WO2022168895A1 - 結晶化ガラスおよび化学強化ガラス - Google Patents
結晶化ガラスおよび化学強化ガラス Download PDFInfo
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- WO2022168895A1 WO2022168895A1 PCT/JP2022/004141 JP2022004141W WO2022168895A1 WO 2022168895 A1 WO2022168895 A1 WO 2022168895A1 JP 2022004141 W JP2022004141 W JP 2022004141W WO 2022168895 A1 WO2022168895 A1 WO 2022168895A1
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- WO
- WIPO (PCT)
- Prior art keywords
- glass
- sio
- mgo
- less
- residual
- Prior art date
Links
- 239000011521 glass Substances 0.000 title claims abstract description 313
- 239000005345 chemically strengthened glass Substances 0.000 title claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 46
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 42
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000013078 crystal Substances 0.000 claims abstract description 39
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 23
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 22
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 22
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 22
- 229910011255 B2O3 Inorganic materials 0.000 claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 18
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 18
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 15
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 15
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 15
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 15
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 52
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 46
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 33
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 17
- 238000002425 crystallisation Methods 0.000 claims description 17
- 230000008025 crystallization Effects 0.000 claims description 17
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000005341 toughened glass Substances 0.000 claims description 8
- 239000006018 Li-aluminosilicate Substances 0.000 claims description 6
- 238000002834 transmittance Methods 0.000 claims description 6
- 229910017583 La2O Inorganic materials 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003426 chemical strengthening reaction Methods 0.000 description 25
- 239000011734 sodium Substances 0.000 description 22
- 239000000126 substance Substances 0.000 description 19
- 238000005342 ion exchange Methods 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 11
- 239000006059 cover glass Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 229910001415 sodium ion Inorganic materials 0.000 description 10
- 230000008018 melting Effects 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000010426 asphalt Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004031 devitrification Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003991 Rietveld refinement Methods 0.000 description 4
- 239000006103 coloring component Substances 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 150000003841 chloride salts Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000006060 molten glass Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- -1 B 2 O 3 Inorganic materials 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-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
- 238000002441 X-ray diffraction Methods 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
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000006121 base glass Substances 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052912 lithium silicate Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 229910052670 petalite Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910001753 sapphirine Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 229910052644 β-spodumene Inorganic materials 0.000 description 2
- HEZMWWAKWCSUCB-PHDIDXHHSA-N (3R,4R)-3,4-dihydroxycyclohexa-1,5-diene-1-carboxylic acid Chemical compound O[C@@H]1C=CC(C(O)=O)=C[C@H]1O HEZMWWAKWCSUCB-PHDIDXHHSA-N 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 229910018162 SeO2 Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 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
- 239000003513 alkali Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000003280 down draw process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 1
- 229910000174 eucryptite Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- MRVHOJHOBHYHQL-UHFFFAOYSA-M lithium metaphosphate Chemical compound [Li+].[O-]P(=O)=O MRVHOJHOBHYHQL-UHFFFAOYSA-M 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing 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
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 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
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 229910000500 β-quartz Inorganic materials 0.000 description 1
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
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
- C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0054—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing PbO, SnO2, B2O3
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
Definitions
- the present invention relates to crystallized glass and chemically strengthened glass.
- Chemically strengthened glass is used for the cover glass of mobile devices.
- the glass is brought into contact with a molten salt containing alkali metal ions, ion exchange occurs between the alkali metal ions in the glass and the alkali metal ions in the molten salt, and compressive stress is applied to the glass surface. It is made of layers and has excellent strength.
- crystallized glass is stronger than amorphous glass, it is not easy to obtain high strength such as being hard to break even if dropped on the road.
- crystallized glass by including high-strength crystals in the glass, strength higher than that of the original glass (mother glass) can be obtained.
- glass is a brittle material, and if brittle glass remains in the vicinity of high-strength crystals in crystallized glass, cracks that act as fracture starting points are likely to occur in the residual glass, and sufficient strength cannot be obtained. do not have. Further, if the content of crystals is excessively increased in order to increase the strength of the crystallized glass, the transparency may be lowered.
- an object of the present invention is to provide crystallized glass having excellent impact resistance.
- the present invention provides crystallized glass comprising crystals and residual glass, SiO 2 , Al 2 O 3 , B 2 O 3 , P 2 O 5 , MgO, CaO, SrO, BaO, Li 2 O, Na 2 O, K 2 O in terms of mol % on oxide basis in the residual glass , ZrO 2 , TiO 2 , La 2 O 3 , Y 2 O 3 and ZnO content [SiO 2 ], [Al 2 O 3 ], [B 2 O 3 ], [P 2 O 5 ], [MgO], [CaO], [SrO], [BaO], [ Li2O ], [ Na2O ] , [ K2O ], [ ZrO2 ], [ TiO2 ], [ La2O3 ] , [Y 2 O 3 ] and [ZnO], and the Young's modulus parameter ER of the residual glass is 75 or more.
- the present invention is a chemically strengthened glass having a compressive stress layer on its surface, having a surface compressive stress of 200 MPa or more and a compressive stress layer depth of 80 ⁇ m or more, containing crystals and residual glass, and having an oxide standard in the residual glass.
- the Young's modulus parameter ER of the residual glass is crystallized glass of 75 or more, which is calculated based on the following formula.
- the brittleness of the residual glass is controlled to suppress the occurrence of cracks that serve as fracture starting points, and cracks are prevented. It exhibits excellent strength that is difficult to progress.
- amorphous glass and “crystallized glass” are collectively referred to as "glass”.
- amorphous glass refers to glass in which no diffraction peaks indicating crystals are observed by powder X-ray diffraction. “Crystalized glass” is obtained by heat-treating “amorphous glass” to precipitate crystals, and contains crystals.
- the precipitated crystal is identified by, for example, the three-strength line method.
- amorphous glass When amorphous glass is heat-treated to obtain crystallized glass, the amorphous glass before heat treatment is sometimes called "mother glass of crystallized glass".
- chemically strengthened glass refers to glass that has been subjected to chemical strengthening treatment
- chemically strengthened glass refers to glass that has not been subjected to chemical strengthening treatment
- Crystallized glass consists of a crystalline phase and "residual glass".
- "Residual glass” is the amorphous portion in crystallized glass.
- the composition of residual glass can be calculated by estimating the crystallization rate by the Rietveld method and subtracting the amount of crystals from the charged composition of glass raw materials.
- the crystallinity can be calculated from the X-ray diffraction intensity by the Rietveld method.
- the Rietveld method is described in "Crystal Analysis Handbook” Edited by the Crystallographic Society of Japan, “Crystal Analysis Handbook” (Kyoritsu Shuppan, 1999, pp. 492-499).
- the glass composition is represented by mol% based on oxides, and mol% is simply expressed as "%".
- substantially does not contain means that it is below the level of impurities contained in raw materials, etc., that is, it is not added intentionally. Specifically, it is less than 0.1%, for example.
