WO2024062797A1 - Verre cristallisé - Google Patents

Verre cristallisé Download PDF

Info

Publication number
WO2024062797A1
WO2024062797A1 PCT/JP2023/029313 JP2023029313W WO2024062797A1 WO 2024062797 A1 WO2024062797 A1 WO 2024062797A1 JP 2023029313 W JP2023029313 W JP 2023029313W WO 2024062797 A1 WO2024062797 A1 WO 2024062797A1
Authority
WO
WIPO (PCT)
Prior art keywords
content
component
less
components
crystallized glass
Prior art date
Application number
PCT/JP2023/029313
Other languages
English (en)
Japanese (ja)
Inventor
早矢 吉川
俊剛 八木
Original Assignee
株式会社オハラ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社オハラ filed Critical 株式会社オハラ
Publication of WO2024062797A1 publication Critical patent/WO2024062797A1/fr

Links

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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum

Definitions

  • the present invention relates to crystallized glass, particularly hard crystallized glass.
  • glass materials have begun to be used for the cover glass and housing of smartphones to increase the degree of design freedom. These glass members are required to be resistant to scratches and resistant to breakage even when subjected to impact from external factors, such as when a smartphone is dropped on asphalt.
  • Crystallized glass is a type of glass with increased strength and hardness. Crystallized glass is made by depositing crystals inside glass, and is known to have better mechanical strength than amorphous glass. Furthermore, it is also known to increase strength and hardness by forming a compressive stress layer on the surface by chemical strengthening or the like.
  • Patent Document 1 discloses a glass-ceramic material having a transparent or translucent petalite crystalline phase and a lithium silicate crystalline phase, which has rapid ion exchangeability and high fracture toughness.
  • Patent Document 2 discloses a reinforced crystallized glass containing ⁇ -cristobalite.
  • An object of the present invention is to provide a hard crystallized glass.
  • (Configuration 1) Contains ⁇ -cristobalite and lithium disilicate as the main crystal phase, In terms of oxide mass%, Content of two SiO components: 65.0% to 85.0%, Content of three Al 2 O components: 1.5% to 5.9%, Content of P 2 O 5 components: more than 0% and less than 5.0%, Content of Li 2 O component 5.0% to 10.8%, Content of two ZrO components: 4.0% to 12.5%, and [(Content of 2 SiO components + Content of Li 2 O component)/Content of 3 Al 2 O components] More than 13.9, A crystallized glass characterized by: (Configuration 2) In terms of oxide mass%, Content of three B 2 O components: 0% to 5.0%, Content of Na 2 O component 0% to 5.0%, K 2 O component content 0% to 5.0%, MgO component content 0% to 5.0%, Content of CaO component: 0% to 5.0%, Content of ZnO component: 0% to 5.0%, Content of two TiO components: 0% to 5.0%, Content of Gd
  • (Configuration 4) The crystallized glass according to any one of Structures 1 to 3, wherein the content of the two ZrO components is more than 7% and 12.5% or less.
  • (Configuration 5) In terms of oxide mass%, [(Content of K 2 O component + content of 3 components of Al 2 O) / content of 2 components of ZrO] less than 0.88, The crystallized glass according to any one of Structures 1 to 4, characterized in that: (Configuration 6) In terms of oxide mass%, [(Content of P 2 O 5 components + content of K 2 O component + content of MgO component + content of 3 Al 2 O components) / content of 2 ZrO components] less than 1.32, The crystallized glass according to any one of Structures 1 to 5, characterized in that: (Configuration 7) The crystallized glass according to any one of Structures 1 to 6, which has a compressive stress layer on its surface. (Configuration 8) The crystallized glass according to any one of Structures 1 to 7, which is used for a glass member of a
  • hard crystallized glass can be provided.
  • the crystallized glass of the present invention can be used as a component for smartphone housings, portable electronic devices such as tablet PCs and wearable devices, and for protection used in transportation vehicles such as cars and airplanes. It can be used as a member for protectors, heads-up display boards, etc.
  • each component is expressed in mass % in terms of oxide.
  • “in terms of oxide” refers to the amount of water contained in crystallized glass when the total mass of the oxides is 100% by mass, assuming that all the constituent components of crystallized glass are decomposed and converted to oxides. The amount of oxide of each component contained is expressed in mass %. In this specification, A% to B% represents A% or more and B% or less.
