WO2023127306A1 - Crystallized glass and crystalline glass - Google Patents
Crystallized glass and crystalline glass 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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Abstract
Provided are crystallized glass and crystalline glass which are excellent in ion exchange performance and are excellent in transparency even without containing a large amount of a lithium component. This crystallized glass is characterized by containing, as a composition, 30-70% of SiO2, 1-20% of Al2O3, 3-45% of Na2O, 0-10% of P2O5, 0-10% of ZrO2, and 0-20% of MgO+CaO+SrO+BaO+ZnO by mol%.
Description
本発明は、結晶化ガラス及び結晶性ガラスに関する。
The present invention relates to crystallized glass and crystallizable glass.
携帯電話、デジタルカメラ、ＰＤＡ（携帯端末）等は、益々普及する傾向にある。これらの用途には、タッチパネルディスプレイを保護するために、カバーガラスが用いられている（特許文献１参照）。
Mobile phones, digital cameras, PDAs (portable terminals), etc. are becoming more and more popular. For these uses, cover glass is used to protect the touch panel display (see Patent Document 1).
カバーガラスに求められる特性として、（１）高い機械的強度、（２）高い耐傷性、（３）軽量、（４）低コストが挙げられる。
Properties required for cover glass include (1) high mechanical strength, (2) high scratch resistance, (3) light weight, and (4) low cost.
近年、カバーガラスに結晶化ガラスを用いることが検討されており、特許文献２には、カバーガラス中にペタライト結晶及びリチウムシリケート結晶を析出させることで、破壊靭性を改善する技術が開示されている。特許文献３には、主結晶としてカーネギアイトを析出させて、機械的強度を高める技術が開示されている。
In recent years, the use of crystallized glass for the cover glass has been studied, and 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.
結晶化ガラスをカバーガラスに採用する場合、（５）透明性が更に要求される。また（６）スマートフォンの用途では、カバーガラスの薄型化と落下衝撃に対する耐久性が重要視される。
When using crystallized glass as the cover glass, (5) transparency is further required. In addition, (6) in the use of smartphones, thinning of the cover glass and durability against drop impact are emphasized.
カバーガラスの機械的強度を高める方法として、表面に圧縮応力層を形成し、且つその圧縮応力値を大きくすることが有効である。また、落下衝撃に対する耐久性を高める方法として、圧縮応力層の応力深さを大きくすることが有効である。
As a method of increasing the mechanical strength of the cover glass, it is effective to form a compressive stress layer on the surface and increase the compressive stress value. In addition, increasing the stress depth of the compressive stress layer is effective as a method of increasing the durability against drop impact.
しかし、従来の結晶化ガラスについて、圧縮応力層の応力深さを増加させようとすると、イオン交換時間が極端に長くなる上、表面の圧縮応力値が低下してしまうという問題があった。
However, with conventional crystallized glass, when trying to increase the stress depth of the compressive stress layer, there was a problem that the ion exchange time became extremely long and the surface compressive stress value decreased.
また、特許文献２で開示されているペタライト結晶及びリチウムシリケート結晶は、リチウムを含む結晶である。リチウムは希少な資源であると共に、近年のリチウムイオン電池の需要の高まりを受けて、原料の供給が不安定になることが危惧されている。更に、ガラス中のリチウムイオンと溶融塩中のナトリウムイオンを交換するイオン交換処理は、ガラス中のナトリウムイオンと溶融塩中のカリウムイオンのイオン交換に比べて、応力深さが増大するものの、表面の圧縮応力値が小さくなり易い。
In addition, 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. Furthermore, 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.
結晶化ガラスをカバーガラスに採用する場合には、カバーガラスの透明性も重要になる。特許文献３に記載の結晶化ガラスは、不透明になることが多く、特にネフェリンが析出する場合に不透明になり易い。
When using crystallized glass as the cover glass, 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.
本発明の目的は、リチウム成分を多量に含まなくても、イオン交換性能に優れると共に、透明性に優れた結晶化ガラス及び結晶性ガラスを提供することである。
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.
本発明者は、種々の検討を行った結果、結晶化ガラスのガラス組成を厳密に規制することにより、上記技術的課題を解決できることを見出し、本発明（第１～２８の発明）として、提案するものである。すなわち、第１の発明に係る結晶化ガラスは、組成として、ｍｏｌ％で、ＳｉＯ２ ３０～７０％、Ａｌ２Ｏ３ １～２０％、Ｎａ２Ｏ ３～４５％、Ｐ２Ｏ５ ０～１０％、ＺｒＯ２ ０～１０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ ０～２０％を含有することを特徴とする。ここで、「ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ」は、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ及びＺｎＯの合量を指す。
As a result of various investigations, 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%. Here, "MgO+CaO+SrO+BaO+ZnO" refers to the total amount of MgO, CaO, SrO, BaO and ZnO.
また、第２の発明に係る結晶化ガラスは、第１の発明において、Ｓｉ、Ａｌ、Ｎａ、Ｏを含む結晶が析出してなることが好ましく、Ｓｉ、Ａｌ、Ｎａ、Ｏを含む結晶は主結晶であることが好ましい。「主結晶」は、Ｘ線回折装置（例えば、リガク製全自動多目的水平型Ｘ線回折装置 Ｓｍａｒｔ Ｌａｂ）を用いて評価することができる。前記装置を用いる場合、スキャンモードは２θ／θ測定、スキャンタイプは連続スキャン、散乱及び発散スリット幅は１°、受光スリット幅は０．２°、測定範囲は１０～６０°、測定ステップは０．１°、スキャン速度は５°／分とし、同機種パッケージに搭載された解析ソフトを用いて析出結晶の評価を行うことができる。
Further, 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). When using the above device, the scan mode is 2θ/θ 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°, and the measurement step is 0. 0.1° and a scanning speed of 5°/min, and the analysis software installed in the package of the same model can be used to evaluate precipitated crystals.
また、第３の発明に係る結晶化ガラスは、第２の発明において、Ｓｉ、Ａｌ、Ｎａ、Ｏを含む結晶の平均結晶子サイズが１μｍ以下であることが好ましい。ここで、「平均結晶子サイズ」は、デバイ・シェラー（Ｄｅｂｅｙｅ－Ｓｈｅｒｒｅｒ）法に基づいて、Ｘ線回折ピークを用いて算出することができる。
Further, in the crystallized glass according to the third invention, in the second invention, it is preferable that the average crystallite size of crystals containing Si, Al, Na, and O is 1 μm or less. Here, the "average crystallite size" can be calculated using the X-ray diffraction peak based on the Debeye-Sherrer method.
また、第４の発明に係る結晶化ガラスは、第１～３の発明のいずれかにおいて、結晶化度が１～９５％であることが好ましい。ここで、「結晶化度」は、Ｘ線回折プロファイルに基づいて、（結晶のＸ線回折ピークの積分強度）／（計測されたＸ線回折の全積分強度）×１００［％］によって算出することができる。
Further, in any one of the first to third inventions, the crystallized glass according to the fourth invention preferably has a degree of crystallinity of 1 to 95%. Here, 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.
また、第５の発明に係る結晶化ガラスは、第１～４の発明のいずれかにおいて、Ｎａ４Ａｌ２Ｓｉ２Ｏ９、Ｎａ６Ａｌ４Ｓｉ４Ｏ１７、Ｎａ８Ａｌ４Ｓｉ４Ｏ１８の内、少なくとも１種以上の結晶が析出してなることが好ましい。
Further, 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.
また、第６の発明に係る結晶化ガラスは、第１～５の発明のいずれかにおいて、ｍｏｌ％比Ａｌ２Ｏ３／ＳｉＯ２が０．１～０．５であることが好ましい。ここで、「Ａｌ２Ｏ３／ＳｉＯ２」は、Ａｌ２Ｏ３の含有量をＳｉＯ２の含有量で除した値を指す。
Further, in the crystallized glass according to the sixth invention, in any one of the first to fifth inventions, it is preferable that the mol % ratio Al 2 O 3 /SiO 2 is 0.1 to 0.5. Here, “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 .
また、第７の発明に係る結晶化ガラスは、第１～６の発明のいずれかにおいて、ｍｏｌ％比Ａｌ２Ｏ３／Ｎａ２Ｏが０．０１～０．７であることが好ましい。ここで、「Ａｌ２Ｏ３／Ｎａ２Ｏ」は、Ａｌ２Ｏ３の含有量をＮａ２Ｏの含有量で除した値を指す。
Further, in the crystallized glass according to the seventh invention, in any one of the first to sixth inventions, it is preferable that the mol % ratio Al 2 O 3 /Na 2 O is 0.01 to 0.7. Here, " Al2O3 / Na2O " refers to a value obtained by dividing the content of Al2O3 by the content of Na2O .
また、第８の発明に係る結晶化ガラスは、第１～７の発明のいずれかにおいて、ｍｏｌ％比Ｎａ２Ｏ／ＳｉＯ２が０．１～１であることが好ましい。ここで、「Ｎａ２Ｏ／ＳｉＯ２」は、Ｎａ２Ｏの含有量をＳｉＯ２の含有量で除した値を指す。
Further, in the crystallized glass according to the eighth invention, in any one of the first to seventh inventions, the mol % ratio Na 2 O/SiO 2 is preferably 0.1-1. Here, “Na 2 O/SiO 2 ” refers to a value obtained by dividing the content of Na 2 O by the content of SiO 2 .
また、第９の発明に係る結晶化ガラスは、第１～８の発明のいずれかにおいて、Ｐ２Ｏ５の含有量が０．１～１０ｍｏｌ％であることが好ましい。
Further, in the crystallized glass according to the ninth invention, in any one of the first to eighth inventions, it is preferable that the content of P 2 O 5 is 0.1 to 10 mol %.
また、第１０の発明に係る結晶化ガラスは、第１～９の発明のいずれかにおいて、ＺｒＯ２の含有量が０．１～１０ｍｏｌ％であることが好ましい。
Further, in any one of the first to ninth inventions, the crystallized glass according to the tenth invention preferably has a ZrO 2 content of 0.1 to 10 mol %.
