WO2023127306A1 - Verre cristallisé et verre cristallin - Google Patents
Verre cristallisé et verre cristallin Download PDFInfo
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- WO2023127306A1 WO2023127306A1 PCT/JP2022/041285 JP2022041285W WO2023127306A1 WO 2023127306 A1 WO2023127306 A1 WO 2023127306A1 JP 2022041285 W JP2022041285 W JP 2022041285W WO 2023127306 A1 WO2023127306 A1 WO 2023127306A1
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- crystallized glass
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- 239000011521 glass Substances 0.000 title claims abstract description 173
- 238000005342 ion exchange Methods 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims description 93
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 30
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 28
- 229910052708 sodium Inorganic materials 0.000 claims description 28
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 238000002834 transmittance Methods 0.000 claims description 21
- 239000012634 fragment Substances 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000006059 cover glass Substances 0.000 claims description 15
- 238000012360 testing method Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 230000006378 damage Effects 0.000 claims description 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052681 coesite Inorganic materials 0.000 abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052593 corundum Inorganic materials 0.000 abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 description 49
- 238000000034 method Methods 0.000 description 24
- 238000005452 bending Methods 0.000 description 11
- 230000007423 decrease Effects 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 229910018068 Li 2 O Inorganic materials 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000001376 precipitating effect Effects 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 239000006060 molten glass Substances 0.000 description 7
- 229910006404 SnO 2 Inorganic materials 0.000 description 6
- 239000010438 granite Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000005341 toughened glass Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000013001 point bending Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000003426 chemical strengthening reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000005345 chemically strengthened glass Substances 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 2
- 229910052912 lithium silicate Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910052670 petalite Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001690 polydopamine Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- -1 space group Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 101100371219 Pseudomonas putida (strain DOT-T1E) ttgE gene Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006219 crystal-free glass Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000007656 fracture toughness test Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000007372 rollout process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
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
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
Definitions
- the present invention relates to crystallized glass and crystallizable glass.
- Cover glass Properties required for cover glass include (1) high mechanical strength, (2) high scratch resistance, (3) light weight, and (4) low cost.
- Patent Document 2 discloses a technique for improving fracture toughness by precipitating petalite crystals and lithium silicate crystals in the cover glass.
- Patent Document 3 discloses a technique for increasing mechanical strength by precipitating carnegiite as a main crystal.
- JP 2006-083045 A Japanese Patent No. 6663532 JP-A-59-223249
- the petalite crystals and lithium silicate crystals disclosed in Patent Document 2 are crystals containing lithium.
- Lithium is a scarce resource, and with the recent increase in demand for lithium-ion batteries, there is concern that the supply of raw materials will become unstable.
- the ion exchange treatment of exchanging lithium ions in the glass and sodium ions in the molten salt increases the stress depth compared to the ion exchange of sodium ions in the glass and potassium ions in the molten salt, but the surface The compressive stress value of is likely to be small.
- the transparency of the cover glass is also important.
- the crystallized glass described in Patent Document 3 often becomes opaque, and it tends to become opaque particularly when nepheline precipitates.
- An object of the present invention is to provide a crystallized glass and a crystallizable glass that have excellent ion exchange performance and excellent transparency even if they do not contain a large amount of lithium components.
- the present inventor found that the above technical problems can be solved by strictly regulating the glass composition of the crystallized glass. It is something to do. That is, the crystallized glass according to the first invention has a composition, in mol%, of SiO 2 30 to 70%, Al 2 O 3 1 to 20%, Na 2 O 3 to 45%, P 2 O 5 0 to 10%, ZrO 2 0-10%, MgO+CaO+SrO+BaO+ZnO 0-20%.
- MgO+CaO+SrO+BaO+ZnO refers to the total amount of MgO, CaO, SrO, BaO and ZnO.
- the crystallized glass according to the second invention is preferably formed by depositing crystals containing Si, Al, Na, and O in the first invention, and the crystals containing Si, Al, Na, and O are mainly Crystals are preferred.
- the "main crystal” can be evaluated using an X-ray diffractometer (for example, Rigaku's fully automatic multi-purpose horizontal X-ray diffractometer Smart Lab).
- the scan mode is 2 ⁇ / ⁇ measurement
- the scan type is continuous scan
- the scattering and divergence slit widths are 1°
- the light receiving slit width is 0.2°
- the measurement range is 10 to 60°
- the measurement step is 0. 0.1° and a scanning speed of 5°/min
- the analysis software installed in the package of the same model can be used to evaluate precipitated crystals.
- the average crystallite size of crystals containing Si, Al, Na, and O is 1 ⁇ m or less.
- the "average crystallite size" can be calculated using the X-ray diffraction peak based on the Debeye-Sherrer method.
- the crystallized glass according to the fourth invention preferably has a degree of crystallinity of 1 to 95%.
- the "crystallinity" is calculated based on the X-ray diffraction profile by (integrated intensity of the X-ray diffraction peak of the crystal) / (total integrated intensity of the measured X-ray diffraction) x 100 [%]. be able to.
- the crystallized glass according to the fifth invention is the crystallized glass according to any one of the first to fourth inventions, wherein Na 4 Al 2 Si 2 O 9 , Na 6 Al 4 Si 4 O 17 , Na 8 Al 4 Si 4 O 18 Among them, it is preferable that at least one kind of crystal is precipitated.
- the mol % ratio Al 2 O 3 /SiO 2 is 0.1 to 0.5.
- Al 2 O 3 /SiO 2 refers to a value obtained by dividing the content of Al 2 O 3 by the content of SiO 2 .
- the mol % ratio Al 2 O 3 /Na 2 O is 0.01 to 0.7.
- Al2O3 / Na2O refers to a value obtained by dividing the content of Al2O3 by the content of Na2O .
- the mol % ratio Na 2 O/SiO 2 is preferably 0.1-1.