- Light transmittance refers to the average transmittance of light with a wavelength of 380 nm to 780 nm. Also, the "haze value” is measured according to JIS K3761:2000 using a C light source.
- Crystallized glass is obtained by depositing crystals from mother glass, which is amorphous glass, and is composed of crystals and residual glass. Although it is not easy to directly measure the composition of the residual glass, the composition of the residual glass is the composition of the mother glass minus the precipitated crystals.
- the present crystallized glass preferably contains at least one selected from the group consisting of Li 2 O, Na 2 O and K 2 O in the glass composition. As a result, it not only melts easily at a relatively low temperature, but also can be chemically strengthened by ion exchange of alkali ions.
- the present crystallized glass is preferably lithium aluminosilicate glass containing Li2O.
- Lithium aluminosilicate glass is excellent in chemical strengthening properties, so chemical strengthening can achieve even higher strength.
- the lithium aluminosilicate glass preferably contains 55% or more of SiO 2 , 5% or more of Al 2 O 3 , and 5% or more of Li 2 O, for example. With such a composition, high strength can be obtained by chemical strengthening.
- the haze value of the present crystallized glass is preferably 1.0% or less, more preferably 0.4% or less, still more preferably 0.2% or less, and 0.15% or less. Especially preferred. A smaller haze value is more preferable, but if the crystallinity is lowered or the crystal grain size is reduced in order to reduce the haze value, the mechanical strength is lowered. In order to increase the mechanical strength, the haze value at a thickness of 0.7 mm is preferably 0.02% or more, more preferably 0.03% or more.
- the light transmittance of the present crystallized glass is preferably 85% or more, more preferably 87% or more, and even more preferably 90% or more. Due to its high light transmittance, it has good visibility when used as a cover glass for display images of mobile terminals.
- the present crystallized glass preferably has a crystallization rate of 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% or more.
- the crystallization rate is preferably 90% by mass or less, more preferably 85% or less, and even more preferably 80% or less.
- Crystals contained in the crystallized glass include, for example, lithium metaphosphate, lithium metasilicate, cristobalite, ⁇ -spodumene, spodumene solid solution, petalite, ⁇ -quartz, spinel, sapphirine, lithium disilicate, mullite, and ⁇ -eucryptite. (solid solution), zirconia, and the like.
- Crystallized glass containing these crystals tends to have high transparency.
- Lithium phosphate, lithium metasilicate, lithium disilicate, ⁇ -spodumene solid solution, petalite, spinel, sapphirine, or zirconia is particularly preferable among the above-mentioned crystals from the viewpoint of transparency and strength.
- the combination of these crystals and the preferred residual glass composition results in crystallized glass with excellent chemical durability.
- This crystallized glass is obtained by heat-treating and crystallizing the mother glass, which will be explained later.
- Fracture of brittle materials such as glass is basically caused by stress (mainly tensile stress) concentrating on scratches caused by mechanical contact, and cracks extend from the weakest point to break. up to.
- the fracture toughness value of a brittle material is an index that indicates strength as an index that indicates how difficult it is for cracks to propagate.
- Crystallized glass makes it possible to improve strength as a composite by intentionally precipitating crystals in a glass matrix. Specifically, the hardness can be improved by precipitating high-hardness crystals.
- the residual glass which is the matrix, has a low strength and a low fracture toughness value relative to the crystal phase. Cracks basically start from a portion of low strength, that is, the residual glass phase, propagate through the residual glass phase, and lead to breakage. Therefore, the composition of the residual glass greatly contributes to the brittleness of the glass.
- the crystallized glass of the present invention can suppress the occurrence of cracks that act as fracture starting points and exhibits excellent strength.
- chemical strengthening treatment provides even higher strength.
- the transparency can be further improved by appropriately selecting the precipitated crystals.
- the present crystallized glass is characterized by the Young's modulus parameter ER calculated from the composition of the residual glass, which provides high strength.
- the Young's modulus parameter ER of the residual glass is SiO 2 , Al 2 O 3 , B 2 O 3 , P 2 O 5 , MgO, CaO, SrO, BaO, Li 2 in mol % expression based on oxides in the residual glass composition.
- the Young's modulus parameter ER of the residual glass is 75 or more, preferably 80 or more, more preferably 82 or more, still more preferably 83 or more, and even more preferably 85 or more, from the viewpoint of strength.
- the Young's modulus parameter ER of the residual glass in the present crystallized glass is preferably 100 or less, more preferably 95 or less, even more preferably 92 or less.
- the Young's modulus parameter ER is a parameter derived from the composition analysis results of the residual glass phase, the ion weight ratio of various constituent oxides, and the bond dissociation energy, and has a positive correlation with the Young's modulus E. As described above, the higher the Young's modulus E, the higher the fracture toughness value KIC. Therefore, by increasing the Young's modulus parameter ER, the fracture toughness value can be increased to suppress the occurrence of cracks that serve as fracture starting points, and the strength can be improved. can.
- ⁇ f ⁇ (2 ⁇ E/ ⁇ c) is the fracture surface energy
- E the Young's modulus
- c the crack length. Since it is very difficult to change the fracture surface energy significantly by changing the composition of the glass, controlling the Young's modulus parameter ER, which has a positive correlation with the Young's modulus, is very effective in improving the fracture stress. be.
- the Young's modulus parameter ER can be adjusted by adjusting the content of each composition constituting the above formula and the crystallization conditions in the residual glass. Specifically, for example, by devising the heat treatment conditions, the precipitated crystal species are controlled, and a high Young's modulus component is left in the residual glass. In particular, the ER can be increased by leaving components such as Al 2 O 3 , B 2 O 3 , MgO, Li 2 O, ZrO 2 and TiO 2 in the residual glass phase. On the other hand, the ER decreases when the crystallization conditions are such that large amounts of P2O5, Na2O , and K2O remain in the residual glass.
- the residual glass is 30-70% SiO2 , 5-30% Al 2 O 3 , 0-15 % of B2O3 , 0-10 % of P2O5 ; 0-40% MgO, Li 2 O from 0 to 25%; 0-15% Na 2 O; It preferably contains 0-15% ZrO 2 .
- a preferred composition of the residual glass is described below.
- SiO2 is an essential component of the crystallized glass of the present invention and is also contained in the residual glass.
- SiO 2 in the residual glass is 30% or more, the weather resistance of the residual glass is improved, and the weather resistance of the crystallized glass is also improved, which is preferable. More preferably 35% or more, still more preferably 40% or more.
- it is preferably 70% or less. More preferably 67.5% or less, still more preferably 65% or less.
- Al 2 O 3 is an essential component of the crystallized glass of the present invention and is also contained in residual glass. If the content of Al 2 O 3 in the residual glass is 5% or more, the mechanical properties of the residual glass can be improved. Moreover, not only is the chemical durability improved, but it becomes easier to carry out chemical strengthening. More preferably 7.5%, still more preferably 10% or more. Also, in order to lower the viscosity of the residual glass composition and facilitate bending of the glass, the content is preferably 30% or less. More preferably 27.5% or less, still more preferably 25% or less.
