WO2022215717A1 - 化学強化ガラス及びその製造方法 - Google Patents
化学強化ガラス及びその製造方法 Download PDFInfo
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- WO2022215717A1 WO2022215717A1 PCT/JP2022/017214 JP2022017214W WO2022215717A1 WO 2022215717 A1 WO2022215717 A1 WO 2022215717A1 JP 2022017214 W JP2022017214 W JP 2022017214W WO 2022215717 A1 WO2022215717 A1 WO 2022215717A1
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- Prior art keywords
- chemically strengthened
- depth
- glass
- strengthened glass
- mpa
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- 239000005345 chemically strengthened glass Substances 0.000 title claims abstract description 179
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 238000003426 chemical strengthening reaction Methods 0.000 claims abstract description 66
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 8
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims description 197
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 41
- 238000005342 ion exchange Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 29
- 230000035515 penetration Effects 0.000 claims description 26
- 229910052708 sodium Inorganic materials 0.000 claims description 23
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 19
- 239000002344 surface layer Substances 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 238000005728 strengthening Methods 0.000 claims description 10
- 239000005341 toughened glass Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 11
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 7
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 114
- 239000013078 crystal Substances 0.000 description 43
- 150000002500 ions Chemical class 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 30
- 150000003839 salts Chemical class 0.000 description 18
- 229910001415 sodium ion Inorganic materials 0.000 description 16
- 238000012360 testing method Methods 0.000 description 14
- 229910052681 coesite Inorganic materials 0.000 description 13
- 229910052906 cristobalite Inorganic materials 0.000 description 13
- 239000000377 silicon dioxide Substances 0.000 description 13
- 235000012239 silicon dioxide Nutrition 0.000 description 13
- 229910052682 stishovite Inorganic materials 0.000 description 13
- 229910052905 tridymite Inorganic materials 0.000 description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- 239000003513 alkali Substances 0.000 description 12
- 239000006059 cover glass Substances 0.000 description 12
- 238000002834 transmittance Methods 0.000 description 12
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 239000000523 sample Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000005498 polishing Methods 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 238000004031 devitrification Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 229910006404 SnO 2 Inorganic materials 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 4
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000013001 point bending Methods 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 150000003841 chloride salts Chemical class 0.000 description 3
- 239000006103 coloring component Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000006060 molten glass Substances 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 238000005496 tempering Methods 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 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
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 238000005452 bending Methods 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
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-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
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 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
- 229910001386 lithium phosphate Inorganic materials 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
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 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
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910018162 SeO2 Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 206010040925 Skin striae Diseases 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
- 239000006061 abrasive grain Substances 0.000 description 1
- 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 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 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
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000010287 polarization Effects 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
- 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
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 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
- 238000003756 stirring Methods 0.000 description 1
- 239000006058 strengthened glass Substances 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
- 229910052644 β-spodumene Inorganic materials 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
- 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
- C03C10/0018—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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
Definitions
- the present invention relates to chemically strengthened glass and its manufacturing method.
- 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.
- a layer is formed.
- Amorphous glass containing Li 2 O or crystallized glass containing Li 2 O is particularly excellent as a base material for such chemically strengthened glass. This is because ion exchange between lithium ions contained in the base material and sodium ions contained in the strengthening salt tends to generate compressive stress deep within the chemically strengthened glass. Since lithium ions and sodium ions have relatively small ionic radii, their diffusion coefficients due to ion exchange are large. Amorphous glass and crystallized glass containing Li 2 O have relatively high fracture toughness values and tend to be difficult to break.
- the cover glass of mobile devices is also required to have good finger slipperiness during operation. Therefore, the surface of the cover glass is often coated. However, the formed coating film may be easily peeled off.
- Patent Document 1 discloses crystallized glass with excellent chemical strengthening properties.
- Patent Literature 2 discloses a chemically strengthened glass that is excellent in strength and has a coating that is difficult to peel off for improving finger slipperiness.
- the glass containing Li 2 O is excellent as a cover glass is that the Li ions in the glass can exchange both Na ions and K ions contained in the molten salt. It is easy to control the generated compressive stress value to a preferable value.
- Patent Document 2 describes that the higher the surface resistivity of the chemically strengthened glass, the easier it is for the coating to peel off. It also describes that the content ratio of alkali metal oxides affects the surface resistivity.
- a glass containing three kinds of alkali metal oxides Li 2 O, Na 2 O and K 2 O, contains one or two kinds of alkali metal oxides even if the same amount of alkali metal oxides is contained.
- the so-called mixed alkali effect increases the surface resistivity compared to glasses containing only
- an object of the present invention is to provide chemically strengthened glass that exhibits excellent chemically strengthened properties and that can suppress peeling of the coating.
- the present inventors found that in chemically strengthened glass containing Li 2 O, K 2 O and Na 2 O, by making the region containing potassium an extremely shallow portion from the glass surface, the surface resistivity is improved by the mixed alkali effect. The inventors have found that the increase can be suppressed, and completed the present invention.
- the present invention is a chemically strengthened glass having a thickness of t [ ⁇ m] and containing Li 2 O, K 2 O and Na 2 O, wherein the depth from the surface x
- K x is (K t / 2 + 0.1)
- K x is (K t / 2 + 0.1) It relates to a chemically strengthened glass in which the minimum depth z of [%] or more is 0.5 to 5 ⁇ m.
- the K 2 O concentration at the depth x [ ⁇ m] from the surface is expressed as a molar percentage based on oxides, and the K 2 O content before chemical strengthening is K x [%].
- the concentration of Na 2 O at a depth of 50 ⁇ m from the surface is Na 50 [%] in terms of molar percentage based on oxides, and the content of Na 2 O before chemical strengthening is Na t / 2 [ %], it is preferable that Na 50 ⁇ Na t/2 +7 [%].
- the K 2 O concentration at a depth of 1 ⁇ m from the surface is K 1 [%]
- the Na 2 O concentration is Na 1 [%]
- the Li before chemical strengthening is expressed as a molar percentage based on oxides.
- Na 2 O and K 2 O are respectively Li t/2 [%], Na t/2 [%] and K t/2 [%], (Li t/2 + Na t/ 2 + K t/2 ) ⁇ 2(Na 1 +K 1 )>0[%].
- the surface compressive stress value CS0 is 450 MPa or more
- the compressive stress value CS50 at a depth of 50 ⁇ m from the surface is 150 MPa or more
- the compressive stress value CS90 at a depth of 90 ⁇ m from the surface is 30 MPa or more.
- the compressive stress value CS0 is 450 MPa or more
- the compressive stress value CS50 at a depth of 50 ⁇ m from the surface is 150 MPa or more
- the compressive stress value CS90 at a depth of 90 ⁇ m from the surface is 30 MPa or more.
- the surface compressive stress value CS 0 is 450 MPa or more
- the chemically strengthened glass has a K ion penetration depth D of 0.5 to 5 ⁇ m, a compressive stress value at the K ion penetration depth D and a compressive stress value CS 50 at a depth of 50 ⁇ m from the surface.
- the absolute value of the difference is 150 MPa or less
- the compressive stress value at the K ion penetration depth D is 350 MPa or less
- the surface compressive stress value CS 0 is 450 MPa or more
- the compressive stress value CS 50 at a depth of 50 ⁇ m from the surface is It relates to a chemically strengthened glass having a compressive stress value CS90 of 30 MPa or more at a depth of 90 ⁇ m from the surface of 150 MPa or more.
- the present chemically strengthened glass is preferably made of crystallized glass.
- the present chemically strengthened glass preferably contains 40 to 75% SiO 2 , 1 to 20% Al 2 O 3 , and 5 to 35% Li 2 O in terms of molar percentages based on oxides.
- This chemically strengthened glass is a chemically strengthened glass that has undergone two or more stages of ion exchange, and it is preferable that CTave after the first ion exchange, which is the first ion exchange, is larger than CTA.
- CTA is calculated by the following formula (1)
- CTave is calculated by the following formula (2).
- the present chemically strengthened glass preferably has a thickness t of 300 to 1500 ⁇ m.
- the slope of the stress profile of the chemically strengthened glass in the region between the depth of 50 ⁇ m from the surface and the depth of 90 ⁇ m from the surface is P 50-90 (MPa / ⁇ m), and the depth from the surface
- P 50 ⁇ Preferably, 90
- P 50 -90 can be calculated from the relational expression (CS 50 -CS 90 )/40
- P 90 -DOL can be calculated from the relational expression of CS 90 /(DOL-90).
- the slope of the stress profile of the chemically strengthened glass in the region between the depth of 50 ⁇ m from the surface and the depth of 90 ⁇ m from the surface is P 50-90 (MPa / ⁇ m), and the depth from the surface
- preferably 1.0 ⁇
- P 50 -90 can be calculated from the relational expression (CS 50 -CS 90 )/40
- P 90 -DOL can be calculated from the relational expression of CS 90 /(DOL-90).
- the present invention also provides a method for producing a chemically strengthened glass containing Li 2 O, K 2 O and Na 2 O, which has a thickness of t [ ⁇ m] and includes chemically strengthening the glass containing Li 2 O.
- K 2 O concentration at depth x [ ⁇ m] from the surface is K x [%] in the chemically strengthened glass oxide-based molar percentage display, and K 2 O in the glass before chemical strengthening
- chemical strengthening is performed so that the minimum depth z at which K x is (K t / 2 + 0.1) [%] or more is 0.5 to 5 ⁇ m
- the present invention relates to a method for manufacturing chemically strengthened glass.
- the glass containing Li 2 O is preferably crystallized glass.
- the chemical strengthening includes two or more stages of ion exchange, and CTave after the first ion exchange, which is the first ion exchange, is greater than CTA.
- CTA is calculated by the following formula (1)
- CTave is calculated by the following formula (2).
- the chemically strengthened glass of the present invention exhibits excellent chemical strengthening properties, and since the region containing potassium is an extremely shallow portion from the glass surface, the increase in surface resistivity due to the mixed alkali effect is suppressed and the coating is peeled off. It has the advantage of being hard
- FIG. 1 shows the results of measuring the Na concentration in chemically strengthened glass by EPMA.
- (c) and (d) of FIG. 1 show the results of measuring the K concentration in chemically strengthened glass by EPMA.
- the horizontal axis indicates the depth ( ⁇ m) from the glass surface, and the vertical axis indicates the concentration (%) represented by the molar percentage based on the oxide.
- FIG. 2 shows the stress profile of the chemically strengthened glass of one embodiment of the invention.
- amorphous glass refers to glass in which no diffraction peak indicating crystals is observed by the powder X-ray diffraction method described below.
- Crystalized glass is obtained by heat-treating "amorphous glass” to precipitate crystals, and contains crystals.
- amorphous glass and crystalstallized glass are sometimes collectively referred to as “glass”.
- Amorphous glass that becomes crystallized glass by heat treatment is sometimes referred to as "mother glass of crystallized glass”.
- the powder X-ray diffraction measurement is performed using, for example, CuK ⁇ rays in the range of 2 ⁇ from 10° to 80°, and when a diffraction peak appears, the precipitated crystal is identified by the Hanawalt method.
- the crystal identified from the peak group including the peak with the highest integrated intensity is taken as the main crystal.