- Na 2 O/SiO 2 refers to a value obtained by dividing the content of Na 2 O by the content of SiO 2 .
- the content of P 2 O 5 is 0.1 to 10 mol %.
- the crystallized glass according to the tenth invention preferably has a ZrO 2 content of 0.1 to 10 mol %.
- the crystallized glass according to the eleventh invention preferably has a CaO content of 0 to 5 mol%.
- the crystallized glass according to the twelfth invention is the crystallized glass according to any one of the first to eleventh inventions, wherein the content of Fe 2 O 3 is 0 to 0.5 mol% and the content of TiO 2 is 0 to 0.5 mol. %.
- the crystallized glass according to the thirteenth invention in any one of the first to twelfth inventions, preferably does not substantially contain As 2 O 3 and PbO.
- substantially free from means not intentionally added to the glass, and does not completely exclude unavoidable impurities. Specifically, it means that the content of each of the specified components is less than 0.01 mol %.
- the crystallized glass according to the fourteenth invention in any one of the first to thirteenth inventions, has no compressive stress layer formed on the surface due to ion exchange, and has a scratch depth of 200 ⁇ m or less when scratched.
- the "scratch depth” means that a sample is placed on a granite surface plate, and No. 180 abrasive paper is pressed against the sample with a load of 100 N to scratch it. A three-point bending test is performed and the cross section of the fractured sample is observed with a differential interference microscope, and it means the depth from the glass surface of the semicircular median crack.
- the crystallized glass according to the fifteenth invention preferably has a compressive stress layer formed on the surface by ion exchange.
- the crystallized glass according to the sixteenth invention preferably has a surface compressive stress value of at least 100 MPa or more.
- the "compressive stress value” and the “stress depth (DOC)” can be measured by, for example, a scattered light photoelastic stress meter SLP-1000 or a surface stress meter FSM-6000LE manufactured by Orihara Seisakusho.
- the crystallized glass according to the seventeenth invention preferably has a depth of stress (DOC) of 20 ⁇ m or more.
- the crystallized glass according to the eighteenth invention preferably has a ⁇ CT/t of 20 MPa or more.
- ⁇ CT/t is the depth direction profile of compressive stress obtained with a scattered light photoelastic stress meter (for example, Orihara Seisakusho's scattered light photoelastic stress meter SLP-1000), from the glass surface to the thickness Means the value obtained by integrating the stress up to half the depth of
- the number of fragments after a drop test is 200 or less per 1000 mm 2 .
- the "number of fragments after the drop test” is defined by placing a sample on a granite surface plate and vertically dropping a 53 g weight with a Vickers indenter attached to the tip of the sample from a height of 10 mm. It means the number of fragments when delayed fracture occurred after the test was performed.
- the crystallized glass according to the twentieth invention preferably has a Young's modulus of 50 MPa or more in any one of the first to nineteenth inventions.
- the crystallized glass according to the twenty-first invention preferably has a fracture toughness of less than 1.0 MPa ⁇ m 1/2 .
- the crystallized glass according to the 22nd invention in any one of the 1st to 21st inventions preferably has a visible light transmittance of 50% or more at a wavelength of 380 to 780 nm at a thickness of 0.7 mm.
- the “visible light transmittance” is obtained by measuring the linear transmittance in the thickness direction using a spectrophotometer (eg, Shimadzu UV-3100).
- the crystallized glass according to the twenty-third invention is any one of the first to twenty-second inventions, wherein the coefficient of linear thermal expansion at 30 to 300° C. is 0 ⁇ 10 ⁇ 7 to 150 ⁇ 10 ⁇ 7 /° C. is preferred.
- the crystallized glass according to the twenty-fourth invention is preferably used for the cover glass in any one of the first to twenty-third inventions.
- the crystallized glass according to the twenty-fifth invention has a composition, in mol%, of SiO 2 30 to 70%, Al 2 O 3 1 to 20%, Na 2 O 3 to 45%, P 2 O 5 0.1 to 10%, ZrO 2 0.1-10%, CaO 0-1%, MgO + CaO + SrO + BaO + ZnO 0-20%, mol% ratio Al 2 O 3 /SiO 2 is 0.1-0.3, mol% ratio Al 2 O 3 /Na 2 O is 0.2 to 0.48, and crystals containing Si, Al, Na and O are precipitated.
- the crystallizable glass according to the twenty-sixth invention has a composition, in mol%, of SiO 2 30 to 70%, Al 2 O 3 1 to 20%, Na 2 O 3 to 45%, and P 2 O 5 0.8 to 10%, ZrO 2 0.1-10%, MgO + CaO + SrO + BaO + ZnO 0-20%, CaO 0-1%, mol% ratio Al 2 O 3 /SiO 2 is 0.1-0.3, mol% ratio Al 2 O 3 /Na 2 O is 0.2 to 0.48, and the mol % ratio Na 2 O/SiO 2 is 0.4 to 0.7.
- crystals containing Si, Al, Na, and O are precipitated by heat treatment (more specifically, by firing treatment).
- the crystallizable glass according to the twenty-eighth invention is preferably subjected to an ion exchange treatment in the twenty-sixth or twenty-seventh invention.
- Sample no. 32 is a transmittance curve at a wavelength of 200 to 800 nm at a thickness of 0.7 mm.
- Sample no. 32 (which has undergone a crystallization process but has not been subjected to ion exchange treatment) and conventional chemically strengthened glass are compared in terms of scratch depth when scratched.
- 4 is data showing the relationship between compressive stress values (CS) and stress depths (DOC) of samples A to D of Example 2.
- FIG. Sample no. Data showing 32 XRD curves. 4 is data showing the relationship between compressive stress values (CS) and stress depths (DOC) of samples E to I of Example 3.