  • the crystallized glass of the present invention contains ⁇ -cristobalite and lithium disilicate as main crystal phases. By including both of these crystal phases in a predetermined composition, the present invention has higher hardness than a crystallized glass that contains ⁇ -cristobalite but not lithium disilicate. Crystalline phases also include solid solutions.
  • the "main crystalline phase” refers to the crystalline phase that is contained the most among the main crystalline phases identified from the peak of the X-ray diffraction pattern of crystallized glass, that is, the crystalline phase that is contained the first and second most. It is a crystalline phase.
  • ⁇ -cristobalite may be the first predominant crystalline phase
  • lithium disilicate may be the first predominant crystalline phase.
  • the crystallized glass may further contain one or more other crystal phases selected from petalite, vergilite, quartz, and lithium monosilicate crystals, but it is preferable that these crystal phases are present in small amounts or not included. .
  • Crystallized glass containing ⁇ -cristobalite and lithium disilicate as main crystal phases can be obtained by crystallizing raw glass having the following composition by heat treatment.
  • the composition of crystallized glass is expressed as oxide mass%,
  • the content of two SiO components is 65.0% to 85.0%,
  • the content of the three Al 2 O components is 1.5% to 5.9%,
  • the content of P 2 O 5 components is more than 0% and not more than 5.0%,
  • the content of Li 2 O component is 5.0% to 10.8%,
  • the content of ZrO 2 components is 4.0% to 12.5%
  • [(Content of 2 SiO components + Content of Li 2 O components)/Content of 3 Al 2 O components] is more than 13.9.
  • a predetermined crystal phase can be obtained. If the Al 2 O 3 component is more than the above upper limit, a lithium aluminum silicate crystal phase is likely to be generated, and if the SiO 2 component and Li 2 O component are outside the above range, lithium disilicate is not formed and only ⁇ -cristobalite is generated. It becomes easier.
  • the SiO 2 component is a skeleton component constituting crystallized glass, and is an essential component necessary for increasing stability and precipitating a desired crystal phase. Setting the content of the two SiO components to 85.0% or less can suppress excessive increases in viscosity and deterioration of solubility, and setting the content to 65.0% or more can improve the stability of crystallized glass. can be improved. Therefore, the upper limit is preferably 85.0% or less, more preferably 83.0% or less, even more preferably 80.0% or less. Further, the lower limit is preferably 65.0% or more, more preferably 68.0% or more, and even more preferably more than 70.0%.
  • the three Al 2 O components are skeleton components constituting crystallized glass, and are essential components necessary to improve stability.
  • the content of the Al 2 O 3 components is 5.9% or less, the transmittance at 450 nm can be increased and deterioration of devitrification can be suppressed, and when the content is 1.5% or more, the stability It can suppress sexual deterioration. Therefore, the upper limit is preferably 5.9% or less, more preferably 5.5% or less, even more preferably 5.3% or less. Further, the lower limit is preferably 1.5% or more, more preferably 1.8% or more, and even more preferably 2.0% or more.
  • the P 2 O 5 component is an essential component that promotes crystal formation of crystallized glass.
  • the content of the P 2 O 5 component is 5.0% or less, phase separation of the glass can be suppressed. Moreover, if it is 0%, the desired crystal phase cannot be obtained. Therefore, the upper limit is preferably 5.0% or less, more preferably 4.5% or less, even more preferably 4.0% or less. Further, the lower limit is preferably more than 0%, more preferably 0.5% or more, and even more preferably 1.0% or more.
  • the Li 2 O component is an essential component necessary for improving the meltability of the raw glass, increasing the manufacturability, and precipitating a desired crystal phase.
  • the content of the Li 2 O component is 10.8% or less, deterioration of devitrification can be suppressed, and when it is 5.0% or more, deterioration of viscosity and meltability can be suppressed, Manufacturability can be improved.
  • a desired crystal phase can be obtained. Therefore, the upper limit is preferably 10.8% or less, more preferably 10.5% or less, for example, 10.2% or less, 8.9% or less, or 8.5% or less.
