CN107129160B - Chemically strengthened glass and method for producing chemically strengthened glass - Google Patents
Chemically strengthened glass and method for producing chemically strengthened glass Download PDFInfo
- Publication number
- CN107129160B CN107129160B CN201710102390.7A CN201710102390A CN107129160B CN 107129160 B CN107129160 B CN 107129160B CN 201710102390 A CN201710102390 A CN 201710102390A CN 107129160 B CN107129160 B CN 107129160B
- Authority
- CN
- China
- Prior art keywords
- glass
- chemically strengthened
- amount
- strengthened glass
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000005345 chemically strengthened glass Substances 0.000 title claims abstract description 107
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000011521 glass Substances 0.000 claims abstract description 238
- 150000001768 cations Chemical class 0.000 claims abstract description 50
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 47
- 239000001257 hydrogen Substances 0.000 claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 125000005372 silanol group Chemical group 0.000 claims abstract description 37
- 239000002344 surface layer Substances 0.000 claims abstract description 25
- 239000010410 layer Substances 0.000 claims abstract description 21
- 230000003746 surface roughness Effects 0.000 claims abstract description 20
- 238000005342 ion exchange Methods 0.000 claims description 41
- 238000005498 polishing Methods 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 39
- 239000003513 alkali Substances 0.000 claims description 35
- 238000004381 surface treatment Methods 0.000 claims description 29
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 24
- 238000004544 sputter deposition Methods 0.000 claims description 12
- 239000005407 aluminoborosilicate glass Substances 0.000 claims description 6
- 239000005354 aluminosilicate glass Substances 0.000 claims description 6
- 239000005361 soda-lime glass Substances 0.000 claims description 6
- 238000010190 AFM image analysis Methods 0.000 claims description 3
- 238000007689 inspection Methods 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000009826 distribution Methods 0.000 description 18
- 238000005530 etching Methods 0.000 description 15
- 150000002500 ions Chemical class 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000010306 acid treatment Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000000356 contaminant Substances 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 238000003825 pressing Methods 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 9
- 238000003426 chemical strengthening reaction Methods 0.000 description 9
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 101100072790 Mus musculus Irf4 gene Proteins 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000010079 rubber tapping Methods 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000006124 Pilkington process Methods 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000006059 cover glass Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 241000238413 Octopus Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000006061 abrasive grain Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000003280 down draw process Methods 0.000 description 2
- -1 fluoride compound Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- XVQUOJBERHHONY-UHFFFAOYSA-N isometheptene Chemical compound CNC(C)CCC=C(C)C XVQUOJBERHHONY-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000760 Hardened steel Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000006058 strengthened glass Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 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
- 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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0095—Solution impregnating; Solution doping; Molecular stuffing, e.g. of porous glass
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The present invention relates to a chemically strengthened glass and a method for producing a chemically strengthened glass. The purpose of the present invention is to provide a chemically strengthened glass having excellent surface strength even when the surface of the glass is polished. The present invention relates to a chemically strengthened glass having a compressive stress layer in a surface layer thereof, and satisfying the following conditions (1) to (5): (1) having abrasive damage on the surface; (2) a texture direction index (Stdi) of 0.70 or more; (3) a surface silanol group amount obtained by the following formula (i) is 1 or less, (surface silanol group amount) — … formula (i) (amount of cations in the glass) - (amount of cations on the surface of the glass); (4) a hydrogen concentration C in a region having a depth X of 0.1 to 0.4(μm) from the outermost surface of the glass is less than 0.070 mol/L; (5) the surface roughness (Ra) measured by AFM under the condition of 1 μm square is 0.35nm or less.
Description
Technical Field
The present invention relates to a chemically strengthened glass and a method for producing a chemically strengthened glass.
Background
In flat panel display devices such as Digital cameras, cellular phones, and Personal Digital Assistants (PDAs), and touch panel display devices, a thin plate-like protective glass is disposed on the front surface of a display so as to form a wider area than an image display portion in order to improve the protection and the appearance of the display.
In response to the demand for weight reduction and thickness reduction of flat panel display devices, the cover glass itself is also required to be thin. In addition, a flat panel display device and a touch panel display device are required to have excellent appearance, strength, and water resistance, and a cover glass is required to have high surface strength in order to satisfy the purpose.
Although the theoretical strength of glass is high, the strength is greatly reduced by damage, and therefore, chemically strengthened glass having a compressive stress layer formed on the surface of glass by ion exchange or the like to improve the surface strength is used as a protective glass having required strength.
Contaminants (contamination) typified by adhesion of molten salt are present on the glass sheet after chemical strengthening. Further, since the surface strength of glass is lowered by the presence of hydrogen (moisture) in the surface layer of the glass sheet, the following steps are generally performed: the surface of the glass after chemical strengthening is polished or immersed in hydrofluoric acid or the like to be subjected to etching treatment or the like, thereby removing contaminants adhering to the surface of the glass plate or a layer containing hydrogen (moisture) on the surface of the glass plate.
Documents of the prior art
Patent document
Patent document 1: japanese Kohyo publication No. 2013-516387
Patent document 2: japanese Kokai publication Hei-2014-534945
Disclosure of Invention
Problems to be solved by the invention
In the method of polishing the glass surface after chemical strengthening to remove contaminants adhering to the glass surface or a layer containing hydrogen (moisture) on the glass surface, there is a possibility that the glass surface is damaged by polishing, and the surface strength is rather lowered. In addition, when the surface strength of the glass is ensured only by the acid treatment as in the methods described in patent documents 1 and 2, since the silanol groups on the glass surface are increased by the acid treatment, contaminants are likely to adhere to the glass surface. When contaminants adhere as described above immediately before the film forming step, the contaminants may protrude due to the film formation, resulting in poor appearance.
Accordingly, an object of the present invention is to provide a chemically strengthened glass which has excellent surface strength even when the surface of the glass is polished to have polishing scratches and which is suppressed in the adhesion of contaminants to the surface of the glass.
Means for solving the problems
The inventor finds that: the present inventors have found that by adjusting the grain direction index (Stdi) of the surface of chemically strengthened glass, the hydrogen concentration distribution in the surface layer of glass, and the surface roughness (Ra) to specific ranges, the surface strength of chemically strengthened glass can be improved even when the surface has polishing scratches, and by adjusting the amount of surface silanol groups to specific ranges, the adhesion of contaminants to chemically strengthened glass can be suppressed, and have completed the present invention.
Namely, the present invention is as follows.