- SmartLab manufactured by Rigaku can be used as the measuring device.
- the K concentration, Na concentration, or Li concentration at depth x [ ⁇ m] is measured by an EPMA (Electron Probe Micro Analyzer, electron beam microanalyzer) in a cross section in the plate thickness direction.
- EPMA is specifically measured, for example, as follows. First, a glass sample is embedded in an epoxy resin and mechanically polished in the direction perpendicular to the first main surface and the second main surface opposite to the first main surface to prepare a cross-sectional sample. A C coat is applied to the cross section after polishing, and measurement is performed using an EPMA (manufactured by JEOL: JXA-8500F). The acceleration voltage is 15 kV, the probe current is 30 nA, and the integration time is 1000 msec. A line profile of X-ray intensity of K, Na or Li is obtained at intervals of 1 ⁇ m as /point.
- chemically strengthened glass refers to glass after chemical strengthening treatment
- chemically strengthened glass refers to glass before chemical strengthening treatment
- 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.
- stress profile refers to the compressive stress value expressed with the depth from the glass surface as a variable.
- tensile stress is represented as negative compressive stress.
- the "compressive stress value (CS)" can be measured by slicing the cross section of the glass and analyzing the sliced sample with a birefringence imaging system.
- a birefringence imaging system birefringence stress meter is a device that measures the magnitude of retardation caused by stress using a polarizing microscope and a liquid crystal compensator. .
- CS can be measured by irradiating light from the glass surface and analyzing the polarization of the scattered light.
- a stress measuring device using scattered light photoelasticity for example, there is a scattered light photoelastic stress meter SLP-2000 manufactured by Orihara Seisakusho.
- K ion penetration depth D is obtained by the following procedures (1) to (3).
- the amount of warpage is measured using a contact shape meter (Surftest manufactured by Mitutoyo). The amount of warpage is measured at three or more etching depths. The amount of warp obtained is converted into stress using the formula shown in the following document to obtain a profile of compressive stress values in the depth direction.
- Literature G. G. Stoney, Proc. Roy. Soc. London Ser. A, 82, 172 (1909).
- (3) The two profiles obtained by the procedures (1) and (2) are superimposed, and the depth at the point of intersection is the "K ion penetration depth D".
- warpage caused by polishing using a rotary grinder may be measured with a contact-type shape meter (device name: SV-600, manufacturer: Mitutoyo).
- a rotary grinder equipment name: 9B-5P manufacturer: SPEEDFAM
- a contact shape meter equipment name: SV- 600 Manufacturer: Mitutoyo
- the “compressive stress layer depth (DOL)” is the depth at which the compressive stress value is zero.
- the surface compressive stress value is sometimes referred to as CS 0
- the compressive stress value at a depth of 50 ⁇ m from the surface as CS 50 is sometimes referred to as CS 0
- CT internal tensile stress
- 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 K7136:2000 using a halogen lamp C light source.
- Frracture toughness value is a value obtained by the IF method specified in JIS R1607:2015.
- Silicon resistivity as used herein is measured using a non-contact conductivity meter.
- #180 drop strength and "#80 drop strength” are measured by the following methods.
- a 120 x 60 x 0.6 mmt glass sample is fitted into a structure whose mass and rigidity are adjusted to the size of a general smartphone, and a pseudo smartphone is prepared.
- For 80 drop strength free fall onto #80 SiC sandpaper.
- the drop height if it is dropped from a height of 5 cm and does not crack, the work of raising the height by 5 cm and dropping it again is repeated until it cracks, and the average value of 10 pieces of height when it cracks for the first time is measured.
- the AFP durability (10,000 times) is measured by an eraser wear test under the following conditions.
- Eraser abrasion test conditions The surface of the chemically strengthened glass plate is washed with ultraviolet rays and spray-coated with Optool (registered trademark) DSX (manufactured by Daikin) to form a substantially uniform AFP film on the surface of the glass plate.
- An eraser (Minoan, manufactured by MIRAE SCIENCE) was attached to an indenter of 1 cm 2 , and while a load of 1 kgf was applied, the surface of the AFP film formed on the surface of the glass plate was reciprocated 10,000 times at a stroke width of 20 mm and a speed of 30 mm/sec.
- the surface of the AFP film is wiped dry with a cloth [DUSPER (registered trademark) manufactured by Ozu Sangyo Co., Ltd.], and the water contact angle (°) is measured at three points on the AFP film surface. This is repeated 3 times, and a total of 9 average water contact angles (°) are measured.
- the water contact angle (°) of the AFP film surface is measured by a method based on JIS R 3257 (1999).
- 4PB strength (4-point bending strength) is measured by the following method. Using a strip-shaped test piece of 120 mm ⁇ 60 mm, a four-point bending test is performed under the conditions of a support tool with a distance between external fulcrums of 30 mm, a distance between internal fulcrums of 10 mm, and a crosshead speed of 5.0 mm / min. can be evaluated. The number of test pieces is, for example, ten.
- the chemically strengthened glass of the present invention (hereinafter also abbreviated as the present chemically strengthened glass) is typically a plate-like glass article, and may be flat or curved. Also, there may be portions with different thicknesses.
- the thickness (t) is preferably 3000 ⁇ m or less, more preferably 2000 ⁇ m or less, 1600 ⁇ m or less, 1500 ⁇ m or less, 1100 ⁇ m or less, 900 ⁇ m or less, 800 ⁇ m or less, and 700 ⁇ m in stages. It is below.
- the thickness (t) is preferably 300 ⁇ m or more, more preferably 400 ⁇ m or more, and still more preferably 500 ⁇ m or more so that sufficient strength can be obtained by the chemical strengthening treatment.
- Embodiment 1 of the present chemically strengthened glass has a thickness of t [ ⁇ m], and the K 2 O concentration at the depth x [ ⁇ m] from the surface is K x [%] in terms of oxide-based molar percentage display.
- K t/2 [%] is the content of K 2 O before chemical strengthening
- the minimum depth z at which K x is (K t/2 +0.1) [%] or more is 0.00.
- It is a chemically strengthened glass with a thickness of 5 to 5 ⁇ m.
- z is preferably 0.6-4.5 ⁇ m, more preferably 0.7-4 ⁇ m, even more preferably 0.8-3.5 ⁇ m, and particularly preferably 0.85-3.
- the depth z is 0.5 to 5 ⁇ m, an increase in surface resistivity due to alkali mixing effect can be suppressed.
- the glass composition before chemical strengthening is the same as the composition at the center of plate thickness (glass center portion). Specifically, the content of Li 2 O, Na 2 O and K 2 O before chemical strengthening is equivalent to the content at the position of t / 2, where t is the thickness of the chemically strengthened glass. .
- the K 2 O concentration at the depth x [ ⁇ m] from the surface is K x [%] in mole percentage display based on oxides
- the K 2 O concentration before chemical strengthening is The Na 2 O concentration at the minimum depth z [ ⁇ m] at which K x is (K t / 2 + 0.1) [%] or more when the content is K t / 2 [%] is Na z [% ] and the Na 2 O concentration at a depth of 50 ⁇ m from the surface is Na 50 [%]
- is preferably less than 3%.
- the Na concentration increases from the center of the glass to the surface of the glass.
- the degree of alkali mixing is low, and the increase in surface resistivity can be suppressed more effectively.
- is not particularly limited, it is typically 0.1% or more.
- the concentration of Na 2 O at a depth of 50 ⁇ m from the surface is Na 50 [%] in terms of molar percentage based on oxides, and the content of Na 2 O before chemical strengthening is Na
- Na 50 is preferably less than (Na t/2 +7)%.
- Na 50 is more preferably (Na t/2 +5.5)% or less, still more preferably (Na t/2 +4)% or less.
- Na 50 When Na 50 is less than (Na t/2 +7)%, the degree of alkali mixing on the glass surface becomes low, and an increase in surface resistivity can be more effectively suppressed.
- the lower limit of Na 50 is not particularly limited, it is preferably (Na t/2 +2)% or more in order to balance with suppression of glass breakage due to compressive stress.
- Embodiment 1 of the present chemically strengthened glass has a K 2 O concentration of K 1 [%] and a Na 2 O concentration of Na 1 [%] at a depth of 1 [ ⁇ m] from the surface in terms of molar percentages based on oxides. and the contents of Li 2 O, Na 2 O and K 2 O before chemical strengthening are respectively Li t / 2 [%], Na t / 2 [%] and K t / 2 [%], [ (Li t/2 +Na t/2 +K t/2 )-2(Na 1 +K 1 )] is preferably greater than 0%. [(Li t/2 +Na t/2 +K t/2 )-2(Na 1 +K 1 )] is more preferably 3% or more, still more preferably 5% or more.
- Na z ⁇ Na t/2 is preferably 8% or less, more preferably 7% or less, and still more preferably 6% or less, where t is the plate thickness.
- the degree of alkali mixing on the glass surface is low, and an increase in surface resistivity can be more effectively suppressed.
- the lower limit of Na z -Na t/2 is not particularly limited, it is typically preferably 2% or more.
- the Na ion profile in one embodiment of this chemically strengthened glass is shown in (a) and (b) of FIG. 1, and the K ion profile is shown in (c) and (d) of FIG.
- the amount of Li ions in the glass exchanged with Na ions in the molten salt by chemical strengthening is small, and the Na ion profile in the plate thickness direction is flat.
- the exchange amount of Na ions is small, chemical strengthening with a molten salt containing K causes Na ions and K An exchange with ions occurs, resulting in a chemically strengthened glass with a very thin layer with K ions and a reduced degree of alkali mixing.
- FIG. 2 A stress profile in one embodiment of this chemically strengthened glass is shown in FIG. 2 (Example 1). As shown in FIG. 2, the present chemically strengthened glass has a low alkali mixing degree in the glass surface layer, but exhibits a higher compressive stress in the glass surface layer than conventional chemically strengthened glass, and exhibits excellent strength.
- This chemically strengthened glass preferably has a surface compressive stress value (CS 0 ) of 450 MPa or more because it is less likely to break due to deformation such as bending.
- CS 0 is more preferably 500 MPa or more, and even more preferably 600 MPa or more.
- the higher the CS 0 the higher the strength, but if it is too large, there is a risk of severe crushing when it breaks, so it is preferably 1100 MPa or less, more preferably 900 MPa or less.
- the chemically strengthened glass has a compressive stress value (CS 50 ) of 150 MPa or more at a depth of 50 ⁇ m from the surface, the chemically strengthened glass will be damaged when a mobile terminal or the like equipped with the chemically strengthened glass as a cover glass is dropped. It is preferable because it becomes easier to prevent cracking.
- CS50 is more preferably 180 MPa or higher, and even more preferably 200 MPa or higher. The higher the CS50 , the higher the strength. However, if the CS50 is too large, severe crushing may occur when cracked, so 300 MPa or less is preferable, and 270 MPa or less is more preferable.
- This chemically strengthened glass has a value CS 50 /(Na 50 -Na t/ 2 ) obtained by dividing the compressive stress value CS 50 at a depth of 50 ⁇ m from the surface by (Na 50 -Na t/2 ) is 50 MPa / % or more. It is preferably 55 MPa/% or more, and still more preferably 60 MPa/% or more. Excellent strength is exhibited when CS 50 /(Na 50 -Na t/2 ) is 50 MPa/% or more.
