Classifications

• • 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
  • 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
  • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
  • 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
  • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum

Definitions

• the present invention relates to inorganic composition articles.
• cover glass and housings to protect the displays of mobile electronic devices such as smartphones and tablet PCs, as well as protectors and interior bezels for protecting the lenses of automotive optical devices. It is expected to be used for console panels, touch panel materials, smart keys, etc.
• These glasses are required not only to have high mechanical strength, but also to have excellent heat workability at the same time. Specifically, there is a demand for an inorganic material that facilitates molding of sheet glass into a curved shape by thermal processing during production.
• Patent Document 1 discloses crystallized glass having high bending strength and low coefficient of expansion.
• the crystallized glass described in Patent Document 1 has a high softening point (SP), making it difficult to produce a material having a complicated and highly curved surface shape.
• SP softening point
• the present invention provides the following. (Configuration 1) containing at least one selected from ⁇ -cristobalite and ⁇ -cristobalite solid solution as a main crystal phase, % by mass in terms of oxide,
• the content of SiO2 component is less than 45.0% to 68.0%
• Al 2 O 3 component content is 3.0% to 15.0%
• Li 2 O component content is 3.0% to 10.0%
• the content of B 2 O 3 components is more than 0% to 10.0%
• the content of P 2 O 5 components is more than 0% to 10.0%
• the content of ZrO 2 component is more than 0% to 10.0%, strengthened crystallized glass having a mass ratio of SiO 2 /(B 2 O 3 +Li 2 O) of 3.0 to 10.0
• An inorganic composition article having a compressive stress layer on its surface and a softening point (SP) of less than 795°C.
• SP softening point
• composition 4 The crystallized glass is mass% in terms of oxide, The content of the Nb 2 O 5 component is 0% to 5.0%, The content of Ta 2 O 5 component is 0% to 6.0%, The inorganic composition article according to any one of Structures 1 to 3, wherein the content of the TiO 2 component is 0% or more and less than 1.0%.
• composition 5 The inorganic composition article according to any one of Structures 1 to 4, wherein the crystallized glass has a glass transition temperature (Tg) of 610° C. or less after crystallization.
• Tg glass transition temperature
• the molding temperature is lowered, so that the glass can be produced at a relatively low temperature. Therefore, it is possible to manufacture an inorganic composition article that can be easily manufactured not only by press molding but also by 3D processing, bending processing, and curved surface processing.
• the crystallized inorganic composition article of the present invention has the strength of glass, it has a low softening point (SP), so that it can be press-molded at a relatively low temperature during glass production. In addition, after molding, more complex and difficult processing involving thermal processing is facilitated. Therefore, it can be used as a protective member for equipment, taking advantage of the fact that it is a glass-based material having strength and workability. It can be used as cover glass and housings for smartphones, as components for mobile electronic devices such as tablet PCs and wearable terminals, and as components for protective protectors and head-up display substrates used in vehicles such as cars and airplanes. It is possible. In addition, it can be used for other electronic devices and machinery, construction members, solar panel members, projector members, cover glasses (windshields) for spectacles and watches, and the like.
• SP softening point
• the inorganic composition article of the present invention is a crystallized inorganic composition article having a compressive stress layer on its surface and a softening point (SP) of less than 795°C.
• the crystallized glass of the present invention contains at least one selected from ⁇ -cristobalite and ⁇ -cristobalite solid solution as a main crystal phase. Crystallized glass that precipitates these crystal phases can precipitate crystals with a small grain size, and therefore has good transmittance and high mechanical strength.
• the "main crystalline phase" in the present specification corresponds to the crystalline phase contained most in the crystallized glass determined from the peak of the X-ray diffraction pattern.
• composition range of each component constituting the crystallized glass of the present invention will be specifically described below.
• the Li 2 O component is a component that improves the meltability of the raw glass. By making it 0% or less, it is possible to suppress the formation of lithium disilicate crystals. Also, the Li 2 O component is a component that contributes to 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 10.0% or less, 9.0% or less, or 8.5% or less.