  • the lower limit is preferably 5.0% or more, more preferably 6.2% or more, even more preferably 7.0% or more, and can be, for example, 8.1% or more, or 9.0% or more.
  • the ZrO 2 component is a component that serves as a crystal nucleating agent.
  • the content of the two ZrO components is 12.5% or less, deterioration in solubility can be suppressed.
  • the content of the two ZrO components is 4.0% or more, it becomes easy to increase the transmittance at 450 nm. Therefore, the upper limit is preferably 12.5% or less, for example, 12.0% or less, 11.5% or less, 11.0% or less, 10.0% or less, or 9.0% or less.
  • the lower limit is 4.0% or more, more preferably 4.7% or more, more preferably 5.7% or more, still more preferably more than 6.9%, for example, more than 7%, or 10%. It can be 5% or more.
  • the glass according to the present invention can be produced even when the MgO component is 0%, it is an optional component that improves low-temperature meltability when it is contained in an amount exceeding 0%.
  • optional components are components that may or may not be included.
  • the upper limit is preferably 5.0% or less, more preferably 3.0% or less, and still more preferably less than 2.0%.
  • the lower limit is preferably set to 0% or more, more preferably 0.1% or more, and still more preferably 0.2% or more.
  • the ZnO component is an optional component that improves low-temperature meltability when contained in an amount exceeding 0%, although it is possible to produce the glass according to the present invention even when the ZnO component is 0%.
  • the content of the ZnO component is 5.0% or less, chemical strengthening becomes easier. Therefore, the upper limit is preferably 5.0% or less, more preferably 3.0% or less, and still more preferably less than 2.0%.
  • the lower limit is preferably 0% or more, more preferably more than 0%, more preferably 0.1% or more, and still more preferably 0.2% or more.
  • the glass according to the present invention can be produced even when the CaO component is 0%, it is an optional component that improves low-temperature meltability when it is contained in an amount exceeding 0%.
  • the content of the CaO component is 5.0% or less, chemical strengthening becomes easier. Therefore, the upper limit is preferably 5.0% or less, more preferably 3.0% or less, and even more preferably less than 1.0%.
  • the lower limit is preferably more than 0%, more preferably 0.1% or more, more preferably 0.2% or more, and still more preferably 0.3% or more.
  • the K 2 O component and the Na 2 O component are optional components that improve the meltability of the raw glass and increase the productivity.
  • the content of each of the K 2 O component and the Na 2 O component is 5.0% or less, deterioration of devitrification can be suppressed.
  • the glass according to the present invention can be produced even when the K 2 O component and Na 2 O component are 0%, but when they are contained in excess of 0%, deterioration of viscosity and meltability are suppressed, and productivity is improved. can be increased. Therefore, the upper limit of the Na 2 O component is preferably 5.0% or less, more preferably 4.0% or less, more preferably less than 3.0%, and still more preferably less than 2.0%.
  • the lower limit is preferably 0% or more, more preferably 0.2% or more, and even more preferably 0.3% or more.
  • the upper limit of the K 2 O component is preferably 5.0% or less, more preferably 4.0% or less, and can be, for example, 3.0% or less, 2.0% or less, or 1.0% or less.
  • the lower limit is 0% or more, more preferably 0.2% or more, even more preferably 0.3% or more, for example, 0.5% or more, 1.0% or more, 2.0% or more, It can be 2.5% or more, or 3.0% or more.
  • the Sb 2 O 3 component is an optional component that functions as a clarifying agent when producing raw glass. If the Sb 2 O 3 component is contained excessively, the transmittance in the short wavelength region of the visible light region may deteriorate. Therefore, the upper limit is preferably 3.0% or less, more preferably 2.0% or less, more preferably 1.0% or less, more preferably 0.6% or less, even more preferably 0.5% or less. Preferably, the lower limit is 0% or more, more preferably 0.01% or more, and even more preferably 0.03 or more.
  • the B 2 O 3 component is an optional component that has the effect of lowering the viscosity of the raw glass.
  • the content of the three B 2 O components is 5.0% or less, deterioration of devitrification can be suppressed.