[1] A chemically strengthened glass having a compressive stress layer in a surface layer, wherein the chemically strengthened glass satisfies the following conditions (1) to (5):
(1) having abrasive damage on the surface;
(2) a texture direction index (Stdi) of 0.70 or more;
(3) the amount of surface silanol groups obtained by the following formula (i) is 1 or less;
(amount of surface silanol group) (amount of cation in glass) - (amount of cation on glass surface) … formula (i)
The amount of cations on the glass surface was determined by measuring the atomic concentration of each element on the glass surface by X-ray photoelectron spectroscopy and by the following formula (ii),
the amount of cations in the glass was determined by measuring the atomic concentration of each element in the glass by X-ray photoelectron spectroscopy after sputtering with C60 and by the following formula (ii),
(amount of cation) ═ K/Si + Na/Si +2 xmg/Si +3 × Al/Si … formula (ii);
(4) a hydrogen concentration C in a region having a depth X of 0.1 to 0.4(μm) from the outermost surface of the glass is less than 0.070 mol/L;
(5) the surface roughness (Ra) measured by AFM under the condition of 1 μm square is 0.35nm or less.
[2] The chemically strengthened glass according to [1], wherein the chemically strengthened glass has a texture aspect ratio (Str20) of 0.5 or more.
[3] The chemically strengthened glass according to the above [1] or [2], wherein a core roughness depth (Sk) of the chemically strengthened glass is 1nm or less.
[4] The chemically strengthened glass according to the above [1] or [2], wherein the BOR average surface strength of the chemically strengthened glass is 800N or more.
[5] The chemically strengthened glass according to the above [1] or [2], wherein the glass is aluminosilicate glass, aluminoborosilicate glass, or soda lime glass.
[6] A chemically strengthened glass having a compressive stress layer in a surface layer, wherein the chemically strengthened glass satisfies the following conditions (1) to (3):
(1) a texture direction index (Stdi) of 0.70 or more;
(2) a hydrogen concentration C in a region having a depth X of 0.1 to 0.4(μm) from the outermost surface of the glass is less than 0.070 mol/L;
(3) the surface roughness (Ra) measured by AFM under the condition of 1 μm square is 0.35nm or less.
[7] The chemically strengthened glass according to [6], wherein the chemically strengthened glass satisfies the following conditions:
(Condition) the amount of surface silanol groups determined by the following formula (i) is 1 or less,
(amount of surface silanol group) (amount of cation in glass) - (amount of cation on glass surface) … formula (i)
The amount of cations on the glass surface was determined by measuring the atomic concentration of each element on the glass surface by X-ray photoelectron spectroscopy and by the following formula (ii),
the amount of cations in the glass was determined by measuring the atomic concentration of each element in the glass by X-ray photoelectron spectroscopy after sputtering with C60 and by the following formula (ii),
(amount of cation) ═ K/Si + Na/Si +2 xmg/Si +3 × Al/Si … formula (ii).
[8] The chemically strengthened glass according to the above [6] or [7], which has polishing scratches on the surface.
[9] The chemically strengthened glass according to the above [6] or [7], wherein the chemically strengthened glass has a texture aspect ratio (Str20) of 0.5 or more.
[10] The chemically strengthened glass according to the above [6] or [7], wherein a core roughness depth (Sk) of the chemically strengthened glass is 1nm or less.
[11] The chemically strengthened glass according to any one of [6] and [7], wherein the BOR average surface strength of the chemically strengthened glass is 800N or more.
[12] The chemically strengthened glass according to any one of [6] and [7], wherein the glass is aluminosilicate glass, aluminoborosilicate glass, or soda lime glass.
[13] A method of making chemically strengthened glass, comprising:
an ion exchange step of forming a compressive stress layer on the surface layer of the glass by an ion exchange method, and
a glass surface treatment step of performing an alkali treatment after the ion exchange step, wherein,
the surface treatment step is a surface treatment step of treating the glass surface so as to satisfy the following (a) to (c),
(a) a texture direction index (Stdi) of 0.70 or more;
(b) a hydrogen concentration C in a region having a depth X of 0.1 to 0.4(μm) from the outermost surface of the glass is less than 0.070 mol/L;
(c) the surface roughness (Ra) measured by AFM under the condition of scanning size of 1 μm × 1 μm is 0.35nm or less.
[14] The method for producing chemically strengthened glass according to [13], wherein the surface treatment step is a surface treatment step of treating the glass surface so as to satisfy the following (d),
(d) the amount of surface silanol groups obtained by the following formula (i) is 1 or less,
(amount of surface silanol group) (amount of cation in glass) - (amount of cation on glass surface) … formula (i)
The amount of cations on the glass surface was determined by measuring the atomic concentration of each element on the glass surface by X-ray photoelectron spectroscopy and by the following formula (ii),
the amount of cations in the glass was determined by measuring the atomic concentration of each element in the glass by X-ray photoelectron spectroscopy after sputtering with C60 and by the following formula (ii),
(amount of cation) ═ K/Si + Na/Si +2 xmg/Si +3 × Al/Si … formula (ii).
[15] The method for producing a chemically strengthened glass according to [13] or [14], wherein the method comprises a sampling inspection which is judged to be suitable when a texture direction index (Stdi) obtained by AFM image analysis after the surface treatment step is 0.70 or more.
[16] The method for producing a chemically strengthened glass according to any one of [13] and [14], wherein the method comprises a polishing step of polishing the surface of the glass after the ion exchange step and before the surface treatment step.
Effects of the invention
According to the chemically strengthened glass of the present invention, the surface strength of the chemically strengthened glass can be improved by adjusting the texture direction index (Stdi) of the surface of the chemically strengthened glass, the hydrogen concentration distribution in the surface layer of the glass, and the surface roughness (Ra) to specific ranges, and the contamination on the surface of the glass can be suppressed by adjusting the amount of silanol groups on the surface to specific ranges.
Drawings
Fig. 1 is a graph showing the correlation between the texture direction index (Stdi) and the plane intensity (BOR average plane intensity).
FIG. 2 is a schematic diagram illustrating a method for ball-and-loop testing.
Fig. 3 is a graph showing the correlation of texture aspect ratio (Str20) and face strength (BOR average face strength).
Fig. 4 is a diagram for explaining the core roughness depth (Sk).
Fig. 5 is a graph showing the depth of core roughness (Sk) [ units: nm ] dependence on areal intensity (BOR mean areal intensity).
Detailed Description
The present invention will be described in detail below, but the present invention is not limited to the following embodiments, and can be modified arbitrarily and implemented within a range not departing from the gist of the present invention.
< chemically strengthened glass >
The chemically strengthened glass according to the first embodiment of the present invention has a compressive stress layer in a surface layer thereof, and satisfies the following conditions (1) to (5).