また、第１１の発明に係る結晶化ガラスは、第１～１０の発明のいずれかにおいて、ＣａＯの含有量が０～５ｍｏｌ％であることが好ましい。
In addition, in any one of the first to tenth inventions, the crystallized glass according to the eleventh invention preferably has a CaO content of 0 to 5 mol%.
また、第１２の発明に係る結晶化ガラスは、第１～１１の発明のいずれかにおいて、Ｆｅ２Ｏ３の含有量が０～０．５ｍｏｌ％、ＴｉＯ２の含有量が０～０．５ｍｏｌ％であることが好ましい。
Further, 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. %.
また、第１３の発明に係る結晶化ガラスは、第１～１２の発明のいずれかにおいて、実質的にＡｓ２Ｏ３、ＰｂＯを含有しないことが好ましい。ここで、「実質的に含有しない」とは、意図的にガラスに添加しないという意味であり、不可避的不純物まで完全に排除するものではない。具体的には、明示の成分の含有量が各々０．０１ｍｏｌ％未満であることを意味する。
Further, 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. Here, "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 %.
また、第１４の発明に係る結晶化ガラスは、第１～１３の発明のいずれかにおいて、表面にイオン交換による圧縮応力層が形成されておらず、加傷した際の傷深さが２００μｍ以下になることが好ましい。ここで、「傷深さ」とは、花崗岩の定盤上に試料を載置し、その試料に１８０番の研磨紙を１００Ｎの荷重で押し当て、傷をつける。３点曲げ試験を行って割断した試料の断面を微分干渉顕微鏡で観察し、半円状の圧痕（ｍｅｄｉａｎ ｃｒａｃｋ）のガラス表面からの深さを意味する。
Further, 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 μm or less when scratched. It is preferable to be Here, 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.
また、第１５の発明に係る結晶化ガラスは、第１～１４の発明のいずれかにおいて、表面にイオン交換による圧縮応力層が形成されていることが好ましい。
Further, in any one of the first to fourteenth inventions, the crystallized glass according to the fifteenth invention preferably has a compressive stress layer formed on the surface by ion exchange.
また、第１６の発明に係る結晶化ガラスは、第１５の発明において、表面の圧縮応力値が少なくとも１００ＭＰａ以上であることが好ましい。なお、「圧縮応力値」と「応力深さ（ＤＯＣ）」は、例えば、折原製作所の散乱光光弾性応力計ＳＬＰ－１０００又は表面応力計ＦＳＭ－６０００ＬＥにより測定することができる。
In the fifteenth invention, 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.
また、第１７の発明に係る結晶化ガラスは、第１５又は第１６の発明において、応力深さ（ＤＯＣ）が２０μｍ以上であることが好ましい。
In addition, in the fifteenth or sixteenth invention, the crystallized glass according to the seventeenth invention preferably has a depth of stress (DOC) of 20 μm or more.
また、第１８の発明に係る結晶化ガラスは、第１５～１７の発明のいずれかにおいて、∫ＣＴ／ｔが２０ＭＰａ以上であることが好ましい。ここで、「∫ＣＴ／ｔ」は、散乱光光弾性応力計（例えば折原製作所の散乱光光弾性応力計ＳＬＰ－１０００）で得られた圧縮応力の深さ方向のプロファイルについて、ガラス表面から厚みの半分の深さまでの応力を積分した値を意味する。
Further, in any one of the fifteenth to seventeenth inventions, the crystallized glass according to the eighteenth invention preferably has a ∫CT/t of 20 MPa or more. Here, "∫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
また、第１９の発明に係る結晶化ガラスは、第１～１８の発明のいずれかにおいて、落下試験後の破片数が１０００ｍｍ２当たり２００個以下であることが好ましい。なお、本発明において「落下試験後の破片数」は、花崗岩の定盤上の試料を載置し、その試料に先端にビッカース圧子を付けた５３ｇの重りを１０ｍｍの高さから垂直に落とす落下試験を行った後、遅れ破壊が生じた時の破片の数を意味する。
Further, in the crystallized glass according to the nineteenth invention, in any one of the first to eighteenth inventions, it is preferable that the number of fragments after a drop test is 200 or less per 1000 mm 2 . In the present invention, 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.
また、第２０の発明に係る結晶化ガラスは、第１～１９の発明のいずれかにおいて、ヤング率が５０ＭＰａ以上であることが好ましい。
Further, 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.
また、第２１の発明に係る結晶化ガラスは、第１～２０の発明のいずれかにおいて、破壊靭性が１．０ＭＰａ・ｍ１／２未満であることが好ましい。
In addition, in any one of the first to twentieth inventions, the crystallized glass according to the twenty-first invention preferably has a fracture toughness of less than 1.0 MPa·m 1/2 .
また、第２２の発明に係る結晶化ガラスは、第１～２１の発明のいずれかにおいて、厚み０．７ｍｍにおける波長３８０～７８０ｎｍの可視光透過率が５０％以上であることが好ましい。なお、「可視光透過率」は、分光光度計（例えば島津製ＵＶ－３１００）を用いて、厚み方向の直線透過率を測定したものである。
Further, 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).
また、第２３の発明に係る結晶化ガラスは、第１～２２の発明のいずれかにおいて、３０～３００℃における線熱膨張係数が０×１０－７～１５０×１０－７／℃であることが好ましい。
Further, 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.
また、第２４の発明に係る結晶化ガラスは、第１～２３の発明のいずれかにおいて、カバーガラスに用いることが好ましい。
Also, 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.
第２５の発明に係る結晶化ガラスは、組成として、ｍｏｌ％で、ＳｉＯ２ ３０～７０％、Ａｌ２Ｏ３ １～２０％、Ｎａ２Ｏ ３～４５％、Ｐ２Ｏ５ ０．１～１０％、ＺｒＯ２ ０．１～１０％、ＣａＯ ０～１％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ ０～２０％を含有し、ｍｏｌ％比Ａｌ２Ｏ３／ＳｉＯ２が０．１～０．３、ｍｏｌ％比Ａｌ２Ｏ３／Ｎａ２Ｏが０．２～０．４８であり、Ｓｉ、Ａｌ、Ｎａ、Ｏを含む結晶が析出してなることを特徴とする。
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.
第２６の発明に係る結晶性ガラスは、組成として、ｍｏｌ％で、ＳｉＯ２ ３０～７０％、Ａｌ２Ｏ３ １～２０％、Ｎａ２Ｏ ３～４５％、Ｐ２Ｏ５ ０．８～１０％、ＺｒＯ２ ０．１～１０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ ０～２０％、ＣａＯ ０～１％を含有し、ｍｏｌ％比Ａｌ２Ｏ３／ＳｉＯ２が０．１～０．３、ｍｏｌ％比Ａｌ２Ｏ３／Ｎａ２Ｏが０．２～０．４８、ｍｏｌ％比Ｎａ２Ｏ／ＳｉＯ２が０．４～０．７であることを特徴とする。
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.
また、第２７の発明に係る結晶性ガラスは、第２６の発明において、熱処理により（より特定的には焼成処理により）、Ｓｉ、Ａｌ、Ｎａ、Ｏを含む結晶が析出することが好ましい。
In addition, in the crystallizable glass according to the twenty-seventh aspect of the twenty-sixth aspect, it is preferable that crystals containing Si, Al, Na, and O are precipitated by heat treatment (more specifically, by firing treatment).
また、第２８の発明に係る結晶性ガラスは、第２６又は第２７の発明において、イオン交換処理に供されることが好ましい。
Also, 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.
本発明の結晶化ガラス（結晶性ガラス）は、組成として、ｍｏｌ％で、ＳｉＯ２ ３０～７０％、Ａｌ２Ｏ３ １～２０％、Ｎａ２Ｏ ３～４５％、Ｐ２Ｏ５ ０～１０％、ＺｒＯ２ ０～１０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ ０～２０％を含有することを特徴とする。上記のように組成を限定した理由を以下に説明する。なお、各成分の含有量の説明において、特に断りがない限り、「％」はｍｏｌ％を意味する。
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%. The reason for limiting the composition as described above will be explained below. In the description of the content of each component, "%" means mol% unless otherwise specified.
ＳｉＯ２はガラスの骨格を形成する成分である。ＳｉＯ２の含有量は、好ましくは３０～７０％、３５～６５％、３７～６０％、３９～５８％、特に４０～５５％である。ＳｉＯ２の含有量が少な過ぎると、耐候性が著しく低下する傾向にある。一方、ＳｉＯ２の含有量が多過ぎると、溶融性が低下し易くなる。
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.
Ａｌ２Ｏ３は、イオン交換性能を高める成分であると共に、所望の結晶を析出させるために必要な成分である。Ａｌ２Ｏ３の含有量は、好ましくは１～２０％、２～１８％、３～１６％、４～１４％、５～１２％、特に６～１１％である。Ａｌ２Ｏ３の含有量が少な過ぎると、所望の結晶が析出し難くなる。一方、Ａｌ２Ｏ３の含有量が多過ぎると、溶融性が低下し易くなる。
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.
Ｎａ、Ａｌ、Ｓｉ、Ｏを含む結晶を析出させるためには、結晶を構成する成分の含有比率を制御することが好ましい。ｍｏｌ％比Ａｌ２Ｏ３／ＳｉＯ２は、好ましくは０．０１～０．５、０．０５～０．４、０．１～０．３、０．１１～０．２９、０．１２～０．２８、０．１３～０．２７、０．１４～０．２６、特に０．１５～０．２５である。ｍｏｌ％比Ａｌ２Ｏ３／ＳｉＯ２が上記範囲外になると、Ｎａ、Ａｌ、Ｓｉ、Ｏを含む結晶が析出し難くなると共に、異種結晶の析出によって結晶化ガラスが白濁する虞がある。
In order to precipitate crystals containing Na, Al, Si, and O, it is preferable to control the content ratios of the components that make up the crystals. 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.