- B 2 O 3 is an optional component that lowers the viscosity of the residual glass phase and lowers the molding viscosity of the crystallized glass, and is also a component that improves the mechanical properties.
- the content is preferably 15% or less, more preferably 12.0%. 5% or less, more preferably 11% or less, particularly preferably 10% or less, and most preferably 5% or less.
- P 2 O 5 is a component that functions as a nucleating agent for crystallized glass. It is also a component that improves the chemical strengthening ability and is an optional component. From the viewpoint of chemical durability and mechanical properties of the residual glass, the content of P 2 O 5 contained in the residual glass is preferably 10% or less. It is more preferably 9% or less, still more preferably 8% or less, and even more preferably 7% or less.
- MgO is an optional component of crystallized glass and residual glass. 40% or less is preferable from the viewpoint of polishing processability and chemical durability of crystallized glass. More preferably 37.5% or less, still more preferably 35% or less. From the viewpoint of bending workability, the content is preferably 1% or more, more preferably 2% or more, and still more preferably 4% or more.
- Li 2 O is an optional component of crystallized glass. If the content of Li 2 O in the residual glass is 0.1% or more, the Young's modulus of the residual glass can be improved. More preferably 0.15% or more, still more preferably 0.2% or more. From the viewpoint of chemical durability of the residual glass phase, it is preferably 25% or less. More preferably 22.5% or less, still more preferably 20% or less.
- Na 2 O is a component that reduces the viscosity of residual glass and is an optional component. This effect can be obtained if the content of Na 2 O in the residual glass is 0.1% or more. More preferably 0.2% or more, still more preferably 0.3% or more, still more preferably 0.5% or more. Further, from the viewpoint of the mechanical properties and chemical durability of the residual glass, the content of Na 2 O in the residual glass is preferably 10% or less. More preferably 7.5% or less, still more preferably 5% or less.
- ZrO 2 is a component that not only improves the mechanical properties of the residual glass, but also significantly improves the chemical durability, and is an optional component.
- ZrO 2 in the residual glass is preferably 0.1% or more, more preferably 1% or more, and still more preferably 2% or more. From the viewpoint of forming viscosity of the glass, the content of ZrO 2 in the residual glass is preferably 15% or less. It is more preferably 12.5% or less, still more preferably 10% or less.
- K 2 O is a component that can reduce the viscosity of residual glass and is an optional component.
- K 2 O is preferably 10% or less from the viewpoint of chemical durability of residual glass. More preferably 7.5% or less, still more preferably 5% or less.
- All of CaO, SrO, and BaO are components that lower the viscosity of glass, components that enhance moldability, and are optional components.
- CaO When CaO is contained in the residual glass, its content is preferably 0.5% or more, more preferably 1% or more. From the viewpoint of glass brittleness and chemical strengthening properties, the content of CaO in the residual glass is preferably 5% or less, more preferably 3% or less, and even more preferably 2% or less.
- the residual glass contains SrO
- its content is preferably 0.5% or more, more preferably 1% or more.
- the content of SrO in the residual glass is preferably 10% or less, more preferably 5% or less.
- the residual glass contains BaO
- its content is preferably 0.5% or more, more preferably 1% or more.
- the content of BaO in the residual glass is preferably 10% or less, more preferably 5% or less.
- TiO 2 in the residual glass is preferably 0% or more, more preferably 0.1% or more, and still more preferably 1% or more.
- the content of TiO 2 in the residual glass is preferably 15% or less, more preferably 13% or less, and even more preferably 12% or less.
- MgO , CaO , SrO, BaO, Li 2 O, Na 2 O and K 2 O is 0. It is preferably 45 or more, more preferably 0.48 or more, and still more preferably 0.50 or more.
- the upper limit is not particularly limited, it is preferably 0.80 or less, more preferably 0.70 or less, and still more preferably 0.65 or less from the viewpoint of the chemical durability of the glass.
- Al 2 O 3 / ( SiO2 + Al2O3 + B2O3 + P2O5 ) is preferably 0.08 or more, more preferably 0.09 or more, and still more preferably 0.10 or more.
- the upper limit is not particularly limited, it is preferably 0.31 or less, more preferably 0.30 or less, and still more preferably 0.29 or less from the viewpoint of glass moldability and chemical durability. be.
- the ratio Al2O3 / SiO2 of Al2O3 to SiO2 in the residual glass of the present crystallized glass is preferably 0.1 or more , more preferably. is 0.13 or more, more preferably 0.15 or more.
- the upper limit is not particularly limited, it is preferably 0.6 or less, more preferably 0.5 or less, and still more preferably 0.45 or less from the viewpoint of glass moldability and chemical durability. be.
- composition of the residual glass The following two examples are given as embodiments of the composition of the residual glass.
- the total amount of SiO 2 , Al 2 O 3 , B 2 O 3 and P 2 O 5 contained in the composition of the residual glass is 68% or more in terms of mol% based on oxides.
- Composition [Residual glass composition Embodiment 2] The total amount of SiO 2 , Al 2 O 3 , B 2 O 3 and P 2 O 5 contained in the composition of the residual glass is 60% or less in terms of mol% based on oxides. and a parameter P representing an ion filling rate, which will be described later, is 0.520 or more and 0.570 or less.
- the total amount of SiO 2 , Al 2 O 3 , B 2 O 3 and P 2 O 5 contained in the composition of the residual glass is 68% or more in terms of mol% based on oxides.
- Composition In Embodiment 1 the total amount of SiO 2 , Al 2 O 3 , B 2 O 3 and P 2 O 5 contained in the composition of the residual glass is 68% or more, preferably 69% or more, more preferably 70%. % or more.
- An embodiment in which the total amount of SiO 2 , Al 2 O 3 , B 2 O 3 and P 2 O 5 is 68% or more, so that the crystallized glass is not only excellent in chemical durability but also excellent in strength.
- the total amount of SiO 2 , Al 2 O 3 , B 2 O 3 and P 2 O 5 is preferably, for example, 90% or less, more preferably 89%, from the viewpoint of formability after crystallization. 88% or less, more preferably 88% or less.
- the parameter P in this specification is a parameter representing the ion filling rate of constituent elements of the residual glass, and affects the strength characteristics of the glass.
- Parameter P is SiO 2 , Al 2 O 3 , B 2 O 3 , P 2 O 5 , MgO, CaO, SrO, BaO, Li 2 O, Na 2 O in mol % on oxide basis in residual glass composition.
- the parameter P is preferably 0.495 or more, more preferably 0.497 or more, still more preferably 0.498 or more, and particularly preferably 0.500 or more.
- the Young's modulus of the residual glass can be increased and the strength of the glass can be improved.
- the parameter P is preferably 0.535 or less, more preferably 0.530 or less, and even more preferably 0.525 or less from the viewpoint of stability such as glass durability.
