WO2022050105A1 - 強化結晶化ガラス - Google Patents

強化結晶化ガラス Download PDF

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Publication number
WO2022050105A1
WO2022050105A1 PCT/JP2021/030790 JP2021030790W WO2022050105A1 WO 2022050105 A1 WO2022050105 A1 WO 2022050105A1 JP 2021030790 W JP2021030790 W JP 2021030790W WO 2022050105 A1 WO2022050105 A1 WO 2022050105A1
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component
crystallized glass
compressive stress
mpa
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PCT/JP2021/030790
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English (en)
French (fr)
Japanese (ja)
Inventor
吉川早矢
小笠原康平
八木俊剛
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Ohara Inc
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Ohara Inc
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Priority to EP21864163.7A priority Critical patent/EP4209468A4/en
Priority to CN202180054451.1A priority patent/CN116018327A/zh
Priority to JP2021549978A priority patent/JPWO2022050105A1/ja
Priority to KR1020237007180A priority patent/KR20230061374A/ko
Priority to US18/024,489 priority patent/US20230312401A1/en
Publication of WO2022050105A1 publication Critical patent/WO2022050105A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • 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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0054—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing PbO, SnO2, B2O3
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • 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
    • 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
    • C03C2204/00—Glasses, glazes or enamels with special properties

Definitions

  • the present invention relates to reinforced crystallized glass.
  • Cover glass is used to protect the display in portable electronic devices such as smartphones and tablet PCs.
  • a protector for protecting the lens is also used in an in-vehicle optical device.
  • it has been required to be used for a housing or the like which is an exterior of an electronic device. And there is an increasing demand for materials with higher strength so that these devices can withstand more rigorous use.
  • Patent Document 1 discloses a material composition of a chemically strengthenable crystallized glass substrate for an information recording medium. It is stated that the ⁇ -cristobalite-based crystallized glass described in Patent Document 1 can be chemically strengthened and can be used as a high-strength material substrate. However, the crystallized glass for information recording media represented by a hard disk substrate was not intended for use in a harsh environment.
  • An object of the present invention is to provide a reinforced crystallized glass having high strength and being hard to break.
  • the present invention provides: (Structure 1) Has a compressive stress layer on the surface When the compressive stress at a depth of 50 ⁇ m from the outermost surface is CS 50 ⁇ m (MPa) and the stress depth when the compressive stress is 0 MPa is DOL zero ( ⁇ m), [CS 50 ⁇ m ⁇ (DOL zero -50)] / 2 is Reinforced crystallized glass that is over 2000. (Structure 2) The reinforced crystallized glass according to Configuration 1, wherein the stress depth DOL zero is 70 to 300 ⁇ m. (Structure 3) The strengthened crystallized glass according to the configuration 1 or 2, wherein the CS 50 ⁇ m is 55 to 400 MPa.
  • the main crystal phase contains one or more selected from ⁇ -cristobalite and ⁇ -cristobalite solid solution.
  • the content of SiO 2 component is 50.0% to 75.0%
  • the content of Li 2 O component is 3.0% to 10.0%
  • Al 2 O 3 component content is 5.0% or more and less than 15.0%
  • B 2 O 3 component content is 0% to 10.0%
  • the reinforced crystallized glass of the present invention can be used as a protective member for equipment by taking advantage of the fact that it is a glass-based material having high strength. Used as a cover glass and housing for smartphones, as a component for portable electronic devices such as tablet PCs and wearable terminals, and as a component for protective protectors and head-up display boards used in transport aircraft such as cars and airplanes. It is possible. In addition, it can be used for other electronic devices, machinery and equipment, building members, solar panel members, projector members, cover glasses (windshields) for eyeglasses and watches, and the like.
  • the reinforced crystallized glass of the present invention has a compressive stress layer on the surface.
  • the compressive stress layer can be formed by subjecting the crystallized glass to an ion exchange treatment.
  • the compressive stress layer is formed from the outermost surface of the substrate to the inside with a predetermined thickness, and the compressive stress is highest on the outermost surface and decreases toward the inside to become zero.
  • FIG. 1 is a diagram showing changes in compressive stress (MPa) with respect to the depth ( ⁇ m) from the outermost surface of the compressive stress layer on the surface portion of the tempered crystallized glass produced in Example 20 and Comparative Example 1. .. Zero depth represents the outermost surface.
  • the outermost compressive stress (also referred to as the outermost compressive stress) is represented by CS
  • the depth of the compressive stress layer (also referred to as stress depth) when the compressive stress is 0 MPa is represented by DOL zero .