Ｎａ２Ｏは、高温粘度を低下させて、溶融性を高める成分である。またイオン交換処理に関与する成分であると共に、所望の結晶を析出させるために必要な成分である。Ｎａ２Ｏの含有量は、好ましくは３～４５％、５～４０％、１０～３８％、１５～３５％、１８～３３％、特に２０～３０％である。Ｎａ２Ｏの含有量が少な過ぎると、イオン交換性能が低下し易くなると共に、所望の結晶が析出し難くなる。一方、Ｎａ２Ｏの含有量が多過ぎると、高温粘度が低下し過ぎて、結晶化のための熱処理でガラスが軟化変形してしまう虞がある。
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.
Ｎａ、Ａｌ、Ｓｉ、Ｏを含む結晶を析出させるためには、結晶を構成する成分の含有比率を制御することが好ましい。ｍｏｌ％比Ｎａ２Ｏ／ＳｉＯ２は、好ましくは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、０．４８～０．６２、０．４９～０．６１、特に０．５～０．６である。ｍｏｌ％比Ｎａ２Ｏ／ＳｉＯ２が小さ過ぎると、Ｎａ、Ａｌ、Ｓｉ、Ｏを含む結晶が析出し難くなる上に、高温粘度が高くなり、溶融が困難になる。一方、ｍｏｌ％比Ｎａ２Ｏ／ＳｉＯ２が大き過ぎると、Ｎａ、Ａｌ、Ｓｉ、Ｏを含む結晶が析出し難くなる上に、高温粘度が低くなり、結晶化ための熱処理でガラスが軟化変形し易くなる。
In order to precipitate crystals containing Na, Al, Si, and O, it is preferable to control the content ratios of the components that make up the crystals. 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. On the other hand, if the mol% ratio of Na 2 O/SiO 2 is too large, crystals containing Na, Al, Si, and O are difficult to precipitate, and the high-temperature viscosity is lowered, so that the glass softens and deforms during the heat treatment for crystallization. becomes easier.
Ｎａ、Ａｌ、Ｓｉ、Ｏを含む結晶を析出させるためには、結晶を構成する成分の含有比率を制御することが好ましい。ｍｏｌ％比Ａｌ２Ｏ３／Ｎａ２Ｏは、好ましくは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、特に０．２６～０．４である。ｍｏｌ％比Ａｌ２Ｏ３／Ｎａ２Ｏが上記範囲外になると、Ｎａ、Ａｌ、Ｓｉ、Ｏを含む結晶が析出し難くなると共に、異種結晶の析出によって結晶化ガラスが白濁する虞がある。
In order to precipitate crystals containing Na, Al, Si, and O, it is preferable to control the content ratios of the components that make up the crystals. 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、ＺｎＯは溶融性を高める成分である。ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯの含有量は、好ましくは０～２０％、１～１８％、２～１６％、３～１４％、４～１３％、５～１２％、特に６～１１％である。ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯの含有量が多過ぎると、粗大な結晶が析出し易くなる。一方、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯの含有量が少な過ぎると、溶融温度が高くなり易い。
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は、溶融性を高める成分であると共に、機械的強度を高める成分でもある。ＭｇＯの含有量は、好ましくは０～１５％、０～１０％、０～５％、０～４％、０～３％、０～２％、特に０～１％である。ＭｇＯの含有量が多過ぎると、粗大な結晶が析出し易くなるだけでなく、異種結晶が析出し易くなる。
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は、溶融性を高める成分であると共に、イオン交換を阻害し易い成分である。ＣａＯの含有量は、好ましくは０～５％、０～４％、０～３％、０～２％、０～１％であり、特に実質的に含有しないことが好ましい。ＣａＯの含有量が多過ぎると、イオン交換が阻害され易くなると共に、粗大結晶が析出し易くなり、また異種結晶が析出し易くなる。
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は、溶融性を高める成分である。ＳｒＯの含有量は、好ましくは０～５％、０～４％、０～３％、０～２％、特に０～１％である。ＳｒＯの含有量が多過ぎると、粗大結晶が析出し易くなり、また異種結晶が析出し易くなる。
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は、溶融性を高める成分である。ＢａＯの含有量は、好ましくは０～５％、０～４％、０～３％、０～２％、特に０～１％である。ＢａＯの含有量が多過ぎると、粗大結晶が析出し易くなり、また異種結晶が析出し易くなる。
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は、溶融性を高める成分であると共に、粗大な結晶や異種結晶の析出を生じ難くする成分である。ＺｎＯの含有量は、好ましくは０～２０％、０～１８％、０～１６％、０～１４％、特に０～１２％である。ＺｎＯの含有量が多過ぎると、高温粘度が低下し過ぎて、結晶化のための熱処理でガラスが軟化変形してしまう虞がある。粗大な結晶や異種結晶の析出を抑制することを重視する場合には、ＺｎＯを含有させることが好ましく、その場合、ＺｎＯ含有量は、好ましくは０．１～２０％、０．５～１９％、１～１８％、２～１７％、３～１６％、特に４～１５％である。
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%.
上記成分以外に、以下の成分を含有させることが可能である。
In addition to the above ingredients, it is possible to include the following ingredients.
Ｌｉ２Ｏは、Ｎａ２Ｏと同様に、高温粘度を低下させて、溶融性を高める成分である。Ｌｉ２Ｏの含有量が多過ぎると、異種結晶が析出して、結晶化ガラスの透過率が低下し易くなる。したがって、Ｌｉ２Ｏは、実質的に含まないものとすることができるが、Ｌｉ２Ｏを含有する場合、その含有量は、好ましくは０～５％、特に０～１％である。
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%.
Ｋ２Ｏは、Ｌｉ２Ｏ、Ｎａ２Ｏと同様に高温粘度を低下させて、溶融性を高める成分である。Ｋ２Ｏの含有量が多過ぎると、結晶化ガラスの主結晶以外の結晶、つまり異種結晶が析出し易くなり、透過率が低下し易くなる。また、Ｋ２Ｏを添加すれば、イオン交換速度が速くなり、短時間でもガラス表面から深い領域まで圧縮応力を形成することができる。一方、Ｋ２Ｏが多過ぎると、圧縮応力値が小さくなり易い。Ｋ２Ｏの含有量は、好ましくは０～５％、特に０～１％である。
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%.
所望の結晶の析出には、Ｎａ２Ｏが必要になるが、アルカリ金属酸化物の含有量においてＮａ２Ｏ＞Ｌｉ２Ｏ及びＮａ２Ｏ＞Ｋ２Ｏが好ましく、Ｎａ２Ｏ＞Ｋ２Ｏ≧Ｌｉ２Ｏが更に好ましく、Ｎａ２Ｏ＞Ｋ２Ｏ＞Ｌｉ２Ｏが特に好ましい。
Although 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.
Ｐ２Ｏ５は、イオン交換性能を高める成分である。また、結晶化工程で効率的に結晶を析出させるために必要な成分でもある。一方、Ｐ２Ｏ５を多量に含有すると、ガラスが顕著に分相し易くなる。Ｐ２Ｏ５の含有量は、好ましくは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％。特に１～７．５％である。Ｐ２Ｏ５の含有量が少な過ぎると、イオン交換が起こり難くなり、イオン交換に要する時間が長くなるため生産性が低下し易くなる。また結晶核が十分に形成されず、粗大な結晶が析出してガラスが白濁し易くなると共に、破損し易くなる虞がある。一方、Ｐ２Ｏ５の含有量が多過ぎると、ガラスが分相して、結晶化ガラスが白濁し易くなると共に、耐候性が低下し易くなる。
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. In addition, 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 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.
ＺｒＯ２は、結晶化工程で効率的に結晶を析出させる成分である。ＺｒＯ２の含有量は、好ましくは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％、特に０．８～６％である。ＺｒＯ２の含有量が少な過ぎると、結晶核が十分に形成されず、粗大な結晶が析出してガラスが白濁し易くなると共に、破損し易くなる虞がある。一方、ＺｒＯ２の含有量が多過ぎると、粗大なＺｒＯ２結晶が析出して、ガラスが失透し易くなり、また結晶化ガラスが破損し易くなる。
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.
ＳｎＯ２は、溶融中に価数変化することで酸素を放出し、溶融ガラス中の気泡をより大きくすることで泡の浮上速度を高めて、清澄を促す成分である。ＳｎＯ２の含有量は、好ましくは０～５％、０～４％、０～３％、０～２％、特に０～１％である。またＳｎＯ２にはＺｒＯ２の分相を促進する効果もある。液相温度を低く抑えながら（初相析出による失透のリスクを抑えながら）、分相を効率的に発生させて、後の工程における核形成、結晶成長工程を迅速に行うために、ＳｎＯ２を加えることが好ましい。この場合のＳｎＯ２含有量は、０．０１～５％、０．０３～４％、０．０５～３％、０．０８～２．５％、特に好ましくは０．１～２％である。
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% .
Ｆｅ２Ｏ３は、不可避な不純物として原料に含まれる成分である。Ｆｅ２Ｏ３の含有量が多過ぎると、結晶化ガラスが着色し、透過率が低下する虞がある。Ｆｅ２Ｏ３の含有量は、好ましくは０～４％であり、０～３％、０～２％、０～１％、０～０．５％、特に０～０．１％である。
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%.