- FIG. 4 is data showing the relationship between the number of fragments of Samples F to J of Example 3 and Comparative Example L and ⁇ CT/t.
- the crystallized glass (crystalline glass) of the present invention has a composition of SiO 2 30 to 70%, Al 2 O 3 1 to 20%, Na 2 O 3 to 45%, P 2 O 5 0 to 10%, ZrO 2 0-10%, MgO+CaO+SrO+BaO+ZnO 0-20%.
- % means mol% unless otherwise specified.
- SiO2 is a component that forms the skeleton of glass.
- the content of SiO 2 is preferably 30-70%, 35-65%, 37-60%, 39-58%, especially 40-55%. If the SiO2 content is too low, the weather resistance tends to be significantly reduced. On the other hand, if the content of SiO2 is too high, the meltability tends to decrease.
- Al 2 O 3 is a component that enhances ion exchange performance and is a component necessary for precipitating desired crystals.
- the content of Al 2 O 3 is preferably 1-20%, 2-18%, 3-16%, 4-14%, 5-12%, especially 6-11%. If the content of Al 2 O 3 is too small, it becomes difficult to deposit desired crystals. On the other hand, if the content of Al 2 O 3 is too high, the meltability tends to deteriorate.
- the mol % ratio Al 2 O 3 /SiO 2 is preferably from 0.01 to 0.5, from 0.05 to 0.4, from 0.1 to 0.3, from 0.11 to 0.29, from 0.12 to 0.28, 0.13-0.27, 0.14-0.26, especially 0.15-0.25. If the mol % ratio of Al 2 O 3 /SiO 2 is out of the above range, crystals containing Na, Al, Si, and O are difficult to precipitate, and the crystallized glass may become cloudy due to precipitation of heterogeneous crystals.
- Na 2 O is a component that lowers high-temperature viscosity and enhances meltability. In addition to being a component involved in the ion exchange treatment, it is a component necessary for precipitating desired crystals.
- the content of Na 2 O is preferably 3-45%, 5-40%, 10-38%, 15-35%, 18-33%, especially 20-30%. If the content of Na 2 O is too small, the ion exchange performance tends to deteriorate and the desired crystals are difficult to precipitate. On the other hand, if the content of Na 2 O is too large, the high-temperature viscosity is too low, and the glass may be softened and deformed during the heat treatment for crystallization.
- the mol % ratio Na 2 O/SiO 2 is preferably 0.1-1, 0.2-0.9, 0.3-0.8, 0.4-0.7, 0.41-0.69 , 0.42-0.68, 0.43-0.67, 0.44-0.66, 0.45-0.65, 0.46-0.64, 0.47-0.63, 0 0.48-0.62, 0.49-0.61, especially 0.5-0.6. If the mol % ratio of Na 2 O/SiO 2 is too small, crystals containing Na, Al, Si, and O are difficult to precipitate, and high-temperature viscosity increases, making melting difficult.
- the mol % ratio Al 2 O 3 /Na 2 O is preferably 0.01-0.7, 0.05-0.6, 0.1-0.5, 0.2-0.48, 0.21 ⁇ 0.45, 0.22-0.44, 0.23-0.43, 0.24-0.42, 0.25-0.41, especially 0.26-0.4. If the mol % ratio of Al 2 O 3 /Na 2 O is out of the above range, crystals containing Na, Al, Si, and O are difficult to precipitate, and the crystallized glass may become cloudy due to the precipitation of heterogeneous crystals.
- MgO, CaO, SrO, BaO, and ZnO are components that increase meltability.
- the content of MgO+CaO+SrO+BaO+ZnO is preferably 0-20%, 1-18%, 2-16%, 3-14%, 4-13%, 5-12%, especially 6-11%. If the content of MgO+CaO+SrO+BaO+ZnO is too high, coarse crystals tend to precipitate. On the other hand, if the content of MgO+CaO+SrO+BaO+ZnO is too small, the melting temperature tends to increase.
- MgO is a component that enhances meltability and also a component that enhances mechanical strength.
- the content of MgO is preferably 0-15%, 0-10%, 0-5%, 0-4%, 0-3%, 0-2%, especially 0-1%. If the content of MgO is too high, not only coarse crystals are likely to precipitate but also heterogeneous crystals are likely to precipitate.
- CaO is a component that enhances meltability and is a component that easily inhibits ion exchange.
- the content of CaO is preferably 0 to 5%, 0 to 4%, 0 to 3%, 0 to 2%, 0 to 1%, and it is particularly preferably substantially free. If the content of CaO is too high, ion exchange is likely to be inhibited, coarse crystals are likely to precipitate, and heterogeneous crystals are likely to precipitate.
- SrO is a component that enhances meltability.
- the content of SrO is preferably 0-5%, 0-4%, 0-3%, 0-2%, especially 0-1%. If the SrO content is too high, coarse crystals are likely to precipitate, and heterogeneous crystals are likely to precipitate.
- BaO is a component that enhances meltability.
- the content of BaO is preferably 0-5%, 0-4%, 0-3%, 0-2%, especially 0-1%. If the BaO content is too high, coarse crystals tend to precipitate, and heterogeneous crystals tend to precipitate.
- ZnO is a component that enhances meltability and also makes it difficult for coarse crystals and heterogeneous crystals to precipitate.
- the content of ZnO is preferably 0-20%, 0-18%, 0-16%, 0-14%, especially 0-12%. If the content of ZnO is too high, the high-temperature viscosity is too low, and the glass may be softened and deformed during the heat treatment for crystallization. When it is important to suppress the precipitation of coarse crystals and heterogeneous crystals, it is preferable to contain ZnO. In that case, the ZnO content is preferably 0.1 to 20%, 0.5 to 19%. , 1-18%, 2-17%, 3-16%, especially 4-15%.