  • the glass according to the present invention can be produced even when the content of the three B 2 O components is 0%, but when the content exceeds 0%, deterioration of the viscosity and meltability of the original glass can be suppressed. . Therefore, the upper limit is preferably 5.0% or less, more preferably 4.5% or less, even more preferably 4.0% or less. Further, the lower limit is preferably 0% or more, more preferably more than 0%, more preferably 0.1% or more, and still more preferably 0.3% or more.
  • the TiO2 component is an optional component that has the effect of increasing the refractive index.
  • the content of the two TiO components is 5.0% or less, deterioration of devitrification can be suppressed.
  • the glass according to the present invention can be produced even when the content of the TiO 2 component is 0%, the refractive index can be increased when the content exceeds 0%. Therefore, the upper limit is preferably 5.0% or less, more preferably 4.5% or less, and even more preferably 4.0% or less. Further, the lower limit is preferably 0% or more, more preferably more than 0%, more preferably 0.1% or more, and still more preferably 0.3% or more.
  • the Gd 2 O 3 component is an optional component that has the effect of increasing the refractive index.
  • the content of the three Gd 2 O components is 5.0% or less, deterioration of devitrification can be suppressed.
  • the glass according to the present invention can be produced even when the content of the Gd 2 O 3 component is 0%, the refractive index can be increased when the content exceeds 0%. Therefore, the upper limit is preferably 5.0% or less, more preferably 4.5% or less, and even more preferably 4.0% or less. Further, the lower limit is preferably 0% or more, more preferably more than 0%, more preferably 0.1% or more, and still more preferably 0.3% or more.
  • the Nb 2 O 5 component is an optional component that has the effect of increasing the refractive index.
  • the content of the Nb 2 O 5 component is 3.0% or less, deterioration of devitrification can be suppressed.
  • the glass according to the present invention can be produced even when the content of the Nb 2 O 5 component is 0%, but when the content exceeds 0%, the refractive index can be increased. Therefore, the upper limit is preferably 3.0% or less, more preferably 2.0% or less, and even more preferably 1.0% or less. Further, the lower limit is preferably 0% or more, more preferably more than 0%, more preferably 0.1% or more, and still more preferably 0.3% or more.
  • the glass according to the present invention can be produced even with 0% of the SrO component and the BaO component, these are optional components that improve low-temperature melting property when contained in excess of 0%.
  • the content of each of the SrO component and the BaO component is 5.0% or less, the glass is easily strengthened when chemically strengthened. Therefore, the upper limit of each of the SrO component and the BaO component can be preferably set to 5.0% or less, more preferably 3.0% or less, and further preferably 1.0% or less.
  • the glass according to the present invention can be made.
  • the preferable upper limit of [content of CaO component + content of MgO component] is 5.0% or less, more preferably 3.0% or less, more preferably less than 3.0%, and still more preferably 1.0% or less.
  • the preferable lower limit of [content of CaO component+content of MgO component] is 0% or more, more preferably 0.1% or more, and still more preferably 0.2% or more.
  • the glass according to the present invention can be produced even if the total content of the K 2 O component and the Na 2 O component [content of the K 2 O component + content of the Na 2 O component] is 0%; In some cases, deterioration of viscosity can be suppressed and an increase in melting temperature can be suppressed. Further, by setting the content to 5.0% or less, deterioration of devitrification can be suppressed. Therefore, [content of K 2 O component + content of Na 2 O component] preferably has an upper limit of 5.0% or less, more preferably 4.0% or less, more preferably less than 4.0%, and more preferably 3 It should be less than .0%, more preferably less than 2.0%. Further, the lower limit is preferably 0% or more, more preferably 0.2% or more, and still more preferably 0.3% or more.
  • the preferable upper limit of [(content of SiO 2 components + content of Li 2 O components)/content of Al 2 O 3 components] is 50.0 or less, more preferably 48.0 or less, still more preferably 45.0 or less. do. Further, the preferable lower limit is more than 13.9, more preferably 14.5 or more, and still more preferably 15.0 or more.