  • first inclination S1 after the compressive stress suddenly decreases inward from the outermost surface
  • second inclination S2 the compressive stress gradually decreases (second inclination S2).
  • the DOL zero is deep and the first inclination S1 is larger than that of Comparative Example 1.
  • the compressive stress value from the depth of 50 ⁇ m from the outermost surface to DOL zero that is, the integrated value from CS 50 ⁇ m MPa to 0 MPa is approximated to the area of the triangle [CS 50 ⁇ m ⁇ (DOL zero -50)]. It becomes / 2.
  • this [CS 50 ⁇ m ⁇ (DOL zero -50)] / 2 is 2000 or more.
  • the lower limit can be 3000 or more, or 4000 or more.
  • the upper limit can be 12000 or less, 11000 or less, or 10000 or less.
  • the outermost surface compressive stress CS is usually 600 to 1200 MPa, and can be, for example, 650 to 1100 MPa or 700 to 1000 MPa.
  • the compressive stress CS 50 ⁇ m at a depth of 50 ⁇ m is usually 55 to 400 MPa, and can be, for example, 58 to 300 MPa or 60 to 280 MPa.
  • the compression depth DOL zero determined by curve analysis may be 70 to 300 ⁇ m, for example 80 to 250 ⁇ m, 90 to 230 ⁇ m, or 100 to 200 ⁇ m.
  • the strengthened crystallized glass becomes difficult to break.
  • the stress depth, stress gradient and surface compressive stress can be adjusted by adjusting the composition and chemical strengthening conditions.
  • the lower limit of the thickness of the substrate is preferably 0.10 mm or more, more preferably 0.30 mm or more, more preferably 0.40 mm or more, still more preferably 0.50 mm or more.
  • the upper limit of the thickness of the strengthened crystallized glass is preferably 1.10 mm or less, more preferably 1.00 mm or less, more preferably 0.90 mm or less, still more preferably 0.80 mm or less.
  • the strengthened crystallized glass of the present invention preferably contains one or more selected from ⁇ -cristobalite and ⁇ -cristobalite solid solution as the main crystal phase. Having these crystalline phases increases the mechanical strength.
  • the "main crystal phase" in the present specification corresponds to the crystal phase most contained in the crystallized glass determined from the peak of the X-ray diffraction pattern.
  • the suitable composition range constituting the strengthened crystallized glass is described below.
  • the content of each component is indicated by mass% in terms of oxide unless otherwise specified.
  • oxide conversion means toughened crystallized glass when it is assumed that all the constituents of the strengthened crystallized glass are decomposed and changed into an oxide, and the total mass of the oxide is 100% by mass.
  • the amount of oxides of each component contained therein is expressed in% by mass.
  • A% to B% represent A% or more and B% or less.
  • the reinforced crystallized glass of the present invention is preferably preferred.
  • the content of SiO 2 component is 50.0% to 75.0%
  • the content of Li 2 O component is 3.0% to 10.0%
  • Al 2 O 3 component content is 5.0% or more and less than 15.0%
  • B 2 O 3 component content is 0% to 10.0%, Is.
  • the SiO 2 component is an essential component necessary for constituting one or more kinds selected from ⁇ -cristobalite and ⁇ -cristobalite solid solution. If the content of the SiO 2 component exceeds 75.0%, the viscosity may be excessively increased and the meltability may be deteriorated, and if it is less than 50.0%, the devitrification resistance may be easily deteriorated.
  • the upper limit is preferably 75.0% or less, 74.0% or less, 73.0% or less, 72.0% or less, or 70.0% or less. Further, the lower limit is preferably 50.0% or more, 55.0% or more, 58.0% or more, or 60.0% or more.
  • the Li 2 O component is a component that improves the meltability of the raw glass, but if the amount is less than 3.0%, the above effect cannot be obtained and it becomes difficult to melt the raw glass, and 10.0% is added. If it exceeds, the production of lithium disilicate crystals increases.
  • the Li 2 O component is a component involved in chemical strengthening.
  • the lower limit is 3.0% or more, 3.5% or more, 4.0% or more, 4.5% or more, 5.0% or more, or 5.5% or more.
  • the upper limit is preferably 10.0% or less, 9.0% or less, 8.5% or less, or 8.0% or less.
  • the Al 2 O 3 component is a component suitable for improving the mechanical strength of the tempered crystallized glass. If the content of the Al 2 O 3 component is 15.0% or more, the meltability and devitrification resistance may deteriorate, and if it is less than 5.0%, the effect of improving the mechanical strength may be poor.