- Li 2 O like Na 2 O, is a component that lowers high-temperature viscosity and enhances meltability. If the content of Li 2 O is too high, heterogeneous crystals are precipitated, and the transmittance of the crystallized glass tends to decrease. Therefore, Li 2 O can be substantially free, but when Li 2 O is contained, its content is preferably 0 to 5%, particularly 0 to 1%.
- K 2 O like Li 2 O and Na 2 O, is a component that lowers high-temperature viscosity and enhances meltability. If the K 2 O content is too high, crystals other than the main crystals of the crystallized glass, that is, heterogeneous crystals are likely to precipitate, resulting in a decrease in transmittance. Also, if K 2 O is added, the ion exchange speed increases, and compressive stress can be formed from the surface of the glass to a deep region even in a short period of time. On the other hand, if K 2 O is too much, the compressive stress value tends to be small.
- the content of K 2 O is preferably 0-5%, especially 0-1%.
- Na 2 O is required for the precipitation of the desired crystals
- Na 2 O>Li 2 O and Na 2 O>K 2 O are preferable in the content of the alkali metal oxide, and Na 2 O>K 2 O.
- ⁇ Li 2 O is more preferred, and Na 2 O>K 2 O>Li 2 O is particularly preferred.
- P 2 O 5 is a component that enhances ion exchange performance. It is also a necessary component for efficiently precipitating crystals in the crystallization process. On the other hand, when a large amount of P 2 O 5 is contained, the glass tends to be remarkably phase-separated.
- the content of P 2 O 5 is preferably 0-10%, 0.1-9%, 0.3-8%, 0.5-7%, 0.6-6.5%, 0.7- 6%, 0.8-5.5%, 0.9-5%. Especially 1 to 7.5%. If the content of P 2 O 5 is too small, ion exchange becomes difficult to occur and the time required for ion exchange becomes longer, which tends to reduce productivity.
- crystal nuclei are not sufficiently formed, and coarse crystals are precipitated, making the glass more likely to become cloudy and likely to break.
- the content of P 2 O 5 is too high, the glass will undergo phase separation, and the crystallized glass will tend to become cloudy, and the weather resistance will tend to decrease.
- ZrO 2 is a component that efficiently deposits crystals in the crystallization process.
- the content of ZrO 2 is preferably 0-10%, 0.1-9.5%, 0.2-9%, 0.3-8.5%, 0.4-8%, 0.5- 7.5%, 0.6-7%, 0.7-6.5%, especially 0.8-6%. If the content of ZrO 2 is too low, crystal nuclei are not sufficiently formed, and coarse crystals are precipitated, making the glass more likely to become cloudy and likely to break. On the other hand, if the ZrO 2 content is too high, coarse ZrO 2 crystals are precipitated, the glass tends to devitrify, and the crystallized glass tends to break.
- SnO 2 is a component that releases oxygen by changing its valence during melting, increases the bubble floating speed in the molten glass, and promotes clarification.
- the SnO 2 content is preferably 0-5%, 0-4%, 0-3%, 0-2%, especially 0-1%.
- SnO 2 also has the effect of promoting phase separation of ZrO 2 . While keeping the liquidus temperature low (while suppressing the risk of devitrification due to primary phase precipitation), in order to efficiently generate phase separation and rapidly perform the nucleation and crystal growth steps in the subsequent steps, SnO 2 is preferably added.
- the SnO 2 content in this case is 0.01-5%, 0.03-4%, 0.05-3%, 0.08-2.5%, particularly preferably 0.1-2% .
- Fe 2 O 3 is a component contained in the raw material as an unavoidable impurity. If the content of Fe 2 O 3 is too high, the crystallized glass may be colored and transmittance may be lowered.
- the content of Fe 2 O 3 is preferably 0-4%, 0-3%, 0-2%, 0-1%, 0-0.5%, especially 0-0.1%.
- TiO 2 is a component that promotes precipitation of crystals in the crystallization process.
- the glass may be markedly colored.
- a zirconia titanate-based crystal containing ZrO 2 and TiO 2 acts as a crystal nucleus, but electrons transition from the valence band of oxygen, which is a ligand, to the conduction band of zirconia and titanium, which are central metals (LMCT transition ), involved in the coloring of crystallized glass.
- LMCT transition central metals
- an LMCT transition can occur from the valence band of the SiO2 framework to the conduction band of tetravalent titanium in the residual glass phase.
- the content of TiO 2 is preferably 0-4%, 0-3%, 0-2%, 0-1%, 0-0.5%, especially 0-0.1%.
- the lower limit of the content of TiO2 is preferably 0.0003% or more, 0.001% or more, 0.01% or more, especially 0.02% or more.
- B 2 O 3 is a component that lowers high-temperature viscosity and improves meltability and moldability. It is also a component that can contribute to the tendency of phase separation to occur during crystal nucleus formation.
- the content of B 2 O 3 is preferably 0-3%, 0-2%, 0-1%, especially 0-0.1%. If the content of B 2 O 3 is too high, the amount of the compound containing B evaporates at the time of melting, which may increase the environmental load.
- CeO 2 is a component that not only increases the solubility but also has an effect as an oxidizing agent, suppresses the increase of Fe 2+ in the total Fe impurities, and increases the visible light transmittance of the crystallized glass.
- the content of CeO 2 is preferably 0-0.5%, 0-0.4%, in particular 0-0.3%. If the content of CeO 2 is too high, the coloration due to Ce 4+ may become too strong, and the crystallized glass may take on a brown color.
- SO3 can be introduced from Glauber's salt.
- SO 3 is a component that releases sulfur dioxide and oxygen during melting to expand bubbles in the molten glass and promote clarification. It is also a component that works as an oxidizing agent like CeO 2 and increases the effect of CeO 2 by allowing it to coexist with CeO 2 .