- the parameter P is preferably 0.495 or more, more preferably 0.496 or more, still more preferably 0.497 or more, from the viewpoint of the mechanical properties of the glass.
- the parameter P can be adjusted by adjusting the content of each composition constituting the above formula and the crystallization conditions in the residual glass. Specifically, for example, by controlling the crystallization conditions, components such as Al 2 O 3 , B 2 O 3 , and ZrO 2 are left in the residual glass, and crystals mainly composed of other components are deposited. P rises. On the other hand, when the residual glass contains a large amount of components such as SiO 2 , Na 2 O, or K 2 O, P decreases.
- the total amount of SiO 2 , Al 2 O 3 , B 2 O 3 and P 2 O 5 contained in the composition of the residual glass is 60% or less in terms of mol% based on oxides. and a parameter P representing an ion filling rate , which will be described later , is 0.520 or more and 0.570 or less.
- the total amount of P 2 O 5 is 60% or less, preferably 58% or less, more preferably 56% or less.
- the Young's modulus of residual glass can be improved.
- the total amount of SiO 2 , Al 2 O 3 , B 2 O 3 and P 2 O 5 is preferably 30% or more, more preferably 32%, from the viewpoint of chemical durability. or above, more preferably 34% or above.
- the parameter P is 0.520 or more, preferably 0.523 or more, more preferably 0.525 or more from the viewpoint of the mechanical properties of the glass.
- the parameter P is 0.570 or less, preferably 0.560 or less, more preferably 0.555 or less, from the standpoint of formability and workability after glass crystallization.
- the mother glass of the crystallized glass of the present invention is not particularly limited, it is preferably lithium aluminosilicate glass. That is, it is preferable to contain SiO 2 , Al 2 O 3 and Li 2 O as main components of the base glass. Since the mother glass is lithium aluminosilicate glass, high strength can be obtained by chemically strengthening the glass by ion exchange treatment.
- the mother composition of the present crystallized glass preferably has the following composition expressed in mol% based on oxides. SiO2 30-80% Al 2 O 3 3-35% MgO 0-35% Li2O 0-30 % Na2O 0-10% K2O 0-3% ZrO2 0-10% Preferred compositions are described below.
- SiO2 is a component that constitutes the glass network. It is also a component that increases chemical durability.
- the content of SiO 2 is preferably 30% or more, more preferably 32% or more, even more preferably 35% or more.
- the content of SiO 2 is preferably 80% or less, more preferably 77% or less, even more preferably 75% or less.
- Al 2 O 3 is a component effective not only for improving the mechanical properties of the glass, but also for improving the ion exchangeability during chemical strengthening and increasing the surface compressive stress after strengthening.
- the content of Al 2 O 3 is preferably 3% or more, more preferably 4% or more, and even more preferably 5% or more.
- the content of Al 2 O 3 is preferably 35% or less, more preferably 32% or less, and even more preferably 30% or less, in order to improve meltability.
- Li 2 O is a component that not only improves the melting properties of the glass, but also improves the mechanical properties. Chemical strengthening is also possible. Li 2 O is an optional component, but when it is included, the content is preferably 1% or more, more preferably 3% or more, in order to increase the melting properties of the glass and the compressive stress layer depth DOL after chemical strengthening. Preferably, 5% or more is more preferable. In order to suppress devitrification during glass production, the Li 2 O content is preferably 30% or less, more preferably 27% or less, and even more preferably 25% or less.
- Na 2 O is a component that improves the melting properties of glass and is also a component that enables chemical strengthening.
- Na 2 O is an optional component, but when it is included, the content is preferably 0.1% or more, more preferably 0.5% or more, and even more preferably 1.0% or more. In order to maintain chemical durability, the content of Na 2 O is preferably 10% or less, more preferably 8% or less, and even more preferably 6% or less.
- K 2 O is a component that improves the meltability of glass, and is a component that promotes ion exchange during chemical strengthening.
- K 2 O is an optional component, and when it is included, its content is preferably 0.5% or more, more preferably 1% or more.
- the content of K 2 O is preferably 3% or less, more preferably 2% or less, and even more preferably 1% or less in order to maintain chemical durability.
- CaO, SrO, and BaO are all components that increase the meltability of glass, but tend to reduce ion exchange performance.
- MgO, CaO, SrO and BaO are optional components, and the total content (MgO+CaO+SrO+BaO) when at least one of them is contained is preferably 0.1% or more, more preferably 0.5% or more.
- MgO is a component that improves the melting properties, a component that improves the mechanical properties of the glass, and is an optional component.
- the content is preferably 1% or more, more preferably 2% or more.
- the MgO content is preferably 37% or less, more preferably 35% or less, and even more preferably 33% or less.
- the content is preferably 0.5% or more, more preferably 1% or more.
- the content of CaO is preferably 5% or less, more preferably 3% or less, in order to improve the ion exchange performance.
- the content is preferably 0.5% or more, more preferably 1% or more.
- the SrO content is preferably 5% or less, more preferably 3% or less, in order to improve the ion exchange performance.
- the content When containing BaO, the content is preferably 0.5% or more, more preferably 1% or more.
- the content of BaO is preferably 5% or less, more preferably 1% or less, in order to improve the ion exchange performance.
- ZnO is a component that improves the meltability of glass and may be contained.
- the content is preferably 0.2% or more, more preferably 0.5% or more.
- the ZnO content is preferably 5% or less, more preferably 3% or less.
- TiO 2 is a component that improves the mechanical properties of the glass and increases the surface compressive stress due to ion exchange, and may be contained.
- the content is preferably 0.1% or more, more preferably 1% or more.
- the content of TiO 2 is preferably 12% or less, more preferably 10% or less, in order to suppress devitrification during melting. In order to avoid coloration of the glass, it is preferably 5% or less, more preferably 3% or less, still more preferably 1% or less, and more preferably substantially free.
- ZrO 2 is a component that improves the mechanical properties of the glass and increases the surface compressive stress during chemical strengthening, and is an optional component.
- the content of ZrO 2 is preferably 0.5% or more, more preferably 1% or more. In order to suppress devitrification during melting, it is preferably 13% or less, more preferably 12% or less, and even more preferably 10% or less.
- a coloring component When coloring the glass, a coloring component may be added within a range that does not impede the achievement of the desired chemical strengthening properties.
- coloring components include Co3O4 , MnO2 , Fe2O3 , NiO , CuO , Cr2O3 , V2O5 , Bi2O3 , SeO2 , CeO2 , Er2O3 , Nd2O3 is mentioned . These may be used alone or in combination.
- the total content of coloring components is preferably 7% or less. Thereby, devitrification of the glass can be suppressed.
- the content of the coloring component is more preferably 5% or less, still more preferably 3% or less, and particularly preferably 1% or less. When it is desired to increase the visible light transmittance of the glass, it is preferred that these components are not substantially contained.