(1) Having abrasive damage on the surface;
(2) a texture direction index (Stdi) of 0.70 or more;
(3) the amount of surface silanol groups obtained by the following formula (i) is 1 or less;
(amount of surface silanol group) (amount of cation in glass) - (amount of cation on glass surface) … formula (i)
The amount of cations on the glass surface was determined by measuring the atomic concentration of each element on the glass surface by X-ray photoelectron spectroscopy and by the following formula (ii),
the amount of cations in the glass was determined by measuring the atomic concentration of each element in the glass by X-ray photoelectron spectroscopy after sputtering with C60 and by the following formula (ii),
(amount of cation) ═ K/Si + Na/Si +2 xmg/Si +3 × Al/Si … formula (ii);
(4) a hydrogen concentration C in a region having a depth X of 0.1 to 0.4(μm) from the outermost surface of the glass is less than 0.070 mol/L;
(5) the surface roughness (Ra) measured by AFM under the condition of 1 μm square is 0.35nm or less.
The chemically strengthened glass according to the second embodiment of the present invention has a compressive stress layer in a surface layer thereof, and satisfies the following conditions (1) to (3).
(1) A texture direction index (Stdi) of 0.70 or more;
(2) a hydrogen concentration C in a region having a depth X of 0.1 to 0.4(μm) from the outermost surface of the glass is less than 0.070 mol/L;
(3) the surface roughness (Ra) measured by AFM under the condition of 1 μm square is 0.35nm or less.
The chemically strengthened glass of the present invention has a compressive stress layer formed on a surface layer by an ion exchange method. The compressive stress layer is a high-density layer formed by bringing glass as a raw material into contact with an inorganic salt such as potassium nitrate to ion-exchange Na ions on the surface of the glass with K ions in the inorganic salt.
[ grinding Damage ]
The chemically strengthened glass of the present invention may have polishing damage on the surface. Here, the polishing in the present invention means that the glass surface is ground with abrasive grains to smooth the surface. The method of surface polishing is not particularly limited. The presence or absence of polishing scratches can be judged by surface observation with an AFM (Atomic Force Microscope). when one or more polishing scratches having a length of 5 μm or more exist in a5 μm × 5 μm region, the polishing scratches are referred to as having polishing scratches on the surface.
[ texture Direction index (Stdi) ]
The texture direction index (Stdi) is an index indicating the quality of the directionality of the texture (the property and state uniformly possessed by the processed surface) formed on the glass surface, and has a value from 0 to 1. In the case where the texture has a dominant direction, Stdi is close to 0. On the other hand, in the case where the texture has no directivity, Stdi is close to 1. That is, when the texture such as the polishing damage has a dominant direction, Stdi has a value close to 0. However, it is considered that Stdi is close to 1 by smoothing the polishing scratches and making the texture unclear.
The present inventors analyzed the correlation between Stdi and the plane strength [ the BOR (sphere-ring) plane strength measured by the sphere-ring test described later, hereinafter also referred to as BOR plane strength ], and found that the correlation is as shown in fig. 1. As shown in fig. 1, the closer Stdi is to 1, the higher the plane strength. The Stdi of the chemically strengthened glass of the present invention is 0.70 or more, preferably 0.75 or more, and more preferably 0.80 or more.
It is considered that the chemically strengthened glass of the present invention has a polishing flaw smoothed and an improved surface strength when Stdi falls within this range. Stdi can be obtained by obtaining a shape Image with an Atomic Force Microscope (AFM) and then obtaining the shape Image with Image analysis software (for example, SPIP manufactured by Image Metrology).
[ ball-and-Ring test ]
A schematic diagram illustrating the ball-and-loop test is shown in fig. 2. In a Ball-and-Ring (BOR) test, the glass plate 1 was pressed by a pressing jig 2 (hardened steel, 10mm in diameter, mirror finish) made of SUS304 in a state where the glass plate 1 was horizontally placed, and the surface strength of the glass plate 1 was measured.
In FIG. 2, a glass plate 1 as a sample was horizontally placed on a support jig 3 (diameter 30mm, curvature R2.5mm of contact portion, quenched steel for contact portion, mirror finish) made of SUS 304. A pressing jig 2 for pressing the glass plate 1 is provided above the glass plate 1.
The central region of the glass plate 1 is pressurized from above the glass plate 1. The test conditions are as follows.
Lowering speed of the pressing jig 2: 1.0 (mm/min)
At this time, the breaking load (unit N) when the glass was broken was defined as the BOR surface strength, and the average value of 20 measurements was defined as the BOR average surface strength (BOR average strength). However, the case where the breakage start point of the glass plate is 2mm or more from the ball pressing position is excluded from the data for calculating the average value.
The BOR average surface strength of the chemically strengthened glass of the present invention is preferably 800N or more, more preferably 900N or more, and particularly preferably 1000N or more.
[ amount of silanol groups on the surface ]
The chemically strengthened glass according to the first embodiment of the present invention has a surface silanol group content of 1 or less, preferably 0.9 or less, and more preferably 0.85 or less.
The amount of surface silanol groups in the chemically strengthened glass according to the second embodiment of the present invention is preferably 1 or less, more preferably 0.9 or less, and still more preferably 0.85 or less.
[ method for measuring the amount of silanol groups on the surface ]
The amount of surface silanol groups was determined by the following steps 1) to 5).
1) The atomic concentrations of the respective elements on the glass surface were measured by X-ray photoelectron spectroscopy (XPS).
2) The amount of cations on the glass surface was calculated by the following formula (ii).
3) After sputtering with C60, the atomic concentrations of the respective elements in the glass were measured by X-ray photoelectron spectroscopy.
4) The amount of cations inside the glass was calculated by the following formula (ii).
5) The amount of surface silanol groups was determined by subtracting the amount of cations on the glass surface from the amount of cations in the glass according to formula (i).
(amount of surface silanol group) (amount of cation in glass) - (amount of cation on glass surface) … formula (i)
(amount of cation) ═ K/Si + Na/Si +2 XMg/Si +3 XAl/Si … formula (ii)
When the amount of the surface silanol group is 1 or less, the adhesion of contaminants is difficult, and contaminants in the film forming step after cleaning of the protective glass can be suppressed.
[ Hydrogen concentration ]
In the chemically strengthened glass of the present invention, the hydrogen concentration distribution in the surface layer of the glass is in a specific range. Specifically, the hydrogen concentration C in a region having a depth X of 0.1 to 0.4(μm) from the outermost surface of the glass is less than 0.070mol/L, preferably 0.060mol/L or less. When the hydrogen concentration C is less than 0.070mol/L, the surface strength of the chemically strengthened glass can be improved.