• the B 2 O 3 component is a suitable component for lowering the softening point temperature of the crystallized glass, but if the amount is 10.0% or less, the decrease in chemical durability can be suppressed.
• the upper limit is 10.0% or less, 8.0% or less, 7.0% or less, 5.0% or less, or 4.0% or less.
• the lower limit is preferably more than 0%, 0.001% or more, 0.01% or more, 0.05% or more, 0.10% or more, or 0.30% or more.
• the P 2 O 5 component is an essential component added to act as a crystal nucleating agent for glass.
• the amount of the P 2 O 5 component is 10.0% or less, 8.0% or less, 6.0% or less, 5.0% or less, or 4.0% or less.
• the lower limit can be more than 0%, 0.5% or more, 1.0% or more, or 1.5% or more.
• the ZrO 2 component is a component that can improve the mechanical strength, but if the amount is 10.0% or less, deterioration of the meltability can be suppressed.
• the upper limit is 10.0% or less, 9.0% or less, 8.5% or less, or 8.0% or less.
• the lower limit can be more than 0%, 1.0% or more, 1.5% or more, or 2.0% or more.
• the mass ratio SiO 2 /(B 2 O 3 +Li 2 O) is preferably 3.0 to 10.0.
• the lower limit of the mass ratio SiO 2 /(B 2 O 3 +Li 2 O) is preferably 3.0 or more, more preferably 3.5 or more, still more preferably 4.64 or more.
• the upper limit of the mass ratio SiO 2 /(B 2 O 3 +Li 2 O) is preferably 10.0 or less, more preferably 9.5 or less, still more preferably less than 8.6 and 7.5 or less. 3 or less.
• the compressive stress on the surface increases when the steel is reinforced.
• 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.
• a Na 2 O component is an optional component involved in chemical strengthening when it is contained in an amount exceeding 0%.
• the Na 2 O component By setting the Na 2 O component to 4.0% or less, a desired crystal phase can be easily obtained.
• the upper limit is 4.0% or less, 3.5% or less, more preferably 3.0% or less, and even more preferably 2.5% or less.
• the lower limit of the Na 2 O component is not particularly limited, but can be, for example, 0% or more, 0% or more, 0.1% or more, 0.3% or more, or 0.5% or more.
• the MgO component, CaO component, SrO component, BaO component, and ZnO component are optional components that improve low-temperature meltability when contained in an amount exceeding 0%, and can be contained within a range that does not impair the effects of the present invention. Therefore, the MgO component can preferably have an upper limit of 4.0% or less, 3.5% or less, 3.0% or less, or 2.5% or less. Also, the MgO component can preferably have a lower limit of 0% or more, more than 0%, 0.3% or more, and 0.4% or more.
• the CaO component preferably has an upper limit of 4.0% or less, 3.0% or less, 2.5% or less, or 2.0% or less.
• the upper limit can be 6.0% or less, 5.5% or less, 5.0% or less, or 4.0% or less.
• the lower limit can be 0% or more, more than 0%, 0.3% or more, and 0.4% or more.
• the TiO 2 component is an optional component that improves the chemical durability of crystallized glass when it is contained in an amount exceeding 0%.
• the upper limit can be less than 1.0%, 0.8% or less, 0.5% or less, or 0.1% or less.
• the lower limit can be 0% or more, more than 0%, 0.3% or more, and 0.4% or more.
• the crystallized glass contains 3 La 2 O components, 3 Gd 2 O components, 3 Y 2 O components, 3 WO components, 2 TeO components, and 3 Bi 2 O components within a range that does not impair the effects of the present invention. may or may not be included.
• the content can be 0% to 2.0%, 0% to less than 2.0%, or 0% to 1.0%, respectively.
• the Sb 2 O 3 component may be contained as a refining agent for glass.
• the Sb 2 O 3 component by setting the Sb 2 O 3 component to 3.0% or less, deterioration of the transmittance in the short wavelength region of the visible light region can be suppressed. Therefore, preferably, the upper limit can be 1.0% or less, 0.5% or less, or 0.3% or less.
