A1 WO2018199046 A1 WO 2018199046A1 JP 2018016505 W JP2018016505 W JP 2018016505W WO 2018199046 A1 WO2018199046 A1 WO 2018199046A1
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WIPO (PCT)
Prior art keywords
glass
less
chemically strengthened
compressive stress
chemical strengthening
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PCT/JP2018/016505
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English (en)
Japanese (ja)
Inventor
優 村山
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Ａｇｃ株式会社
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Application filed by Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Priority to CN201880027496.8A priority Critical patent/CN110546115B/zh
Priority to CN202211102763.8A priority patent/CN115385571B/zh
Publication of WO2018199046A1 publication Critical patent/WO2018199046A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • 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
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • 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
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • 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 chemically strengthened glass and a chemically strengthened glass.
  • cover glasses made of chemically strengthened glass have been used to enhance the protection and aesthetics of display devices of mobile devices such as mobile phones, smartphones, personal digital assistants (PDAs), and tablet terminals.
  • mobile devices such as mobile phones, smartphones, personal digital assistants (PDAs), and tablet terminals.
  • PDAs personal digital assistants
  • Patent Document 1 discloses Equation (10) indicating the allowable limit of internal tensile stress of chemically strengthened glass, and even if the strength of chemically strengthened glass is increased by adjusting CT ′ below, the scattering of fragments is small. It was said that chemically tempered glass was obtained.
  • the internal tensile stress CT ′ described in Patent Document 1 is derived from the following formula (11) using measured values of CS and DOL ′.
  • CT ′ ⁇ ⁇ 38.7 ⁇ ln (t) +48.2 (10)
  • CS ⁇ DOL ′ (t ⁇ 2 ⁇ DOL ′) ⁇ CT ′ (11)
  • DOL ′ corresponds to the depth of the ion exchange layer.
  • an object of the present invention is to provide a chemically strengthened glass and a chemically strengthened glass having improved strength and scratch resistance.
  • the present invention relates to the following ⁇ 1> to ⁇ 5>.
  • Oxide-based molar percentage display 38 to 75% of SiO 2 Al 2 O 3 1-30%, 3-20% MgO, Li 2 O more than 0 and 20% or less, Y 2 O 3 more than 0 and 20% or less, 0 to 5% of B 2 O 3 0-6% of P 2 O 5 Na 2 O 0-8%, 0 to 10% of K 2 O, 0-20% CaO, 0-20% SrO, BaO 0-15%, ZnO 0-10%, TiO 2 0 to 1%, ZrO 2 0 to 8%, Young's modulus is 90 GPa or more, Vickers hardness is 700 kgf / mm 2 or more, A chemically strengthened glass having a surface compressive stress (CS) of 300 MPa or more and a compressive stress value (CS 50 ) of a depth portion of 50 ⁇ m from the glass surface of 30 MPa or more.
  • CS surface compressive stress
  • CS 50 compressive stress value
  • a chemically strengthened glass and a chemically strengthened glass having improved strength and scratch resistance can be provided.
  • FIG. 1 is a view showing a scratch test result of the present invention.
  • the chemically strengthened glass and the chemically strengthened glass of the present invention will be described in detail.
  • the present invention is not limited to the following embodiments, and can be arbitrarily modified without departing from the gist of the present invention. Can be implemented.
  • the glass composition of the chemically strengthened glass is sometimes referred to as a mother composition of the chemically strengthened glass.
  • “to” indicating a numerical range is used in the sense of including the numerical values described before and after the numerical value as a lower limit value and an upper limit value.
  • the portion having the tensile stress of the chemically tempered glass (hereinafter also referred to as the tensile stress portion) is not ion-exchanged. It has the same composition as the previous glass. In that case, the composition of the tensile stress portion of the chemically strengthened glass can be regarded as the mother composition of the chemically strengthened glass.
  • the composition of the glass can be measured by a wet analysis method such as ICP emission analysis. Moreover, it calculates
  • the chemically tempered glass of the present invention is expressed in terms of oxide-based mole percentage, and SiO 2 is 38 to 75%, Al 2 O 3 is 1 to 30%, MgO is 3 to 20%, Li 2 O is more than 0 to 20%.