  • the upper limit is preferably less than 15.0%, 14.5% or less, 14.0% or less, 13.5% or less, or 13.0% or less. Further, the lower limit is preferably 5.0% or more, 5.5% or more, 5.8% or more, 6.0% or more, 6.5% or more, or 8.0% or more.
  • the B 2 O 3 component is a component suitable for lowering the glass transition temperature of the tempered crystallized glass, but if the amount exceeds 10.0%, the chemical durability may be easily lowered. ..
  • the upper limit is preferably 10.0% or less, 8.0% or less, 7.0% or less, 5.0% or less, or 4.0% or less.
  • the lower limit can be 0%, 0.001% or more, 0.01% or more, 0.05% or more, 0.10% or more, or 0.30% or more.
  • the ZrO2 component is an optional component, but the content is preferably more than 0% and 10.0% or less.
  • the ZrO 2 component is a component that can improve the mechanical strength, but if the amount exceeds 10.0%, the meltability may be deteriorated.
  • the upper limit is preferably 10.0% or less, 9.0% or less, 8.5% or less, or 8.0% or less.
  • the lower limit is preferably more than 0%, 1.0% or more, 1.5% or more, or 2.0% or more.
  • the compressive stress on the surface becomes large when the material is strengthened.
  • the lower limit of [Al 2 O 3 + ZrO 2 ] is 10.0% or more, 11.0% or more, 12.0% or more, or 13.0% or more.
  • the upper limit of [Al 2 O 3 + ZrO 2 ] is preferably 22.0% or less, 21.0% or less, 20.0% or less, or 19.0% or less.
  • the lower limit of the total content of the SiO 2 component, Li 2 O component, Al 2 O 3 component and B 2 O 3 component is preferably 75.0% or more, 80.0% or more, 83.0% or more, or 85. It can be 0.0% or more.
  • the P 2 O 5 component is an optional component that can be added to act as a crystal nucleation agent for glass, but if the amount exceeds 10.0%, devitrification resistance deteriorates and glass phase separation occurs. It may be easier.
  • the upper limit is preferably 10.0% or less, 8.0% or less, 6.0% or less, 5.0% or less, or 4.0% or less. Further, the lower limit can be preferably 0% or more, 0.5% or more, 1.0% or more, or 1.5% or more.
  • the K2O component is an optional component involved in chemical fortification.
  • the lower limit can be 0% or more, 0.1% or more, 0.3% or more, or 0.5% or more.
  • the upper limit can be preferably 5.0% or less, 4.0% or less, 3.5% or less, or 3.0% or less.
  • the Na 2 O component is an optional component involved in chemical fortification. If it is contained in an excessive amount, it may be difficult to obtain a desired crystal phase.
  • the upper limit can be preferably 4.0% or less, 3.5% or less, more preferably 3.0% or less, still more preferably 2.5% or less.
  • the MgO component, CaO component, SrO component, BaO component, and ZnO component are optional components that improve low-temperature meltability, and can be contained within a range that does not impair the effects of the present invention. Therefore, the upper limit of the MgO component can be preferably 4.0% or less, 3.5% or less, 3.0% or less, or 2.7% or less. Further, the MgO component can preferably have a lower limit of more than 0%, 0.3% or more, and 0.4% or more.
  • the CaO component can preferably have an upper limit of 4.0% or less, 3.0% or less, 2.5% or less, or 2.0% or less.
  • the SrO component can preferably have an upper limit of 4.0% or less, 3.0% or less, 2.5% or less, or 2.0% or less.
  • the upper limit of the BaO component can be preferably 5.0% or less, 4.0% or less, 3.0% or less, 2.5% or less, or 2.0% or less.
  • the ZnO component can preferably have an upper limit of 10.0% or less, 9.0% or less, 8.5% or less, 8.0% or less, or 7.5% or less. Further, the ZnO component can preferably have a lower limit of more than 0%, 0.5% or more, and 1.0% or more.
  • the tempered crystallized glass may or may not contain the Nb 2 O 5 component, the Ta 2 O 5 component, and the TiO 2 component, respectively, as long as the effects of the present invention are not impaired.
  • the Nb 2 O 5 component is an optional component that improves the mechanical strength of the crystallized glass when it is contained in excess of 0%.
  • the upper limit can be 5.0% or less, 4.0% or less, 3.5% or less, or 3.0% or less.
  • the Ta 2 O 5 component is an optional component that improves the mechanical strength of the crystallized glass when it is contained in excess of 0%.