- SO 3 may be appropriately contained as clarifiers and the like in melting the glass.
- 2 O 3 is preferably not substantially contained.
- Sb 2 O 3 is contained, it is preferably 0.3% or less, more preferably 0.1% or less, and most preferably not substantially contained.
- the present crystallized glass is produced by heat-treating the mother glass.
- the present crystallized glass is preferably chemically strengthened.
- Amorphous glass can be produced, for example, by the following method.
- the manufacturing method described below is an example in the case of manufacturing plate-shaped chemically strengthened glass.
- the raw materials for glass are mixed so that glass with the desired composition is obtained, and then heated and melted in a glass melting kiln. Thereafter, the molten glass is homogenized by bubbling, stirring, addition of a clarifier, etc., formed into a glass plate having a predetermined thickness by a known forming method, and slowly cooled. Alternatively, the molten glass may be formed into a block, cooled slowly, and then cut into a plate.
- Forming methods for sheet glass include, for example, the float method, press method, fusion method, and down-draw method.
- Crystallized glass is obtained by heat-treating the base glass obtained by the above procedure.
- the heat treatment is preferably a two-stage heat treatment in which the temperature is raised from room temperature to a first treatment temperature and held for a certain period of time, and then held for a certain period of time at a second treatment temperature that is higher than the first treatment temperature. .
- the first treatment temperature is preferably a temperature range in which the crystal nucleation rate increases in the glass composition
- the second treatment temperature is a temperature range in which the crystal growth rate increases in the glass composition. is preferred.
- the first treatment temperature is, for example, 450° C. to 700° C.
- the second treatment temperature is, for example, 600° C. to 800° C., and after holding at the first treatment temperature for 1 hour to 6 hours, the second treatment temperature for 1 to 6 hours.
- the crystallized glass obtained by the above procedure is ground and polished as necessary to form a crystallized glass plate.
- a crystallized glass plate is used after being chemically strengthened, it is preferable to perform cutting or chamfering before the chemical strengthening treatment, because the subsequent chemical strengthening treatment forms a compressive stress layer on the end face.
- the crystallized glass of the present invention may be subjected to chemical strengthening treatment.
- the glass is brought into contact with a metal salt by a method such as immersion in a melt of a metal salt (eg, potassium nitrate) containing metal ions with a large ionic radius (typically, Na ions or K ions).
- a metal salt eg, potassium nitrate
- metal ions with a large ionic radius typically, Na ions or K ions.
- the small ionic radius metal ions (typically Na ions or Li ions) in the glass are large ionic radius metal ions, typically Na ions or K ions for Li ions, This is a process of replacing Na ions with K ions).
- Li-Na exchange which exchanges Li ions in the glass with Na ions.
- Na--K exchange in which Na ions in the glass are exchanged for K ions.
- molten salts for chemical strengthening include nitrates, sulfates, carbonates, and chlorides.
- nitrates include lithium nitrate, sodium nitrate, potassium nitrate, cesium nitrate, and silver nitrate.
- Sulfates include, for example, lithium sulfate, sodium sulfate, potassium sulfate, cesium sulfate, and silver sulfate.
- Carbonates include, for example, lithium carbonate, sodium carbonate, potassium carbonate, and the like.
- chlorides include lithium chloride, sodium chloride, potassium chloride, cesium chloride, and silver chloride. These molten salts may be used alone, or may be used in combination.
- the time and temperature should be appropriately selected in consideration of the glass composition and the type of molten salt.
- This tempered glass is preferably obtained by, for example, the following two-stage chemical strengthening treatment.
- this crystallized glass is immersed in a metal salt containing Na ions (eg, sodium nitrate) at about 350-500° C. for about 0.1-10 hours.
- a metal salt containing Na ions eg, sodium nitrate
- ion exchange occurs between Li ions in the crystallized glass and Na ions in the metal salt, and, for example, a compressive stress layer having a surface compressive stress value of 200 MPa or more and a compressive stress layer depth of 80 ⁇ m or more can be formed.
- the chemically strengthened glass obtained by chemically strengthening the present crystallized glass (this tempered glass) preferably has a surface compressive stress value of 200 MPa or more, more preferably 250 MPa or more.
- the surface compressive stress value is 200 MPa or more, it is difficult to crack due to deformation such as bending.
- the present tempered glass preferably has a compressive stress layer depth DOL of 50 ⁇ m or more, more preferably 80 ⁇ m or more, and even more preferably 100 ⁇ m or more. Since the DOL is 50 ⁇ m or more, it is difficult to crack even when the surface is scratched.
- the compressive stress value CS50 at a depth of 30 ⁇ m is preferably 100 MPa or more, more preferably 140 MPa or more, and even more preferably 160 MPa or more.
- the asphalt drop strength can be evaluated by the following asphalt drop test.
- a glass plate (120 mm ⁇ 60 mm ⁇ 0.8 mm) to be evaluated is used as a smartphone cover glass, attached to a housing that simulates a smartphone, and dropped onto a flat asphalt surface.
- the total mass of the glass plate and the housing shall be approximately 140 g.
- This test is regarded as one set, and 10 sets are repeated, and the average value of the heights when it breaks is taken as the "drop height".
- the drop height of the tempered glass in the asphalt drop test is preferably 100 cm or more.
- This tempered glass is also useful as a cover glass for electronic devices such as mobile phones and smartphones. Furthermore, it is also useful for cover glass of electronic devices such as televisions, personal computers, and touch panels that are not intended for portability, walls of elevators, walls of buildings such as houses and buildings (full-surface displays). It is also useful as building materials such as window glass, table tops, interiors of automobiles, airplanes, etc., cover glasses thereof, and housings having curved surfaces.
- this tempered glass has good high-frequency characteristics, it is suitable as a cover glass for high-frequency communication equipment.
- the resulting molten glass was poured into a mold, held at the temperature of the glass transition point for 1 hour, and then cooled to room temperature at a rate of 0.5°C/min to obtain a glass block.
- Crystallized glass can be obtained by heat-treating the glass having the composition shown in Table 1.
- Table 1 blanks indicate non-containing.
- the upper row (heat treatment 1) is the nucleation treatment condition
- the lower row (heat treatment 2) is the crystal growth treatment condition.
- the sample was held at 650° C. for 2 hours and then at 850° C. for 2 hours.
- Examples 1 and 2 are comparative examples and Examples 3-9 are working examples.
- a blank column indicates that the obtained glass block was processed into a size of 50 mm ⁇ 50 mm ⁇ 1.5 mm, and then heat treatment for crystallization was not performed.