  • Y 2 O 3 is more than 0 and less than 20%
  • B 2 O 3 is 0 to 5%
  • P 2 O 5 is 0 to 6%
  • Na 2 O is 0 to 8%
  • K 2 O is 0 to 10%.
  • the rate is 90 GPa or more, the Vickers hardness is 700 kgf / mm 2 or more, the surface compressive stress (CS) is 300 MPa or more, and the compressive stress value (CS 50 ) at a depth of 50 ⁇ m from the glass surface is 30 MPa or more. is there.
  • composition of the glass for chemical strengthening of the present invention (the mother composition of the chemically strengthened glass of the present invention) is expressed in terms of mole percentages based on oxides, 38 to 75% for SiO 2 , 1 to 30% for Al 2 O 3 , MgO 3-20%, Li 2 O over 0-20%, Y 2 O 3 over 0-20%, B 2 O 3 0-5%, P 2 O 5 0-6%, Na 2 O 0-8%, K 2 O 0-10%, CaO 0-20%, SrO 0-20%, BaO 0-15%, ZnO 0-10%, TiO 2 0-1% , And 0 to 8% of ZrO 2 , Young's modulus is 90 GPa or more, and Vickers hardness is 650 kgf / mm 2 or more.
  • SiO 2 is a component that constitutes the skeleton of the glass, and is a component that increases chemical durability.
  • the SiO 2 content is preferably 38% or more.
  • the content of SiO 2 is more preferably 42% or more, 46% or more, 50% or more, 54% or more, 58% or more, or 62% or more stepwise.
  • the content of SiO 2 is 75% or less, more preferably 72% or less, further preferably 70% or less, particularly preferably 68% or less, and most preferably 66% or less in order to increase the meltability of the glass. It is.
  • Al 2 O 3 is a component that reduces the number of fragments when the chemically strengthened glass is broken and suppresses the scattering of the fragments.
  • the content of Al 2 O 3 is 1% or more. %, 5%, 7%, 8%, 9%, 10%, 11%, 12%, 13% or more.
  • the content of Al 2 O 3 is preferably 30% or less, more preferably 25% or less, even more preferably 20% or less, particularly Preferably it is 18% or less, Most preferably, it is 15% or less.
  • the content of Al 2 O 3 is preferably 11% or less, and is preferably 10% or less, 9% or less, 8% or less, or 7% or less stepwise.
  • MgO is a component that increases the surface compressive stress of chemically strengthened glass. Further, in order to reduce the number of fragments when the chemically strengthened glass is broken and to suppress the scattering of the fragments, the content of MgO is preferably 3% or more, more preferably 4 steps below. % Or more, 5% or more, 6% or more, 7% or more, or 8% or more. On the other hand, in order to suppress devitrification at the time of glass melting, the content of MgO is preferably 20% or less, more preferably 18% or less, 15% or less, 14% or less, 13% or less, stepwise. 12% or less, 11% or less, 10% or less.
  • Li 2 O is a component that forms surface compressive stress by ion exchange, and is a component that reduces the number of fragments when the chemically strengthened glass is broken and suppresses the scattering of the fragments.
  • the content of Li 2 O is preferably more than 0%, more preferably 4%. More preferably, it is 5% or more, more preferably 6% or more, and particularly preferably 7% or more.
  • the content of Li 2 O is preferably 20% or less, more preferably 18% or less, still more preferably 16% or less, particularly preferably 15% or less, and most preferably 13 % Or less.
  • Y 2 O 3 is a component that increases the Young's modulus without increasing the density so much and improves the chipping resistance.
  • the content of Y 2 O 3 is more than 0%, preferably 1% or more, more preferably 1.5% or more, further preferably 3% or more, particularly preferably 5% or more, most preferably 7.5. % Or more.
  • the acid resistance of the glass is lowered or the devitrification temperature is increased, so that it is preferably 20% or less, more preferably 15% or less, and still more preferably 12 % Or less, particularly preferably 9% or less.
  • B 2 O 3 is a component that improves the chipping resistance of the chemically strengthened glass and improves the meltability.
  • B 2 O 3 is not essential, but the content in the case of containing B 2 O 3 is preferably 0.5% or more, more preferably 1% or more, further preferably, in order to improve the meltability. 2% or more.
  • the content of B 2 O 3 is preferably 5% or less.