- the content of SO3 is preferably 0-0.5%, 0.01-0.45%, 0.02-0.4%, 0.03-0.35%, 0.04-0.3 %, especially 0.05-0.25%. If the content of SO 3 is too high, heterogeneous crystals may precipitate and the surface quality of the crystallized glass may deteriorate.
- MoO 3 is a component that can be slightly mixed into the molten glass from the electrode in the melting method in which the glass is heated by applying an electric current from an electrode immersed in the molten glass.
- the content of MoO 3 is preferably 0-0.5%, 0-0.1%, 0-0.05%, 0-0.01%, 0-0.005%, 0-0.001% , 0 to 0.0005%, especially 0 to 0.0003%.
- the Cl content is preferably 0.1% or less, 0.05% or less, 0.01% or less, 0.005% or less, and particularly 0.04% or less.
- Cr 2 O 3 , La 2 O 3 , WO 3 , Nb 2 O 3 , Y 2 O 3 and the like are added at 3% or less, 2% or less, and 1% or less, respectively, in order to improve chemical durability, high-temperature viscosity, etc. , less than 1%, and up to 0.5%.
- components such as H 2 , CO 2 , CO, H 2 O, He, Ne, Ar, and N 2 may be introduced up to 0.1% each.
- the mixed amount of noble metal elements such as Pt, Rh, and Au is preferably 500 ppm or less, more preferably 300 ppm or less.
- the crystallized glass of the present invention preferably has the following characteristics and properties.
- the crystallized glass of the present invention is preferably formed by precipitating crystals containing Na, Al, Si and O, more preferably by precipitating crystals containing Na, Al, Si and O as main crystals.
- it preferably contains crystals represented by Na 4 Al 2 Si 2 O 9 , Na 6 Al 4 Si 4 O 17 or Na 8 Al 4 Si 4 O 18 .
- crystals represented by Na 4 Al 2 Si 2 O 9 , Na 6 Al 4 Si 4 O 17 or Na 8 Al 4 Si 4 O 18 .
- precipitation of crystals other than the above crystals is not excluded.
- the main crystal of the crystallized glass of the present invention preferably has a triclinic system, a monoclinic system, a cubic system, a tetragonal system, a hexagonal system or a cubic system, more preferably a monoclinic system or a cubic system.
- tetragonal system, hexagonal system, cubic system, more preferably rectangular system, tetragonal system, hexagonal system, cubic system, more preferably tetragonal system, hexagonal system, cubic system particularly preferably is hexagonal, cubic, most preferably cubic.
- the degree of crystallinity is preferably 1% or more, 5% or more, 10% or more, 15% or more, 20% or more, particularly 25% or more. If the degree of crystallinity is too low, the effect of increasing the allowable limit of internal tensile stress tends to decrease. On the other hand, if the degree of crystallinity is too high, the transmittance tends to decrease. In addition, when ion exchange treatment is performed, the proportion of the glass phase to be ion exchanged decreases, making it difficult to form a high compressive stress value. Therefore, the crystallinity is preferably 99% or less, 96% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, particularly 30% or less.
- the crystallite size is preferably 1 ⁇ m or less, 0.5 ⁇ m or less, particularly 0.3 ⁇ m or less. If the crystallite size is too large, the transmittance tends to decrease. Although the lower limit of the crystallite size is not particularly limited, it is practically 1 nm or more.
- the average visible light transmittance at a thickness of 0.7 mm and a wavelength of 380 to 780 nm is preferably 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, and particularly 80% or more. If the thickness is 0.7 mm and the average visible light transmittance at a wavelength of 380 to 780 nm is too low, it will be difficult to use as a cover glass for smartphones.
- the whiteness L* value is preferably 50 or higher, 60 or higher, 70 or higher, 80 or higher, particularly 90 or higher. If the whiteness is too low, the transmittance tends to decrease.
- the "whiteness L* value" means the one defined in JIS Z 8730.
- the crystallized glass of the present invention preferably has a compressive stress layer on its surface.
- the surface compressive stress value (CS) is preferably 100 MPa or more, 200 MPa or more, 300 MPa or more, 400 MPa or more, 500 MPa or more, 550 MPa or more, 600 MPa or more, 650 MPa or more, 700 MPa or more, 750 MPa or more, 800 MPa or more, 850 MPa or more, 900 MPa or more. , especially above 950 MPa. If the compressive stress value is too small, the bending strength may become low.
- the upper limit range of the compressive stress value (CS) is preferably 1800 MPa or less. If the compressive stress value (CS) is too large, the internal tensile stress becomes excessive, and when the crystallized glass is broken, fragments are likely to scatter.
- the depth of stress (DOC) is preferably 10 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, 40 ⁇ m or more, 50 ⁇ m or more, 50 ⁇ m or more, 60 ⁇ m or more, 70 ⁇ m or more, 80 ⁇ m or more, 90 ⁇ m or more, 100 ⁇ m or more, 110 ⁇ m or more, especially 120 ⁇ m or more. be. If the stress depth is too small, the drop strength may become low.
- the upper limit of the depth of stress (DOC) is 300 ⁇ m or less, and practically 1/4 or less of the thickness of the glass.
- the stress integral value ⁇ CT/t is obtained from a scattered light photoelastic stress meter (for example, Orihara Seisakusho's scattered light photoelastic stress meter SLP-1000). It is the value obtained by integrating the stress up to the depth of ⁇ CT/t of the crystallized glass of the present invention is preferably 10 MPa or more, 12 MPa or more, 14 MPa or more, 16 MPa or more, 18 MPa or more, 20 MPa or more, 21 MPa or more, 22 MPa or more, 23 MPa or more, 24 MPa or more, 25 MPa or more, 26 MPa or more. , 27 MPa or more, 28 MPa or more, 29 MPa or more, in particular 30 MPa or more.