- CS 50 /(Na 50 ⁇ Na t/2 ) can increase the strength without increasing the surface resistance with a small amount of ion exchange as the value increases, but if it is too large, it may be susceptible to deterioration of the strengthening salt Therefore, 400 MPa/% or less is preferable, and 300 MPa/% or less is more preferable.
- Na 50 refers to the Na 2 O concentration [%] expressed as a molar percentage based on oxides at a depth of 50 ⁇ m from the surface.
- Na t/2 refers to the content [%] of Na 2 O in mole percentage display based on oxides before chemical strengthening.
- the chemically strengthened glass has a compressive stress value CS90 of 30 MPa or more at a depth of 90 ⁇ m from the surface, the chemically strengthened glass when a mobile terminal or the like equipped with the chemically strengthened glass as a cover glass is dropped on coarse sand. This is preferable because it prevents the glass from breaking.
- CS 90 is more preferably 50 MPa or higher, even more preferably 70 MPa or higher. The higher the CS 90 , the higher the strength. However, if the CS 90 is too large, severe crushing may occur when cracked, so 170 MPa or less is preferable, and 150 MPa or less is more preferable.
- the present chemically strengthened glass preferably has a compressive stress value CS t / 2 at a depth t / 2 from the surface of ⁇ 120 MPa or more, more preferably ⁇ 115 MPa or more, further preferably ⁇ 110 MPa or more.
- CS t/2 is ⁇ 120 MPa or more, explosive cracking can be prevented when the glass is scratched.
- the upper limit of CS t/2 is not particularly limited, but it is preferably -80 MPa or less in order to maintain sufficient compressive stress.
- the chemically strengthened glass has a DOL of 90 ⁇ m or more because it is difficult to break even if the surface is scratched.
- DOL is more preferably 95 ⁇ m or more, still more preferably 100 ⁇ m or more, and particularly preferably 110 ⁇ m or more. The larger the DOL, the less likely it is to break even if it is scratched, but in chemically strengthened glass, tensile stress is generated inside according to the compressive stress formed near the surface, so it cannot be made extremely large.
- the DOL is preferably t/4 or less, more preferably t/5 or less.
- DOL is preferably 200 ⁇ m or less, more preferably 180 ⁇ m or less, in order to shorten the time required for chemical strengthening.
- the slope of the stress profile of the chemically strengthened glass in the region between the depth of 50 ⁇ m from the surface and the depth of 90 ⁇ m from the surface is P 50-90 (MPa / ⁇ m), and the depth of 90 ⁇ m from the surface and the compressive stress
- P 50-90 and P 90-DOL are obtained by the following formulas.
- P50-90 ( CS50 - CS90 )/40
- P90-DOL CS90/(DOL- 90 )
- the slope of the stress profile of the chemically strengthened glass in the region between a depth of 50 ⁇ m from the surface and a depth of 90 ⁇ m from the surface is P 50-90
- the compressive stress value is zero at a depth of 90 ⁇ m from the surface.
- preferably 1.0 ⁇
- the preferred range for the thickness t of the chemically strengthened glass is 300 to 1500 ⁇ m.
- Embodiment 2 of the present chemically strengthened glass has a K ion penetration depth D of 0.5 to 5 ⁇ m, and the absolute difference between the compressive stress value at the depth D and the compressive stress value CS 50 at a depth of 50 ⁇ m from the surface value is 150 MPa or less, the compressive stress value at the K ion penetration depth D is 350 MPa or less, the surface compressive stress value CS 0 is 450 MPa or more, the compressive stress value CS 50 at a depth of 50 ⁇ m from the surface is 150 MPa or more, and the surface It is a chemically strengthened glass having a compressive stress value CS90 of 30 MPa or more at a depth of 90 ⁇ m from.
- the K ion penetration depth D is 0.5 to 5 ⁇ m, so that the degree of alkali mixing on the glass surface is low, and an increase in surface resistivity can be suppressed.
- D is preferably 0.7-4 ⁇ m, more preferably 0.8-3 ⁇ m.
- the absolute value of the difference between the compressive stress value at the K ion penetration depth D and the compressive stress value CS50 at a depth of 50 ⁇ m from the surface is 150 MPa or less. Cracking due to deformation can be suppressed.
- the absolute value of the difference between the compressive stress value at the K ion penetration depth D and the compressive stress value CS50 at a depth of 50 ⁇ m from the surface is preferably 130 MPa or less, more preferably 110 MPa or less.
- the lower limit of the absolute value of the difference between the compressive stress value at depth D and the compressive stress value CS50 at a depth of 50 ⁇ m from the surface is not particularly limited.
- Embodiment 2 of the present chemically strengthened glass has a compressive stress value of 350 MPa or less at K ion penetration depth D, so that CS 50 and CS 90 can be sufficiently increased without increasing CT too much.
- the compressive stress value at the K ion penetration depth D is preferably 330 MPa or less, more preferably 300 MPa or less.
- the lower limit of the compressive stress value at the K ion penetration depth D is not particularly limited, but from the viewpoint of suppressing cracks near the surface, it is preferably 100 MPa or more.
- the chemically strengthened glass preferably has a surface resistance log ⁇ of 12 ⁇ cm or less, more preferably 11.5 ⁇ cm or less, and still more preferably 11 ⁇ cm or less.
- the surface resistance log ⁇ is 12 ⁇ cm or less, peeling of the coating film can be suppressed.
- the lower limit of the surface resistance log ⁇ is not particularly limited, it is typically 8 ⁇ cm or more.
- the chemically strengthened glass preferably has a #180 drop strength of 100 cm or more, more preferably 140 cm or more, and still more preferably 180 cm or more.
- the #180 drop strength of 100 cm or more makes it possible to suppress breakage of the chemically strengthened glass when a mobile terminal or the like having the chemically strengthened glass as a cover glass is dropped on sand or the like.
- the upper limit of the #180 drop strength is not particularly limited, it is typically 300 cm or less.
- the chemically strengthened glass preferably has a #80 drop strength of 40 cm or more, more preferably 50 cm or more, and still more preferably 60 cm or more.
- #80 drop strength is 40 cm or more, cracking of the chemically strengthened glass can be suppressed when a mobile terminal or the like having the chemically strengthened glass as a cover glass is dropped on coarse sand or the like.
- the upper limit of the #80 drop strength is not particularly limited, it is typically 150 cm or less.
- the preferred range of thickness t of the chemically strengthened glass is 300 to 1500 ⁇ m.
- the chemically strengthened glass preferably has an AFP durability (10,000 times) of 100 degrees or more, more preferably 105 degrees or more, and still more preferably 110 degrees or more.
- AFP durability (10000 times) is 100 degrees or more, peeling of the coating film can be suppressed.
- the upper limit of AFP durability (10000 times) is not particularly limited, it is typically 125 degrees or less.
- This chemically strengthened glass is also useful as a cover glass for use in electronic devices such as mobile devices such as mobile phones and smart phones. 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.
- the ion profile and stress characteristics in this chemically strengthened glass can be adjusted by the mother composition of this chemically strengthened glass and the conditions of chemical strengthening treatment.
- the chemically strengthened glass is preferably crystallized glass in order to improve the stress characteristics of the chemically strengthened glass.
- the base composition of the present chemically strengthened glass and the crystallized glass are described below.
- the mother composition of the present chemically strengthened glass preferably contains SiO 2 , Li 2 O and Al 2 O 3 .
- This chemically strengthened glass is expressed in mol% based on oxides in the mother composition, 40-75% SiO2 , Li 2 O from 5 to 35%, It preferably contains 1 to 20% of Al 2 O 3 . again, 40-70% SiO2 , Li 2 O from 5 to 35%, It is more preferable to contain 1 to 20% of Al 2 O 3 .
- SiO2 10-30% Li 2 O, 1-15% Al 2 O 3 ; 0-5 % of P2O5 ; 0-8 % ZrO2, 0-10% MgO, 0-5 % of Y2O3 0-10% of B2O3 , 0-5% Na 2 O; 0-5% K2O , More preferably, 0-2% SnO 2 is contained.
- the following glasses (i) to (iii) are preferable.
- the base composition of chemically strengthened glass refers to the composition of crystallized glass before chemical strengthening. This composition will be described later.
- the composition of this chemically strengthened glass has a composition similar to that of crystallized glass before tempering, except for the case of extreme ion exchange treatment. Normally, the composition of crystallized glass before tempering is It is equivalent to the composition at the center of the plate thickness in chemically strengthened glass. In particular, the composition of the deepest part from the glass surface is the same as the composition of the crystallized glass before tempering, except for the case of extreme ion exchange treatment.
- the present chemically strengthened glass is preferably made of crystallized glass (hereinafter also referred to as the present crystallized glass) from the viewpoint of increasing strength. Since crystallized glass has superior strength compared to amorphous glass, it is easy to form a favorable stress profile even when the glass surface has a low alkali mixing degree compared to conventional chemically strengthened glass. , it is easy to achieve both the strength and surface properties of the glass.
- Crystals contained in crystallized glass include, for example, lithium phosphate crystals, lithium metasilicate crystals, and ⁇ -spodumene crystals. Among these, lithium phosphate crystals and lithium metasilicate crystals are preferable from the viewpoint of increasing the strength. Also, the crystals contained in the crystallized glass may be solid solution crystals. By containing these crystals, the strength is improved, the light transmittance is increased, and the haze is reduced.
- the crystallization rate of the present crystallized glass is preferably 5% or more, more preferably 10% or more, still more preferably 15% or more, and particularly preferably 20% or more, in order to increase the mechanical strength. In order to increase transparency, it is preferably 70% or less, more preferably 60% or less, and even more preferably 50% or less. A low crystallinity is excellent in that it is easy to heat and bend.
- the average grain size of precipitated crystals of the present crystallized glass is preferably 5 nm or more, particularly preferably 10 nm or more, in order to increase the strength. In order to improve transparency, it is preferably 80 nm or less, more preferably 60 nm or less, even more preferably 50 nm or less, particularly preferably 40 nm or less, and most preferably 30 nm or less.
- the average grain size of precipitated crystals is obtained from a transmission electron microscope (TEM) image.
- the thickness (t) is preferably 3000 ⁇ m or less, more preferably 2000 ⁇ m or less, 1600 ⁇ m or less, 1100 ⁇ m or less, 900 ⁇ m or less, 800 ⁇ m or less, and 700 ⁇ m or less in stages. .
- the thickness (t) is preferably 300 ⁇ m or more, more preferably 400 ⁇ m or more, and still more preferably 500 ⁇ m or more so that sufficient strength can be obtained by the chemical strengthening treatment.
- the light transmittance of this crystallized glass is 85% or more when the thickness is 700 ⁇ m, so when it is used as a cover glass for a portable display, the screen of the display is easy to see.
- the light transmittance is preferably 88% or higher, more preferably 90% or higher. The higher the light transmittance, the better, but it is usually 91% or less.
- the thickness is 700 ⁇ m, the light transmittance of 90% is comparable to ordinary amorphous glass.