  • the upper limit can be 6.0% or less, 5.5% or less, 5.0% or less, or 4.0% or less.
  • the TiO 2 component is an optional component that improves the chemical durability of the crystallized glass when it is contained in an amount of more than 0%.
  • the upper limit can be less than 1.0%, 0.8% or less, 0.5% or less, or 0.1% or less.
  • the strengthened crystallized glass contains La 2 O 3 component, Gd 2 O 3 component, Y 2 O 3 component, WO 3 component, TeO 2 component, and Bi 2 O 3 component, respectively, as long as the effect of the present invention is not impaired. It may or may not be included.
  • the blending amount can be 0% to 2.0%, 0% to less than 2.0%, or 0% to 1.0%, respectively.
  • the strengthened crystallized glass may or may not contain other components not described above as long as the characteristics of the strengthened crystallized glass of the present invention are not impaired.
  • metal components such as Yb, Lu, V, Cr, Mn, Fe, Co, Ni, Cu, Ag and Mo (including these metal oxides) and the like.
  • the Sb 2 O 3 component may be contained as a glass clarifying agent.
  • the upper limit can be preferably 2.0% or less, more preferably 1.0% or less, and further preferably 0.6% or less.
  • the glass clarifying agent in addition to the Sb 2 O 3 component, the SnO 2 component, the CeO 2 component, the As 2 O 3 component, and one or more selected from the group of F, NOx, and SOx may be contained. However, it does not have to be included. However, the content of the clarifying agent can be preferably an upper limit of 3.0% or less, more preferably 1.0% or less, and most preferably 0.6% or less.
  • the tempered crystallized glass can be produced, for example, by the following method. That is, the raw materials are uniformly mixed so that each component is within a predetermined content range, and melt-molded to produce raw glass. Next, this raw glass is crystallized to produce crystallized glass.
  • the heat treatment for crystal precipitation may be a one-step heat treatment or a two-step temperature heat treatment.
  • a nucleation step is first performed by heat-treating at a first temperature, and after this nucleation step, a crystal growth step is performed by heat-treating at a second temperature higher than that of the nucleation step.
  • the first temperature of the two-step heat treatment is preferably 450 ° C. to 750 ° C., more preferably 500 ° C. to 720 ° C., and even more preferably 550 ° C. to 680 ° C.
  • the holding time at the first temperature is preferably 30 minutes to 2000 minutes, more preferably 180 minutes to 1440 minutes.
  • the second temperature of the two-step heat treatment is preferably 550 ° C to 850 ° C, more preferably 600 ° C to 800 ° C.
  • the holding time at the second temperature is preferably 30 minutes to 600 minutes, more preferably 60 minutes to 400 minutes.
  • the nucleation step and the crystal growth step are continuously performed at the one-step temperature.
  • the temperature is raised to a predetermined heat treatment temperature, the temperature is maintained for a certain period of time after reaching the heat treatment temperature, and then the temperature is lowered.
  • the heat treatment temperature is preferably 600 ° C. to 800 ° C., more preferably 630 ° C. to 770 ° C.
  • the holding time at the heat treatment temperature is preferably 30 minutes to 500 minutes, more preferably 60 minutes to 400 minutes.
  • a compressive stress layer is formed on the crystallized glass base material by ion exchange by the chemical strengthening method.
  • the crystallized glass base material is chemically fortified with a mixed molten salt of potassium salt and sodium salt (mixed bath) or a single molten salt of sodium salt (single bath) (first stage), and then the potassium salt alone. Chemically fortified with the molten salt (single bath) of (second stage).
  • the crystallized glass base material is a salt containing potassium or sodium, for example, a mixed salt or a composite salt such as potassium nitrate (KNO 3 ) and sodium nitrate (NaNO 3 ), or a single salt of sodium nitrate.
  • KNO 3 potassium nitrate
  • NaNO 3 sodium nitrate
  • a salt containing potassium for example, potassium nitrate (KNO 3 )
  • KNO 3 potassium nitrate
  • Examples 1-42, Comparative Example 1 1. Production of Crystallized Glass and Reinforced Crystallized Glass Select raw materials such as oxides, hydroxides, carbonates, nitrates, fluorides, chlorides, and metaphosphoric acid compounds that correspond to each component of the crystallized glass. These raw materials were weighed so as to have the compositions shown in Tables 1 to 3 and mixed uniformly.