  • the content of B 2 O 3 is more preferably 4% or less, still more preferably 3% or less, and particularly preferably 1% or less. In order to prevent the occurrence of striae at the time of melting, it is preferably not substantially contained.
  • P 2 O 5 is a component that improves ion exchange performance and chipping resistance.
  • P 2 O 5 may not be contained, but the content in the case of containing P 2 O 5 is preferably 0.5% or more, more preferably 1% or more, and further preferably 2% or more. is there.
  • the content of P 2 O 5 is 6% or less, preferably 4% or less, more preferably 3 in order to reduce the number of fragments when the chemically strengthened glass is broken and to suppress the scattering of the fragments. % Or less, more preferably 2% or less, and particularly preferably 1% or less. In order to prevent the occurrence of striae at the time of melting, it is preferably not substantially contained.
  • Na 2 O is a component that forms a surface compressive stress layer by ion exchange and improves the meltability of the glass.
  • Na 2 O may not be contained, but the content when the Li ion on the glass surface is exchanged with Na ion and Na 2 O is contained is preferably 1% or more.
  • the content of Na 2 O is more preferably 2% or more, and further preferably 3% or more.
  • the content of Na 2 O is excessive, the surface compressive stress formed by ion exchange is significantly reduced.
  • the content of Na 2 O is preferably 8% or less, more preferably 7% or less, still more preferably 6% or less, particularly preferably 5% or less, and most preferably 4% or less.
  • the content of Na 2 O is more preferably It is 7% or less, particularly preferably 6% or less, and most preferably 5% or less. Further, the content of Na 2 O is preferably 2% or more, more preferably 3% or more, and further preferably 4% or more.
  • K 2 O may be included to improve ion exchange performance.
  • the content is preferably 0.5% or more, more preferably 1% or more, still more preferably 2% or more, and particularly preferably 3% or more.
  • the content of K 2 O is excessive, the number of pieces when the chemically strengthened glass is broken is reduced, and the content of K 2 O is preferably 10% or less in order to suppress scattering of the pieces.
  • the content of K 2 O is more preferably 8% or less, further preferably 6% or less, particularly preferably 4% or less, and most preferably 2% or less.
  • CaO is a component that improves the meltability of the glass, is a component that reduces the number of fragments when the chemically strengthened glass is broken, and suppresses the scattering of the fragments, and may be included.
  • the content is preferably 0.5% or more, more preferably 1% or more, further preferably 2% or more, particularly preferably 3% or more, and most preferably 5% or more. is there. On the other hand, 20% or less is preferable in order to increase the ion exchange performance.
  • the content of CaO is more preferably 14% or less, and still more preferably 10% or less, 8% or less, 6% or less, 3% or less, 1% or less stepwise.
  • SrO is a component that improves the meltability of the glass, is a component that reduces the number of fragments when the chemically strengthened glass is broken, and suppresses the scattering of the fragments, and may be included.
  • the content is preferably 0.5% or more, more preferably 1% or more, further preferably 2% or more, particularly preferably 3% or more, and most preferably 5% or more. is there. On the other hand, 20% or less is preferable in order to improve ion exchange performance.
  • the content of the SrO content is more preferably 14% or less, and further preferably 10% or less, 8% or less, 6% or less, 3% or less, or 1% or less stepwise.
  • BaO is a component that improves the meltability of the chemically strengthened glass, is a component that reduces the number of fragments when the chemically strengthened glass is broken, and suppresses the scattering of the fragments, and may be included.
  • the content is preferably 0.5% or more, more preferably 1% or more, still more preferably 2% or more, particularly preferably 3% or more, and most preferably 5% or more. is there.
  • the content of BaO is preferably 15% or less in order to improve ion exchange performance, and more preferably, 10% or less, 8% or less, 6% or less, 3% or less, 1% or less in steps. It is. In order to improve chipping resistance, it is preferably not contained.
  • ZnO is a component that improves the meltability of the glass and may be contained. Content in the case of containing ZnO becomes like this. Preferably it is 0.25% or more, More preferably, it is 0.5% or more. On the other hand, in order to maintain the weather resistance of the glass, the content of ZnO is preferably 10% or less, more preferably 7% or less, further preferably 5% or less, particularly preferably 2% or less, and most preferably 1% or less. is there.
  • TiO 2 is a component that reduces the number of fragments when the chemically strengthened glass is broken and suppresses the scattering of the fragments, and may be contained.