- the light transmittance at 700 ⁇ m can be calculated from the Lambert-Beer law based on the measured value. If the plate thickness t is greater than 700 ⁇ m, the plate thickness may be adjusted to 700 ⁇ m by polishing, etching, or the like before measurement.
- the haze value is 0.5% or less, preferably 0.4% or less, more preferably 0.3% or less, further preferably 0.2% or less, and 0.15%. % or less is particularly preferred.
- the haze value is preferably as small as possible, it is usually 0.01% or more. At a thickness of 700 ⁇ m, a haze value of 0.02% is comparable to ordinary amorphous glass.
- H 0.7 100 ⁇ [1-(1-H) ⁇ ((1-R)2-T0.7)/((1-R)2-T) ⁇ ] [%] If the plate thickness t is greater than 700 ⁇ m, the plate thickness may be adjusted to 700 ⁇ m by polishing, etching, or the like before measurement.
- the present crystallized glass has a high fracture toughness value, and even if a large compressive stress is formed by chemical strengthening, severe fracture is unlikely to occur.
- the fracture toughness value of the present crystallized glass is preferably 0.81 MPa ⁇ m 1/2 or more, more preferably 0.84 MPa ⁇ m 1/2 or more, still more preferably 0.87 MPa ⁇ m 1/2 or more. , a glass with high impact resistance is obtained.
- the upper limit of the fracture toughness value of the present crystallized glass is not particularly limited, it is typically 1.5 MPa ⁇ m 1/2 or less.
- the Young's modulus of the present crystallized glass is preferably 80 GPa or higher, more preferably 85 GPa or higher, still more preferably 90 GPa or higher, and particularly preferably 95 GPa or higher, so that warping can be suppressed during chemical strengthening treatment.
- This crystallized glass may be polished before use.
- the Young's modulus is preferably 130 GPa or less, more preferably 120 GPa or less, and even more preferably 110 GPa or less.
- This crystallized glass is obtained by heating and crystallizing amorphous glass, which will be described later.
- the present crystallized glass preferably contains SiO 2 , Li 2 O and Al 2 O 3 .
- This crystallized glass is expressed in mol % based on oxides, 40-75% SiO2 , Li 2 O from 5 to 35%, It preferably contains 1 to 20% of Al 2 O 3 . again, 40-70% SiO2 , Li 2 O from 5 to 35%, It is more preferable to contain 1 to 20% of Al 2 O 3 .
- This crystallized glass is expressed in mol % based on oxides, In addition, 50 to 70% of SiO2 , 10-30% Li 2 O, 1-15% Al 2 O 3 ; 0-5 % of P2O5 ; 0-8 % ZrO2, 0-10% MgO, 0-5 % of Y2O3 0-10% of B2O3 , 0-5% Na 2 O; 0-5% K2O , More preferably, 0-2% SnO 2 is contained.
- the following glasses (i) to (iii) are preferable.
- the total amount of SiO 2 , Al 2 O 3 , P 2 O 5 and B 2 O 3 is preferably 60 to 80% in terms of mol % based on oxides.
- SiO 2 , Al 2 O 3 , P 2 O 5 and B 2 O 3 are glass network formers (hereinafter also abbreviated as NWF).
- NWF glass network formers
- a large total amount of these NWFs increases the strength of the glass.
- the total amount of NWFs is preferably 60% or more, more preferably 63% or more, and particularly preferably 65% or more, because it increases the fracture toughness value of the crystallized glass.
- glass with too much NWF has a high melting temperature and is difficult to manufacture.
- NWF Li 2 O, Na 2 O and K 2 O are network modifiers, and lowering the ratio to NWF increases the voids in the network and thus improves the impact resistance. Therefore, NWF is preferably 0.60 or less, more preferably 0.55 or less, and particularly preferably 0.50 or less. On the other hand, since these are components necessary for chemical strengthening, NWF is preferably 0.20 or more, more preferably 0.25 or more, and particularly preferably 0.30 or more, in order to improve chemical strengthening properties.
- the composition of the present crystallized glass is described below.
- SiO2 is a component that forms the network structure of the glass.
- the content of SiO 2 is preferably 40% or more, which is a component that increases chemical durability.
- the content of SiO 2 is more preferably 48% or more, even more preferably 50% or more, particularly preferably 52% or more, very preferably 54% or more.
- the content of SiO 2 is preferably 75% or less, more preferably 70% or less, still more preferably 68% or less, still more preferably 66% or less, and particularly preferably 64% or less in order to improve meltability. be.
- Li 2 O is a component that forms surface compressive stress by ion exchange, and is essential because it is a constituent component of the main crystal.
- the content of Li 2 O is preferably 5% or more, more preferably 8% or more, more preferably 11% or more, still more preferably 15% or more, particularly preferably 20% or more, and most preferably 22% or more.
- the content of Li 2 O is preferably 35% or less, more preferably 32% or less, still more preferably 30% or less, particularly preferably 28% or less, and most preferably 26% or less. is.
- Al 2 O 3 is a component that increases the surface compressive stress due to chemical strengthening and is essential.
- the content of Al 2 O 3 is preferably 1% or more, more preferably 2% or more, still more preferably 3% or more, 5% or more, 5.5% or more, 6% or more, particularly preferably 6% or more. .5% or more, most preferably 7% or more.
- the content of Al 2 O 3 is preferably 20% or less, more preferably 15% or less, still more preferably 12% or less, and particularly preferably 10% or less, in order to prevent the devitrification temperature of the glass from becoming too high. 9% or less is most preferred.
- P 2 O 5 is a constituent component of Li 3 PO 4 crystals and is essential when precipitating the crystals.
- the content of P 2 O 5 is preferably 0.5% or more, more preferably 1% or more, still more preferably 1.5% or more, and particularly preferably 2% or more, in order to promote crystallization. , very preferably at least 2.5%.
- the P 2 O 5 content is too high , the phase separation tends to occur during melting and the acid resistance is significantly lowered. It is 8% or less, more preferably 4.5% or less, and particularly preferably 4.2% or less.
- ZrO 2 is a component that increases mechanical strength and chemical durability, and is preferably contained because it significantly improves CS.
- the content of ZrO2 is preferably 0.5% or more, more preferably 1% or more, even more preferably 1.5% or more, particularly preferably 2% or more, most preferably 2.5% or more. is.
- ZrO2 is preferably 8 % or less, more preferably 7.5% or less, and particularly preferably 6% or less. If the content of ZrO 2 is too high, the devitrification temperature increases and the viscosity decreases.
- the ZrO 2 content is preferably 5% or less, more preferably 4.5% or less, and 3.5% or less. More preferred.
- MgO is a component that stabilizes the glass and also a component that enhances mechanical strength and chemical resistance. Therefore, it is preferable to contain MgO when the Al 2 O 3 content is relatively small.
- the content of MgO is preferably 1% or more, more preferably 2% or more, still more preferably 3% or more, and particularly preferably 4% or more.
- MgO is 7% or less.
- Y 2 O 3 is a component that has the effect of making it difficult for fragments to scatter when the chemically strengthened glass is broken, and may be contained.
- the content of Y 2 O 3 is preferably 1% or more, more preferably 1.5% or more, still more preferably 2% or more, particularly preferably 2.5% or more, and extremely preferably 3% or more.
- the content of Y 2 O 3 is preferably 5% or less, more preferably 4% or less.
- B 2 O 3 is a component that improves the chipping resistance of chemically strengthened glass or chemically strengthened glass and improves the meltability, and may be contained.
- the content is preferably 0.5% or more, more preferably 1% or more, and still more preferably 2% or more, in order to improve meltability.
- the content of B 2 O 3 is more preferably 8% or less, still more preferably 6% or less, and particularly preferably 4% or less.
- Na 2 O is a component that improves the meltability of glass.
- Na 2 O is not essential, but when it is included, it is preferably 0.5% or more, more preferably 1% or more, and particularly preferably 2% or more. Too much Na 2 O makes it difficult for crystals such as Li 3 PO 4 , which is the main crystal, to precipitate, or deteriorates the chemical strengthening properties .
- the following is more preferable, 4% or less is still more preferable, and 3.5% or less is particularly preferable.
- K 2 O is a component that lowers the melting temperature of the glass and may be contained.
- the content is preferably 0.5% or more, more preferably 1% or more, still more preferably 1.5% or more, and particularly preferably 2% or more. If the amount of K 2 O is too large, the chemical strengthening properties or the chemical durability will decrease, so it is preferably 5% or less, more preferably 4% or less, still more preferably 3.5% or less, and particularly preferably 3%. % or less, most preferably 2.5% or less.
- the total content of Na 2 O and K 2 O, Na 2 O+K 2 O is preferably 1% or more, more preferably 2% or more, in order to improve the meltability of the glass raw material.
- K 2 O/R 2 O of the K 2 O content to the total content of Li 2 O, Na 2 O and K 2 O (hereinafter referred to as R 2 O) is 0.2 or less. It is preferred because it can enhance the reinforcing properties and enhance the chemical durability. K 2 O/R 2 O is more preferably 0.15 or less, even more preferably 0.10 or less.
- the R 2 O content is preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more. Also, R 2 O is preferably 29% or less, more preferably 26% or less.
- ZrO 2 /R 2 O is preferably 0.02 or more, more preferably 0.03 or more, still more preferably 0.04 or more, and particularly 0.1 or more. Preferably, 0.15 or more is most preferred. In order to increase transparency after crystallization, ZrO 2 /R 2 O is preferably 0.6 or less, more preferably 0.5 or less, still more preferably 0.4 or less, and particularly 0.3 or less. preferable.
- SnO 2 has the effect of promoting the formation of crystal nuclei and may be contained.
- SnO 2 is not essential, but when it is contained, it is preferably 0.5% or more, more preferably 1% or more, still more preferably 1.5% or more, and particularly preferably 2% or more.
- the SnO 2 content is preferably 5% or less, more preferably 4% or less, even more preferably 3.5% or less, and particularly preferably 3% or less.
- TiO 2 is a component that can promote crystallization and may be contained. TiO 2 is not essential, but if it is included, it is preferably 0.2% or more, more preferably 0.5% or more. On the other hand, in order to suppress devitrification during melting, the content of TiO 2 is preferably 4% or less, more preferably 2% or less, and even more preferably 1% or less.
- BaO, SrO, MgO, CaO and ZnO are all components that improve the meltability of the glass and may be contained.
- the total content of BaO, SrO, MgO, CaO and ZnO (hereinafter, BaO + SrO + MgO + CaO + ZnO) is preferably 0.5% or more, more preferably 1% or more, and still more preferably 1.5% 2% or more, particularly preferably 2% or more.
- the content of BaO+SrO+MgO+CaO+ZnO is preferably 8% or less, more preferably 6% or less, still more preferably 5% or less, and particularly preferably 4% or less, because the ion exchange rate decreases.
- BaO, SrO, and ZnO may be contained in order to improve the light transmittance of the crystallized glass by improving the refractive index of the residual glass and bring it closer to the precipitated crystal phase, thereby lowering the haze value.
- the total content of BaO, SrO and ZnO (hereinafter, BaO + SrO + ZnO) is preferably 0.3% or more, more preferably 0.5% or more, still more preferably 0.7% or more, and particularly 1% or more. preferable.
- these components may reduce the ion exchange rate.