  • [(Content of K 2 O component + content of 3 Al 2 O components)/content of 2 ZrO components] may be less than 0.88. By setting it to less than 0.88, ⁇ -cristobalite and lithium disilicate can be easily produced as the main crystal phases. Therefore, the preferable upper limit of [(content of K 2 O component + content of 3 components of Al 2 O)/content of 2 components of ZrO] is less than 0.88, more preferably 0.87 or less, still more preferably 0.85 or less. do. Further, the lower limit is preferably 0.10 or more, more preferably 0.15 or more, and still more preferably 0.20 or more.
  • [(Content of P 2 O 5 components + content of K 2 O component + content of MgO component + content of 3 Al 2 O components)/content of 2 ZrO components] may be less than 1.32. By setting it to less than 1.32, ⁇ -cristobalite and lithium disilicate can be easily produced as the main crystal phases. Therefore, the preferable upper limit of [(content of P 2 O 5 components + content of K 2 O component + content of MgO component + content of 3 Al 2 O components)/content of 2 ZrO components] is less than 1.32, more preferably 1. 28 or less, more preferably 1.25 or less. Further, the lower limit is preferably 0.2 or more, more preferably 0.3 or more, and still more preferably 0.4 or more.
  • [Content of 3 Al 2 O components/content of 2 ZrO components] may be greater than 0 and less than or equal to 1.0. By setting it to 1.0 or less, it becomes easier to obtain a desired crystal phase, and by setting it to more than 0, it becomes easier to suppress deterioration of devitrification. Therefore, the preferable upper limit of [content of 3 Al 2 O components/content of 2 ZrO components] is 1.0 or less, more preferably 0.9 or less, still more preferably 0.8 or less. Further, the preferable lower limit is more than 0, more preferably 0.1 or more, and still more preferably 0.2 or more.
  • [Li 2 O component content + Al 2 O 3 component content] may be 6.5% to 15.5%.
  • the content is 15.5% or less, the formation of a lithium aluminum silicate crystal phase can be easily suppressed, and when the content is 6.5% or more, a desired crystal phase can be obtained and the glass can be easily stabilized. Therefore, the preferable upper limit of [content of Li 2 O component + content of three Al 2 O components] is 15.5% or less, more preferably 15.0% or less, and more preferably 14.0% or less. Further, the preferable lower limit is 6.5% or more, more preferably 8.0% or more, and still more preferably 10.0% or more.
  • [(Li 2 O component content + Al 2 O 3 component content)/ZrO 2 component content] may be set to 1.0 to 2.7.
  • the preferable upper limit of [(content of Li 2 O component + content of 3 Al 2 O components)/content of 2 ZrO components] is 2.7 or less, more preferably 2.4 or less, and even more preferably 2.1 or less.
  • the preferable lower limit is 1.0 or more, more preferably 1.3 or more, and even more preferably 1.6 or more.
  • [Content of 2 SiO components/(Content of 5 P 2 O components+Content of Li 2 O component+Content of Na 2 O component+Content of K 2 O component)] may be set to 4.5 or more. When it is 4.5 or more, it becomes easier to obtain a desired crystal phase. Therefore, the lower limit is preferably 4.5 or more, more preferably 5.0 or more.
  • the upper limit of [SiO 2 component content/(P 2 O 5 component content + Li 2 O component content + Na 2 O component content + K 2 O component content)] is, for example, 20.0 or less, 10.0 or less , or 7.5 or less.
  • [Content of K 2 O component/Content of ZrO 2 component] may be greater than 0 and less than 0.5. When it is less than 0.5, it becomes easier to obtain a desired crystalline phase, and when it is more than 0, deterioration in viscosity and meltability can be suppressed, and productivity can be easily improved. Therefore, the upper limit of [K 2 O component content/ZrO 2 component content] is preferably less than 0.5, more preferably 0.4 or less, and even more preferably 0.3 or less. Further, the lower limit is preferably greater than 0, more preferably 0.1 or more.
  • [(Content of K 2 O component + content of 3 Al 2 O components)/content of 2 ZrO components] may be greater than 0 and not more than 0.85. When it is 0.85 or less, it becomes easier to suppress the formation of lithium aluminum silicate crystal phase, and when it is more than 0, it becomes easier to stabilize the glass. Therefore, the preferable upper limit of [(content of K 2 O component + content of 3 components of Al 2 O)/content of 2 components of ZrO] is 0.85 or less, more preferably 0.80 or less, still more preferably 0.75 or less. do. Further, the preferable lower limit is more than 0, more preferably 0.1 or more, and still more preferably 0.2 or more.