  • the content in the case of containing TiO 2 is preferably 0.1% or more, more preferably 0.15% or more, and further preferably 0.2% or more.
  • the content of TiO 2 is preferably 1% or less, more preferably 0.5% or less, and further preferably 0.25% or less.
  • ZrO 2 is a component that increases the surface compressive stress due to ion exchange, has the effect of reducing the number of fragments when the chemically strengthened glass is broken, and suppressing the scattering of fragments, and may be contained.
  • the content is preferably 0.5% or more, more preferably 1% or more.
  • the content of ZrO 2 is preferably 8% or less, more preferably 6% or less, further preferably 4% or less, particularly preferably 2% or less, and most preferably 1.2% in order to prevent devitrification when melted. % Or less.
  • La 2 O 3 and Nb 2 O 5 are components that reduce the number of fragments when the chemically strengthened glass is broken and suppress the scattering of the fragments, and may be contained.
  • the content is preferably 0.5% or more, more preferably 1% or more, still more preferably 1.5% or more, particularly preferably 2% or more, most preferably Preferably it is 2.5% or more.
  • the contents of La 2 O 3 and Nb 2 O 5 are each preferably 8% or less, more preferably 6% or less, still more preferably 5% or less, and particularly preferably 4% or less. Preferably it is 3% or less.
  • Ta 2 O 5 and Gd 2 O 3 may be contained in a small amount in order to reduce the number of fragments when the chemically strengthened glass is broken and to suppress the scattering of the fragments, but the refractive index and reflectivity are increased. It is preferably 1% or less, more preferably 0.5% or less, and still more preferably not contained.
  • Fe 2 O 3 is a component that improves the meltability of the glass. Since Fe 2 O 3 is a component that absorbs heat rays, it promotes thermal convection of the molten glass to increase the homogeneity of the glass, and prevents the bottom brick of the melting kiln from being heated to prolong the life of the kiln. It is effective and is preferably included in the composition in the melting process of plate glass using a large kiln.
  • the content of Fe 2 O 3 is preferably 0.002% or more, more preferably 0.006% or more, still more preferably 0.01% or more, and particularly preferably 0.02% or more. On the other hand, if excessively contained coloring by Fe 2 O 3 becomes a problem.
  • Fe 2 O 3 in the oxidized state causes yellow coloring
  • FeO in the reduced state causes blue coloring
  • the balance between the two is known to cause the glass to turn green. Yes.
  • the content of Fe 2 O 3 is preferably 0.3% or less, more preferably 0.04% or less, further preferably 0.03% or less, and particularly preferably 0.025% or less.
  • a coloring component may be added within a range that does not hinder achievement of desired chemical strengthening characteristics.
  • the coloring component include Co 3 O 4 , MnO 2 , Fe 2 O 3 , NiO, CuO, Cr 2 O 3 , V 2 O 5 , Bi 2 O 3 , SeO 2 , TiO 2 , CeO 2 , and Er 2.
  • O 3 , Nd 2 O 3 and the like are preferable.
  • the content of the coloring component is preferably in a range of 7% or less in total in terms of oxide-based mole percentage. If it exceeds 7%, the glass tends to be devitrified, which is not desirable. This content is preferably 5% or less, more preferably 3% or less, and even more preferably 1% or less. When giving priority to the visible light transmittance of glass, it is preferable that these components are not substantially contained.
  • SO 3 As a fining agent for melting the glass, SO 3 , chloride, fluoride and the like may be appropriately contained. It is preferable not to contain As 2 O 3 . When containing Sb 2 O 3 content of preferably 0.3% or less, more preferably 0.1% or less, and most preferably not contained.
  • the chemically strengthened glass or the chemically strengthened glass of the present invention can impart antibacterial properties by having silver ions on the surface.
  • the glass for chemical strengthening or the chemically strengthened glass of the present invention preferably has a fracture toughness value (K1c) of 0.7 MPa ⁇ m 1/2 or more, and preferably 0.75 MPa ⁇ m 1/2 or more. more preferably, further preferably 0.77MPa ⁇ m 1/2 or more, particularly preferably at 0.80 MPa ⁇ m 1/2 or more, and most preferably 0.82 MPa ⁇ m 1/2 or more .