- BaO+SrO+ZnO is preferably 2.5% or less, more preferably 2% or less, even more preferably 1.7% or less, and particularly preferably 1.5% or less.
- La 2 O 3 , Nb 2 O 5 and Ta 2 O 5 are all components that make it difficult for fragments to scatter when the chemically strengthened glass is broken, and may be contained in order to increase the refractive index.
- the total content of La 2 O 3 , Nb 2 O 5 and Ta 2 O 5 (hereinafter referred to as La 2 O 3 +Nb 2 O 5 +Ta 2 O 5 ) is preferably 0.5% or more. more preferably 1% or more, still more preferably 1.5% or more, and particularly preferably 2% or more.
- La 2 O 3 +Nb 2 O 5 +Ta 2 O 5 is preferably 4% or less, more preferably 3% or less, still more preferably 2% or less, so that the glass is less likely to devitrify during melting. It is preferably 1% or less.
- CeO 2 may suppress coloration by oxidizing the glass.
- the content is preferably 0.03% or more, more preferably 0.05% or more, and even more preferably 0.07% or more.
- the content of CeO 2 is preferably 1.5% or less, more preferably 1.0% or less, in order to increase transparency.
- coloring component When the present chemically strengthened glass is colored and used, a coloring component may be added within a range that does not hinder the achievement of desired chemical strengthening properties.
- coloring components include Co3O4 , MnO2 , Fe2O3 , NiO , CuO , Cr2O3 , V2O5 , Bi2O3 , SeO2 , Er2O3 , Nd2O . 3 is mentioned.
- the total content of coloring components is preferably in the range of 1% or less. If it is desired to increase the visible light transmittance of the glass, it is preferred that these components are not substantially contained.
- SO 3 , chlorides, and fluorides may be appropriately contained as clarifiers and the like when melting the glass.
- 2 O 3 is preferably not contained.
- Sb 2 O 3 is contained, it is preferably 0.3% or less, more preferably 0.1% or less, and most preferably not contained.
- the chemically strengthened glass of the present invention is produced by chemically strengthening the crystallized glass described above.
- the crystallized glass is produced by heat-treating an amorphous glass having the same composition to crystallize it.
- 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 glass raw materials are mixed so that a glass with the desired composition can be 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.
- Crystallized glass is obtained by heat-treating the amorphous glass obtained by the above procedure.
- the heat treatment may be a two-stage heat treatment in which the temperature is raised from room temperature to the first treatment temperature and held for a certain period of time, and then held at a second treatment temperature higher than the first treatment temperature for a certain period of time.
- a one-step heat treatment of cooling to room temperature after holding at a specific treatment temperature may be used.
- 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 crystallized glass obtained by the above procedure is ground and polished as necessary to form a crystallized glass plate.
- a crystallized glass plate is cut into a predetermined shape and size or chamfered, if the cutting or chamfering is performed before the chemical strengthening treatment, the compressive stress will also be applied to the end face due to the subsequent chemical strengthening treatment. It is preferred because layers are formed.
- 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, for example, 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 can be selected in consideration of the glass composition and the type of molten salt.
- the present crystallized glass may be chemically strengthened at 450° C. or less for preferably 1 hour or less.
- a molten salt containing 0.3% by mass of Li and 99.7% by mass of Na at 450° C. (for example, a mixed salt of lithium nitrate and sodium nitrate) is preferably heated for 0.5 hours.
- a treatment that is immersed to a certain extent can be mentioned.
- the chemical strengthening treatment may be performed by two or more stages of ion exchange.
- the two-step ion exchange is performed, for example, as follows.
- the present crystallized glass is preferably immersed in a metal salt containing Na ions (eg, sodium nitrate) at about 350 to 500° C. for about 0.1 to 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, forming a relatively deep compressive stress layer.
- the maximum tensile stress value of the stress profile formed inside the glass by the first ion exchange is preferably greater than the CT limit.
- the maximum tensile stress value after the first ion exchange is greater than the CT limit, so that the first ion exchange introduces sufficient compressive stress to reduce the stress value of the glass surface layer in the subsequent second ion exchange step.
- CS 50 and CS 90 can be kept high even after
- CT limit is obtained by the following formula (1).
- CTA corresponds to CT limit and is a value determined by the composition of the glass for chemical strengthening.
- CTave is a value corresponding to the average value of tensile stress, and CTave is obtained by the following formula (2). If CTave ⁇ CTA, it is below the CT limit, and an explosive increase in the number of fractures during injury can be suppressed.
- a metal salt containing K ions eg, potassium nitrate
- K ions eg, potassium nitrate
- a large compressive stress is generated in the compressive stress layer formed by the previous process, for example, within a depth of about 10 ⁇ m.
- a stress profile with a large surface compressive stress value is likely to be obtained.
- Chemically strengthened glass having a minimum depth z at which K x is (K t/2 +0.1) [%] or more is 0.5 to 5 ⁇ m.
- the K 2 O concentration at the depth x [ ⁇ m] from the surface is K x [%]
- the K 2 O content before chemical strengthening is K t / 2 [%] expressed as a molar percentage based on oxides.
- the surface compressive stress value CS0 is 450 MPa or more, the compressive stress value CS50 at a depth of 50 ⁇ m from the surface is 150 MPa or more, and the compressive stress value CS90 at a depth of 90 ⁇ m from the surface is 30 MPa or more.
- the surface compressive stress value CS 0 is 450 MPa or more
- K ion penetration depth D is 0.5 to 5 ⁇ m
- the absolute value of the difference between the compressive stress value at the K ion penetration depth D and the compressive stress value CS50 at a depth of 50 ⁇ m from the surface is 150 MPa or less
- the compressive stress value at the K ion penetration depth D is 350 MPa or less
- Chemically strengthened glass having a surface compressive stress value CS0 of 450 MPa or more, a compressive stress value CS50 at a depth of 50 ⁇ m from the surface of 150 MPa or more, and a compressive stress value CS90 at a depth of 90 ⁇ m from the surface of 30 MPa or more.
- CS 0 is the surface compressive stress value (MPa) and D is the K ion penetration depth ( ⁇ m). 13.
- the slope of the stress profile of the chemically strengthened glass in the region between the depth of 50 ⁇ m from the surface and the depth of 90 ⁇ m from the surface is P 50-90 (MPa / ⁇ m), and the depth of 90 ⁇ m from the surface and the compressive stress value are When the slope of the stress profile of the chemically strengthened glass in the region between the zero depth (DOL) ( ⁇ m) is P90-DOL (MPa/ ⁇ m),
- the P 50-90 and the P 90-DOL are obtained by the following equations.
- P50-90 ( CS50 - CS90 )/40
- P90-DOL CS90/(DOL- 90 ) 14.
- the slope of the stress profile of the chemically strengthened glass in the region between the depth of 50 ⁇ m from the surface and the depth of 90 ⁇ m from the surface is P 50-90 (MPa / ⁇ m), and the depth of 90 ⁇ m from the surface and the compressive stress value are When the slope of the stress profile of the chemically strengthened glass in the region between the zero depth ( DOL ) ( ⁇ m) is P90 -DOL (MPa/ ⁇ m), -DOL
- the K 2 O concentration at the depth x [ ⁇ m] from the surface is defined as K x [%] in the chemically strengthened glass oxide-based molar percentage display, and the K 2 O content in the glass before the chemical strengthening is When K t/2 [%],
- 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.
- Some of the obtained blocks were used to evaluate the glass transition point, specific gravity, Young's modulus and fracture toughness of the amorphous glass, and Table 1 shows the results.
- R 2 O in the table represents the total content of Li 2 O, Na 2 O and K 2 O
- NWF represents the total content of SiO 2 , Al 2 O 3 , P 2 O 5 and B 2 O 3 . .
- Glass transition point Tg Glass was pulverized using an agate mortar, and about 80 mg of powder was placed in a platinum cell and heated from room temperature to 1100°C at a rate of 10/min while a differential scanning calorimeter (manufactured by Bruker; DSC3300SA) was measured. A DSC curve was measured using the glass transition point Tg.
- a thermal expansion meter manufactured by Bruker AXS; TD5000SA
- a thermal expansion curve is obtained at a temperature increase rate of 10 ° C./min, and from the obtained thermal expansion curve
- a glass transition point Tg [unit: °C] was determined.
- haze value Using a haze meter (manufactured by Suga Test Instruments; HZ-V3), a haze value [unit: %] was measured with a halogen lamp C light source.
- the resulting glass block was processed into a size of 50 mm ⁇ 50 mm ⁇ 1.5 mm and then heat-treated under the conditions shown in Table 2 to obtain crystallized glass.
- the upper row is the nucleation treatment condition
- the lower row is the crystal growth treatment condition. , means that it was held at 730° C. for 2 hours.
- the obtained crystallized glass was processed and mirror-polished to obtain a crystallized glass plate with a thickness t of 700 ⁇ m.
- a rod-shaped sample was also prepared for measuring the coefficient of thermal expansion.
- a portion of the remaining crystallized glass was pulverized and used for analysis of precipitated crystals. Table 2 shows the evaluation results of the crystallized glass.
- the main crystals detected are shown in the column of crystals in Table 2. Since it is difficult to distinguish between Li 3 PO 4 and Li 4 SiO 4 by powder X-ray diffraction, both are shown together.
- haze value Using a haze meter (manufactured by Suga Test Instruments; HZ-V3), a haze value [unit: %] was measured with a halogen lamp C light source.
- Table 4 shows the evaluation results of chemically strengthened glass.
- a blank (slanted line) indicates non-evaluation.
- the stress profiles of Examples 1 and 5 are shown in FIG.
- the plate thickness of Examples 1 to 7 in Table 4 is 700 mm
- the plate thickness of Examples 8 and 9 is 550 mm.
- Examples 1 to 4 and 6 to 9 are examples, and Example 5 is a comparative example.
- Examples 8 and 9 were chemically strengthened under the same conditions as Examples 6 and 7 shown in Table 3, respectively.
- EPMA Measurement by EPMA was performed as follows. First, a glass sample was embedded in an epoxy resin and mechanically polished in the direction perpendicular to the first main surface and the second main surface opposite to the first main surface to prepare a cross-sectional sample. A C coat was applied to the cross section after polishing, and measurement was performed using an EPMA (manufactured by JEOL: JXA-8500F). The acceleration voltage is 15 kV, the probe current is 30 nA, and the integration time is 1000 msec. A line profile of the X-ray intensity of K, Na or Li was acquired at intervals of 1 ⁇ m as /point.
- the K ion penetration depth D was determined by the following procedures (1) to (3).
- Example 6 the warpage caused by polishing using a rotary polishing machine (device name: 9B-5P, manufacturer: SPEEDFAM) was measured using a contact shape meter (device name: SV-600, manufacturer: Mitutoyo ) was used.
- stress profile The stress profile was measured using a scattered light photoelastic stress meter SLP-2000 manufactured by Orihara Seisakusho.
- Drop test In the drop test, the obtained 120 ⁇ 60 ⁇ 0.6 mmt glass sample was fitted into a structure whose mass and rigidity were adjusted to the size of a general smartphone currently in use, and after preparing a pseudo smartphone, # Free fall onto #180 SiC sandpaper for 180 drop strength or #80 SiC sandpaper for #80 drop strength.