- a scattered light photoelastic stress meter for example, Orihara Seisakusho's scattered light photoelastic stress meter SLP-1000. It is the value obtained by integrating the stress up to the depth of ⁇ CT/t of the crystallized glass of the present invention is
- ⁇ CT/t is preferably 50 MPa or less, 48 MPa or less, 46 MPa or less, 45 MPa or less, 44 MPa or less, 43 MPa or less, 42 MPa or less, 41 MPa or less, 40 MPa or less, 39 MPa or less, or 38 MPa. 37 MPa or less, 36 MPa or less, particularly 35 MPa or less.
- the depth of the scratch when scratched means that the sample is placed on a granite surface plate, and the sample is pressed with No. 180 abrasive paper with a load of 100 N to scratch it. A three-point bending test is performed and the cross section of the fractured sample is observed with a differential interference microscope, and it means the depth from the glass surface of the semicircular median crack.
- the scratch depth when scratched is preferably 200 ⁇ m or less, 190 ⁇ m or less, 180 ⁇ m or less, 170 ⁇ m or less, 160 ⁇ m or less, 150 ⁇ m or less, 140 ⁇ m or less, or 130 ⁇ m.
- the scratch depth is 120 ⁇ m or less, 110 ⁇ m or less, particularly 100 ⁇ m or less. If the scratch depth is too deep, conspicuous scratches are likely to occur when dropped. Although the lower limit of the scratch depth is not particularly limited, it is practically 30 ⁇ m or more.
- the number of fragments after the drop test is 500 or less, 450 or less, 400 or less, 350 or less, 300 or less, 250 or less, 200 or less, 190 or less, 180 or less, 170 or less per 1000 mm 2 , 160 or less, 150 or less, 140 or less, 130 or less, 120 or less, 110 or less, 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, especially 50 or less preferable. If the number of fragments is too high, the transparency will be lost after dropping. In addition, there is a risk of injury due to fine fragments. Although the lower limit of the number of fragments is not particularly limited, it is actually two or more.
- the bending strength is preferably 100 MPa or higher, 120 MPa or higher, 150 MPa or higher, 180 MPa or higher, 200 MPa or higher, 230 MPa or higher, and particularly 250 MPa or higher. If the bending strength is too low, the crystallized glass will easily break. Although the upper limit of the bending strength is not particularly limited, it is practically 3000 MPa or less.
- the drop resistance height is preferably 5 mm or more, 7 mm or more, particularly 10 mm or more. If the drop resistance is too low, the crystallized glass is likely to break when dropped.
- the Young's modulus is preferably 50 GPa or higher, 60 GPa or higher, 70 GPa or higher, 75 GPa or higher, and particularly 80 GPa or higher. If the Young's modulus is too low, the tempered glass will easily bend when the plate thickness is thin. Although the upper limit of the Young's modulus is not particularly limited, it is practically 150 GPa or less.
- the fracture toughness is preferably 0.5 MPa ⁇ m 1/2 or more, 0.55 MPa ⁇ m 1/2 or more, 0.6 MPa ⁇ m 1/2 or more, 0.65 MPa ⁇ m 1 /2 or more, particularly 0.7 MPa ⁇ m 1/2 or more. Too low a fracture toughness tends to increase the number of fragments in a drop test. On the other hand, if, for example, the degree of crystallinity is excessively increased in order to increase the fracture toughness, the average visible light transmittance of the crystallized glass tends to decrease. Therefore, when emphasizing the transmittance, the fracture toughness is preferably 2 or less, 1.5 or less, 1.3 or less, 1.2 or less, 1.1 or less, 1.0 or less, especially less than 1.0 .
- the strain point is preferably 450°C or higher, particularly 500°C or higher. If the strain point is too low, the glass may be deformed during the crystallization process. Although the upper limit of the strain point is not particularly limited, it is practically 1000° C. or less.
- the coefficient of thermal expansion at 30 to 380°C is preferably 0 ⁇ 10 -7 to 160 ⁇ 10 -7 /°C, 10 ⁇ 10 -7 to 155 ⁇ 10 -7 /°C, especially 20 ⁇ 10 -7 to 150 ⁇ 10 -7 /°C. If the coefficient of thermal expansion is too low, it will be difficult to match the coefficient of thermal expansion with the surrounding members. On the other hand, if the coefficient of thermal expansion is too high, the thermal shock resistance tends to decrease.
- glass raw materials are blended so as to have the desired composition.
- the mixed raw material batch is melted at 1300 to 1600° C. for 8 to 16 hours and formed into a predetermined shape to obtain crystallizable glass.
- a molding method a well-known molding method such as a float method, an overflow down-draw method, a roll-out method, or a mold press method can be employed.
- processing such as bending may be performed as necessary.
- the crystallizable glass is subjected to heat treatment (that is, firing treatment) at 500 to 800°C for 0.1 to 15 hours to precipitate crystals and obtain crystallized glass.
- the heat treatment for crystallization may be performed only at a specific temperature, the heat treatment may be performed stepwise by holding the temperature at two or more levels, or the heat treatment may be performed while giving a temperature gradient. According to such treatment, the number of crystals deposited and the degree of crystal growth can be individually adjusted. Also, crystallization may be promoted by applying or irradiating sound waves or electromagnetic waves.
- the obtained crystallized glass is subjected to an ion exchange treatment to increase the bending strength.
- the ion exchange treatment the crystallized glass is brought into contact with a molten salt of 350° C. or higher to replace alkali ions (such as Na ions) in the glass with alkali ions having a larger ionic radius (such as K ions). .
- a compressive stress layer can be formed on the surface.
- Nitrates (potassium nitrate, sodium nitrate, etc.), carbonates (potassium carbonate, sodium carbonate, etc.), sulfates (potassium sulfate, sodium sulfate, etc.), chloride salts (potassium chloride, sodium chloride, etc.) are used as molten salts for the ion exchange treatment. ) or a combination thereof can be used.