ＴｉＯ２は、結晶化工程で結晶の析出を促進させる成分である。一方、ＴｉＯ２を多量に含有すると、ガラスが著しく着色する虞がある。ＺｒＯ２とＴｉＯ２を含むジルコニアチタネート系の結晶は結晶核として作用するが、配位子である酸素の価電子帯から中心金属であるジルコニア及びチタンの伝導帯へと電子が遷移し（ＬＭＣＴ遷移）、結晶化ガラスの着色に関与する。また残存ガラス相にチタンが残っている場合、ＳｉＯ２骨格の価電子帯から残存ガラス相の４価のチタンの伝導帯へとＬＭＣＴ遷移が起こり得る。また残存ガラス相の３価のチタンではｄ－ｄ遷移が起こり、結晶化ガラスの着色に関与する。更にチタンと鉄が共存する場合は、イルメナイト（ＦｅＴｉＯ３）様の着色が発現する。またチタンと錫が共存する場合は、黄色が強まることが知られている。よって、ＴｉＯ２の含有量は、好ましくは０～４％、０～３％、０～２％、０～１％、０～０．５％、特に０～０．１％である。但し、ＴｉＯ２は不純物として混入し易いため、ＴｉＯ２を完全に除去しようとすると、原料コストが増加する。原料コストの増加を抑制するために、ＴｉＯ２の含有量の下限は、好ましくは０．０００３％以上、０．００１％以上、０．０１％以上、特に０．０２％以上である。
TiO 2 is a component that promotes precipitation of crystals in the crystallization process. On the other hand, if TiO 2 is contained in a large amount, 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. Also, when titanium remains in the residual glass phase, 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. Further, trivalent titanium in the residual glass phase undergoes a dd transition, which contributes to the coloring of the crystallized glass. Furthermore, when titanium and iron coexist, ilmenite (FeTiO 3 )-like coloring develops. It is also known that when titanium and tin coexist, the yellow color is enhanced. Thus, the content of TiO 2 is preferably 0-4%, 0-3%, 0-2%, 0-1%, 0-0.5%, especially 0-0.1%. However, since TiO 2 is easily mixed as an impurity, if TiO 2 is completely removed, raw material costs increase. In order to suppress an increase in raw material costs, 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.
Ｂ２Ｏ３は、高温粘度を低下させて、溶融性及び成形性を高める成分である。また結晶核形成時の分相の起こり易さに関与し得る成分でもある。Ｂ２Ｏ３の含有量は、好ましくは０～３％、０～２％、０～１％、特に０～０．１％である。Ｂ２Ｏ３の含有量が多過ぎると、溶融時にＢを含む化合物の蒸発量が多くなり、環境負荷が高くなる虞がある。
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.
ＣｅＯ２は、溶解性を高めるだけではなく、酸化剤としての効果があり、不純物である全Ｆｅ中のＦｅ２＋の増加を抑えて、結晶化ガラスの可視光透過率を高める成分である。ＣｅＯ２の含有量は、好ましくは０～０．５％、０～０．４％、特に０～０．３％である。ＣｅＯ２の含有量が多過ぎると、Ｃｅ４＋による着色が強くなり過ぎて、結晶化ガラスが褐色を呈する虞がある。
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は、芒硝から導入することができる。ＳＯ３は、溶融時に二酸化硫黄と酸素を放出することで、溶融ガラス中の泡を拡大させて、清澄を促す成分である。またＣｅＯ２と同様に酸化剤として働き、ＣｅＯ２と共存させることによりＣｅＯ２の効果を高める成分である。ＳＯ３の含有量は、好ましくは０～０．５％、０．０１～０．４５％、０．０２～０．４％、０．０３～０．３５％、０．０４～０．３％、特に０．０５～０．２５％である。ＳＯ３の含有量が多過ぎると、異種結晶が析出して、結晶化ガラスの表面品位が低下する虞がある。
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.
ＭｏＯ３は、溶融ガラス中に浸漬させた電極からガラス中に電流を流すことで加熱する溶融方法において、電極から僅かに溶融ガラスに混入し得る成分である。溶融ガラスの加熱を電極通電のみで行う場合、ＭｏＯ３の混入量が増加し易いため注意が必要である。ＭｏＯ３の混入量が多過ぎると、ガラスが着色し、透過率が低下する虞がある。ＭｏＯ３の含有量は、好ましくは０～０．５％、０～０．１％、０～０．０５％、０～０．０１％、０～０．００５％、０～０．００１％、０～０．０００５％、特に０～０．０００３％である。
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. When the molten glass is heated only by energizing the electrodes, it is necessary to pay attention to the fact that the amount of MoO 3 mixed in tends to increase. If the amount of MoO 3 mixed is too large, the glass may be colored and the transmittance may be lowered. 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%.
Ａｓ２Ｏ３、ＰｂＯは、環境及び人体に対して有害であるため実質的に含有しないことが好ましい。
Since As 2 O 3 and PbO are harmful to the environment and human body, it is preferable not to substantially contain them.
清澄剤として、Ｆ、Ｃｌ、Ｓｂ２Ｏ３等を１種類以上導入してもよい。これらの清澄剤の合計含有量及び個別含有量は、好ましくは０～５％、０．００１～３％、０．００３～１％、０．００５～０．５％、特に０．０１～０．３％である。なお、Ｃｌを清澄剤として加えない場合でも、Ｃｌはバッチ原料に含まれる不純物としてガラス中に含まれ得る。Ｃｌの含有量が多過ぎると、ガラスを加熱加工する際に白色の欠陥を生じ易くなる。よって、Ｃｌの含有量は、好ましくは０．１％以下、０．０５％以下、０．０１％以下、０．００５％以下、特に０．０４％以下である。
As a refining agent, one or more of F, Cl, Sb 2 O 3 and the like may be introduced. The total and individual contents of these refining agents are preferably 0-5%, 0.001-3%, 0.003-1%, 0.005-0.5%, especially 0.01-0. .3%. Note that even when Cl is not added as a fining agent, Cl can be contained in the glass as an impurity contained in batch raw materials. If the Cl content is too high, white defects tend to occur during heat processing of the glass. Therefore, 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.
化学的耐久性、高温粘度等の改良のために、Ｃｒ２Ｏ３、Ｌａ２Ｏ３、ＷＯ３、Ｎｂ２Ｏ３、Ｙ２Ｏ３等をそれぞれ３％以下、２％以下、１％以下、１％未満、０．５％以下で導入してもよい。
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%.
不純物として、Ｈ２、ＣＯ２、ＣＯ、Ｈ２Ｏ、Ｈｅ、Ｎｅ、Ａｒ、Ｎ２等の成分をそれぞれ０．１％まで導入してもよい。またＰｔ、Ｒｈ、Ａｕ等の貴金属元素の混入量はそれぞれ５００ｐｐｍ以下、更には３００ｐｐｍ以下であることが好ましい。
As impurities, 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. Also, 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.
本発明の結晶化ガラスは下記の特性、性質を有することが好ましい。
The crystallized glass of the present invention preferably has the following characteristics and properties.
本発明の結晶化ガラスは、Ｎａ、Ａｌ、Ｓｉ、Ｏを含む結晶が析出してなることが好ましく、主結晶としてＮａ、Ａｌ、Ｓｉ、Ｏを含む結晶が析出してなることがより好ましく、特にＮａ４Ａｌ２Ｓｉ２Ｏ９、Ｎａ６Ａｌ４Ｓｉ４Ｏ１７又はＮａ８Ａｌ４Ｓｉ４Ｏ１８で表される結晶を含んでいることが好ましい。このような結晶を析出させると、内部引っ張り応力の許容限界を高める効果が発現して、結晶化ガラスが破壊する際に発生する破片の数を少なくすることができる。なお、本発明では、上記結晶以外の結晶の析出を排除するものではない。
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. In particular, 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 . When such crystals are precipitated, the effect of increasing the permissible limit of internal tensile stress is exhibited, and the number of fragments generated when the crystallized glass is broken can be reduced. In addition, in the present invention, precipitation of crystals other than the above crystals is not excluded.
本発明の結晶化ガラスの主結晶は、三斜晶系、単斜晶系、直方晶系、正方晶系、六方晶系、立方晶系が好ましく、より好ましくは単斜晶系、直方晶系、正方晶系、六方晶系、立方晶系、更に好ましくは直方晶系、正方晶系、六方晶系、立方晶系、更に好ましくは、正方晶系、六方晶系、立方晶系、特に好ましくは六方晶系、立方晶系、最も好ましくは立方晶系である。主結晶が対称性の高い結晶である程、光が通ることに対しての異方性が小さいため、結晶化ガラスが透明になり易い。一方、主結晶の対称性が低いと、結晶の向きによって光の通り方が異なるため、光が散乱され易く、半透明又は不透明になり易い。
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. When the main crystal is a highly symmetrical crystal, the crystallized glass tends to be transparent because the anisotropy with respect to the passage of light is small. On the other hand, if the symmetry of the main crystal is low, the direction of light travels differently depending on the orientation of the crystal.
本発明の結晶化ガラスにおいて、結晶化度は、好ましくは１％以上、５％以上、１０％以上、１５％以上、２０％以上、特に２５％以上である。結晶化度が低過ぎると、内部引っ張り応力の許容限界を高める効果が小さくなり易い。一方、結晶化度が高過ぎると、透過率が低下し易くなる。また、イオン交換処理を行う場合、イオン交換処理の対象となるガラス相の比率が少なくなるため、高い圧縮応力値を形成することが困難になる。よって、結晶化度は、好ましくは９９％以下、９６％以下、８０％以下、７０％以下、６０％以下、５０％以下、４０％以下、特に３０％以下である。
In the crystallized glass of the present invention, 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.
結晶子サイズは、好ましくは１μｍ以下、０．５μｍ以下、特に０．３μｍ以下である。結晶子サイズが大き過ぎると、透過率が低下し易くなる。なお、結晶子サイズの下限は特に限定されないが、現実的には１ｎｍ以上である。
The crystallite size is preferably 1 μm or less, 0.5 μm or less, particularly 0.3 μm 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.
厚み０．７ｍｍ、波長３８０～７８０ｎｍにおける可視光平均透過率は、好ましくは５０％以上、５５％以上、６０％以上、６５％以上、７０％以上、７５％以上、特に８０％以上である。厚み０．７ｍｍ、波長３８０～７８０ｎｍにおける可視光平均透過率が低過ぎると、スマートフォンのカバーガラスとして使用し難くなる。
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.