  • K1c fracture toughness value
  • the fracture toughness value (K1c) in this specification is a stress intensity factor K1 at which a K1-v curve is measured by a DCDC method (Double Cleavage Drilled Compression method) and a crack growth rate v is 10 ⁇ 1 m / sec. Fracture toughness value calculated as (MPa ⁇ m 1/2 ).
  • the Young's modulus of the chemically strengthened glass is 70 GPa or more, the compressive stress value (CS) at the outermost surface of the chemically strengthened glass, and the compressive stress value (CS) at a depth of 1 ⁇ m from the glass surface.
  • the difference from 1 ) is preferably 50 MPa or less. This is preferable because warpage hardly occurs when the glass surface is polished after the chemical strengthening treatment.
  • the Young's modulus (E) of the chemically strengthened glass or the chemically strengthened glass is more preferably 90 GPa or more, particularly preferably 95 GPa or more, and further preferably 100 GPa or more.
  • the upper limit of the Young's modulus is not particularly limited, but when considering the acid resistance and devitrification properties of the glass, for example, it is 150 GPa or less, preferably 145 GPa or less, more preferably 135 GPa or less, particularly preferably 125 GPa or less, and most preferably. Is 118 GPa or less.
  • the Young's modulus can be measured by, for example, an ultrasonic pulse method.
  • the density ( ⁇ ) of the glass for chemical strengthening is preferably 3.2 g / cm 3 or less, more preferably 3.1 g / cm 3 or less, in order to reduce the weight of the product and further improve the chipping resistance. More preferably, it is 3.0 g / cm 3 or less.
  • the lower limit of the density is not particularly limited, but is, for example, 2.3 g / cm 3 or more, preferably 2.5 g / cm 3 or more, more preferably 2.7 g / cm 3 in order to maintain chemical resistance such as acid resistance. That's it.
  • the average linear thermal expansion coefficient (linear expansion coefficient ⁇ ) of the glass for chemical strengthening of 50 to 350 ° C. is preferably 120 ⁇ 10 ⁇ 7 / ° C. or less, more preferably 100 ⁇ 10 6 in order to reduce warpage after chemical strengthening. It is ⁇ 7 / ° C. or less, more preferably 90 ⁇ 10 ⁇ 7 / ° C. or less, and particularly preferably 80 ⁇ 10 ⁇ 7 / ° C. or less.
  • the linear expansion coefficient is, for example, 45 ⁇ 10 ⁇ 7 / ° C. or more, preferably 55 ⁇ 10 ⁇ 7 / ° C. or more.
  • the glass transition point (Tg) of the glass for chemical strengthening is preferably 550 ° C. or higher, more preferably 570 ° C. or higher, and further preferably 590 ° C. or higher in order to reduce warpage after chemical strengthening.
  • Tg glass transition point
  • members that can be used at the time of plate forming such as float forming are limited.
  • it is 750 degrees C or less, More preferably, it is 720 degrees C or less, More preferably, it is 700 degrees C or less, Most preferably, it is 660 degrees C or less.
  • Chemically strengthened glass for Vickers hardness (Hv) preferably being 650 kgf / mm 2 or more, further preferably 700 kgf / mm 2 or more.
  • the upper limit of the Vickers hardness (Hv) of the glass for chemical strengthening is not particularly limited. However, when considering the production characteristics of the glass, for example, it is 1000 kgf / mm 2 or less, preferably 900 kgf / mm 2 or less. Preferably it is 800 kgf / mm 2 or less.
  • Chemically tempered glass Vickers hardness is preferably 700 kgf / mm 2 or more, more preferably 750 kgf / mm 2 or more, further preferably 800 kgf / mm 2 or more.
  • the upper limit is not particularly limited in the chemically tempered glass of Vickers hardness (Hvct), when considering the manufacturing properties of the glass, for example, at 1,100 kgf / mm 2 or less, preferably 1000 kgf / mm 2 or less, more preferably Is 900 kgf / mm 2 or less.
  • the surface of the chemically strengthened glass of the present invention has a compressive stress value (CS 0 ) (hereinafter sometimes referred to as “surface compressive stress value” or simply “CS”), preferably 300 MPa or more, more preferably 350 MPa. Above, more preferably 400 MPa or more.
  • CS 0 is not particularly limited, but is, for example, 1200 MPa or less, preferably 1000 MPa or less, and more preferably 800 MPa or less.