- surface processing such as filming, machining such as cutting, drilling, etc. may be applied.
- Tables 1 to 4 show sample Nos., which are examples. 1 to 34 and sample No. 35 as a comparative example.
- N.D means unmeasured.
- firing in the density measurement values in the table means a heat treatment process for precipitating and growing crystals
- annealing means crystallizing the glass for the purpose of relaxing the strain in the glass. It means a heat treatment process that does not cause
- a batch raw material prepared to have the composition shown in the table was put into a melting furnace and melted at 1300 to 1500° C., and then the molten glass dough was roll-formed to prepare a crystallizable glass of 200 ⁇ 500 ⁇ 5 mm. .
- crystallized glass was obtained by heat-treating the resulting crystallizable glass at the temperature and time indicated in the table.
- crystallized glass sample thus produced, density, appearance (transparent, translucent or opaque), main crystal, space group, crystal system, crystallinity, average crystallite size, scratch depth, precipitated crystal, Transmittance and coefficient of thermal expansion were evaluated.
- Sample no. For 32 to 34, strain point, annealing point, temperature at high temperature viscosity of 10 4.0 dPa s, temperature at high temperature viscosity of 10 3.0 dPa s, L* value, a* value, b* value, heat The coefficient of expansion was also evaluated. The results are shown in the table.
- the density is a value measured by the well-known Archimedes method. The density was measured before and after firing, and the difference between the measured values was calculated.
- the main crystal, space group, crystal system, crystallinity, and average crystallite size were evaluated using an X-ray diffractometer (Rigaku fully automatic multi-purpose horizontal X-ray diffractometer Smart Lab).
- Scan mode is 2 ⁇ / ⁇ measurement
- scan type is continuous scan
- scattering and divergence slit width is 1°
- receiving slit width is 0.2°
- measurement range is 10 to 60°
- measurement step is 0.1°
- scan speed was set to 5°/min
- the average crystallite size of precipitated crystals was calculated based on the Debye-Sherrer method using the measured X-ray diffraction peaks.
- the scanning speed was 1°/min.
- the crystallinity is based on the X-ray diffraction profile obtained by the above method, (integrated intensity of X-ray diffraction peak of crystal) / (total integrated intensity of measured X-ray diffraction) ⁇ 100 [%] Calculated.
- strain point and annealing point were measured based on the methods of ASTM C336 and C338.
- the temperature at a high temperature viscosity of 10 4.0 dPa ⁇ s and the temperature at a high temperature viscosity of 10 3.0 dPa ⁇ s were measured by the platinum ball pull-up method.
- the L* value, a* value, and b* value were calculated from the transmittance measurement results at a wavelength of 200 to 800 nm using a spectrophotometer for a plate-shaped sample optically polished on both sides to a thickness of 0.7 mm.
- a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation was used for the measurement.
- FIG. 1 shows sample no. 32 is a transmittance curve at a wavelength of 200 to 800 nm at a thickness of 0.7 mm.
- the coefficient of thermal expansion was measured in the temperature range of 30-380°C using a sample processed to 20mm x 3.8mm ⁇ .
- a NETZSCH dilatometer was used for the measurement.
- sample No. 1-34 were transparent or translucent.
- Sample No. 35 which is a comparative example, was translucent and white.
- FIG. 32 had a high transmittance of 85% or more in the visible region (wavelength of 400 to 700 nm).
- Table 5 shows samples A to D that are examples.
- Samples A to D were produced as follows.
- sample No. 1 of Example 1 A batch raw material prepared to have a composition of No. 32 was put into a melting kiln and melted at 1300 to 1500° C., and then the molten glass material was roll-formed to prepare a crystallizable glass of 200 ⁇ 500 ⁇ 5 mm.
- the above crystallizable glass was heat-treated at 600°C for 4 hours and at 740°C for 1 hour to obtain crystallized glass.
- FIG. 2 shows data comparing the depth of scratches when this crystallized glass and conventional glass for chemical strengthening (that is, glass not subjected to ion exchange) are scratched.
- the wound depth was measured using the following procedure. A sample is placed on a granite surface plate, and No. 180 abrasive paper is pressed against the sample with a load of 100 N to scratch it. After that, a three-point bending test was performed, and the cross section of the fractured sample was observed with a differential interference microscope, and the depth of the semicircular median crack from the glass surface was measured.
- the obtained crystallized glass was subjected to ion exchange treatment under the conditions described in the table to obtain crystallized glass having a compressive stress layer on the surface.
- FIG. 3 shows data representing the relationship between the compressive stress value (CS) and stress depth (DOC) of samples AD.
- CS Surface compressive stress value
- DOC stress depth
- the Vickers hardness is a value measured by pressing a Vickers indenter with a load of 100 gf using a Vickers hardness tester in accordance with JIS Z2244-1992, and is the average value of 10 measurements.
- the Young's modulus was calculated by a method based on JIS R1602-1995 "Elastic modulus test method for fine ceramics".
- the bending strength was measured using the three-point loading method according to ASTM C880-78.
- the drop resistance height was determined by a drop test. A sample of 50mm x 50mm x 0.7mm thick is placed on a granite surface plate, and a drop test is performed by vertically dropping a 53g weight with a Vickers indenter attached to the tip onto the sample from a specific height. The drop height was defined as the maximum height at which the original shape was maintained.
- samples A to D have a surface compressive stress value (CS) of 271 MPa or more and a stress depth (DOC) of 21 ⁇ m or more, and are considered to have high mechanical strength. .
- CS surface compressive stress value
- DOC stress depth
- Tables 6 and 7 show samples E to K, which are examples.
- Samples E to K were produced as follows.