- the drop height if it was dropped from a height of 5 cm and did not crack, the work of raising the height by 5 cm and dropping it again was repeated until it cracked, and the average value of 10 sheets of the height when it cracked for the first time was calculated.
- AFP durability (10000 times) was measured under the following conditions by an eraser wear test.
- Eraser abrasion test conditions The surface of the chemically strengthened glass plate was washed with ultraviolet rays and spray-coated with OPTOOL (registered trademark) DSX (manufactured by Daikin) to form a substantially uniform AFP film on the surface of the glass plate.
- An eraser (Minoan, manufactured by MIRAE SCIENCE) was attached to an indenter of 1 cm 2 , and while a load of 1 kgf was applied, the surface of the AFP film formed on the surface of the glass plate was reciprocated 10,000 times at a stroke width of 20 mm and a speed of 30 mm/sec.
- the surface of the AFP membrane was washed by wiping with a cloth [DUSPER (registered trademark), manufactured by Ozu Sangyo Co., Ltd.], and then the water contact angle (°) was measured at three points on the AFP membrane surface. This was repeated three times, and a total of nine average water contact angles (°) were measured.
- the water contact angle (°) of the AFP film surface was measured by a method based on JIS R 3257 (1999).
- Chemically strengthened glass is processed into a strip of 120 mm ⁇ 60 mm, and a four-point bending test is performed under the conditions of a support tool with a distance between external fulcrums of 30 mm, a distance between internal fulcrums of 10 mm, and a crosshead speed of 5.0 mm / min. Four-point bending strength was measured. The number of test pieces was 10.
- the chemically strengthened glass was processed into a strip shape, then automatically chamfered (C chamfering) using a 1000-grit grindstone (manufactured by Tokyo Diamond Tool Manufacturing Co., Ltd.), and a 0.1 mm diameter nylon brush and Shorox NZ abrasive grains.
- 4PB strength is 779 MPa or more.
- B The 4PB strength is 600 MPa or more and less than 779 MPa.
- C 4PB strength is less than 600 MPa.
- Examples 1 to 4 and 6 to 9 which are examples, are superior in chemical strengthening properties, have high AFP durability, and have excellent coating properties compared to Example 5, which is a comparative example. It was found that peeling can be effectively suppressed. Further, in Examples 1 to 4, compressive stress was introduced to a range exceeding the CT limit after the first ion exchange, and the stress value of the glass surface layer was reduced in the second ion exchange step.
- Table 5 shows the results of measuring the 4PB strength for Examples 1, 6 and 7.
- the chemically strengthened glasses of Examples 6 and 7 exhibited higher 4PB strength (MPa) than the chemically strengthened glass of Example 1. From the viewpoint of seeking chemically strengthened glass with higher bending strength, Examples 6 and 7 are preferable because the 4PB strength (MPa) exceeds 550 MPa. It was found that the condition of
- Table 6 shows the chemically strengthened glass of Examples 1 to 9, the surface layer slope P 0 in the glass surface layer, the stress profile of the chemically strengthened glass in the region between the depth of 50 ⁇ m from the surface and the depth of 90 ⁇ m from the surface.
- the slope of the stress profile of the chemically strengthened glass in the region between the depth of 90 ⁇ m from the surface and the depth (DOL) ( ⁇ m) at which the compressive stress value is zero
- Example 6 As shown in Table 6, in Examples 1 to 4 and 6 to 9, which are examples, the value of P 0 is ⁇ 1000 MPa/ ⁇ m ⁇ P 0 ⁇ 225 MPa/ ⁇ m compared to Example 5 which is a comparative example. It was confirmed that the 4PB strength was in the range exceeding 550 MPa.
- (MPa/ ⁇ m) is
- ⁇ 4.0 were confirmed to have a #180 drop strength of 100 cm or more.
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Abstract
Description
K1c:破壊靱性値(MPa・m1/2)
CTave=ICT/LCT…式(2)
ICT:引張応力の積分値(Pa・m)
LCT:引張応力領域の板厚方向長さ(μm)
K1c:破壊靱性値(MPa・m1/2)
CTave=ICT/LCT…式(2)
ICT:引張応力の積分値(Pa・m)
LCT:引張応力領域の板厚方向長さ(μm)
まず、ガラス試料をエポキシ樹脂で包埋し、第1の主面および第1の主面に対向する第2の主面に対して垂直方向に機械研磨して断面試料を作製する。研磨後の断面にCコートを施し、EPMA(JEOL社製:JXA-8500F)を用いて測定を行う。加速電圧は15kV、プローブ電流は30nA、積算時間は1000msec./pointとして1μm間隔でK、NaまたはLiのX線強度のラインプロファイルを取得する。
(1)まず、上記した折原製作所製散乱光光弾性応力計SLP-2000を用いて、化学強化ガラスの圧縮応力値(CS)の深さ方向プロファイルを測定する。
(2)次に、(1)においてSLP-2000を用いて圧縮応力値の深さ方向プロファイルを測定したものと同じ化学強化ガラスについて、次の方法により深さ方向プロファイルを測定する。
ガラスの片面をシールした状態で、体積分率で1%HF-99%H2Oの酸に浸漬し、片面のみを任意の厚さエッチングする。これにより、化学強化ガラスの表裏面に応力差が発生し、その応力差に応じてガラスが反る。その反り量を、接触式形状計(ミツトヨ製Surftest)を用いて測定する。反り量はエッチング深さ3点以上で測定する。
得られた反り量から、以下の文献に示された式を用いて応力に換算し、圧縮応力値の深さ方向プロファイルを得る。
文献:G. G. Stoney, Proc. Roy. Soc. London Ser. A, 82, 172 (1909).
(3)(1)及び(2)の手順で得られた2つのプロファイルを重ねて、交差する点の深さが「Kイオン侵入深さD」である。
このエッチング処理は、回転研磨機(装置名:9B-5P メーカー:SPEEDFAM)を用いた研磨によって生じた反りを接触式形状計(装置名:SV-600メーカー:ミツトヨ)で測定してもよい。特に本化学強化ガラスに、結晶化ガラスを使用する場合、上記酸によるエッチング処理が正しくできないため、回転研磨機(装置名:9B-5P メーカー:SPEEDFAM)と接触式形状計(装置名:SV-600メーカー:ミツトヨ)を用いて反り量を測定することが好ましい。
120×60×0.6mmtのガラスサンプルを一般的なスマートフォンのサイズに質量と剛性を調節した構造体にはめ込み、疑似スマートフォンを用意した上で、#180落下強度については#180SiCサンドペーパー、または#80落下強度については#80SiCサンドペーパーの上に自由落下させた。落下高さは、5cmの高さから落下させて割れなかった場合は5cm高さを上げて再度落下させる作業を割れるまで繰り返し、初めて割れたときの高さの10枚の平均値を測定する。
消しゴム摩耗試験条件:
化学強化したガラス板表面を紫外線洗浄し、オプツール(登録商標)DSX(ダイキン社製)をスプレーコーティングしてガラス板表面上に略均一なAFP膜を形成する。
1cm2の圧子に消しゴム(MIRAE SCIENCE社製、minoan)を取り付け、1kgfの荷重をかけた状態で、ガラス板表面上に形成されたAFP膜表面をストローク幅20mm、速度30mm/secで10000回往復摩擦した後、布[小津産業社製、DUSPER(登録商標)]にて乾拭きしてAFP膜表面を洗浄した後、AFP膜表面の3カ所で水接触角(°)を測定する。これを3回繰り返し、合計9個の平均水接触角(°)を測定する。AFP膜表面の水接触角(°)は、JIS R 3257(1999年)に準拠した方法により測定する。
120mm×60mmの短冊状の試験片を用いて、支持具の外部支点間距離が30mm、内部支点間距離が10mm、クロスヘッド速度が5.0mm/minの条件で4点曲げ試験を行うことで評価できる。試験片の個数は、たとえば10個とする。
本発明の化学強化ガラス(以下、本化学強化ガラスとも略す。)は、典型的には板状のガラス物品であり、平板状でもよく曲面状でもよい。また、厚さの異なる部分があってもよい。
本化学強化ガラスの実施態様1は、厚さがt[μm]であり、酸化物基準のモル百分率表示で、表面からの深さx[μm]におけるK2O濃度をKx[%]とし、化学強化前のK2Oの含有量をそれぞれKt/2[%]としたとき、Kxが(Kt/2+0.1)[%]以上となる最小の深さzが0.5~5μmである化学強化ガラスである。zは好ましくは0.6~4.5μmであり、より好ましくは0.7~4μmであり、さらに好ましくは0.8~3.5μm、特に好ましくは0.85~3である。前記深さzが0.5~5μmであることにより、アルカリ混合効果による表面抵抗率の増大を抑制できる。
P50-90及びP90-DOLは、それぞれ下記式により求められる。
P50-90=(CS50-CS90)/40
P90-DOL=CS90/(DOL-90)
本化学強化ガラスの実施態様2は、Kイオン侵入深さDが0.5~5μmであり、深さDにおける圧縮応力値と表面からの深さ50μmにおける圧縮応力値CS50との差の絶対値が150MPa以下であり、Kイオン侵入深さDにおける圧縮応力値が350MPa以下であり、表面圧縮応力値CS0が450MPa以上、表面からの深さ50μmにおける圧縮応力値CS50が150MPa以上、表面からの深さ90μmにおける圧縮応力値CS90が30MPa以上である、化学強化ガラスである。
本化学強化ガラスは、表面抵抗logρが12Ω・cm以下であることが好ましく、より好ましくは11.5Ω・cm以下、さらに好ましくは11Ω・cm以下である。表面抵抗logρが12Ω・cm以下であることにより、コーティング膜の剥がれを抑制できる。表面抵抗logρの下限は特に制限されないが、典型的には8Ω・cm以上である。
本化学強化ガラスは、#180落下強度が100cm以上であることが好ましく、より好ましくは140cm以上、さらに好ましくは180cm以上である。#180落下強度が100cm以上であることにより、本化学強化ガラスをカバーガラスとして備える携帯端末等を砂などに落とした際の本化学強化ガラスの割れを抑制できる。#180落下強度の上限は特に制限されないが、典型的には300cm以下である。