白色度Ｌ＊値は、好ましくは５０以上、６０以上、７０以上、８０以上、特に９０以上である。白色度が低過ぎると、透過率が低下し易くなる。なお、「白色度Ｌ＊値」はＪＩＳ Ｚ ８７３０に定義されているものを意味している。
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.
本発明の結晶化ガラスは、表面に圧縮応力層を有することが好ましい。表面の圧縮応力値（ＣＳ）は、好ましくは１００ＭＰａ以上、２００ＭＰａ以上、３００ＭＰａ以上、４００ＭＰａ以上、５００ＭＰａ以上、５５０ＭＰａ以上、６００ＭＰａ以上、６５０ＭＰａ以上、７００ＭＰａ以上、７５０ＭＰａ以上、８００ＭＰａ以上、８５０ＭＰａ以上、９００ＭＰａ以上、特に９５０ＭＰａ以上である。圧縮応力値が小さ過ぎると、曲げ強度が低くなる虞がある。圧縮応力値（ＣＳ）の上限範囲は、１８００ＭＰａ以下であることが好ましい。圧縮応力値（ＣＳ）が大き過ぎると、内部引張応力が過大となり、結晶化ガラスが破損した際に破片が飛散し易くなる。
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.
応力深さ（ＤＯＣ）は、好ましくは１０μｍ以上、２０μｍ以上、３０μｍ以上、４０μｍ以上、５０μｍ以上、５０μｍ以上、６０μｍ以上、７０μｍ以上、８０μｍ以上、９０μｍ以上、１００μｍ以上、１１０μｍ以上、特に１２０μｍ以上である。応力深さが小さ過ぎると、落下強度が低くなる虞がある。応力深さ（ＤＯＣ）の上限範囲は、３００μｍ以下であり、現実的にはガラスの厚みの１／４以下である。
The depth of stress (DOC) is preferably 10 μm or more, 20 μm or more, 30 μm or more, 40 μm or more, 50 μm or more, 50 μm or more, 60 μm or more, 70 μm or more, 80 μm or more, 90 μm or more, 100 μm or more, 110 μm or more, especially 120 μm 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 μm or less, and practically 1/4 or less of the thickness of the glass.
応力積分値∫ＣＴ／ｔは、散乱光光弾性応力計（例えば折原製作所の散乱光光弾性応力計ＳＬＰ－１０００）で得られた圧縮応力の深さ方向のプロファイルについて、ガラス表面から厚みの半分の深さまでの応力を積分した値である。本発明の結晶化ガラスの∫ＣＴ／ｔは、好ましくは１０ＭＰａ以上、１２ＭＰａ以上、１４ＭＰａ以上、１６ＭＰａ以上、１８ＭＰａ以上、２０ＭＰａ以上、２１ＭＰａ以上、２２ＭＰａ以上、２３ＭＰａ以上、２４ＭＰａ以上、２５ＭＰａ以上、２６ＭＰａ以上、２７ＭＰａ以上、２８ＭＰａ以上、２９ＭＰａ以上、特に３０ＭＰａ以上である。∫ＣＴ／ｔが大きい程、結晶化ガラスに大きな圧縮応力を形成することができる。一方、∫ＣＴ／ｔが大き過ぎると、結晶化ガラスが破壊した際に発生する破片数が多くなり易い。破片数を少なくすることを重視する場合、∫ＣＴ／ｔは、好ましくは５０ＭＰａ以下、４８ＭＰａ以下、４６ＭＰａ以下、４５ＭＰａ以下、４４ＭＰａ以下、４３ＭＰａ以下、４２ＭＰａ以下、４１ＭＰａ以下、４０ＭＰａ以下、３９ＭＰａ以下、３８ＭＰａ以下、３７ＭＰａ以下、３６ＭＰａ以下、特に３５ＭＰａ以下である。
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. The larger ∫CT/t is, the larger compressive stress can be formed in the crystallized glass. On the other hand, if ∫CT/t is too large, the number of fragments generated when the crystallized glass breaks tends to increase. When emphasizing reducing the number of fragments, ∫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.
加傷した際の傷深さとは、花崗岩の定盤上に試料を載置し、その試料に１８０番の研磨紙を１００Ｎの荷重で押し当て、傷をつける。３点曲げ試験を行って割断した試料の断面を微分干渉顕微鏡で観察し、半円状の圧痕（ｍｅｄｉａｎ ｃｒａｃｋ）のガラス表面からの深さを意味する。表面にイオン交換による圧縮応力層が形成されていない場合に、加傷した際の傷深さは、好ましくは２００μｍ以下、１９０μｍ以下、１８０μｍ以下、１７０μｍ以下、１６０μｍ以下、１５０μｍ以下、１４０μｍ以下、１３０μｍ以下、１２０μｍ以下、１１０μｍ以下、特に１００μｍ以下である。傷深さが深過ぎると、落下した際に目立つ傷ができ易い。傷深さの下限範囲は特に限定されないが、現実的には３０μｍ以上である。
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. When a compressive stress layer is not formed on the surface by ion exchange, the scratch depth when scratched is preferably 200 μm or less, 190 μm or less, 180 μm or less, 170 μm or less, 160 μm or less, 150 μm or less, 140 μm or less, or 130 μm. 120 μm or less, 110 μm or less, particularly 100 μm 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 μm or more.
落下試験後の破片数は、１０００ｍｍ２当たり５００個以下、４５０個以下、４００個以下、３５０個以下、３００個以下、２５０個以下、２００個以下、１９０個以下、１８０個以下、１７０個以下、１６０個以下、１５０個以下、１４０個以下、１３０個以下、１２０個以下、１１０個以下、１００個以下、９０個以下、８０個以下、７０個以下、６０個以下、特に５０個以下が好ましい。破片数が多過ぎると、落下後に、透明性が損なわれる。また細かい破片によって怪我をする虞がある。破片数の下限範囲は特に限定されないが、現実的には２個以上である。
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.
曲げ強度は、好ましくは１００ＭＰａ以上、１２０ＭＰａ以上、１５０ＭＰａ以上、１８０ＭＰａ以上、２００ＭＰａ以上、２３０ＭＰａ以上、特に２５０ＭＰａ以上である。曲げ強度が低過ぎると、結晶化ガラスが割れ易くなる。なお、曲げ強度の上限範囲は特に限定されないが、現実的には３０００ＭＰａ以下である。
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.
耐落下高さは、好ましくは５ｍｍ以上、７ｍｍ以上、特に１０ｍｍ以上である。耐落下高さが低過ぎると、落下の際に結晶化ガラスが割れ易くなる。
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.
本発明の結晶化ガラスにおいて、ヤング率は、好ましくは５０ＧＰａ以上、６０ＧＰａ以上、７０ＧＰａ以上、７５ＧＰａ以上、特に８０ＧＰａ以上である。ヤング率が低過ぎると、板厚が薄い場合に強化ガラスが撓み易くなる。ヤング率の上限範囲は特に限定されないが、現実的には１５０ＧＰａ以下である。
In the crystallized glass of the present invention, 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.
本発明の結晶化ガラスにおいて、破壊靭性は、好ましくは０．５ＭＰａ・ｍ１／２以上、０．５５ＭＰａ・ｍ１／２以上、０．６ＭＰａ・ｍ１／２以上、０．６５ＭＰａ・ｍ１／２以上、特に０．７ＭＰａ・ｍ１／２以上である。破壊靭性が低過ぎると、落下試験の破片数が増加し易い。一方、破壊靭性を高めるべく、例えば結晶化度を上げ過ぎると、結晶化ガラスの可視光平均透過率が低下し易い。したがって、透過率を重視する場合、破壊靭性は、好ましくは２以下、１．５以下、１．３以下、１．２以下、１．１以下、１．０以下、特に１．０未満である。
In the crystallized glass of the present invention, 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 .
歪点は、好ましくは４５０℃以上、特に５００℃以上である。歪点が低過ぎると、結晶化工程でガラスが変形する虞がある。歪点の上限範囲は特に限定されないが、現実的には１０００℃以下である。
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.
３０～３８０℃における熱膨張係数は、好ましくは０×１０－７～１６０×１０－７／℃、１０×１０－７～１５５×１０－７／℃、特に２０×１０－７～１５０×１０－７／℃である。熱膨張係数が低過ぎると、熱膨張係数が周辺部材と整合し難くなる。一方、熱膨張係数が高過ぎると、耐熱衝撃性が低下し易くなる。
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.
次に、本発明の結晶化ガラスの製造方法を説明する。
Next, the method for producing the crystallized glass of the present invention will be explained.
まず、所望の組成となるようにガラス原料を調合する。次に調合した原料バッチを１３００～１６００℃で８～１６時間溶融し、所定の形状に成形し結晶性ガラスを得る。なお成形方法として、フロート法、オーバーフローダウンドロー法、ロールアウト法、モールドプレス法等の周知の成形法を採用することができる。なお、必要に応じて曲げ加工等の処理を施しても構わない。
First, glass raw materials are blended so as to have the desired composition. Next, 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. As 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. In addition, processing such as bending may be performed as necessary.
次いで結晶性ガラスを所望の結晶化度にするために、５００～８００℃で０．１～１５時間熱処理（すなわち焼成処理）することにより、結晶を析出させて結晶化ガラスを得る。なお、結晶化のための熱処理は、ある特定の温度のみで行ってよく、二水準以上の温度に保持して段階的に熱処理してもよく、温度勾配を与えながら熱処理してもよい。このような処理によれば、結晶の析出数および結晶の成長の程度を個別に調整し得る。また音波や電磁波を印加、照射することで結晶化を促進してもよい。
Next, in order to obtain the desired degree of crystallinity, 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.