  • [(Content of K 2 O component + content of 3 Al 2 O components)/(content of ZnO component + content of 2 ZrO components)] may be greater than 0 and not more than 0.95. When it is 0.95 or less, it becomes easier to suppress the formation of lithium aluminum silicate crystal phase, and when it is more than 0, it becomes easier to stabilize the glass. Therefore, the preferable upper limit of [(content of K 2 O component + content of 3 components of Al 2 O)/(content of ZnO component + content of 2 components of ZrO)] is 0.95 or less, more preferably 0.90 or less, even more preferably shall be 0.85 or less. Further, the preferable lower limit is more than 0, more preferably 0.1 or more, and still more preferably 0.2 or more.
  • the crystallized glass of the present invention contains Bi 2 O 3 , Cr 2 O 3 , CuO, La 2 O 3 , MnO, MoO 3 , PbO, V 2 O 5 , WO 3 , within a range that does not impair the effects of the present invention.
  • Each of the three Y 2 O components may or may not be included. Not including these components has the effect of preventing deterioration of transmittance.
  • the crystallized glass may or may not contain other components not mentioned above as long as the characteristics of the crystallized glass of the present invention are not impaired.
  • metal components such as Yb, Lu, Fe, Co, Ni, and Ag (including oxides of these metals) are used.
  • the upper limit of the content of the fining agent can be preferably set to 3.0% or less, more preferably 2.0% or less, more preferably 1.0% or less, and most preferably 0.6% or less.
  • the Vickers hardness (Hv0.2: Hv at a test load of 200 gf) of the crystallized glass of the present invention is preferably 630 or more, more preferably 690 or more, and still more preferably 710 or more. Vickers hardness tends to increase by decreasing the ZrO 2 component, increasing the Li 2 O component, or decreasing the K 2 O component.
  • the transmittance at a wavelength of 450 nm is 0% to 80%, and may be, for example, 20% or more, 30% or more, or 50% or more. Further, it may be less than 20%.
  • the transmittance can be adjusted by adjusting the content of the ZrO 2 component, Li 2 O component, or K 2 O component.
  • the crystallized glass of the present invention can be produced by the following method. Specifically, raw glass is manufactured by uniformly mixing raw materials so that each component is within a predetermined content range, and melt-molding. Next, this raw glass is crystallized to produce crystallized glass.
  • the heat treatment for crystal precipitation may be carried out in one step or may be carried out in two steps.
  • first a nucleation step is performed by heat treatment at a first temperature
  • a crystal growth step is performed by heat treatment at a second temperature higher than the nucleation step.
  • the first temperature of the two-step heat treatment is preferably 400°C to 680°C, more preferably 450°C to 650°C, still more preferably 500°C to 600°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 680°C or higher, for example 700°C to 800°C, preferably 700°C to 750°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 carried out consecutively at a single temperature step.
  • 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 680° C. or higher, for example, 700° C. to 800° C., and preferably 700° C. to 750° C.
  • the holding time at the heat treatment temperature is preferably 30 minutes to 500 minutes, and more preferably 60 minutes to 400 minutes.
  • a compressive stress layer may be formed on the surface by strengthening the crystallized glass.
  • a method for forming a compressive stress layer in strengthened crystallized glass for example, an alkali component present in the surface layer of the crystallized glass is exchange-reacted with an alkali component having a larger ionic radius to form a compressive stress layer in the surface layer. There is a chemical strengthening method to do this.
  • the chemical strengthening method can be carried out, for example, in the following steps.
  • the crystallized glass is brought into contact with or immersed in a molten salt containing potassium or sodium, such as potassium nitrate (KNO 3 ), sodium nitrate (NaNO 3 ), or a mixed or complex salt thereof.
  • a molten salt containing potassium or sodium such as potassium nitrate (KNO 3 ), sodium nitrate (NaNO 3 ), or a mixed or complex salt thereof.
  • KNO 3 potassium nitrate
  • NaNO 3 sodium nitrate
  • the treatment of contacting or immersing in this molten salt may be carried out in one step or in two steps.