As for the surface strength of glass, it is known that the surface strength of glass is reduced by the presence of hydrogen (moisture) in the surface layer of glass, but the strength may be reduced after the chemical strengthening treatment. The results of various studies were performed presuming: the main reason for this is the formation of chemical defects due to the ingress of atmospheric moisture into the glass.
When the concentration of hydrogen in the surface layer of the glass is high, hydrogen enters the Si-O-Si bond network of the glass in the form of Si-OH, and the Si-O-Si bond is cut. Consider that: when the hydrogen concentration in the glass surface layer is high, the amount of the Si-O-Si bonds cleaved increases, chemical defects are easily generated, and the surface strength is lowered.
The hydrogen concentration C is within a specific range in a region where the depth X from the outermost surface is 0.1 to 0.4 μm. The thickness of the compressive stress layer formed by ion exchange depends on the degree of chemical strengthening, but is formed in the range of 5 μm to 50 μm. Further, the depth of hydrogen entry into the glass depends on the diffusion coefficient, temperature and time, and the amount of hydrogen entry is affected by the amount of moisture in the atmosphere in addition to these. The hydrogen concentration after chemical strengthening is highest at the outermost surface and gradually decreases toward the deep portion (bulk portion) where the compressive stress layer is not formed. Since the water concentration may change with time due to deterioration at the outermost surface (X ═ 0 μm), the hydrogen concentration C is set to a specific range in a region near the surface (X ═ 0.1 μm to 0.4 μm) where this influence is not expected.
[ method for measuring Hydrogen concentration distribution ]
Here, the hydrogen concentration distribution (H) in the surface layer of the glass2O equivalent concentration, mol/L) is a distribution measured under the following analysis conditions. Secondary Ion Mass spectrometry (Secondary Ion Mass spectrometry: SIMS) was used for the measurement of the hydrogen concentration distribution in the surface layer of the glass.
When obtaining a quantitative hydrogen concentration distribution by SIMS, a standard sample having a known hydrogen concentration is required. The method for preparing the standard sample and the method for determining the hydrogen concentration are described below.
1) A part of the glass to be measured is cut out.
2) The cut glass is removed by polishing or chemical etching in a region of 50 μm or more from the surface. The removal process may be performed for both sides. That is, the total removal thickness of both sides is 100 μm or more. The glass after the removal treatment was used as a standard sample.
3) The standard sample was subjected to Infrared spectroscopy (Infrared spectroscopy: IR) was obtained, 3550cm of IR spectrum was obtained-1Absorbance height A of nearby peak top3550And 4000cm-1Absorbance height A of4000(baseline).
4) The thickness d (cm) of the standard sample is measured by a thickness measuring instrument such as a micrometer.
5) Reference s.ilievski et al, glastech.ber.glass sci.technol.,73(2000)39, glass H2Infrared actual extinction coefficient epsilon of Opract[L/(mol·cm)]Assuming that 75, the hydrogen concentration (H) of the standard sample was obtained by the formula (a)2In terms of O, mol/L).
Hydrogen concentration of standard sample ═ A3550-A4000)/(εpractD) … formula (a)
The glass to be measured and the standard sample having a known hydrogen concentration obtained by the above method are simultaneously transported into the SIMS apparatus and measured sequentially to obtain1H-And30the depth-direction distribution of the intensity of Si-. Then, use1H-Distribution divided by30Si-distribution to obtain1H-/30The depthwise distribution of the Si-intensity ratio.
From standard samples1H-/30The distribution of the Si-intensity ratio in the depth direction was calculated as the average in the region of a depth of 1 μm to 2 μm1H-/30The Si-intensity ratio was plotted by means of the origin against the hydrogen concentration (standard curve of a horizontal standard sample). Using the standard curve, the distribution of the glass to be measured is plotted on the vertical axis1H-/30The Si-intensity ratio is converted into a hydrogen concentration. Thereby, the hydrogen concentration distribution of the glass to be measured is obtained.
The measurement conditions of SIMS and IR are as follows.
[ measurement conditions for SIMS ]
The device comprises the following steps: ADEPT1010 manufactured by ULVAC. PHI
Primary ion species: cs+
Acceleration voltage of primary ions: 5kV
Current value of primary ion: 500nA
Incident angle of primary ion: the normal line to the sample surface is 60 °
Grating size of primary ions: 300X 300 (. mu.m)2)
Polarity of primary ion: negative pole
Detection area of primary ions: 60X 60(μm)2) (4% of the grating size of the primary ion.)
Electrostatic analyzer Input Lens (ESA Input Lens): 0
Neutralizing gun
Method of converting the horizontal axis from sputter time to depth: the depth of the analysis arc pit was measured by a stylus type surface texture measuring instrument (Dektak 150 manufactured by Veeco) to determine the sputtering rate of the primary ions. The horizontal axis is converted from the sputtering time to the depth by this sputtering rate.
1H-Field Axis Potential at the time of detection (Field Axis Potential): the optimum value of each device may vary. The person to be measured setting the field axis potential while paying attention to itValues such that the background is substantially eliminated.
[ measurement conditions of IR ]
The device comprises the following steps: Nic-plan/Nicolet 6700 manufactured by Thermo Fisher Scientific Co., Ltd
Resolution ratio: 4cm-1
And (3) accumulation: 16
A detector: TGS detector
[ surface roughness (Ra) ]
The chemically strengthened glass of the present invention has a surface roughness (Ra) of 0.35nm or less, preferably 0.3nm or less, and more preferably 0.2nm or less, as measured by AFM under a condition of a scanning dimension of 1. mu. m.times.1 μm square. The surface strength of the chemically strengthened glass can be improved by setting the surface roughness (Ra) to 0.35nm or less.
[ texture aspect ratio (Str20) ]
The texture aspect ratio (Str20) can be obtained as follows. That is, the shape Image is obtained by an Atomic Force Microscope (AFM), and then the shape Image is flattened (レべリング) and subjected to L-filter processing (ISO value 2.0 μm) by Image analysis software (SPIP Image analysis software version 6.4.3 manufactured by Image Metrology), and the texture aspect ratio (Str20) is obtained by roughness analysis.
The inventors analyzed the correlation between Str20 and the areal intensity (BOR average areal intensity), and found that there was a correlation as shown in FIG. 3. As shown in fig. 3, the closer to 1 the Str20 is, the higher the areal strength is. Str20 of the chemically strengthened glass of the present invention is preferably 0.5 or more, more preferably 0.6 or more, further preferably 0.65 or more, and particularly preferably 0.75 or more.
Since Str20 in the chemically strengthened glass of the present invention is in this range, it is considered that the glass has polishing flaws with small irregularities or polishing flaws cannot be confirmed.