• the compressive stress CS (MPa) of the compressive stress layer of the inorganic composition article of the present invention is preferably 550 MPa or higher, more preferably 600 MPa or higher, and still more preferably 700 MPa or higher.
• the upper limit is, for example, 1400 MPa or less, 1300 MPa or less, 1200 MPa or less, or 1100 MPa or less.
• the central tensile stress CT (MPa) is an indicator of the degree of glass strengthening by chemical strengthening. Due to the impact resistance of glass, the central tensile stress CT (MPa) of the inorganic composition article of the present invention is preferably 40 MPa or higher, more preferably 70 MPa or higher, and still more preferably 100 MPa or higher. The upper limit is, for example, 250 MPa or less, 230 MPa or less, or 210 MPa or less. By having such central tensile stress, desired strengthened crystallized glass can be obtained by chemical strengthening.
• the thickness DOLzero ( ⁇ m) of the compressive stress layer is not limited because it also depends on the thickness of the crystallized glass. It can be 70 ⁇ m or more, or 100 ⁇ m or more. The upper limit is, for example, 180 ⁇ m or less, or 160 ⁇ m or less.
• the lower limit of the thickness of the substrate is preferably 0.05 mm or more, more preferably 0.1 mm or more, more preferably 0.2 mm or more, more preferably 0.3 mm or more, and even more preferably. is 0.4 mm or more, and the upper limit of the thickness of the crystallized glass is preferably 2.0 mm or less, more preferably 1.5 mm or less, more preferably 1.1 mm or less, more preferably 1.0 mm or less, and more It is preferably 0.9 mm or less, more preferably 0.8 mm or less.
• Crystallized glass can be produced by the following method. That is, raw materials are uniformly mixed so that the content of each component falls within a predetermined range, and the mixture is melt-molded to produce raw glass. Next, this raw glass is crystallized to produce crystallized glass.
• the Tg of the crystallized glass of the inorganic composition article of the present invention is preferably 610°C or lower, more preferably 600°C or lower, and still more preferably 590°C or lower.
• the heat treatment for crystal precipitation may be performed in one stage or in two stages of temperature.
• the nucleation step is first performed by heat treatment at a first temperature, and after this nucleation step, the crystal growth step is performed by heat treatment at a second temperature higher than the nucleation step.
• the first temperature of the two-stage 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 retention 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 performed continuously at one step of temperature.
• the temperature is raised to a predetermined heat treatment temperature, and after reaching the heat treatment temperature, the temperature is maintained for a certain period of time, 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.
• an alkali component present in the surface layer of crystallized glass is exchange-reacted with an alkali component having a larger ionic radius to form a compressive stress layer on the surface layer.
• a chemical strengthening method to There are also a thermal strengthening method in which crystallized glass is heated and then rapidly cooled, and an ion implantation method in which ions are implanted into the surface layer of crystallized glass.
• the inorganic composition article of the present invention can be produced, for example, by the following chemical strengthening method.
• the crystallized glass is brought into contact with or immersed in a molten salt containing potassium and sodium, such as a mixed salt or composite salt of potassium nitrate (KNO 3 ) and sodium nitrate (NaNO 3 ).
• a molten salt containing potassium and sodium such as a mixed salt or composite salt of potassium nitrate (KNO 3 ) and sodium nitrate (NaNO 3 ).
• KNO 3 potassium nitrate
• NaNO 3 sodium nitrate
• the first stage treatment is a single bath of sodium nitrate (NaNO 3 ) or a salt containing potassium and sodium, such as a mixed salt or complex salt of potassium nitrate (KNO 3 ) and sodium nitrate (NaNO 3 ). It is desirable to use a molten salt and the second stage treatment to be a single bath of potassium nitrate (KNO 3 ) or a salt containing potassium and sodium.