- sample no. A batch raw material prepared to have a composition of No. 32 was put into a melting kiln and melted at 1300 to 1500°C. Several sheets of this crystallizable glass were heat-treated at 600° C. for 4 hours and at 740° C. for 1 hour to obtain crystallized glasses (Samples E to J).
- FIG. 4 shows sample no. The data show the XRD curve of No. 32, and it was confirmed that Na 6 Al 4 Si 4 O 17 was precipitated. Sample K was a glass that was not crystallized.
- the resulting crystallizable glass and crystallized glass were polished to a thickness of 0.7 mm.
- the fracture toughness was determined by measuring K IC by the SEPB method based on JIS R1607 "Fine Ceramic Fracture Toughness Test Method". The fracture toughness value of each sample was obtained from the average value of three points.
- Examples E to J were polished to a thickness of 0.7 mm. Thereafter, the crystallized glass was subjected to an ion exchange treatment under the conditions shown in the table to obtain a crystallized glass having a compressive stress layer on its surface.
- FIG. 5 shows data representing the relationship between the compressive stress value (CS) and stress depth (DOC) of samples E to I.
- the compressive stress value, stress depth, Vickers hardness, Young's modulus, bending strength, and drop resistance were measured in the same manner as in Example 2.
- ⁇ CT/t means a value obtained by integrating the stress from the surface of the glass to a depth half the thickness of the stress profile in the depth direction of the compressive stress.
- the number of fragments was determined by placing a sample on a granite surface plate and dropping a 53g weight with a Vickers indenter on the tip vertically onto the sample from a height of 10mm. means the number of pieces of the sample when .
- samples E to J were subjected to ion exchange treatment with high-temperature molten salt, and therefore had a surface compressive stress value of 1101 MPa or more and a stress depth of 26 ⁇ m or more. It is considered to have high strength.
- FIG. 6 shows the result of comparing Samples F to J, which are crystallized tempered glasses, with a conventional tempered glass containing no crystals (Comparative Example L).
- FIG. 6 shows the relationship between the number of fragments and ⁇ CT/t for Samples F to J and Comparative Example L, which is conventional tempered glass (Example No. 2 in the specification of WO 2015/125584). Data.
- Comparative Example L has a glass composition of SiO 2 66.5%, Al 2 O 3 11.4%, B 2 O 3 0.5%, Na 2 O 15.2%, K 2 O 1.5%, in terms of mol %. 4%, MgO 4.8%, SnO 2 0.2%, 0.7 mm thick, crystal-free glass.
- Comparative Example L For Comparative Example L, a plurality of samples were subjected to ion exchange treatment at different tempering times and temperatures to prepare a plurality of samples having different ⁇ CT/t shown in FIG. 6, and each sample was subjected to a drop test. and counted the number of fragments. As can be seen from FIG. 6, the number of fragments in Samples EJ was less than Comparative Example L, which is a conventional chemically strengthened glass.
- the crystallized glass of the present invention is suitable as a cover glass for touch panel displays such as mobile phones, digital cameras, and PDAs (portable terminals).
- the crystallized glass of the present invention can also be used in applications requiring high bending strength, high drop resistance, and transparency, such as window glass, magnetic disk substrates, flat panel display substrates, and solar cells. It is expected to be applied to cover glass for electronic devices and cover glass for solid-state imaging devices.
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- Organic Chemistry (AREA)
- Theoretical Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
L'invention concerne un verre cristallisé et un verre cristallin qui sont excellents en termes de performance d'échange d'ions et sont excellents en termes de transparence même sans contenir une grande quantité d'un composant de lithium. Ce verre cristallisé est caractérisé en ce qu'il contient, en tant que composition, de 30 à 70 % de SiO2, de 1 à 20 % d'Al2O3, de 3 à 45 % de Na2O, de 0 à 10 % de P2O5, de 0 à 10 % de ZrO2, et de 0 à 20 % de MgO + CaO + SrO + BaO + ZnO en % en moles.
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PCT/JP2022/041285 WO2023127306A1 (fr) | 2021-12-27 | 2022-11-07 | Verre cristallisé et verre cristallin |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03193640A (ja) * | 1989-12-20 | 1991-08-23 | Hoya Corp | 結晶化ガラス |
JP2015060614A (ja) * | 2013-09-20 | 2015-03-30 | Hoya株式会社 | 情報記録媒体用ガラス基板の製造方法 |
JP2017515779A (ja) * | 2014-05-13 | 2017-06-15 | コーニング インコーポレイテッド | 透明ガラスセラミック物品、ガラスセラミック前駆体ガラス、およびその形成方法 |
WO2017104514A1 (fr) * | 2015-12-16 | 2017-06-22 | 日本電気硝子株式会社 | Substrat de support en vitrocéramique, et stratifié mettant en œuvre celui-ci |
JP2021084828A (ja) * | 2019-11-27 | 2021-06-03 | 株式会社オハラ | 光フィルター用ガラスセラミックスおよび光フィルター |
-
2022
- 2022-11-07 WO PCT/JP2022/041285 patent/WO2023127306A1/fr active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03193640A (ja) * | 1989-12-20 | 1991-08-23 | Hoya Corp | 結晶化ガラス |
JP2015060614A (ja) * | 2013-09-20 | 2015-03-30 | Hoya株式会社 | 情報記録媒体用ガラス基板の製造方法 |
JP2017515779A (ja) * | 2014-05-13 | 2017-06-15 | コーニング インコーポレイテッド | 透明ガラスセラミック物品、ガラスセラミック前駆体ガラス、およびその形成方法 |
WO2017104514A1 (fr) * | 2015-12-16 | 2017-06-22 | 日本電気硝子株式会社 | Substrat de support en vitrocéramique, et stratifié mettant en œuvre celui-ci |
JP2021084828A (ja) * | 2019-11-27 | 2021-06-03 | 株式会社オハラ | 光フィルター用ガラスセラミックスおよび光フィルター |
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