本化学強化ガラスは、AFP耐久性(10000回)が100度以上であることが好ましく、より好ましくは105度以上、さらに好ましくは110度以上である。AFP耐久性(10000回)が100度以上であることにより、コーティング膜の剥がれを抑制できる。AFP耐久性(10000回)の上限は特に制限されないが、典型的には125度以下である。
本化学強化ガラスは、携帯電話、スマートフォン等のモバイル機器等の電子機器に用いられるカバーガラスとしても有用である。さらに、携帯を目的としない、テレビ、パーソナルコンピュータ、タッチパネル等の電子機器のカバーガラス、エレベータ壁面、家屋やビル等の建築物の壁面(全面ディスプレイ)にも有用である。また、窓ガラス等の建築用資材、テーブルトップ、自動車や飛行機等の内装等やそれらのカバーガラスとして、また曲面形状を有する筺体等にも有用である。
本化学強化ガラスの母組成は、SiO2、Li2O、Al2O3を含有することが好ましい。本化学強化ガラスは、母組成が酸化物基準のモル%表示で、
SiO2を40~75%、
Li2Oを5~35%、
Al2O3を1~20%、含有することが好ましい。
また、
SiO2を40~70%、
Li2Oを5~35%、
Al2O3を1~20%、含有することがより好ましい。
Li2Oを10~30%、
Al2O3を1~15%、
P2O5を0~5%、
ZrO2を0~8%、
MgOを0~10%、
Y2O3を0~5%
B2O3を0~10%、
Na2Oを0~5%、
K2Oを0~5%、
SnO2を0~2%、含有することがさらに好ましい。
(i)SiO2を61.0%、Li2Oを21.0%、Al2O3を5.0%、Na2Oを2.0%、P2O5を2.0%、ZrO2を3.0%、MgOを5.0%、Y2O3を1.0%、含有するガラス。
(ii)SiO2を51.2%、Li2Oを34.1%、Al2O3を5.0%、Na2Oを1.8%、P2O5を2.3%、ZrO2を4.5%、Y2O3を1.0%、含有するガラス。
(iii)SiO2を54.0%、Li2Oを30.9%、Al2O3を5.4%、Na2Oを1.7%、K2Oを1.2%、P2O5を1.9%、ZrO2を3.9%、Y2O3を0.7%、含有するガラス。
また、微量成分としてSb2O3、HfO2などの不純物を含んでもよい。
本化学強化ガラスは、強度を高める点から、結晶化ガラス(以下、本結晶化ガラスともいう)からなることが好ましい。結晶化ガラスは、非晶質ガラスと比較して優れた強度を有するため、従来の化学強化ガラスと比較してガラス表面のアルカリ混合度が低い場合であっても、好ましい応力プロファイルを形成しやすく、ガラスの強度と表面特性とを両立し易い。
すなわち、ヘーズ値は、板厚が増すごとに内部直線透過率に比例した分増えると考えることができるので、700μmの場合のヘーズ値H0.7は、以下の式で求められる。
H0.7=100×[1-(1-H){((1-R)2-T0.7)/((1-R)2-T)}][%]
また、板厚tが700μmよりも大きい場合は、研磨やエッチングなどで板厚を700μmに調整して測定してもよい。
本結晶化ガラスは、SiO2、Li2O、Al2O3を含有することが好ましい。本結晶化ガラスは、酸化物基準のモル%表示で、
SiO2を40~75%、
Li2Oを5~35%、
Al2O3を1~20%、含有することが好ましい。
また、
SiO2を40~70%、
Li2Oを5~35%、
Al2O3を1~20%、含有することがより好ましい。
また、SiO2を50~70%、
Li2Oを10~30%、
Al2O3を1~15%、
P2O5を0~5%、
ZrO2を0~8%、
MgOを0~10%、
Y2O3を0~5%
B2O3を0~10%、
Na2Oを0~5%、
K2Oを0~5%、
SnO2を0~2%、含有することがさらに好ましい。
(i)SiO2を61.0%、Li2Oを21.0%、Al2O3を5.0%、Na2Oを2.0%、P2O5を2.0%、ZrO2を3.0%、MgOを5.0%、Y2O3を1.0%、含有するガラス。
(ii)SiO2を51.2%、Li2Oを34.1%、Al2O3を5.0%、Na2Oを1.8%、P2O5を2.3%、ZrO2を4.5%、Y2O3を1.0%、含有するガラス。
(iii)SiO2を54.0%、Li2Oを30.9%、Al2O3を5.4%、Na2Oを1.7%、K2Oを1.2%、P2O5を1.9%、ZrO2を3.9%、Y2O3を0.7%、含有するガラス。
また、微量成分としてSb2O3、HfO2などの不純物を含んでもよい。
以下、本結晶化ガラスの組成を説明する。
本発明の化学強化ガラスは、上記した結晶化ガラスを化学強化処理して製造する。該結晶化ガラスは、同じ組成の非晶質ガラスを加熱処理して結晶化する方法で製造する。
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非晶質ガラスを加熱処理することで結晶化ガラスが得られる。
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。
K1c:破壊靱性値(MPa・m1/2)
CTave=ICT/LCT…式(2)
ICT:引張応力の積分値(Pa・m)
LCT:引張応力領域の板厚方向長さ(μm)
1.厚さがt[μm]であり、Li2O、K2OおよびNa2Oを含有する化学強化ガラスであって、
酸化物基準のモル百分率表示で、表面からの深さx[μm]におけるK2O濃度をKx[%]とし、化学強化前のK2Oの含有量をKt/2[%]としたとき、
Kxが(Kt/2+0.1)[%]以上となる最小の深さzが0.5~5μmである、化学強化ガラス。
2.酸化物基準のモル百分率表示で、表面からの深さx[μm]におけるK2O濃度をKx[%]、とし、化学強化前のK2Oの含有量をKt/2[%]としたときのKxが(Kt/2+0.1)[%]以上となる最小の深さz[μm]におけるNa2O濃度をNaz[%]とし、
表面からの深さ50μmにおけるNa2O濃度をNa50[%]としたとき、
|Naz-Na50|<3[%]である、前記1に記載の化学強化ガラス。
3.酸化物基準のモル百分率表示で、表面からの深さ50μmにおけるNa2O濃度をNa50[%]とし、化学強化前のNa2Oの含有量をNat/2[%]としたとき、
Na50<Nat/2+7[%]である、前記1に記載の化学強化ガラス。
4.酸化物基準のモル百分率表示で、表面からの深さ1μmにおけるK2O濃度をK1[%]、Na2O濃度をNa1[%]とし、
化学強化前のLi2O、Na2OおよびK2Oの含有量をそれぞれLit/2[%]、Nat/2[%]およびKt/2[%]としたとき、
(Lit/2+Nat/2+Kt/2)-2(Na1+K1)>0[%]である、前記1~3のいずれか1に記載の化学強化ガラス。
5.表面圧縮応力値CS0が450MPa以上、表面からの深さ50μmにおける圧縮応力値CS50が150MPa以上、且つ表面からの深さ90μmにおける圧縮応力値CS90が30MPa以上である、前記1~4のいずれか1に記載の化学強化ガラス。
6.表面圧縮応力値CS0が450MPa以上、表面からの深さ50μmにおける圧縮応力値CS50がy=124.7×t+21.5[MPa]以上、且つ表面からの深さ90μmにおける圧縮応力値CS90がy=99.1×t-38.3[MPa]以上である、前記1~4のいずれか1に記載の化学強化ガラス。
7.Kイオン侵入深さDが0.5~5μmであり、
前記Kイオン侵入深さDにおける圧縮応力値と表面からの深さ50μmにおける圧縮応力値CS50との差の絶対値が150MPa以下であり、
前記Kイオン侵入深さDにおける圧縮応力値が350MPa以下であり、
表面圧縮応力値CS0が450MPa以上、表面からの深さ50μmにおける圧縮応力値CS50が150MPa以上、表面からの深さ90μmにおける圧縮応力値CS90が30MPa以上である、化学強化ガラス。
8.結晶化ガラスからなる、前記1~7のいずれか1に記載の化学強化ガラス。
9.母組成が酸化物基準のモル百分率表示で、SiO2を40~75%、Al2O3を1~20%、Li2Oを5~35%含有する、前記1~8のいずれか1に記載の化学強化ガラス。
10.2段階以上のイオン交換がされた化学強化ガラスであり、最初のイオン交換である第1イオン交換後のCTaveがCTAより大きい、前記1~9のいずれか1に記載の化学強化ガラス。CTAは下式(1)により、CTaveは下式(2)によりそれぞれ求められる。
K1c:破壊靱性値(MPa・m1/2)
CTave=ICT/LCT…式(2)
ICT:引張応力の積分値(Pa・m)
LCT:引張応力領域の板厚方向長さ(μm)
11.厚さtが300~1500μmである前記1~10のいずれか1に記載の化学強化ガラス。
12.式CS0/Dで定義されるガラス表層における表層傾きをP0とした場合に、-1000MPa/μm<P0<-225MPa/μmである前記1~11のいずれか1に記載の化学強化ガラス。前記式において、CS0は表面圧縮応力値(MPa)、DはKイオン侵入深さ(μm)である。
13.表面からの深さ50μmと表面からの深さ90μmとの間の領域の化学強化ガラスの応力プロファイルの傾きをP50-90(MPa/μm)とし、表面からの深さ90μmと圧縮応力値がゼロとなる深さ(DOL)(μm)との間の領域の化学強化ガラスの応力プロファイルの傾きをP90-DOL(MPa/μm)とした場合に、|P50-90|>|P90-DOL|であって、1.8<|P50-90|<6.0且つ1.5<|P90-DOL|<4.0である前記1~12のいずれか1に記載の化学強化ガラス。
前記P50-90及び前記P90-DOLは、下記式により求められる。
P50-90=(CS50-CS90)/40
P90-DOL=CS90/(DOL-90)
14.表面からの深さ50μmと表面からの深さ90μmとの間の領域の化学強化ガラスの応力プロファイルの傾きをP50-90(MPa/μm)とし、表面からの深さ90μmと圧縮応力値がゼロとなる深さ(DOL)(μm)との間の領域の化学強化ガラスの応力プロファイルの傾きをP90-DOL(MPa/μm)とした場合に、|P50-90|<|P90-DOL|であって、1.0<|P50-90|<3.0且つ1.2<|P90-DOL|<4.0である前記1~13のいずれか1に記載の化学強化ガラス。
前記P50-90及び前記P90-DOLは、下記式により求められる。
P50-90=(CS50-CS90)/40
P90-DOL=CS90/(DOL-90)
15.厚さがt[μm]であり、Li2Oを含有するガラスを化学強化することを含む、Li2O、K2OおよびNa2Oを含有する化学強化ガラスの製造方法であって、
前記化学強化ガラスの酸化物基準のモル百分率表示で、表面からの深さx[μm]におけるK2O濃度をKx[%]とし、前記化学強化前のガラスにおけるK2Oの含有量をKt/2[%]としたとき、
Kxが(Kt/2+0.1)[%]以上となる最小の深さzが0.5~5μmとなるように化学強化する、化学強化ガラスの製造方法。
16.前記Li2Oを含有するガラスが結晶化ガラスからなる前記15に記載の化学強化ガラスの製造方法。
17.前記化学強化が2段階以上のイオン交換を含み、最初のイオン交換である第1イオン交換後のCTaveがCTAより大きい、請求項16に記載の化学強化ガラスの製造方法。CTAは下式(1)により、CTaveは下式(2)によりそれぞれ求められる。
K1c:破壊靱性値(MPa・m1/2)
CTave=ICT/LCT…式(2)
ICT:引張応力の積分値(Pa・m)
LCT:引張応力領域の板厚方向長さ(μm)
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。
アルキメデス法で測定した。
メノウ乳鉢を用いてガラスを粉砕し、約80mgの粉末を白金セルに入れて昇温速度を10/分として室温から1100℃まで昇温しながら、示差走査熱量計(ブルカー社製;DSC3300SA)を用いてDSC曲線を測定し、ガラス転移点Tgを求めた。
または、JIS R1618:2002に基づき、熱膨張計(ブルカー・エイエックスエス社製;TD5000SA)を用いて、昇温速度を10℃/分として熱膨張曲線を得て、得られた熱膨張曲線からガラス転移点Tg[単位:℃]を求めた。
ヘーズメーター(スガ試験機製;HZ-V3)を用いて、ハロゲンランプC光源でのヘーズ値[単位:%]測定した。
超音波法で測定した。
JIS R1607:2015に準拠してIF法で測定した。
CTA値は下記式(1)より求めた。
K1c:破壊靱性値(MPa・m1/2)
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に記載の条件で熱処理して結晶化ガラスを得た。表の結晶化条件欄は、上段が核生成処理条件、下段が結晶成長処理条件であり、たとえば上段に550℃2h、下段に730℃2hと記載した場合は、550℃で2時間保持した後、730℃で2時間保持したことを意味する。
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。
測定装置:リガク社製 Smart Lab
使用X線:CuKα線
測定範囲:2θ=10°~80°
スピード:1°/分
ステップ:0.01°
ヘーズメーター(スガ試験機製;HZ-V3)を用いて、ハロゲンランプC光源でのヘーズ値[単位:%]測定した。
結晶化ガラスCG1、CG2について表3に示す条件で化学強化し、それぞれ例1~7とした。表3の例1~4、6、7は実施例、例5は比較例である。表3中「%」は「質量%」を表す。
EPMAによる測定は、以下のようにして行った。まず、ガラス試料をエポキシ樹脂で包埋し、第1の主面および第1の主面に対向する第2の主面に対して垂直方向に機械研磨して断面試料を作製した。研磨後の断面にCコートを施し、EPMA(JEOL社製:JXA-8500F)を用いて測定を行った。加速電圧は15kV、プローブ電流は30nA、積算時間は1000msec./pointとして1μm間隔でK、NaまたはLiのX線強度のラインプロファイルを取得した。
Kイオン侵入深さDは、以下の(1)~(3)の手順により求めた。
(1)折原製作所製散乱光光弾性応力計SLP-2000を用いて、化学強化ガラスの圧縮応力値(CS)の深さ方向プロファイルを測定した。
(2)次に、(1)においてSLP-2000を用いて圧縮応力値の深さ方向プロファイルを測定したものと同じ化学強化ガラスについて、次の方法により深さ方向プロファイルを測定した。
ガラスの片面をシールした状態で、体積分率で1%HF-99%H2Oの酸に浸漬し、片面のみを任意の厚さエッチングした。これにより、化学強化ガラスの表裏面に応力差が発生し、その応力差に応じてガラスが反った。その反り量を、接触式形状計(ミツトヨ製Surftest)を用いて測定した。反り量はエッチング深さ3点以上で測定した。
得られた反り量から、以下の文献に示された式を用いて応力に換算し、圧縮応力値の深さ方向プロファイルを得た。
文献:G. G. Stoney, Proc. Roy. Soc. London Ser. A, 82, 172 (1909).