  • the depth (DOL) of the compressive stress layer of the chemically strengthened glass of the present invention is preferably 50 ⁇ m or more, more preferably 70 ⁇ m or more, still more preferably 90 ⁇ m or more, and particularly preferably 110 ⁇ m or more.
  • DOL is more than 200 ⁇ m, the CT becomes large, and there is a risk of debris scattering when cracked.
  • DOL is preferably 200 ⁇ m or less, more preferably 160 ⁇ m or less.
  • the compressive stress value (CS 50 ) at a depth of 50 ⁇ m from the glass surface of the chemically strengthened glass of the present invention is preferably 30 MPa or more. More preferably, it is 40 MPa or more, More preferably, it is 50 MPa or more, Especially preferably, it is 60 MPa or more.
  • the compressive stress value (CS 90 ) at a depth of 90 ⁇ m from the glass surface of the chemically strengthened glass of the present invention is preferably 25 MPa or more. More preferably, it is 30 MPa or more, More preferably, it is 40 MPa or more, Most preferably, it is 50 MPa or more.
  • the relationship between the surface compressive stress (CS) and the compressive stress value (CS 50 ) is preferably expressed by at least two different functions.
  • two different functions are the first region from the glass surface to a predetermined depth, and the second region from the first region to the depth at which the surface compressive stress is zero.
  • the function indicating the first area and the function indicating the second area are both linear functions
  • the slope of the linear function indicating the first area is a linear function indicating the second area. It is preferable that it is larger than the slope of the function.
  • the chemically strengthened glass of the present invention can be produced, for example, as follows.
  • the glass for chemical strengthening treatment is preferably the glass for chemical strengthening of the present invention.
  • the glass used for the chemical strengthening treatment can be produced by a usual method. For example, the raw material of each component of glass is prepared and heated and melted in a glass melting furnace. Thereafter, the glass is homogenized by a known method, formed into a desired shape such as a glass plate, and slowly cooled.
  • Examples of the glass plate forming method include a float method, a press method, a fusion method, and a downdraw method.
  • a float method suitable for mass production is preferable.
  • continuous molding methods other than the float method, that is, the fusion method and the downdraw method are also preferable.
  • the molded glass is ground and polished as necessary to form a glass substrate.
  • the glass substrate is cut into a predetermined shape and size or chamfered, if the glass substrate is cut or chamfered before performing the chemical strengthening process described later, the end face is obtained by the subsequent chemical strengthening process. Since a compressive stress layer is also formed, it is preferable.
  • the chemically strengthened glass of the present invention can be produced by subjecting the obtained glass plate to chemical strengthening treatment, followed by washing and drying.
  • the chemical strengthening treatment can be performed by a conventionally known method.
  • the glass plate is brought into contact with a melt of a metal salt (for example, potassium nitrate) containing a metal ion (typically, K ions) having a large ionic radius by dipping or the like.
  • a metal salt for example, potassium nitrate
  • K ions typically, K ions
  • Small ion radius metal ions typically Na or Li ions
  • K ions are large ion radius metal ions (typically K ions for Na ions, Na ions or K for Li ions) Ion).
  • the chemical strengthening treatment can be performed, for example, by immersing the glass plate in a molten salt such as potassium nitrate heated to 360 to 600 ° C. for 0.1 to 500 hours.
  • a molten salt such as potassium nitrate heated to 360 to 600 ° C. for 0.1 to 500 hours.
  • the heating temperature of the molten salt is preferably 375 to 500 ° C.
  • the immersion time of the glass plate in the molten salt is preferably 0.3 to 200 hours.
  • Examples of molten salts for performing chemical strengthening treatment include nitrates, sulfates, carbonates, and chlorides.
  • examples of the nitrate include lithium nitrate, sodium nitrate, potassium nitrate, cesium nitrate, and silver nitrate.
  • examples of the sulfate include lithium sulfate, sodium sulfate, potassium sulfate, cesium sulfate, and silver sulfate.
  • Examples of the carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.
  • Examples of the chloride include lithium chloride, sodium chloride, potassium chloride, cesium chloride, silver chloride and the like. These molten salts may be used alone or in combination of two or more.