[ core roughness depth (Sk) ]
The core roughness depth (Sk) (DIN 4776) is an index for the variation of the unevenness. In the support curve (ベアリング curve) of the ebott (アボット) curve (integral value of histogram of height distribution) shown in fig. 4, "Sk" shown in fig. 4 when a line reaching the minimum slope is drawn out of the approximation line of the ibott (アボット curve) is the core roughness depth, "Spk" is the reduced peak height (サミット height さ), "Svk" is the reduced valley height (alkali バレー height さ).
The present inventors analyzed the correlation between Sk and the areal intensity (BOR average areal intensity), and found that there is a correlation as shown in fig. 5. The chemically strengthened glass of the present invention preferably has Sk of 1nm or less. Consider that: when Sk is in this range, the ratio of small concavities and convexities increases, and the surface strength improves. Sk can be obtained by obtaining a shape Image with an Atomic Force Microscope (AFM) and then obtaining it with Image analysis software (for example, SPIP Image analysis software version 6.4.3 manufactured by Image Metrology).
(glass composition)
The glass used in the present invention may have any composition as long as it contains sodium, and it can be formed and strengthened by chemical strengthening treatment. Specific examples thereof include aluminosilicate glass, soda-lime glass, borosilicate glass, lead glass, alkali barium glass, and aluminoborosilicate glass. Among them, aluminosilicate glass, aluminoborosilicate glass, and soda lime glass are preferable.
The glass can be produced by a method including, but not limited to, charging a desired glass raw material into a continuous melting furnace, heating and melting the glass raw material at preferably 1500 to 1600 ℃, fining the glass raw material, supplying the glass raw material to a forming apparatus, forming the molten glass into a sheet, and annealing the sheet.
Various methods can be used for forming glass. For example, various forming methods such as a down-draw method (for example, an overflow down-draw method, a slit down-draw method, a redraw method (リドロー method), and the like), a float method, a roll method, and a press method can be used.
The thickness of the glass is not particularly limited, but is usually preferably 5mm or less, more preferably 3mm or less, for effective chemical strengthening treatment.
The shape of the glass used in the present invention is not particularly limited. For example, glass having various shapes such as a flat plate shape having a uniform plate thickness, a shape having a curved surface at least one of the front surface and the back surface, and a three-dimensional shape having a curved portion or the like can be used.
The composition of the chemically strengthened glass of the present invention is not particularly limited, and examples thereof include the following glass compositions.
(i) Contains 50 to 80% of SiO in terms of a composition expressed by mol% 22 to 25 percent of Al2O30 to 10% of Li2O, 0 to 18 percent of Na2O, 0 to 10 percent of K2O, 0 to 15 percent of MgO, 0 to 5 percent of CaO and 0 to 5 percent of ZrO2Glass of
(ii) Contains 50 to 74% of SiO in terms of the composition expressed by mol% 21 to 10 percent of Al2O36 to 14 percent of Na2O, 3 to 11 percent of K2O, 2 to 15 percent of MgO, 0 to 6 percent of CaO and 0 to 5 percent of ZrO2，SiO2And Al2O3The total content of (A) is less than 75%, Na2O and K2Glass with a total of 12-25% of O and 7-15% of MgO and CaO
(iii) Contains 68 to 80% of SiO in terms of a composition expressed by mol%24 to 10 percent of Al2O35 to 15 percent of Na2O, 0 to 1 percent of K2O, 4 to 15 percent of MgO and 0 to 1 percent of ZrO2Glass of
(iv) Contains 67 to 75% of SiO in terms of a composition expressed by mol% 20 to 4 percent of Al2O37 to 15 percent of Na2O, 1 to 9 percent of K2O, 6 to 14 percent of MgO and 0 to 1.5 percent of ZrO2，SiO2And Al2O3The total content of (A) is 71-75%, Na2O and K2Glass containing 12 to 20% of total O and less than 1% of CaO
< method for producing chemically strengthened glass >
The method for producing chemically strengthened glass of the present invention comprises:
an ion exchange step of forming a compressive stress layer on the surface layer of the glass by an ion exchange method, and
and a glass surface treatment step of performing an alkali treatment after the ion exchange step.
The surface treatment step is a surface treatment step of treating the glass surface so as to satisfy the following (a) to (c). Further, it is preferable to perform a surface treatment step of treating the glass surface so as to satisfy the following (d).
(a) The texture direction index (Stdi) is 0.70 or more.
(b) The hydrogen concentration C in a region having a depth X of 0.1 to 0.4 (mu m) from the outermost surface of the glass is less than 0.070 mol/L.
(c) The surface roughness (Ra) measured by AFM under the condition of the scanning size of 1 μm multiplied by 1 μm square is below 0.35 nm.
(d) The amount of surface silanol groups obtained by the following formula (i) is 1 or less,
(amount of surface silanol group) (amount of cation in glass) - (amount of cation on glass surface) … formula (i)
The cation amount on the glass surface was determined by measuring the atomic concentration of each element on the glass surface by X-ray photoelectron spectroscopy and using the following formula (ii).
The amount of cations in the glass was determined by measuring the atomic concentration of each element in the glass by X-ray photoelectron spectroscopy after sputtering with C60 and by the following formula (ii).
(amount of cation) ═ K/Si + Na/Si +2 XMg/Si +3 XAl/Si … formula (ii)
Hereinafter, each step will be explained.
[ ion exchange Process ]
The chemically strengthened glass of the present invention has a compressive stress layer formed by ion exchange on the surface of the glass. In the ion exchange method, the surface of the glass is ion-exchanged to form a surface layer having a residual compressive stress. Specifically, at a temperature not higher than the glass transition temperature, alkali metal ions (typically, Li ions and Na ions) having a small ion radius in the glass surface layer are replaced by alkali ions (typically, Na ions or K ions for Li ions and K ions for Na ions) having a large ion radius by ion exchange. This causes a compressive stress to remain on the surface of the glass, thereby improving the surface strength of the glass.
The method of the ion exchange treatment is not particularly limited, and a known method can be used. As the method of ion exchange treatment, any method may be used as long as Li in the glass surface layer can be formed2O or Na2O and Na in molten salt2O or K2The method for ion-exchanging O is not particularly limited, and examples thereof include: immersing glass in heated potassium nitrate (KNO)3) The molten salt of (1).
The conditions of the ion exchange treatment are not particularly limited, and vary depending on the thickness of the glass, but the temperature conditions are preferably 520 ℃ or less, more preferably 500 ℃ or less, and preferably 350 ℃ or more, more preferably 400 ℃ or more.