- NWF total amount of SiO2 , Al2O3 , B2O3 and P2O5 in the residual glass
- Al/ NWF SiO2 , Al2O3 , B2O3 and P2O in the residual glass 5
- Al/Si Ratio of Al 2 O 3 content to SiO 2 content in residual glass
- NWM MgO , CaO, SrO, BaO in residual glass , Li 2 O, Na 2 O and K 2 O
- Young's modulus parameter ER SiO 2 , Al 2 O 3 , B 2 O 3 , P 2 O 5 , MgO, expressed in mol % on oxide basis in residual glass , CaO, SrO, BaO, Li 2 O, Na 2 O, K 2 O, ZrO 2 , TiO 2 , La 2 O 3 , Y 2 O 3 and ZnO content [SiO 2 ], [Al 2 O3 ] , [ B2O3 ]
- the Young's modulus parameter ER of the residual glass is 75 or more, and the brittleness of the residual glass is controlled to generate cracks that serve as fracture starting points and cracks. Since the progress of the crack can be suppressed, the strength is superior to that of the comparative example.
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Abstract
Description
前記残留ガラスにおける酸化物基準のモル%表示による、SiO2、Al2O3、B2O3、P2O5、MgO、CaO、SrO、BaO、Li2O、Na2O、K2O、ZrO2、TiO2、La2O3、Y2O3及びZnOの各成分の含有量[SiO2]、[Al2O3]、[B2O3]、[P2O5]、[MgO]、[CaO]、[SrO]、[BaO]、[Li2O]、[Na2O]、[K2O]、[ZrO2]、[TiO2]、[La2O3]、[Y2O3]及び[ZnO]を用いて下記式に基づき算出される、前記残留ガラスのヤング率パラメータERが75以上である結晶化ガラスを提供する。
ER=62.2×[SiO2]+134.9×[Al2O3]+121.7×[B2O3]+33.0×[P2O5]+72.6×[MgO]+121.5×[CaO]+43.7×[SrO]+38.6×[BaO]+84.0×[Li2O]+26.2×[Na2O]+17.8×[K2O]+156.8×[ZrO2]+154.3×[TiO2]+74.7×[La2O3]+80.3×[Y2O3]+54.3×[ZnO]
ER=62.2×[SiO2]+134.9×[Al2O3]+121.7×[B2O3]+33.0×[P2O5]+72.6×[MgO]+121.5×[CaO]+43.7×[SrO]+38.6×[BaO]+84.0×[Li2O]+26.2×[Na2O]+17.8×[K2O]+156.8×[ZrO2]+154.3×[TiO2]+74.7×[La2O3]+80.3×[Y2O3]+54.3×[ZnO]
結晶化ガラスは、非晶質ガラスである母ガラスから結晶が析出したものであって、結晶と残留ガラスとで構成される。残留ガラスの組成を直接測定することは容易ではないが、残留ガラスの組成は、母ガラスの組成から析出した結晶を除いた組成になる。
本結晶化ガラスは、残留ガラスの組成から算出されるヤング率パラメータERに特徴を有し、それによって高い強度が得られる。残留ガラスのヤング率パラメータERは、残留ガラス組成における酸化物基準のモル%表示による、SiO2、Al2O3、B2O3、P2O5、MgO、CaO、SrO、BaO、Li2O、Na2O、K2O、ZrO2、TiO2、La2O3、Y2O3及びZnOの各成分の含有量[SiO2]、[Al2O3]、[B2O3]、[P2O5]、[MgO]、[CaO]、[SrO]、[BaO]、[Li2O]、[Na2O]、[K2O]、[ZrO2]、[TiO2]、[La2O3]、[Y2O3]及び[ZnO]を用いて下記式に基づき算出される。
ER=62.2×[SiO2]+134.9×[Al2O3]+121.7×[B2O3]+33.0×[P2O5]+72.6×[MgO]+121.5×[CaO]+43.7×[SrO]+38.6×[BaO]+84.0×[Li2O]+26.2×[Na2O]+17.8×[K2O]+156.8×[ZrO2]+154.3×[TiO2]+74.7×[La2O3]+80.3×[Y2O3]+54.3×[ZnO]
前記式において、γは破壊表面エネルギーであり、Eはヤング率、cはクラックの長さを示す。破壊表面エネルギーはガラスの組成変更で大きく変更することは非常に困難であるため、ヤング率と正の相関を有するヤング率パラメータERをコントロールすることが、破壊応力を向上させるために非常に有効である。
SiO2を30~70%、
Al2O3を5~30%、
B2O3を0~15%、
P2O5を0~10%、
MgOを0~40%、
Li2Oを0~25%、
Na2Oを0~15%、
ZrO2を0~15%、含有することが好ましい。
以下、前記した残留ガラスの好ましい組成を説明する。
[残留ガラス組成 実施形態1]残留ガラスの組成に含まれる、SiO2、Al2O3、B2O3およびP2O5の総量が、酸化物基準のモル%表示で68%以上である組成
[残留ガラス組成 実施形態2]残留ガラスの組成に含まれる、SiO2、Al2O3、B2O3およびP2O5の総量が、酸化物基準のモル%表示で60%以下であり、かつ、後述するイオン充填率を表すパラメータPが0.520以上0.570以下である組成
以下、各実施形態について説明する。
実施形態1において、残留ガラスの組成に含まれる、SiO2、Al2O3、B2O3およびP2O5の総量は68%以上であり、好ましくは69%以上、より好ましくは70%以上である。SiO2、Al2O3、B2O3およびP2O5の総量が68%以上であることにより、化学的耐久性に優れるだけでなく、強度面でも優れた結晶化ガラスとなる実施形態1において、SiO2、Al2O3、B2O3およびP2O5の総量は、結晶化後の成形性の点から、例えば、90%以下であることが好ましく、より好ましくは89%以下、さらに好ましくは88%以下である。
P=0.458×[SiO2]+0.515×[Al2O3]+0.735×[B2O3]+0.586×[P2O5]+0.567×[MgO]+0.675×[CaO]+0.481×[SrO]+0.489×[BaO]+0.539×[Li2O]+0.410×[Na2O]+0.463×[K2O]+0.701×[ZrO2]+0.762×[TiO2]+0.567×[La2O3]+0.552×[Y2O3]+0.544×[ZnO]
実施形態2において、残留ガラスの組成に含まれる、SiO2、Al2O3、B2O3およびP2O5の総量は60%以下であり、好ましくは58%以下、より好ましくは56%以下である。SiO2、Al2O3、B2O3およびP2O5の総量が60%以下であることにより、残留ガラスのヤング率を向上させることができる。実施形態2において、SiO2、Al2O3、B2O3およびP2O5の総量は、化学的耐久性の点から、例えば、30%以上であることが好ましく、より好ましくは32%以上、さらに好ましくは34%以上である。