(3)(1)及び(2)の手順で得られた2つのプロファイルを重ねて、交差する点の深さを「Kイオン侵入深さD」とした。
例6、例7、例8、例9は回転研磨機(装置名:9B-5P メーカー:SPEEDFAM)を用いた研磨によって生じた反りを、接触式形状計(装置名:SV-600メーカー:ミツトヨ)を用いて測定した。
応力プロファイルは折原製作所製散乱光光弾性応力計SLP-2000を用いて測定した。
表面抵抗率は、非接触導電率計(DELCOM社製)を用いて測定した。
落下試験は、得られた120×60×0.6mmtのガラスサンプルを現在使用されている一般的なスマートフォンのサイズに質量と剛性を調節した構造体にはめ込み、疑似スマートフォンを用意した上で、#180落下強度については#180SiCサンドペーパー、または#80落下強度については#80SiCサンドペーパーの上に自由落下させた。落下高さは、5cmの高さから落下させて割れなかった場合は5cm高さを上げて再度落下させる作業を割れるまで繰り返し、初めて割れたときの高さの10枚の平均値を算出した。
消しゴム摩耗試験条件:
化学強化したガラス板表面を紫外線洗浄し、オプツール(登録商標)DSX(ダイキン社製)をスプレーコーティングしてガラス板表面上に略均一なAFP膜を形成した。
1cm2の圧子に消しゴム(MIRAE SCIENCE社製、minoan)を取り付け、1kgfの荷重をかけた状態で、ガラス板表面上に形成されたAFP膜表面をストローク幅20mm、速度30mm/secで10000回往復摩擦した後、布[小津産業社製、DUSPER(登録商標)]にて乾拭きしてAFP膜表面を洗浄した後、AFP膜表面の3カ所で水接触角(°)を測定した。これを3回繰り返し、合計9個の平均水接触角(°)を測定した。AFP膜表面の水接触角(°)は、JIS R 3257(1999年)に準拠した方法により測定した。
化学強化ガラスを120mm×60mmの短冊状に加工し、支持具の外部支点間距離が30mm、内部支点間距離が10mm、クロスヘッド速度が5.0mm/minの条件で4点曲げ試験を行い、4点曲げ強度を測定した。試験片の個数は、10個とした。なお、前記化学強化ガラスは、短冊状に加工した後、1000番手の砥石(東京ダイヤモンド工具製作所製)を用いて自動面取り加工(C面取り)し、0.1mm径ナイロンブラシとショウロックスNZ砥粒(昭和電工社製)を用いて端面を鏡面加工して得られた120x60x0.7mm厚のものを測定した。4PB強度の測定値を下記指標により評価した結果を示す。
A:4PB強度が779MPa以上である。
B:4PB強度が600MPa以上779MPa未満である。
C:4PB強度が600MPa未満である。
Claims (17)
- 厚さがt[μm]であり、Li2O、K2OおよびNa2Oを含有する化学強化ガラスであって、
酸化物基準のモル百分率表示で、表面からの深さx[μm]におけるK2O濃度をKx[%]とし、化学強化前のK2Oの含有量をKt/2[%]としたとき、
Kxが(Kt/2+0.1)[%]以上となる最小の深さzが0.5~5μmである、化学強化ガラス。 - 酸化物基準のモル百分率表示で、表面からの深さx[μm]におけるK2O濃度をKx[%]、とし、化学強化前のK2Oの含有量をKt/2[%]としたときのKxが(Kt/2+0.1)[%]以上となる最小の深さz[μm]におけるNa2O濃度をNaz[%]とし、
表面からの深さ50μmにおけるNa2O濃度をNa50[%]としたとき、
|Naz-Na50|<3[%]である、請求項1に記載の化学強化ガラス。 - 酸化物基準のモル百分率表示で、表面からの深さ50μmにおけるNa2O濃度をNa50[%]とし、化学強化前のNa2Oの含有量をNat/2[%]としたとき、
Na50<Nat/2+7[%]である、請求項1に記載の化学強化ガラス。 - 酸化物基準のモル百分率表示で、表面からの深さ1μmにおけるK2O濃度をK1[%]、Na2O濃度をNa1[%]とし、
化学強化前のLi2O、Na2OおよびK2Oの含有量をそれぞれLit/2[%]、Nat/2[%]およびKt/2[%]としたとき、
(Lit/2+Nat/2+Kt/2)-2(Na1+K1)>0[%]である、請求項1に記載の化学強化ガラス。 - 表面圧縮応力値CS0が450MPa以上、表面からの深さ50μmにおける圧縮応力値CS50が150MPa以上、且つ表面からの深さ90μmにおける圧縮応力値CS90が30MPa以上である、請求項1に記載の化学強化ガラス。
- 表面圧縮応力値CS0が450MPa以上、表面からの深さ50μmにおける圧縮応力値CS50がy=124.7×t+21.5[MPa]以上、且つ表面からの深さ90μmにおける圧縮応力値CS90がy=99.1×t-38.3[MPa]以上である、請求項1に記載の化学強化ガラス。
- Kイオン侵入深さDが0.5~5μmであり、
前記Kイオン侵入深さDにおける圧縮応力値と表面からの深さ50μmにおける圧縮応力値CS50との差の絶対値が150MPa以下であり、
前記Kイオン侵入深さDにおける圧縮応力値が350MPa以下であり、
表面圧縮応力値CS0が450MPa以上、表面からの深さ50μmにおける圧縮応力値CS50が150MPa以上、表面からの深さ90μmにおける圧縮応力値CS90が30MPa以上である、化学強化ガラス。 - 結晶化ガラスからなる、請求項1~7のいずれか1項に記載の化学強化ガラス。
- 母組成が酸化物基準のモル百分率表示で、SiO2を40~75%、Al2O3を1~20%、Li2Oを5~35%含有する、請求項1~7のいずれか1項に記載の化学強化ガラス。
- 厚さtが300~1500μmである請求項1~7のいずれか1項に記載の化学強化ガラス。
- 式CS0/Dで定義されるガラス表層における表層傾きをP0とした場合に、-1000MPa/μm<P0<-225MPa/μmである請求項1~7のいずれか1項に記載の化学強化ガラス。前記式において、CS0は表面圧縮応力値(MPa)、DはKイオン侵入深さ(μm)である。
- 表面からの深さ50μmと表面からの深さ90μmとの間の領域の化学強化ガラスの応力プロファイルの傾きをP50-90(MPa/μm)とし、表面からの深さ90μmと圧縮応力値がゼロとなる深さ(DOL)(μm)との間の領域の化学強化ガラスの応力プロファイルの傾きをP90-DOL(MPa/μm)とした場合に、|P50-90|>|P90-DOL|であって、1.8<|P50-90|<6.0且つ1.5<|P90-DOL|<4.0である請求項1~7のいずれか1項に記載の化学強化ガラス。
前記P50-90及び前記P90-DOLは、下記式により求められる。
P50-90=(CS50-CS90)/40
P90-DOL=CS90/(DOL-90) - 表面からの深さ50μmと表面からの深さ90μmとの間の領域の化学強化ガラスの応力プロファイルの傾きをP50-90(MPa/μm)とし、表面からの深さ90μmと圧縮応力値がゼロとなる深さ(DOL)(μm)との間の領域の化学強化ガラスの応力プロファイルの傾きをP90-DOL(MPa/μm)とした場合に、|P50-90|<|P90-DOL|であって、1.0<|P50-90|<3.0且つ1.2<|P90-DOL|<4.0である請求項1~7のいずれか1項に記載の化学強化ガラス。
前記P50-90及び前記P90-DOLは、下記式により求められる。
P50-90=(CS50-CS90)/40
P90-DOL=CS90/(DOL-90) - 厚さがt[μm]であり、Li2Oを含有するガラスを化学強化することを含む、Li2O、K2OおよびNa2Oを含有する化学強化ガラスの製造方法であって、
前記化学強化ガラスの酸化物基準のモル百分率表示で、表面からの深さx[μm]におけるK2O濃度をKx[%]とし、前記化学強化前のガラスにおけるK2Oの含有量をKt/2[%]としたとき、
Kxが(Kt/2+0.1)[%]以上となる最小の深さzが0.5~5μmとなるように化学強化する、化学強化ガラスの製造方法。 - 前記Li2Oを含有するガラスが結晶化ガラスからなる請求項15に記載の化学強化ガラスの製造方法。
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