その後、得られた結晶化ガラスに対して、曲げ強度を高くするためにイオン交換処理を行う。イオン交換処理は、３５０℃以上の溶融塩に、結晶化ガラスを接触させることにより、ガラス中のアルカリイオン（例えばＮａイオン）をそれよりもイオン半径が大きいアルカリイオン（例えばＫイオン）と置換させる。このようにして、表面に圧縮応力層を形成することができる。
After that, the obtained crystallized glass is subjected to an ion exchange treatment to increase the bending strength. In 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). . In this way, a compressive stress layer can be formed on the surface.
イオン交換処理に際して、溶融塩として、硝酸塩（硝酸カリウム、硝酸ナトリウム等）、炭酸塩（炭酸カリウム、炭酸ナトリウム等）、硫酸塩（硫酸カリウム、硫酸ナトリウム等）、塩化物塩（塩化カリウム、塩化ナトリウム等）やこれらを組み合わせたものを用いることができる。
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.
必要に応じて、イオン交換処理前又は後に、膜付け等の表面加工、切断、穴開け等の機械加工等を施してもよい。
If necessary, before or after ion exchange treatment, surface processing such as filming, machining such as cutting, drilling, etc. may be applied.
以下、本発明を実施例に基づいて詳細に説明する。表１～４は、実施例である試料Ｎｏ．１～３４及び比較例である試料Ｎｏ.３５を示すものである。なお、表中で「Ｎ．Ｄ．」は未測定を意味している。また、表中の密度測定値における「焼成」とは、結晶を析出および成長させるための熱処理工程を意味し、「アニール」とはガラス中の歪を緩和することを目的としたガラスを結晶化させない熱処理工程を意味する。
Hereinafter, the present invention will be described in detail based on examples. Tables 1 to 4 show sample Nos., which are examples. 1 to 34 and sample No. 35 as a comparative example. In the table, "N.D." means unmeasured. In addition, "firing" in the density measurement values in the table means a heat treatment process for precipitating and growing crystals, and "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
Hereinafter, the present invention will be described in detail based on examples. Tables 1 to 4 show sample Nos., which are examples. 1 to 34 and sample No. 35 as a comparative example. In the table, "N.D." means unmeasured. In addition, "firing" in the density measurement values in the table means a heat treatment process for precipitating and growing crystals, and "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
以下のようにして試料Ｎｏ．１～３５を作製した。
Sample No. 1-35 were produced.
まず、表中の組成になるように調合したバッチ原料を溶融窯に投入し、１３００～１５００℃で溶融した後、溶融ガラス生地をロール成形し、２００×５００×５ｍｍの結晶性ガラスを作製した。
First, 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. .
さらに、得られた結晶性ガラスを表中に記載の温度、時間にて熱処理することにより、結晶化ガラスを得た。
Furthermore, crystallized glass was obtained by heat-treating the resulting crystallizable glass at the temperature and time indicated in the table.
このようにして作製した結晶化ガラスの試料について、密度、外観（透明、半透明又は不透明）、主結晶、空間群、結晶系、結晶化度、平均結晶子サイズ、傷深さ、析出結晶、透過率、及び熱膨張係数を評価した。試料Ｎｏ．３２～３４については、歪点、徐冷点、高温粘度１０４．０ｄＰａ・ｓにおける温度、高温粘度１０３．０ｄＰａ・ｓにおける温度、Ｌ＊値、ａ＊値、ｂ＊値、熱膨張係数も評価した。その結果を表に示す。
Regarding the 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.
密度は周知のアルキメデス法によって測定した値である。なお、密度の測定は焼成を行う前後で行い、測定値の差を算出した。
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.
外観は目視で透明、半透明、不透明の３つの水準から判定した。基準としては、試料を通して文字（ＭＳＰゴシック、１２ｐｔ）を見た際に、文字が明瞭に見える場合を透明、文字が見えるが霞んで見える場合を半透明、文字が見えない場合を不透明とした。
The appearance was visually judged from three levels: transparent, translucent, and opaque. As a standard, when characters (MSP Gothic, 12pt) were viewed through the sample, the case where the characters were clearly visible was defined as transparent, the case where the characters were visible but vague was defined as translucent, and the case where the characters were not visible was defined as opaque.
主結晶、空間群、結晶系、結晶化度、平均結晶子サイズはＸ線回折装置（リガク製 全自動多目的水平型Ｘ線回折装置 Ｓｍａｒｔ Ｌａｂ）を用いて評価した。スキャンモードは２θ／θ測定、スキャンタイプは連続スキャン、散乱及び発散スリット幅は１°、受光スリット幅は０．２°、測定範囲は１０～６０°、測定ステップは０．１°、スキャン速度は５°／分とし、同機種パッケージに搭載された解析ソフトを用いて析出結晶の評価を行った。また析出結晶の平均結晶子サイズはデバイ・シェラー（Ｄｅｂｅｙｅ－Ｓｈｅｒｒｅｒ）法に基づいて、測定したＸ線回折ピークを用いて算出した。なお、平均結晶子サイズ算出用の測定では、スキャン速度は１°／分とした。また、結晶化度は上記方法で得られたＸ線回折プロファイルを基づいて、（結晶のＸ線回折ピークの積分強度）／（計測されたＸ線回折の全積分強度）×１００［％］によって算出した。
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 2θ/θ 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, and the precipitated crystals were evaluated using the analysis software installed in the package of the same model. The average crystallite size of precipitated crystals was calculated based on the Debye-Sherrer method using the measured X-ray diffraction peaks. In addition, in the measurement for calculating the average crystallite size, the scanning speed was 1°/min. In addition, 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.
歪点、徐冷点は、ＡＳＴＭ Ｃ３３６及びＣ３３８の方法に基づいて測定した。
The strain point and annealing point were measured based on the methods of ASTM C336 and C338.
高温粘度１０４．０ｄＰａ・ｓにおける温度、高温粘度１０３．０ｄＰａ・ｓにおける温度は、白金球引き上げ法で測定した。
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.
Ｌ＊値、ａ＊値、ｂ＊値は、厚み０．７ｍｍに両面光学研磨した板状の試料について、分光光度計を用いて波長２００～８００ｎｍの透過率測定結果から算出した。測定には島津製作所製分光光度計ＵＶ－３１００ＰＣを用いた。図１は、試料Ｎｏ．３２の厚み０．７ｍｍにおける波長２００～８００ｎｍの透過率曲線である。
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.
熱膨張係数は、２０ｍｍ×３．８ｍｍφに加工した試料を用いて、３０～３８０℃の温度域で測定した。測定にはＮＥＴＺＳＣＨ製 Ｄｉｌａｔｏｍｅｔｅｒを用いた。
The coefficient of thermal expansion was measured in the temperature range of 30-380°C using a sample processed to 20mm x 3.8mmφ. A NETZSCH dilatometer was used for the measurement.
表１～４から明らかなように、試料Ｎｏ．１～３４は、透明又は半透明であった。一方、比較例である試料Ｎｏ.３５は、半透明且つ白色であった。また、図１から分かるように、試料Ｎｏ．３２の可視域（波長４００～７００ｎｍ）での透過率が８５％以上と高かった。
As is clear from Tables 1 to 4, sample No. 1-34 were transparent or translucent. On the other hand, Sample No. 35, which is a comparative example, was translucent and white. Moreover, as can be seen from FIG. 32 had a high transmittance of 85% or more in the visible region (wavelength of 400 to 700 nm).
表５は、実施例である試料Ａ～Ｄを示している。
Table 5 shows samples A to D that are examples.
以下のようにして試料Ａ～Ｄを作製した。
Samples A to D were produced as follows.
まず、実施例１の試料Ｎｏ．３２の組成になるように調合したバッチ原料を溶融窯に投入し、１３００～１５００℃で溶融した後、溶融ガラス生地をロール成形し、２００×５００×５ｍｍの結晶性ガラスを作製した。
First, 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.
次に、上記の結晶性ガラスを６００℃で４時間、７４０℃で１時間熱処理することにより、結晶化ガラスを得た。
Next, the above crystallizable glass was heat-treated at 600°C for 4 hours and at 740°C for 1 hour to obtain crystallized glass.
さらに、得られた結晶化ガラスを厚みが０．７ｍｍになるよう研磨した。このようにして得られた試料Ｎｏ．３２の組成を有する結晶化ガラスについて、加傷した際の傷深さを測定した。図２は、この結晶化ガラスと従来の化学強化用ガラス（すなわちイオン交換を行っていないガラス）との加傷した際の傷深さを比較したデータである。
Furthermore, the resulting crystallized glass was polished to a thickness of 0.7 mm. Sample no. Crystallized glasses having compositions of 32 were measured for scratch depth when scratched. 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.
傷深さは、次のような手順で測定した。花崗岩の定盤上に試料を載置し、その試料に１８０番の研磨紙を１００Ｎの荷重で押し当て、傷をつける。その後、３点曲げ試験を行って割断した試料の断面を微分干渉顕微鏡で観察し、半円状の圧痕（ｍｅｄｉａｎ ｃｒａｃｋ）のガラス表面からの深さを測定した。
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.
その後、得られた結晶化ガラスについて、表中に記載の条件でイオン交換処理を行い、表面に圧縮応力層を有する結晶化ガラスを得た。
After that, 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.
このようにして作製した試料について、表面の圧縮応力値（ＣＳ）、応力深さ（ＤＯＣ）、ヤング率、ビッカース硬度、曲げ強度、耐落下高さを評価した。その結果を表中に示す。図３は、試料Ａ～Ｄの圧縮応力値（ＣＳ）と応力深さ（ＤＯＣ）の関係を表したデータである。
The surface compressive stress value (CS), stress depth (DOC), Young's modulus, Vickers hardness, bending strength, and drop resistance height of the samples thus prepared were evaluated. The results are shown in the table. FIG. 3 shows data representing the relationship between the compressive stress value (CS) and stress depth (DOC) of samples AD.