The time for performing the ion exchange treatment is preferably 1 hour to 72 hours, and more preferably 2 hours to 24 hours. In order to improve productivity, it is preferably 12 hours or less. Examples of the molten salt include KNO3And the like.
Specifically, for example, the glass is typically KNO at 400 ℃ to 500 ℃3Immersing in molten salt for 1-72 hr. After the ion exchange treatment, it is preferable to wash the glass with water for the purpose of removing deposits such as molten salt adhering to the glass.
[ polishing Process ]
The method for producing chemically strengthened glass of the present invention may further include a polishing step of polishing the glass surface after the ion exchange step and before a surface treatment step described later. The polishing step is a step of polishing the glass with a polishing pad while supplying the polishing slurry. The polishing conditions are not particularly limited, and may be carried out under conditions to achieve a desired surface roughness. The glass surface is polished to remove macroscopic damage on the glass surface.
The polishing step can be carried out by a general method such as preparing a slurry having a specific gravity of 0.9 by dispersing cerium oxide having an average particle diameter of about 0.7 μm in water, and polishing the surface of glass by 0.5 μm or more per surface with a nonwoven fabric-type or suede-type polishing pad under a polishing pressure of 10 kPa.
When a glass surface is polished with a polishing abrasive grain having an average particle diameter (d50) of cerium oxide of usually 0.5 to 1.5 μm, the surface strength may be reduced if polishing flaws caused by the polishing remain on the glass surface, but the polishing flaws can be made thinner to have Stdi within a predetermined range by performing a surface treatment step described later after the polishing step, thereby improving the surface strength.
[ surface treatment Process ]
In the method for producing a chemically strengthened glass of the present invention, it is preferable that the ion exchange treatment is followed by a surface treatment including an alkali treatment. In addition, the alkali treatment and the acid treatment or the etching treatment may be combined. It is considered that the removal of the hydrated layer on the surface by the alkali treatment can provide a surface on which cracks are less likely to propagate on the glass surface. In addition, it is considered that: by the alkali treatment, a surface layer having a surface silanol group amount satisfying the above-mentioned specific relational expression (i) is formed, whereby the contamination adhering to the glass surface can be suppressed.
By the surface treatment, hydrogen in the surface layer of the glass is removed and the hydrogen concentration C is within a predetermined range. In addition, it is considered that: the damage present on the glass surface is removed by the surface treatment, and the Stdi and the surface roughness (Ra) are brought into predetermined ranges, whereby the surface strength is improved.
The amount of surface removal by surface treatment is usually preferably 5nm or more, and more preferably 50nm or more. By setting the surface removal amount to 5nm or more, when polishing scratches are present, unevenness due to the scratches can be reduced, and chemically strengthened glass having high surface strength can be produced. The surface removal amount can be adjusted by appropriately adjusting the composition of the glass to be chemically strengthened, the temperature or concentration of the solution used for surface treatment, and the like.
(alkali treatment)
The alkali treatment is performed by immersing the chemically strengthened glass in an alkaline solution. The solution is not particularly limited as long as it is alkaline, and the solution may have a pH of more than 7, and either a weak base or a strong base may be used. Specifically, bases such as lithium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, ammonia, and organic amines are preferable. These bases may be used alone or in combination of two or more. In addition, an organic acid salt or the like may be added as a chelating agent.
The temperature for the alkali treatment varies depending on the kind, concentration and time of the alkali used, but is preferably 10 to 80 ℃, more preferably 20 to 70 ℃, and particularly preferably 40 to 60 ℃. In this temperature range, the glass is not corroded, and therefore, it is preferable.
The time for the alkali treatment varies depending on the type, concentration and temperature of the alkali to be used, but is preferably 1 to 120 minutes, and more preferably 1 to 60 minutes from the viewpoint of productivity. The concentration of the solution subjected to the alkali treatment varies depending on the kind, time, and temperature of the alkali used, but is preferably 0.1 to 10% by mass, more preferably 1 to 5% by mass, from the viewpoint of removability of the glass surface.
(acid treatment)
The acid treatment may be performed by immersing the chemically strengthened glass in an acidic solution. The solution is not particularly limited as long as it is acidic, and the pH of the solution may be less than 7, and the acid used may be either weak or strong. Specifically, acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, carbonic acid, and citric acid are preferable. These acids may be used alone or in combination of two or more.
The temperature at which the acid treatment is carried out varies depending on the kind, concentration and time of the acid used, but is preferably 100 ℃ or lower. The time for performing the acid treatment varies depending on the kind, concentration and temperature of the acid used, but is preferably 10 seconds to 5 hours, and more preferably 1 minute to 2 hours from the viewpoint of productivity.
The concentration of the solution to be subjected to the acid treatment varies depending on the kind, time, and temperature of the acid used, but is preferably a concentration at which the possibility of corrosion of the vessel is low, and more specifically, is preferably 0.1 to 20% by mass.
(etching treatment)
As an etching solution used for the etching treatment, an aqueous solution containing a chemical soluble in glass is used. As the chemical that dissolves glass, an aqueous solution containing fluoride is preferable. Examples of the fluoride include hydrogen fluoride, ammonium fluoride, potassium fluoride, and sodium fluoride. In addition, at least one of an inorganic acid and an organic acid may be contained in these aqueous solutions. The inorganic acid may be one or more selected from hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and the like, and the organic acid may be one or more selected from acetic acid, succinic acid, and the like.
The etching rate is preferably 0.1 μm/min or less, more preferably 0.05 μm/min or less. By setting the etching rate to 0.1 μm/min or less, chemically strengthened glass having a small roughness of the glass surface can be produced. The etching rate can be adjusted by appropriately adjusting the composition of the glass to be subjected to the ion exchange step, the temperature or concentration of the etching solution, and the like.
The etching temperature is usually preferably 10 to 60 ℃ and more preferably 20 to 40 ℃. The etching time is preferably 30 seconds to 30 minutes, and more preferably 1 minute to 10 minutes. The conditions for these etching can be appropriately selected by those skilled in the art according to the material of the glass used and the like so that the reaction product is not precipitated.
The method for producing the chemically strengthened glass varies depending on the application, and is not particularly limited as a step other than the surface treatment step after the ion exchange step. The following describes an example, but the present invention is not limited to this example.
First, the prepared glass blank is subjected to cutting, boring, slitting, grinding or light chamfering (with respect to the plane り) to be formed into a desired size and shape for final finishing. In this case, in order to improve the workability of the subsequent steps and reduce the process cost, the workpiece may be cut into a size larger than the desired size of the final finish, and after all the machining steps are finished, the workpiece may be formed into a desired size and shape.