  • the processing conditions of the chemical strengthening treatment include the characteristics and composition of the glass, the type of the molten salt, and the surface compressive stress (CS) desired for the finally obtained chemically strengthened glass and the depth of the compressive stress layer.
  • Appropriate conditions may be selected in consideration of chemical strengthening characteristics such as (DOL).
  • the chemical strengthening treatment may be performed only once, or multiple times of chemical strengthening treatment (multi-stage strengthening) may be performed under two or more different conditions.
  • multi-stage strengthening may be performed under two or more different conditions.
  • the first-stage chemical strengthening process after performing the chemical strengthening process under the condition that the CS is relatively low, the second-stage chemical strengthening process is performed under the condition that the CS is relatively high.
  • the tempering process is performed, the internal tensile stress area (St) can be suppressed while increasing the CS on the outermost surface of the chemically strengthened glass, and as a result, the internal tensile stress (CT) can be suppressed to a low level.
  • the chemically tempered glass of the present invention is particularly useful as a cover glass used for mobile devices such as mobile phones, smartphones, personal digital assistants (PDAs), and tablet terminals.
  • mobile devices such as mobile phones, smartphones, personal digital assistants (PDAs), and tablet terminals.
  • non-portable products such as televisions (TVs), personal computers (PCs), cover glass for display devices such as touch panels, wall surfaces of elevators, wall surfaces of buildings such as houses and buildings (full display), and construction of window glass, etc.
  • TVs televisions
  • PCs personal computers
  • cover glass for display devices such as touch panels, wall surfaces of elevators, wall surfaces of buildings such as houses and buildings (full display), and construction of window glass, etc.
  • materials such as construction materials, table tops, interiors of automobiles, airplanes, etc., and cover glasses thereof, and also for applications such as a case having a curved surface shape that is not flat by bending or processing.
  • the devitrification temperature T is preferably a temperature T4 or less at which the viscosity becomes 10 4 dPa ⁇ s. This is because when the devitrification temperature T is higher than T4, quality deterioration due to devitrification is likely to occur during glass plate forming by the float method or the like.
  • the glass for chemical strengthening of the present invention preferably has a surface compressive stress value (CSg) after performing chemical strengthening of NaNO 3 : 100%, 500 ° C. for 15 hours to glass having a thickness of 0.8 mm, preferably 300 MPa. It is above, More preferably, it is 350 Mpa or more, More preferably, it is 400 Mpa or more.
  • the upper limit of CSg is not particularly limited, but is, for example, 1200 MPa or less, preferably 1000 MPa or less, and more preferably 800 MPa or less.
  • chemically tempered glass of the present invention to the glass of a thickness 0.8mm, NaNO 3: 100%, 500 °C, the depth of the compressive stress layer after the chemical strengthening of 15 hours (DOLg) is The thickness is preferably 30 ⁇ m or more, more preferably 40 ⁇ m or more, still more preferably 50 ⁇ m or more, and particularly preferably 60 ⁇ m or more.
  • the thickness (t) thereof is, for example, 2 mm or less, preferably 1.5 mm or less in order to increase the effect of chemical strengthening. More preferably 1 mm or less, still more preferably 0.9 mm or less, particularly preferably 0.8 mm or less, and most preferably 0.7 mm or less.
  • the plate thickness is, for example, 0.1 mm or more, preferably 0.2 mm or more, more preferably 0.4 mm or more, from the viewpoint of obtaining a sufficient strength improvement effect by the chemical strengthening treatment. More preferably, it is 0.5 mm or more.
  • the chemically tempered glass of the present invention may have a shape other than a plate shape depending on a product to be applied, an application, and the like. Further, the glass plate may have an edge shape with different outer peripheral thicknesses. Moreover, the said glass plate has two main surfaces and the end surface which forms plate thickness adjacent to these, and the two main surfaces may form the flat surface mutually parallel. However, the form of the glass plate is not limited to this. For example, the two main surfaces may not be parallel to each other, and all or a part of one or both of the two main surfaces may be a curved surface. More specifically, the glass plate may be, for example, a flat glass plate without warpage or a curved glass plate having a curved surface.