表面の圧縮応力値（ＣＳ）、応力深さ（ＤＯＣ）は、表面応力計（株式会社折原製作所製ＦＳＭ－６０００）及び表面応力計ＦＳＭ－６０００（株式会社折原製作所製）を用いて観察される干渉縞の本数とその間隔から圧縮応力値と応力深さを算出した。なお、応力特性の算出に当たり、各試料の屈折率を１．５４８、光学弾性定数を３１．０［（ｎｍ／ｃｍ）／ＭＰａ］とした。なお、イオン交換処理の前後では、ガラス表層におけるガラス組成が微視的に異なるものの、ガラス全体として見た場合、ガラス組成は実質的に相違しない。
Surface compressive stress value (CS) and stress depth (DOC) are observed using a surface stress meter (FSM-6000 manufactured by Orihara Seisakusho Co., Ltd.) and a surface stress meter FSM-6000 (manufactured by Orihara Seisakusho Co., Ltd.). Compressive stress value and stress depth were calculated from the number of interference fringes and their intervals. In calculating the stress characteristics, the refractive index of each sample was set to 1.548, and the optical elastic constant was set to 31.0 [(nm/cm)/MPa]. Although the glass composition in the glass surface layer is microscopically different before and after the ion exchange treatment, the glass composition as a whole does not substantially differ.
ビッカース硬度は、ＪＩＳ Ｚ２２４４－１９９２に準拠すると共に、ビッカース硬度計にて１００ｇｆの荷重でビッカース圧子を押し込むことで測定した値であり、測定１０回の平均値である。
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.
ヤング率は、ＪＩＳ Ｒ１６０２－１９９５「ファインセラミックスの弾性率試験方法」に準拠した方法で算出したものである。
The Young's modulus was calculated by a method based on JIS R1602-1995 "Elastic modulus test method for fine ceramics".
曲げ強度は、ＡＳＴＭ Ｃ８８０－７８に準じた３点荷重法を用いて測定したものである。
The bending strength was measured using the three-point loading method according to ASTM C880-78.
耐落下高さは、落下試験により求めた。花崗岩の定盤の上に、５０ｍｍ×５０ｍｍ×０．７ｍｍ厚の試料を置き、試料の上に先端にビッカース圧子を付けた５３ｇの重りを特定の高さから垂直に落とす落下試験を行い、割れることなく元の形状を維持した最大高さを落下高さとした。
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.
図２から分かるように、試料Ｎｏ．３２の組成を有するイオン交換を行っていない結晶化ガラスは、従来の化学強化用ガラスよりも落下した際の傷が目立たないと考えられる。また、表５及び図３から分かるように、試料Ａ～Ｄは、表面の圧縮応力値（ＣＳ）が２７１ＭＰａ以上、応力深さ（ＤＯＣ）が２１μｍ以上であり、機械的強度が高いと考えられる。
As can be seen from Fig. 2, sample No. It is considered that the crystallized glass having the composition of No. 32 and not undergoing ion exchange has less conspicuous scratches when dropped than the conventional glass for chemical strengthening. In addition, as can be seen from Table 5 and FIG. 3, samples A to D have a surface compressive stress value (CS) of 271 MPa or more and a stress depth (DOC) of 21 μm or more, and are considered to have high mechanical strength. .
表６及び７は、実施例である試料Ｅ～Ｋを示している。
Tables 6 and 7 show samples E to K, which are examples.
以下のようにして試料Ｅ～Ｋを作製した。
Samples E to K were produced as follows.
まず、実施例１の試料Ｎｏ．３２の組成になるように調合したバッチ原料を溶融窯に投入し、１３００～１５００℃で溶融した後、溶融ガラス生地をロール成形し、２００×５００×５ｍｍの結晶性ガラスを複数枚作製した。この結晶性ガラスの内、数枚を６００℃４時間、７４０℃１時間熱処理することにより、結晶化ガラスを得た（試料Ｅ～Ｊ）。図４は、試料Ｎｏ．３２のＸＲＤ曲線を示すデータであり、Ｎａ６Ａｌ４Ｓｉ４Ｏ１７が析出していることが確認できた。また、結晶化を行わなかったガラスを試料Ｋとした。
First, 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.
次に、得られた結晶性ガラスおよび結晶化ガラスを厚みが０．７ｍｍになるよう研磨した。
Next, the resulting crystallizable glass and crystallized glass were polished to a thickness of 0.7 mm.
このようにして作製した試料Ｅ～Ｋについて、ヤング率、破壊靭性を評価した。その結果を表６に示す。なお、ヤング率については実施例２と同様の方法で測定した。
The Young's modulus and fracture toughness were evaluated for samples E to K produced in this way. Table 6 shows the results. The Young's modulus was measured in the same manner as in Example 2.
破壊靭性は、ＪＩＳ Ｒ１６０７「ファインセラミックスの破壊靱性試験方法」に基づき、ＳＥＰＢ法によりＫＩＣを測定したものである。なお、各試料の破壊靱性値は３点の平
均値より求めた。 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.
均値より求めた。 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.
さらに、得られた結晶化ガラス（試料Ｅ～Ｊ）及び試料Ｌを厚みが０．７ｍｍになるよう研磨した。その後、結晶化ガラスを表中に記載の条件でイオン交換処理を行い、表面に圧縮応力層を有する結晶化ガラスを得た。
Furthermore, the obtained crystallized glass (Samples E to J) and Sample L 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.
このようにして作製した試料について、圧縮応力値（ＣＳ）、応力深さ（ＤＯＣ）、ビッカース硬度、ヤング率、曲げ強度、耐落下高さ、板面積、∫ＣＴ／ｔ、破片数を評価した。その結果を表７に示す。また、図５は、試料Ｅ～Ｉの圧縮応力値（ＣＳ）と応力深さ（ＤＯＣ）の関係を表したデータである。なお、圧縮応力値、応力深さ、ビッカース硬度、ヤング率、曲げ強度、耐落下高さについては、実施例２と同様の方法で測定した。
The samples thus prepared were evaluated for compressive stress value (CS), stress depth (DOC), Vickers hardness, Young's modulus, bending strength, drop height, plate area, ∫CT/t, and number of fragments. . Table 7 shows the results. 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は、圧縮応力の深さ方向の応力プロファイルについて、ガラス表面から厚みの半分の深さまでの応力を積分した値を意味する。
∫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.
破片数は、花崗岩の定盤の上に試料を載置し、その試料の上に先端にビッカース圧子を付けた５３ｇの重りを１０ｍｍの高さから垂直に落とす落下試験を行った後、遅れ破壊が生じた時の試料の破片の数を意味する。
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 .
表６から明らかなように、熱処理を施した結晶化ガラスであるＥ～Ｊは、Ｋよりも高いヤング率を有しているが破壊靭性は試料Ｌと同等である。
As is clear from Table 6, heat-treated crystallized glasses E to J have a higher Young's modulus than K, but the fracture toughness is equivalent to that of sample L.
表７及び図５から明らかなように、試料Ｅ～Ｊは、高温の溶融塩にてイオン交換処理を施したため、表面の圧縮応力値が１１０１ＭＰａ以上、応力深さが２６μｍ以上であり、機械的強度が高いと考えられる。
As is clear from Table 7 and FIG. 5, 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 μm or more. It is considered to have high strength.
また、結晶化強化ガラスである試料Ｆ～Ｊについて、従来の結晶を含まない強化ガラス（比較例Ｌ）と対比を行った結果を図６に示す。図６は、試料Ｆ～Ｊ及び従来の強化ガラス（国際公開第２０１５／１２５５８４号の明細書中の実施例Ｎｏ．２）である比較例Ｌの破片数と∫ＣＴ／ｔの関係を表したデータである。比較例Ｌはガラス組成として、モル％で、ＳｉＯ２ ６６．５％、Ａｌ２Ｏ３ １１．４％、Ｂ２Ｏ３ ０．５％、Ｎａ２Ｏ １５．２％、Ｋ２Ｏ １．４％、ＭｇＯ ４．８％、ＳｎＯ２ ０．２％を含有し、厚み０．７ｍｍのガラスであり、結晶を含まないガラスである。比較例Ｌについては、複数枚の試料について各々異なる強化時間及び温度でイオン交換処理を行ない、図６に示す異なる∫ＣＴ／ｔを有する複数のサンプルを作製した上で、各サンプルについて落下試験を行い、破片数を測定した。図６から分かるように、試料Ｅ～Ｊの破片数は、従来の化学強化ガラスである比較例Ｌよりも少なかった。
Further, 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. 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.
本発明の結晶化ガラスは、携帯電話、デジタルカメラ、ＰＤＡ（携帯端末）等のタッチパネルディスプレイのカバーガラスとして好適である。また、本発明の結晶化ガラスは、これらの用途以外にも、高い曲げ強度、高落下耐性、透明性が要求される用途、例えば窓ガラス、磁気ディスク用基板、フラットパネルディスプレイ用基板、太陽電池用カバーガラス、固体撮像素子用カバーガラスへの応用が期待される。
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). In addition to these uses, 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.
Claims (28)
- 組成として、ｍｏｌ％で、ＳｉＯ２ ３０～７０％、Ａｌ２Ｏ３ １～２０％、Ｎａ２Ｏ ３～４５％、Ｐ２Ｏ５ ０～１０％、ＺｒＯ２ ０～１０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ ０～２０％を含有する結晶化ガラス。 Composition: SiO 2 30-70%, Al 2 O 3 1-20%, Na 2 O 3-45%, P 2 O 5 0-10%, ZrO 2 0-10%, MgO+CaO+SrO+BaO+ZnO 0- Crystallized glass containing 20%.
- Ｓｉ、Ａｌ、Ｎａ及びＯを含む結晶が析出してなることを特徴とする請求項１に記載の結晶化ガラス。 The crystallized glass according to claim 1, characterized in that crystals containing Si, Al, Na and O are precipitated.
- Ｓｉ、Ａｌ、Ｎａ及びＯを含む結晶の平均結晶子サイズが１μｍ以下であることを特徴とする請求項２に記載の結晶化ガラス。 The crystallized glass according to claim 2, wherein the average crystallite size of crystals containing Si, Al, Na and O is 1 μm or less.