  • the material is brought into contact with or immersed in a salt containing potassium or sodium, or a mixed salt thereof heated at 350° C. to 550° C. for 1 minute to 1440 minutes.
  • a two-step chemical strengthening treatment for example, first, it is contacted or immersed in a sodium salt or a mixed salt of a potassium salt and a sodium salt heated at 350° C. to 550° C. for 1 minute to 1440 minutes, preferably 30 minutes to 1000 minutes. .
  • secondly it is brought into contact with or immersed in potassium salt or a mixed salt of potassium salt and sodium salt heated at 350° C. to 550° C. for 1 minute to 1440 minutes, preferably 60 minutes to 600 minutes.
  • the present invention contains lithium disilicate as the main crystal phase, but can be chemically strengthened in two stages, where the lithium is exchanged for sodium, and then the sodium is exchanged for potassium. This two-stage chemical strengthening can increase the compressive stress value of the outermost surface.
  • the compressive stress value (CS) of the outermost surface of the strengthened crystallized glass is preferably 400 MPa or more, more preferably 500 MPa or more.
  • the depth (DOL zero) when the compressive stress of the compressive stress layer is 0 MPa is preferably 120 ⁇ m or more, more preferably 130 ⁇ m or more.
  • the central tensile stress (CT) can be, for example, 30 MPa or more, or 40 MPa or more.
  • (Si+Li)/Al is an abbreviation for [( SiO2 component content + Li2O component content)/ Al2O3 component content]
  • (K+Al)/Zr is an abbreviation for [( K2O component content + Al2O3 component content)/ ZrO2 component content]
  • (P+K+ Mg + Al )/Zr is an abbreviation for [( P2O5 component content + K2O component content + MgO component content + Al2O3 component content)/ ZrO2 component content].
  • 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 melting difficulty of the glass composition. Thereafter, the molten glass was stirred to homogenize, the temperature was lowered to 1000°C to 1450°C, and then poured into a mold and slowly cooled to produce raw glass. The obtained raw glass was heated under the crystallization conditions shown in Tables 1 to 4 to produce crystallized glass.
  • the crystal phase of the crystallized glass was determined from the angle of the peak appearing in the X-ray diffraction pattern using an X-ray diffraction analyzer (D8 Discover, manufactured by Bruker).
  • the precipitated crystal phases are listed in Tables 1 to 4.
  • cri. is an abbreviation for ⁇ -cristobalite
  • LS2 is an abbreviation for lithium disilicate
  • LS is an abbreviation for lithium monosilicate crystal
  • Quartz is an abbreviation for quartz
  • Petalite is an abbreviation for petalite. It is.
  • the main crystalline phases in all examples were ⁇ -cristobalite and lithium disilicate.
  • crystallized glass having the following composition (% by mass) was used. This crystallized glass contains petalite and lithium disilicate as main crystal phases. 78.3% of SiO 2 component, 8.1% of Al 2 O 3 component, 0.2% of B 2 O 3 component, 11.9% of Li 2 O component, 1.7% of Na 2 O component. , K 2 O component 0.0%, ZnO component 0.0%, ZrO 2 component 4.0%, P 2 O 5 component 2.2%.
  • Example 8 the produced crystallized glass was cut and ground to obtain crystallized glass substrates having the material thicknesses (substrate thicknesses) shown in Table 5.
  • substrate thicknesses material thicknesses shown in Table 5.
  • primary strengthening (first stage) and secondary strengthening (second stage) were performed under the conditions shown in Table 5 to obtain strengthened crystallized glass.
  • the compressive stress value (CS [MPa]) at the outermost surface was measured using a glass surface stress meter FSM-6000LE series manufactured by Orihara Seisakusho.
  • a light source with a wavelength of 596 nm was used as the light source of the measuring device.
  • 28.2 was used as a representative value in the examples, and 26.2 was used in the comparative examples. The results are shown in Table 5.
  • the depth (DOL zero [ ⁇ m]) and center tensile stress (CT [(MPa)]) when the compressive stress of the compressive stress layer is 0 MPa were measured using a scattered light photoelastic stress meter (manufactured by Orihara Seisakusho, SLP-1000). It was measured using A light source with a wavelength of 518 nm was used as the measurement light source. For the photoelastic constant at a wavelength of 518 nm, 28.8 was used as a representative value in the examples, and 26.6 was used in the comparative examples. The results are shown in Table 5.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Glass Compositions (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