本発明の結晶化ガラスの母ガラスは、特に限定されないが、リチウムアルミノシリケートガラスであることが好ましい。すなわち、母ガラスの主要成分としてSiO2、Al2O3、Li2Oを含有することが好ましい。母ガラスがリチウムアルミノシリケートガラスであることにより、イオン交換処理によって化学強化することにより高い強度が得られる。
SiO2 30~80%
Al2O3 3~35%
MgO 0~35%
Li2O 0~30%
Na2O 0~10%
K2O 0~3%
ZrO2 0~10%
以下、好ましい組成を説明する。
本結晶化ガラスは、上記の母ガラスを加熱処理して製造する。
本結晶化ガラスは化学強化処理することが好ましい。
非晶質ガラスは、例えば、以下の方法で製造できる。なお、以下に記す製造方法は、板状の化学強化ガラスを製造する場合の例である。
上記の手順で得られた母ガラスを加熱処理することで結晶化ガラスが得られる。
本発明の結晶化ガラスは化学強化処理を施してもよい。化学強化処理は、大きなイオン半径の金属イオン(典型的には、NaイオンまたはKイオン)を含む金属塩(例えば、硝酸カリウム)の融液に浸漬する等の方法で、ガラスを金属塩に接触させることにより、ガラス中の小さなイオン半径の金属イオン(典型的には、NaイオンまたはLiイオン)が大きなイオン半径の金属イオン典型的には、Liイオンに対してはNaイオンまたはKイオンであり、Naイオンに対してはKイオン)と置換させる処理である。
(アスファルト落下試験)
評価対象のガラス板(120mm×60mm×0.8mm)をスマートフォンのカバーガラスに見立てて、スマートフォンを模擬した筐体に取り付けて、平坦なアスファルト面上に落下する。ガラス板と筐体を合わせた質量は約140gとする。
高さ30cmから試験を開始し、化学強化ガラス板が割れなかったら、高さを10cm高くして落下させる試験を繰り返し、割れたときの高さ[単位:cm]を記録する。この試験を1セットとして、10セット繰り返し、割れたときの高さの平均値を「落下高さ」とする。本強化ガラスのアスファルト落下試験における落下高さは、100cm以上が好ましい。
表1に酸化物基準のモル%表示で示したガラス組成となるようにガラス原料を調合し、800gのガラスが得られるように秤量した。ついで、混合したガラス原料を白金るつぼに入れ、1600℃の電気炉に投入して5時間程度溶融し、脱泡し、均質化した。
ガラス1~9について、得られたガラスブロックを50mm×50mm×1.5mmに加工してから、表2及び表3に記載した条件で熱処理して結晶化ガラスを得た。得られた結晶化ガラスを加工し、鏡面研磨して厚さtが0.7mmの結晶化ガラス板を得た。
結晶化ガラスの一部を粉砕して、以下の条件で粉末X線回折を測定し、析出結晶を同定した。また、得られた回折強度からリートベルト法で結晶化率を算出した。結果を表2及び3に示す。酸化物基準のモル%表示による残留ガラス組成を表2及び3のSiO2~Y2O3欄に示す。表2及び3の残留ガラス組成の欄及び結晶の欄において、空欄は非含有であることを表す。
測定装置:リガク社製 SmartLab
使用X線:CuKα線
測定範囲:2θ=10°~80°
スピード:10°/分
ステップ:0.02°
NWF:残留ガラス中のSiO2、Al2O3、B2O3およびP2O5の総量
Al/NWF:残留ガラス中の、SiO2、Al2O3、B2O3およびP2O5の総量に対するAl2O3の含有量の比率
Al/Si:残留ガラス中の、SiO2の含有量に対するAl2O3の含有量の比率NWM:残留ガラス中のMgO、CaO、SrO、BaO、Li2O、Na2OおよびK2Oの総量
ヤング率パラメータER:残留ガラスにおける酸化物基準のモル%表示による、SiO2、Al2O3、B2O3、P2O5、MgO、CaO、SrO、BaO、Li2O、Na2O、K2O、ZrO2、TiO2、La2O3、Y2O3及びZnOの各成分の含有量[SiO2]、[Al2O3]、[B2O3]、[P2O5]、[MgO]、[CaO]、[SrO]、[BaO]、[Li2O]、[Na2O]、[K2O]、[ZrO2]、[TiO2]、[La2O3]、[Y2O3]及び[ZnO]を用いて下記式に基づき算出される、ヤング率パラメータER。
ER=62.2×[SiO2]+134.9×[Al2O3]+121.7×[B2O3]+33.0×[P2O5]+72.6×[MgO]+121.5×[CaO]+43.7×[SrO]+38.6×[BaO]+84.0×[Li2O]+26.2×[Na2O]+17.8×[K2O]+156.8×[ZrO2]+154.3×[TiO2]+74.7×[La2O3]+80.3×[Y2O3]+54.3×[ZnO]
パラメータP:残留ガラスにおける酸化物基準のモル%表示による、SiO2、Al2O3、B2O3、P2O5、MgO、CaO、SrO、BaO、Li2O、Na2O、K2O、ZrO2、TiO2、La2O3、Y2O3及びZnOの各成分の含有量[SiO2]、[Al2O3]、[B2O3]、[P2O5]、[MgO]、[CaO]、[SrO]、[BaO]、[Li2O]、[Na2O]、[K2O]、[ZrO2]、[TiO2]、[La2O3]、[Y2O3]及び[ZnO]を用いて下記式に基づき算出されるパラメータP。
P=0.458×[SiO2]+0.515×[Al2O3]+0.735×[B2O3]+0.586×[P2O5]+0.567×[MgO]+0.675×[CaO]+0.481×[SrO]+0.489×[BaO]+0.539×[Li2O]+0.410×[Na2O]+0.463×[K2O]+0.701×[ZrO2]+0.762×[TiO2]+0.567×[La2O3]+0.552×[Y2O3]+0.544×[ZnO]
Claims (12)
- 結晶と、残留ガラスと、を含む結晶化ガラスであって、
前記残留ガラスにおける酸化物基準のモル%表示による、SiO2、Al2O3、B2O3、P2O5、MgO、CaO、SrO、BaO、Li2O、Na2O、K2O、ZrO2、TiO2、La2O3、Y2O3及びZnOの各成分の含有量[SiO2]、[Al2O3]、[B2O3]、[P2O5]、[MgO]、[CaO]、[SrO]、[BaO]、[Li2O]、[Na2O]、[K2O]、[ZrO2]、[TiO2]、[La2O3]、[Y2O3]及び[ZnO]を用いて下記式に基づき算出される、前記残留ガラスのヤング率パラメータERが75以上である結晶化ガラス。
ER=62.2×[SiO2]+134.9×[Al2O3]+121.7×[B2O3]+33.0×[P2O5]+72.6×[MgO]+121.5×[CaO]+43.7×[SrO]+38.6×[BaO]+84.0×[Li2O]+26.2×[Na2O]+17.8×[K2O]+156.8×[ZrO2]+154.3×[TiO2]+74.7×[La2O3]+80.3×[Y2O3]+54.3×[ZnO] - 前記残留ガラスの組成が、酸化物基準のモル%表示で、
30~70%をSiO2、
5~30%をAl2O3、
0~15%をB2O3、
0~10%をP2O5、
0~40%をMgO、
0~25%をLi2O、
0~15%をNa2O、
0~15%をZrO2、含有する請求項1に記載の結晶化ガラス。 - 結晶化率が10~90質量%である請求項1または2に記載の結晶化ガラス。
- 前記残留ガラスの組成に含まれる、SiO2、Al2O3、B2O3およびP2O5の総量が、酸化物基準のモル%表示で68%以上であることを特徴とする、請求項1~3のいずれか1項に記載の結晶化ガラス。