- 結晶化度が１～９５％であることを特徴とする請求項１又は２に記載の結晶化ガラス。 The crystallized glass according to claim 1 or 2, which has a crystallinity of 1 to 95%.
- Ｎａ４Ａｌ２Ｓｉ２Ｏ９、Ｎａ６Ａｌ４Ｓｉ４Ｏ１７、Ｎａ８Ａｌ４Ｓｉ４Ｏ１８の内、少なくとも１種以上の結晶が析出してなることを特徴とする請求項１又は２に記載の結晶化ガラス。 3. Crystals of at least one of Na4Al2Si2O9 , Na6Al4Si4O17 and Na8Al4Si4O18 are deposited . Crystallized glass according to .
- ｍｏｌ％比Ａｌ２Ｏ３／ＳｉＯ２が０．０１～０．５であることを特徴とする請求項１又は２に記載の結晶化ガラス。 3. The crystallized glass according to claim 1, wherein the mol % ratio Al 2 O 3 /SiO 2 is 0.01 to 0.5.
- ｍｏｌ％比Ａｌ２Ｏ３／Ｎａ２Ｏが０．０１～０．７であることを特徴とする請求項１又は２に記載の結晶化ガラス。 3. The crystallized glass according to claim 1, wherein the mol % ratio Al 2 O 3 /Na 2 O is 0.01 to 0.7.
- ｍｏｌ％比Ｎａ２Ｏ／ＳｉＯ２が０．１～１であることを特徴とする請求項１又は２に記載の結晶化ガラス。 3. The crystallized glass according to claim 1, wherein the mol % ratio Na 2 O/SiO 2 is 0.1-1.
- Ｐ２Ｏ５の含有量が０．１～１０ｍｏｌ％であることを特徴とする請求項１又は２に記載の結晶化ガラス。 3. Crystallized glass according to claim 1, wherein the content of P 2 O 5 is 0.1 to 10 mol %.
- ＺｒＯ２の含有量が０．１～１０ｍｏｌ％であることを特徴とする請求項１又は２に記載の結晶化ガラス。 3. Crystallized glass according to claim 1, wherein the content of ZrO 2 is 0.1-10 mol %.
- ＣａＯの含有量が０～５ｍｏｌ％であることを特徴とする請求項１又は２に記載の結晶化ガラス。 The crystallized glass according to claim 1 or 2, characterized in that the content of CaO is 0 to 5 mol%.
- Ｆｅ２Ｏ３の含有量が０～０．５ｍｏｌ％、ＴｉＯ２の含有量が０～０．５ｍｏｌ％であることを特徴とする請求項１又は２に記載の結晶化ガラス。 3. Crystallized glass according to claim 1, 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 %.
- 実質的にＡｓ２Ｏ３、ＰｂＯを含有しないことを特徴とする請求項１又は２に記載の結晶化ガラス。 3. The crystallized glass according to claim 1, which contains substantially no As2O3 and PbO .
- 表面にイオン交換による圧縮応力層が形成されておらず、加傷した際の傷深さが２００μｍ以下になることを特徴とする請求項１又は２に記載の結晶化ガラス。 Crystallized glass according to claim 1 or 2, characterized in that no compressive stress layer is formed on the surface due to ion exchange, and the depth of damage when damaged is 200 µm or less.
- 表面にイオン交換による圧縮応力層が形成されていることを特徴とする請求項１又は２に記載の結晶化ガラス。 Crystallized glass according to claim 1 or 2, characterized in that a compressive stress layer is formed on the surface by ion exchange.
- 表面の圧縮応力値が少なくとも１００ＭＰａ以上であることを特徴とする請求項１５に記載の結晶化ガラス。 Crystallized glass according to claim 15, characterized in that the surface compressive stress value is at least 100 MPa or more.
- 応力深さが２０μｍ以上であることを特徴とする請求項１５に記載の結晶化ガラス。 The crystallized glass according to claim 15, wherein the stress depth is 20 µm or more.
- ∫ＣＴ／ｔが２０ＭＰａ以上であることを特徴とする請求項１５に記載の結晶化ガラス。 Crystallized glass according to claim 15, characterized in that ∫CT/t is 20 MPa or more.
- 落下試験後の破片数が１０００ｍｍ２当たりの２００個以下であることを特徴とする請求項１又は２に記載の結晶化ガラス。 The crystallized glass according to claim 1 or 2, wherein the number of fragments after a drop test is 200 or less per 1000 mm 2 .
- ヤング率が５０ＭＰａ以上であることを特徴とする請求項１又は２に記載の結晶化ガラス。 The crystallized glass according to claim 1 or 2, which has a Young's modulus of 50 MPa or more.
- 破壊靭性が１．０ＭＰａ・ｍ１／２未満であることを特徴とする請求項１又は２に記載の結晶化ガラス。 Crystallized glass according to claim 1 or 2, characterized in that the fracture toughness is less than 1.0 MPa·m 1/2 .
- 厚み０．７ｍｍにおける波長３８０～７８０ｎｍの可視光透過率が５０％以上であることを特徴とする請求項１又は２に記載の結晶化ガラス。 The crystallized glass according to claim 1 or 2, wherein the visible light transmittance at a wavelength of 380 to 780 nm at a thickness of 0.7 mm is 50% or more.
- ３０～３００℃における線熱膨張係数が０×１０－７～１５０×１０－７／℃であることを特徴とする請求項１又は２に記載の結晶化ガラス。 3. The crystallized glass according to claim 1, wherein the linear thermal expansion coefficient at 30 to 300° C. is 0×10 −7 to 150×10 −7 /°C.
- カバーガラスに用いることを特徴とする請求項１又は２に記載の結晶化ガラス。 The crystallized glass according to claim 1 or 2, which is used for a cover glass.
- 組成として、ｍｏｌ％で、ＳｉＯ２ ３０～７０％、Ａｌ２Ｏ３ １～２０％、Ｎａ２Ｏ ３～４５％、Ｐ２Ｏ５ ０．１～１０％、ＺｒＯ２ ０．１～１０％、ＣａＯ ０～１％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ ０～２０％を含有し、ｍｏｌ％比Ａｌ２Ｏ３／ＳｉＯ２が０．１～０．３、ｍｏｌ％比Ａｌ２Ｏ３／Ｎａ２Ｏが０．２～０．４８であり、Ｓｉ、Ａｌ、Ｎａ、Ｏを含む結晶が析出してなることを特徴とする結晶化ガラス。 Composition, in mol%, SiO 2 30-70%, Al 2 O 3 1-20%, Na 2 O 3-45%, P 2 O 5 0.1-10%, ZrO 2 0.1-10% , CaO 0-1%, MgO + CaO + SrO + BaO + ZnO 0-20%, the mol% ratio Al 2 O 3 /SiO 2 is 0.1-0.3, the mol% ratio Al 2 O 3 /Na 2 O is 0.2 ∼0.48, crystallized glass characterized by being formed by precipitation of crystals containing Si, Al, Na and O.
- 組成として、ｍｏｌ％で、ＳｉＯ２ ３０～７０％、Ａｌ２Ｏ３ １～２０％、Ｎａ２Ｏ ３～４５％、Ｐ２Ｏ５ ０．８～１０％、ＺｒＯ２ ０．１～１０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ ０～２０％、ＣａＯ ０～１％を含有し、ｍｏｌ％比Ａｌ２Ｏ３／ＳｉＯ２が０．１～０．３、ｍｏｌ％比Ａｌ２Ｏ３／Ｎａ２Ｏが０．２～０．４８、ｍｏｌ％比Ｎａ２Ｏ／ＳｉＯ２が０．４～０．７であることを特徴とする結晶性ガラス。 Composition, in mol%, SiO 2 30-70%, Al 2 O 3 1-20%, Na 2 O 3-45%, P 2 O 5 0.8-10%, 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 ∼0.48, and a mol% ratio Na 2 O/SiO 2 of 0.4 to 0.7.
- 熱処理により、Ｓｉ、Ａｌ、Ｎａ、Ｏを含む結晶が析出することを特徴とする請求項２６に記載の結晶性ガラス。 The crystallizable glass according to claim 26, characterized in that crystals containing Si, Al, Na, and O are precipitated by heat treatment.
- イオン交換処理に供されることを特徴とする請求項２６又は２７に記載の結晶性ガラス。
28. The crystallizable glass according to claim 26 or 27, which is subjected to an ion exchange treatment.
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| JPH03193640A (en) * | 1989-12-20 | 1991-08-23 | Hoya Corp | Crystallized glass |
| JP2015060614A (en) * | 2013-09-20 | 2015-03-30 | Hoya株式会社 | Method for manufacturing glass substrate for information recording medium |
| JP2017515779A (en) * | 2014-05-13 | 2017-06-15 | コーニング インコーポレイテッド | Transparent glass ceramic article, glass ceramic precursor glass, and method for forming the same |
| WO2017104514A1 (en) * | 2015-12-16 | 2017-06-22 | 日本電気硝子株式会社 | Crystallized glass support substrate and laminate body using same |
| JP2021084828A (en) * | 2019-11-27 | 2021-06-03 | 株式会社オハラ | Optical filter glass ceramic and optical filter |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH03193640A (en) * | 1989-12-20 | 1991-08-23 | Hoya Corp | Crystallized glass |
| JP2015060614A (en) * | 2013-09-20 | 2015-03-30 | Hoya株式会社 | Method for manufacturing glass substrate for information recording medium |
| JP2017515779A (en) * | 2014-05-13 | 2017-06-15 | コーニング インコーポレイテッド | Transparent glass ceramic article, glass ceramic precursor glass, and method for forming the same |
| WO2017104514A1 (en) * | 2015-12-16 | 2017-06-22 | 日本電気硝子株式会社 | Crystallized glass support substrate and laminate body using same |
| JP2021084828A (en) * | 2019-11-27 | 2021-06-03 | 株式会社オハラ | Optical filter glass ceramic and optical filter |
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