The formed glass is chemically strengthened by an ion exchange step, and then a layer containing contaminants and moisture is removed by a surface treatment step, thereby obtaining a chemically strengthened glass. The chemically strengthened glass is subjected to, for example, printing, antireflection coating, and lamination of a functional film, thereby producing a cover glass. After the surface treatment step, a sampling inspection may be performed that is determined to be suitable when the texture direction index (Stdi) obtained by AFM image analysis is 0.70 or more.
The chemically strengthened glass of the present invention can be used as a protective glass for displays such as flat panel display devices and touch panel display devices used in mobile phones, digital cameras, in-vehicle display devices, and the like.
Examples
The following specifically describes examples of the present invention, but the present invention is not limited to these examples.
< evaluation method >
Various evaluations in the present example were carried out by the following analytical methods.
[ removal amount ]
The thickness of the amount of glass removed was determined by measuring the weight before AND after the treatment with the reagent using an electronic balance for analysis (HR-202 i; manufactured by AND) AND converting the thickness using the following equation.
(thickness of removal amount per side) [ (weight before treatment) - (weight after treatment) ]/(specific gravity of glass)/(treated area)/2
At this time, the specific gravity of the glass was set to 2.41 (g/cm)3) And (6) performing calculation.
[ texture Direction index (Stdi) ]
First, using an atomic force microscope (PA 400 manufactured by Seiko Instruments), a measurement mode: tapping mode, scan size: 1 μm × 1 μm, scanning speed: 1Hz, cantilever: the shape image was obtained by Cantilever (SI-DF 40 manufactured by SII Co.). Then, the shape Image was flattened by Image analysis software (SPIP Image analysis software version 6.2.6 manufactured by Image Metrology), and the texture direction index (Stdi) was obtained by roughness analysis.
[ texture aspect ratio (Str20) ]
First, using an atomic force microscope (PA 400 manufactured by Seiko Instruments), a measurement mode: tapping mode, scan size: 1 μm × 1 μm, scanning speed: 1Hz, cantilever: the shape image was obtained by Cantilever (SI-DF 40 manufactured by SII Co.). Then, the shape Image was flattened by Image analysis software (SPIP Image analysis software version 6.2.6 manufactured by Image Metrology), and the texture aspect ratio was obtained by roughness analysis (Str 20).
[ core roughness depth (Sk) ]
First, using an atomic force microscope (PA 400 manufactured by Seiko Instruments), a measurement mode: tapping mode, scan size: 1 μm × 1 μm, scanning speed: 1Hz, cantilever: the shape image was obtained by Cantilever (SI-DF 40 manufactured by SII Co.). Then, the shape Image was flattened by Image analysis software (SPIP Image analysis software version 6.2.6 manufactured by Image Metrology) to obtain the core roughness depth (Sk) from the support curve.
[ surface Strength ]
Glass face strength was determined by Ball-and-Ring (BOR) testing. A schematic diagram illustrating the ball-and-loop test used in the present invention is shown in fig. 2. The glass plate 1 was pressed with a pressing jig 2 (quenched steel, diameter 10mm, mirror finish) made of SUS304 in a state where the glass plate 1 was horizontally placed, and the surface strength of the glass plate 1 was measured.
In FIG. 2, a glass plate 1 as a sample was horizontally placed on a support jig 3 (diameter 30mm, curvature R2.5mm of contact portion, quenched steel for contact portion, mirror finish) made of SUS 304. A pressing jig 2 for pressing the glass plate 1 is provided above the glass plate 1.
In the present embodiment, the central region of the glass plate 1 is pressed from above the glass plate 1 obtained in the examples and comparative examples. The test conditions are as follows. Lowering speed of the pressing jig 2: 1.0 (mm/min)
At this time, the breaking load (unit N) when the glass was broken was defined as the BOR surface strength, and the average value of 20 measurements was defined as the BOR average surface strength. However, the case where the breakage start point of the glass plate was 2mm or more from the ball pressing position was excluded from the data for calculating the average value.
[ Hydrogen concentration ]
The hydrogen concentration distribution was measured by the method described in the above [ method for measuring hydrogen concentration distribution ].
[ amount of silanol groups on the surface ]
The amount of surface silanol groups was measured by analyzing the glass surface by X-ray photoelectron spectroscopy (XPS) according to the method described in [ method for measuring amount of surface silanol groups ]. The XPS analysis method and apparatus are as follows.
(XPS analysis)
The device comprises the following steps: ESCA5500 manufactured by ULVAC PHI Inc
For each sample surface, the presence or absence of surface contamination was confirmed by first measuring a broad spectrum, and then measuring a narrow spectrum for C (carbon), O (oxygen), Na (sodium), Mg (magnesium), Al (aluminum), Si (silicon), and K (potassium), and calculating Si standard values for the surface composition and surface silanol group amount of the glass. The measurement conditions are as follows.
Stepping resolution ratio: 0.5 eV/step
Energy application: 117.4eV
Analysis area: diameter of 800 μm phi
[ surface roughness (Ra) ]
Surface roughness (Ra) was measured by using an atomic force microscope (PA 400 manufactured by Seiko Instruments corporation): tapping mode, scan size: 1 μm × 1 μm, scanning speed: 1Hz, cantilever: cantilever (SI-DF 40 manufactured by SII) obtained a shape image and determined Ra.
[ wettability ]
The wettability was evaluated by measuring the contact angle of 2. mu.L of water supplied to the glass surface by PCA-1 manufactured by Kyowa interface science.
< test example 1>
(production of glass plate)
A glass plate was produced by producing a glass having the following composition by a float method so that the plate thickness was 0.7mm, and cutting the glass into a size of 50mm X50 mm.
Consists of the following components: contains 64% SiO in mol%27.5% of Al2O313% of Na2O, 11% MgO
In the following examples, the following steps are combined as appropriate.
(ion exchange Process)
Immersing the glass plate in KNO3The molten salt is subjected to ion exchange treatment and then cooled to around room temperature, thereby being chemically strengthened. At this time, KNO3The temperature of the molten salt was set to 430 ℃ and the immersion time was set to 3.5 hours. The obtained chemically strengthened glass is washed with water and subjected to the next step.
(intensive post-grinding)
Cerium oxide having an average particle diameter (d50) of 0.8 μm was dispersed in water to prepare a slurry as a polishing slurry, and the resulting slurry was used to polish a glass plate with a polishing pad (nonwoven fabric type) at a polishing rate of 0.25 μm/min (single side).
(alkali treatment 1)
A5.0 mass% aqueous solution of sodium hydroxide was prepared in a resin tank, and the temperature was adjusted to 40 ℃ by a fluororesin-coated heater (フッ, resin-coated ヒーター) (KKS 14A; manufactured by October). The glass plate was immersed in the adjusted aqueous sodium hydroxide solution for 10 minutes or 30 minutes to be subjected to alkali treatment, then washed with pure water a plurality of times, and then dried by air blowing.