- 前記残留ガラスにおける酸化物基準のモル%表示による、SiO2、Al2O3、B2O3、P2O5、MgO、CaO、SrO、BaO、Li2O、Na2O、K2O、ZrO2、TiO2、La2O3、Y2O3及びZnOの各成分の含有量[SiO2]、[Al2O3]、[B2O3]、[P2O5]、[MgO]、[CaO]、[SrO]、[BaO]、[Li2O]、[Na2O]、[K2O]、[ZrO2]、[TiO2]、[La2O3]、[Y2O3]及び[ZnO]を用いて下記式に基づき算出されるパラメータPが0.495以上0.535以下である請求項1~4のいずれか1項に記載の結晶化ガラス。
P=0.458×[SiO2]+0.515×[Al2O3]+0.735×[B2O3]+0.586×[P2O5]+0.567×[MgO]+0.675×[CaO]+0.481×[SrO]+0.489×[BaO]+0.539×[Li2O]+0.410×[Na2O]+0.463×[K2O]+0.701×[ZrO2]+0.762×[TiO2]+0.567×[La2O3]+0.552×[Y2O3]+0.544×[ZnO] - 前記残留ガラスの組成に含まれる、SiO2、Al2O3、B2O3およびP2O5の総量が、酸化物基準のモル%表示で60%以下であり、かつ、
前記残留ガラスにおける酸化物基準のモル%表示による、SiO2、Al2O3、B2O3、P2O5、MgO、CaO、SrO、BaO、Li2O、Na2O、K2O、ZrO2、TiO2、La2O3、Y2O3及び[ZnO]の各成分の含有量[SiO2]、[Al2O3]、[B2O3]、[P2O5]、[MgO]、[CaO]、[SrO]、[BaO]、[Li2O]、[Na2O]、[K2O]、[ZrO2]、[TiO2]、[La2O3]、[Y2O3]及び[ZnO]を用いて下記式に基づき算出されるパラメータPが0.520以上0.570以下である請求項1~3のいずれか1項に記載の結晶化ガラス。
P=0.458×[SiO2]+0.515×[Al2O3]+0.735×[B2O3]+0.586×[P2O5]+0.567×[MgO]+0.675×[CaO]+0.481×[SrO]+0.489×[BaO]+0.539×[Li2O]+0.410×[Na2O]+0.463×[K2O]+0.701×[ZrO2]+0.762×[TiO2]+0.567×[La2O3]+0.552×[Y2O3]+0.544×[ZnO] - 酸化物基準のモル%表示で、前記残留ガラス中の、SiO2、Al2O3、B2O3およびP2O5の総量に対するMgO、CaO、SrO、BaO、Li2O、Na2OおよびK2Oの総量の比率(MgO+CaO+SrO+BaO+Li2O+Na2O+K2O)/(SiO2+Al2O3+B2O3+P2O5)が、0.45以上である請求項6に記載の結晶化ガラス。
- 酸化物基準のモル%表示で、前記残留ガラス中の、SiO2、Al2O3、B2O3およびP2O5の総量に対するAl2O3の比率Al2O3/(SiO2+Al2O3+B2O3+P2O5)が、0.08以上である請求項1~7のいずれか1項に記載の結晶化ガラス。
- 酸化物基準のモル%表示で、前記残留ガラス中の、SiO2に対するAl2O3の比率Al2O3/SiO2が、0.1以上である請求項1~8のいずれか1項に記載の結晶化ガラス。
- 厚さ0.7mm換算のヘーズ値が1%以下、かつ厚さ0.7mm換算の光透過率が85%以上である請求項1~9のいずれか1項に記載の結晶化ガラス。
- 前記結晶化ガラスの母ガラスが、リチウムアルミノシリケートガラスである請求項1~10のいずれか1項に記載の結晶化ガラス。
- 表面に圧縮応力層を有する化学強化ガラスであり、
表面圧縮応力が200MPa以上かつ圧縮応力層深さが80μm以上であり、
結晶と残留ガラスとを含み、前記残留ガラスにおける酸化物基準のモル%表示による、SiO2、Al2O3、B2O3、P2O5、MgO、CaO、SrO、BaO、Li2O、Na2O、K2O、ZrO2、TiO2、La2O3、Y2O3及びZnOの各成分の含有量[SiO2]、[Al2O3]、[B2O3]、[P2O5]、[MgO]、[CaO]、[SrO]、[BaO]、[Li2O]、[Na2O]、[K2O]、[ZrO2]、[TiO2]、[La2O3]、[Y2O3]及び[ZnO]を用いて下記式に基づき算出される、前記残留ガラスのヤング率パラメータERが75以上である結晶化ガラスである、化学強化ガラス。
ER=62.2×[SiO2]+134.9×[Al2O3]+121.7×[B2O3]+33.0×[P2O5]+72.6×[MgO]+121.5×[CaO]+43.7×[SrO]+38.6×[BaO]+84.0×[Li2O]+26.2×[Na2O]+17.8×[K2O]+156.8×[ZrO2]+154.3×[TiO2]+74.7×[La2O3]+80.3×[Y2O3]+54.3×[ZnO]
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WO2019022033A1 (ja) * | 2017-07-26 | 2019-01-31 | Agc株式会社 | 化学強化用ガラス、化学強化ガラスおよび電子機器筐体 |
WO2020018309A2 (en) * | 2018-07-16 | 2020-01-23 | Corning Incorporated | Glass-ceramic articles with increased resistance to fracture and methods for making the same |
WO2020073254A1 (en) * | 2018-10-10 | 2020-04-16 | Schott Glass Technologies (Suzhou) Co. Ltd. | Ultrathin glass ceramic article and method for producing an ultrathin glass ceramic article |
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WO2019022033A1 (ja) * | 2017-07-26 | 2019-01-31 | Agc株式会社 | 化学強化用ガラス、化学強化ガラスおよび電子機器筐体 |
WO2020018309A2 (en) * | 2018-07-16 | 2020-01-23 | Corning Incorporated | Glass-ceramic articles with increased resistance to fracture and methods for making the same |
WO2020073254A1 (en) * | 2018-10-10 | 2020-04-16 | Schott Glass Technologies (Suzhou) Co. Ltd. | Ultrathin glass ceramic article and method for producing an ultrathin glass ceramic article |
Non-Patent Citations (1)
Title |
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INABA, SEIJI; FUJINO, SHIGERU: "Mechanical Properties of Glass", NEW GLASS, vol. 23, no. 4, 1 January 2008 (2008-01-01), JP , pages 46 - 52, XP009538572, ISSN: 0914-6563 * |
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