  • the mixed raw materials were put into a platinum crucible and melted in an electric furnace at 1300 ° C to 1600 ° C for 2 to 24 hours depending on the difficulty of melting the glass composition. Then, the molten glass was stirred and homogenized, the temperature was lowered to 1000 ° C. to 1450 ° C., the glass was cast into a mold, and the glass was slowly cooled to prepare a raw glass. The obtained raw glass was heated to prepare a crystallized glass.
  • the crystal phases of the crystallized glasses of Examples 1 to 42 and Comparative Example 1 were discriminated from the angle of the peak appearing in the X-ray diffraction pattern using an X-ray diffraction analyzer (D8Discover, manufactured by Bruker).
  • a main peak (a peak having the highest intensity and a large peak area) was observed at a position corresponding to the peak pattern of the ⁇ -cristobalite and / or the ⁇ -cristobalite solid solution. It was determined that all ⁇ -cristobalite and / or ⁇ -cristobalite solid solution was precipitated as the main crystal phase.
  • no peak of ⁇ -cristobalite and ⁇ -cristobalite solid solution was observed.
  • the crystal phases of MgAl 2 O 4 and MgTi 2 O 4 were confirmed.
  • the produced crystallized glass was cut and ground, and further subjected to face-to-face parallel polishing so as to have the material thicknesses shown in Tables 1 to 3 to obtain a crystallized glass substrate.
  • This crystallized glass substrate was used as a base material and strengthened in two steps to obtain a chemically strengthened crystallized glass substrate. Specifically, after immersion in a NaNO 3 molten salt (Na single bath) or a mixed molten salt of KNO 3 and NaNO 3 (K: Na) at the temperatures and times shown in Tables 1 to 3 (first step). , Soaked in KNO 3 molten salt (K single bath) at the temperature and time shown in Tables 1 to 3 (second step). The ratio of K: Na in the mixed molten salt of the first stage is the weight ratio of KNO 3 and NaNO 3 .
  • the compressive stress value (CS) on the outermost surface was measured using a glass surface stress meter FSM-6000LE series manufactured by Orihara Seisakusho.
  • a light source having a wavelength of 596 nm was used as the light source of the measuring machine. It is also possible to select a light source having a wavelength of 365 nm depending on the strengthening depth.
  • the value of the refractive index used for CS measurement the value of the refractive index of 596 nm was used.
  • a value with a refractive index of 365 nm When using a 365 nm light source, use a value with a refractive index of 365 nm.
  • the value of the refractive index at a wavelength of 596 nm or 365 nm is obtained from the measured values of the refractive index at the wavelengths of C line, d line, F line, and g line according to the V block method specified in JIS B 7071-2: 2018. It can be calculated using a quadratic approximation formula.
  • the value of the photoelastic constant of 596 nm was used.
  • a photoelastic constant of 365 nm is used.
  • the photoelastic constant at a wavelength of 596 nm or 365 nm can be calculated using a quadratic approximation formula from the measured values of the photoelastic constant at a wavelength of 435.8 nm, a wavelength of 546.1 nm, and a wavelength of 643.9 nm.
  • 29.6 was used as the photoelastic constant at the wavelength of 596 nm
  • 29.358 was used as the photoelastic constant at the wavelength of 596 nm.
  • the photoelastic constant ( ⁇ ) is obtained by face-to-face polishing the sample shape into a disk shape with a diameter of 25 mm and a thickness of 8 mm, applying a compressive load in a predetermined direction, and measuring the optical path difference generated in the center of the glass. It was obtained by the relational expression of d ⁇ F.
  • the optical path difference is expressed as ⁇ (nm)
  • the glass thickness is expressed as d (mm)
  • the stress is expressed as F (MPa).
  • the compressive stress value (CS 50 ⁇ m ) at a depth of 50 ⁇ m and the depth DOLzero ( ⁇ m) when the compressive stress of the compressive stress layer was 0 MPa were measured using a scattered photoelastic stress meter SLP-1000.
  • a measurement light source a light source having a wavelength of 640 nm was used.
  • the value of the refractive index at a wavelength of 640 nm is a quadratic approximation from the measured values of the refractive index at the wavelengths of C-line, d-line, F-line, and g-line according to the V-block method specified in JIS B 7071-2: 2018. Calculated using the formula.
  • the photoelastic constant at a wavelength of 640 nm used for CS 50 ⁇ m and DOLzero measurement can be calculated using a quadratic approximation formula from the measured values of the photoelastic constant at a wavelength of 435.8 nm, a wavelength of 546.1 nm, and a wavelength of 643.9 nm.
  • 29.2 was used as a representative value
  • 27.6 was used as a representative value.

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