L'invention concerne un verre cristallisé contenant de l'α-cristobalite et du disilicate de lithium en tant que phases cristallines principales et contenant, en % en masse, 65,0 % à 85,0 % d'un composant SiO2, 1,5 % à 5,9 % d'un composant Al2O3, plus de 0 % et 5,0 % ou moins d'un composant P2O5, 5,0 % à 10,8 % d'un composant Li2O, et 4,0 % à 12,5 % d'un composant ZrO2 en termes d'oxyde, [(la teneur en composant SiO2 + la teneur en composant Li2O)/la teneur en composant Al2O3] étant > 13,9.
PCT/JP2023/029313 2022-09-22 2023-08-10 Verre cristallisé WO2024062797A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022150933A JP2024045871A (ja) 2022-09-22 2022-09-22 結晶化ガラス
JP2022-150933 2022-09-22

Publications (1)

Publication Number Publication Date
WO2024062797A1 true WO2024062797A1 (fr) 2024-03-28

Family

ID=90454311

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/029313 WO2024062797A1 (fr) 2022-09-22 2023-08-10 Verre cristallisé

Country Status (3)

Country Link
JP (1) JP2024045871A (fr)
TW (1) TW202413297A (fr)
WO (1) WO2024062797A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001019490A (ja) * 1998-03-23 2001-01-23 Ohara Inc ガラスセラミックス
JP2001035417A (ja) * 1999-07-21 2001-02-09 Ohara Inc Ｃｒｔ用ガラスセラミックス
JP2001048584A (ja) * 1999-08-10 2001-02-20 Ohara Inc 光フィルター用ガラスセラミックス及び光フィルター
JP2008254984A (ja) * 2007-04-06 2008-10-23 Ohara Inc 無機組成物物品
JP2019517449A (ja) * 2016-05-27 2019-06-24 コーニング インコーポレイテッド 二ケイ酸リチウムガラスセラミック組成物およびその方法
WO2020179872A1 (fr) * 2019-03-06 2020-09-10 株式会社 オハラ Article à base de composition inorganique, et verre cristallisé

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001019490A (ja) * 1998-03-23 2001-01-23 Ohara Inc ガラスセラミックス
JP2001035417A (ja) * 1999-07-21 2001-02-09 Ohara Inc Ｃｒｔ用ガラスセラミックス
JP2001048584A (ja) * 1999-08-10 2001-02-20 Ohara Inc 光フィルター用ガラスセラミックス及び光フィルター
JP2008254984A (ja) * 2007-04-06 2008-10-23 Ohara Inc 無機組成物物品
JP2019517449A (ja) * 2016-05-27 2019-06-24 コーニング インコーポレイテッド 二ケイ酸リチウムガラスセラミック組成物およびその方法
WO2020179872A1 (fr) * 2019-03-06 2020-09-10 株式会社 オハラ Article à base de composition inorganique, et verre cristallisé

Also Published As

Publication number Publication date
TW202413297A (zh) 2024-04-01
JP2024045871A (ja) 2024-04-03

Similar Documents

Publication Publication Date Title
TWI796316B (zh) 結晶化玻璃
JP6765748B2 (ja) 結晶化ガラス及び結晶化ガラス基板
JP7013623B1 (ja) 結晶化ガラスおよび強化結晶化ガラス
JP7189181B2 (ja) ガラスおよび結晶化ガラス
WO2024062797A1 (fr) Verre cristallisé
WO2022050106A1 (fr) Article de composition inorganique
TW202114955A (zh) 結晶化玻璃以及強化結晶化玻璃
JP2021181388A (ja) 結晶化ガラス
JP7460586B2 (ja) 結晶化ガラス
WO2023145965A1 (fr) Article de composition inorganique cristallisé
WO2023145956A1 (fr) Article de composition inorganique
WO2024014500A1 (fr) Article à base de composition inorganique
WO2023095454A1 (fr) Article de composition inorganique
WO2024014507A1 (fr) Article à base de composition inorganique
WO2021044841A1 (fr) Verre cristallisé et verre cristallisé renforcé
WO2024143174A1 (fr) Article de composition inorganique
TW202204281A (zh) 強化結晶化玻璃
WO2022168895A1 (fr) Verre cristallisé et verre renforcé chimiquement
WO2022080226A1 (fr) Verre cristallisé
CN116018327A (zh) 强化结晶化玻璃

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23867922

Country of ref document: EP

Kind code of ref document: A1