  • a glass plate was prepared by melting a platinum crucible so that each glass composition represented by the mole percentage on the oxide basis shown in the table was obtained. Commonly used glass materials such as oxides, hydroxides, carbonates or nitrates were appropriately selected and weighed so as to give 1000 g of glass. Next, the mixed raw materials were put into a platinum crucible, put into a resistance heating electric furnace at 1500 to 1700 ° C., melted for about 3 hours, defoamed and homogenized. The obtained molten glass was poured into a mold material, held at a temperature of glass transition point + 50 ° C.
  • the obtained glass block was cut and ground, and finally both surfaces were processed into mirror surfaces to obtain plate glass (chemical strengthening glass) having a length of 50 mm, a width of 50 mm, and a plate thickness of 0.8 (mm).
  • the amount of Fe 2 O 3 in the glass was 0.0125%.
  • ⁇ Density ( ⁇ )> The density was measured by a submerged weighing method (JISZ 8807: 2012 method for measuring the density and specific gravity of a solid). The unit is g / cm 3 .
  • Young's modulus (E)> Young's modulus E (unit: GPa) was measured by an ultrasonic pulse method (JIS R1602: 1995).
  • ⁇ Vickers hardness (Hv)> With respect to the glass before and after chemical strengthening, the Vickers hardness Hv (unit: kgf / mm 2 ) was measured according to the method of JIS Z 2244: 2009 “Vickers Hardness Test—Test Method” with a load of 100 gf.
  • Tg Glass transition point
  • Tg glass transition point
  • Tg the glass transition point Tg (unit: ° C.) was measured using a thermomechanical analyzer (TMA) according to the method defined in JIS R3103-3: 2001.
  • ⁇ Linear expansion coefficient ( ⁇ )> The linear expansion coefficient ⁇ and the glass transition point Tg are in accordance with the method of JIS R3102: 1995 “Test Method for Average Linear Expansion Coefficient of Glass”, 50 to 350 ° C. average linear thermal expansion coefficient ( ⁇ 50 to 350 ) (unit: / ° C).
  • ⁇ CS, DOL> The surface compressive stress CS (unit: MPa) was measured with a surface stress meter FSM-6000 manufactured by Orihara Seisakusho.
  • the thickness DOL (unit: ⁇ m) of the compressive stress layer, CS 50 , CS 90 , Csg and DOLg were measured by the method using Abrio-IM and flake samples for the glasses of Examples 1 and 2, and Examples 3 to 7
  • the glass was measured using a measuring machine SLP1000 manufactured by Orihara Seisakusho using scattered light photoelasticity.
  • ⁇ Scratch test> A # 80 garnet sandpaper was cut into about 1 cm square, attached to a tribogear manufactured by Shinto Kagaku Co., Ltd., rubbed with a load of 300 gf, and the appearance of the generated scratches was observed.
  • Examples 1 to 6 have excellent scratch resistance because the Vickers hardness Hv after chemical strengthening is 700 (kgf / mm 2 ) or more.
  • the Vickers hardness Hv was 700 (kgf / mm 2 ) or more
  • the DOLg was 30 ⁇ m or more
  • the scratch resistance was excellent
  • the bending fracture resistance was excellent.

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Abstract

L'objet de la présente invention est de pourvoir à un verre chimiquement renforcé présentant une meilleure solidité et une meilleure résistance aux rayures. La présente invention concerne un verre chimiquement renforcé qui contient 38 à 75 % de SiO2, 1 à 30 % d'Al2O3, 3 à 20 % de MgO, plus de 0 % et au plus 20 % de Li2O, plus de 0 % et au plus 20 % d'Y2O3, 0 à 5 % de B2O3, 0 à 6 % de P2O5, 0 à 8 % de Na2O, 0 à 10 % de K2O, 0 à 20 % de CaO, 0 à 20 % de SrO, 0 à 15 % de BaO, 0 à 10 % de ZnO, 0 à 1 % de TiO2 et 0 à 8 % de ZrO2, et qui présente un module de Young supérieur ou égal à une valeur spécifiée, une dureté Vickers supérieure ou égale à une valeur spécifiée, une CS supérieure ou égale à une valeur spécifiée et une CS50 supérieure ou égale à une valeur spécifiée.
PCT/JP2018/016505 2017-04-28 2018-04-23 Verre chimiquement renforcé et verre destiné à un renforcement chimique WO2018199046A1 (fr)

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US20220064055A1 (en) * 2020-08-26 2022-03-03 Corning Incorporated Tunable glass compositions having improved mechanical durability
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