• Examples 1 to 16, Comparative Example 1 Preparation of inorganic composition articles As raw materials for each component of crystallized glass, corresponding raw materials such as oxides, hydroxides, carbonates, nitrates, fluorides, chlorides, and metaphosphate compounds are selected, and these raw materials are used. The components were weighed and uniformly mixed so as to obtain the composition shown in Table 1.
• 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. Thereafter, the molten glass was stirred and homogenized, cooled to 1000° C. to 1450° C., cast into a mold, and gradually cooled to prepare a raw glass.
• the raw glass obtained was subjected to the crystallization conditions of a nucleation step at 600° C. for 5 hours and a crystal growth step at 640° C. to 700° C. for 5 hours.
• crystallized glass was produced by heating at 640° C. to 700° C. for 5 hours under continuous crystallization conditions of a nucleation step and a crystal growth step.
• the crystal phase of the crystallized glass was determined from the angles of the peaks appearing in the X-ray diffraction pattern using an X-ray diffraction analyzer (Bruker, D8Discover).
• a main peak a peak with the highest intensity and a large peak area
• cristobalite and/or ⁇ -cristobalite solid solution was precipitated as the main crystal phase.
• the glass softening point (SP) of the inorganic composition articles after crystallization of Examples 1 to 16 and Comparative Example 1 was measured using a glass parallel plate viscometer PPVM-1100SS manufactured by Opto Enterprise Co., Ltd., and the viscosity was 10 7
• the temperature corresponding to 0.65 dPa ⁇ s was taken as the softening point.
• the glass transition points (Tg) of the crystallized inorganic composition articles of Examples 1 to 16 were measured according to the Japan Optical Glass Industry Standard JOGIS08-2019 "Method for measuring thermal expansion of optical glass”.
• the crystallized glass produced in Table 1 was cut and ground, and then subjected to face-to-face parallel polishing so as to have the material thickness shown in Tables 2 and 3 to obtain a crystallized glass substrate.
• the compressive stress (CS) of the outermost surface was measured using a glass surface stress meter FSM-6000LE series manufactured by Orihara Seisakusho, and a light source with a wavelength of 365 nm was used as the light source of the measuring instrument.
• the value of the refractive index at 365 nm was used.
• the value of the refractive index is a quadratic approximation from the measured values of the refractive index at the wavelengths of the C-line, d-line, F-line, and g-line according to the V-block method specified in JIS B 7071-2:2018. was calculated using
• the value of the photoelastic constant at 365 nm was used as the photoelastic constant used for CS measurement.
• the photoelastic constant can be calculated from the measured values of the photoelastic constant at wavelengths of 435.8 nm, 546.1 nm and 643.9 nm using a quadratic approximation.
• a photoelastic constant of 31.3 was used as a representative value.
• the photoelastic constant ( ⁇ ) was obtained by polishing the sample shape to a disk shape with a diameter of 25 mm and a thickness of 0.8 mm, applying a compressive load in a predetermined direction, and measuring the optical path difference occurring at the center of the glass. It was obtained from the relational expression of ⁇ d ⁇ F. In this relational expression, the optical path difference is expressed as ⁇ (nm), the glass thickness as d (mm), and the stress as F (MPa).
• the depth DOLzero ( ⁇ m) and central tensile stress (CT) when the compressive stress layer had a compressive stress of 0 MPa were measured using a scattered light photoelastic stress meter SLP-1000.
• Light sources with wavelengths of 405 nm and 518 nm were used as measurement light sources.
• the value of the refractive index at a wavelength of 405 nm is a second-order approximation from the measured values of the refractive index at the wavelengths of the 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 constants at wavelengths 405 nm and 518 nm used for DOLzero and CT measurements can be calculated using a quadratic approximation from the measured photoelastic constants at wavelengths 435.8 nm, 546.1 nm, and 643.9 nm.
• 31.0 at a wavelength of 405 nm and 30.1 at a wavelength of 518 nm were used as representative values.

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• 2023
  • 2023-01-31 WO PCT/JP2023/002982 patent/WO2023145956A1/ja not_active Ceased
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