(alkali treatment 2)
A1M aqueous solution of potassium hydroxide was prepared in a tank made of a resin, and the temperature was adjusted to 40 ℃ by a fluororesin-coated heater (KKS 14A; manufactured by Octon Motor). The glass plate was immersed in the adjusted potassium hydroxide aqueous solution for 10 minutes to be subjected to alkali treatment, then washed with pure water a plurality of times, and then dried by air blowing.
(etching treatment)
A0.2 vol% aqueous hydrogen fluoride solution was prepared in a resin tank, and the temperature was adjusted to room temperature by a fluororesin-coated heater (KKS 14A; manufactured by Octopus). The glass plate was immersed in the adjusted aqueous hydrogen fluoride solution for 20 seconds, 60 seconds, or 2 minutes to be etched, then washed with an aqueous NaOH solution having a pH of 10 for 30 seconds, washed with pure water several times, and then dried by air blowing.
Table 1 shows the results of evaluation of Stdi, Str20, Sk, and BOR average surface strengths of the chemically strengthened glass obtained by the above-described method. Examples 1 to 6 are examples, and examples 7 to 10 are comparative examples. Further, based on the numerical values shown in table 1, the results obtained by plotting Stdi and BOR average surface strengths are shown in fig. 1, the results obtained by plotting Str20 and BOR average surface strengths are shown in fig. 3, and the results obtained by plotting Sk and BOR average surface strengths are shown in fig. 5.
In examples 1 to 10, the hydrogen concentration in a region having a depth of 0.1 to 0.4 μm from the outermost surface of the glass was less than 0.070 mol/L. In examples 1 to 6, the surface roughness (Ra) was 0.35nm or less.
[ Table 1]
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | |
| Enhanced post-grinding | Is provided with | Is provided with | Is provided with | Is free of | Is free of | Is free of | Is provided with | Is provided with | Is provided with | Is provided with |
| Grinding damage | Is provided with | Is provided with | Is provided with | Is free of | Is free of | Is free of | Is provided with | Is provided with | Is provided with | Is provided with |
| Alkali treatment 1 | Is free of | Is free of | Is free of | Is free of | Is free of | Is free of | Is provided with | Is provided with | Is free of | Is free of |
| Alkali treatment 2 | Is free of | Is free of | Is free of | Is free of | Is free of | Is free of | Is free of | Is free of | Is provided with | Is free of |
| Etching treatment | Is provided with | Is provided with | Is provided with | Is provided with | Is provided with | Is provided with | Is free of | Is free of | Is free of | Is free of |
| Treatment time (minutes) | 0.3 | 1 | 2 | 0.3 | 1 | 2 | 10 | 30 | 10 | 0 |
| Surface removal amount [ nm ]] | 74 | 158 | 270 | 52 | 97 | 196 | 19 | 40 | 11 | |
| Stdi | 0.74 | 0.79 | 0.8 | 0.77 | 0.78 | 0.78 | 0.35 | 0.65 | 0.54 | 0.59 |
| Str20 | 0.76 | 0.77 | 0.86 | 0.86 | 0.81 | 0.75 | 0.22 | 0.46 | 0.19 | 0.38 |
| sk[nm] | 0.89 | 0.99 | 0.99 | 0.86 | 0.9 | 0.93 | 1.2 | 1.09 | 1.14 | 1.56 |
| BOR average intensity [ N ]] | 906 | 1063 | 1123 | 1093 | 956 | 971 | 659 | 619 | 654 | 615 |
| Hydrogen concentration [ mol/L] | 0.065 | 0.06 | 0.063 | 0.067 | 0.068 | 0.062 | 0.053 | 0.052 | 0.049 | 0.058 |
| Ra[nm] | 0.277 | 0.345 | 0.312 | 0.267 | 0.28 | 0.291 | 0.358 | 0.494 | 0.361 | 0.38 |
As shown in fig. 1, it can be seen that: stdi has a correlation with the plane strength, and a high plane strength can be achieved by setting Stdi to 0.70 or more and setting the BOR average plane strength to 800N or more.
In addition, from the results shown in fig. 3, it is clear that: str20 has a correlation with the surface strength, and high surface strength can be achieved by setting Str20 to 0.5 or more and setting the BOR average surface strength to 800N or more.
As shown in fig. 5, it can be seen that: sk is correlated with the surface strength, and when Sk is 1nm or less, the BOR average surface strength is 800N or more, whereby high surface strength can be achieved.
< test example 2>
[ example 2-1]
A glass plate was produced by producing a glass having the following composition by a float method so that the plate thickness was 0.7mm, and cutting the glass into a size of 50mm X50 mm.
Consists of the following components: contains 64% SiO in mol%27.5% of Al2O313% of Na2O, 11% MgO
(ion exchange Process)
Immersing the glass plate in KNO3The molten salt is subjected to ion exchange treatment and then cooled to around room temperature, thereby performing chemical strengthening. At this time, KNO3The temperature of the molten salt was 430 ℃ and the immersion time was 3.5 hours. Obtained byThe obtained chemically strengthened glass is washed with water and subjected to the next process.
(alkali treatment)
A4.0 mass% aqueous solution of sodium hydroxide was prepared in a resin tank, and the temperature was adjusted to 40 ℃ by a fluororesin-coated heater (KKS 14A; manufactured by Octopus Motor). The glass plate was immersed in the adjusted aqueous sodium hydroxide solution for 30 minutes to be subjected to alkali treatment, then washed with pure water several times, and then dried by air blowing.
The chemically strengthened glass of example 2-1 was obtained in the manner described above.
[ examples 2-2]
A chemically strengthened glass of example 2-2 was obtained in the same manner as in example 2-1, except that the following flash treatment (フレア treatment) was performed after the ion exchange step and before the alkali treatment in example 2-1.
(flash treatment)
An aqueous solution for flash treatment containing 5.0 mass% of hydrogen fluoride and 5.0 mass% of nitric acid was prepared in a tank made of resin. The glass plate obtained in the ion exchange step was immersed in the prepared aqueous solution for flash treatment for 2 minutes, subjected to flash treatment, and then washed with pure water several times. The glass plate thus obtained was subjected to alkali treatment.
[ examples 2 to 3]
A chemically strengthened glass of example 2-3 was obtained in the same manner as in example 2-1, except that the following acid treatment was performed after the ion exchange step and before the alkali treatment in example 2-1.
(acid treatment)
1M nitric acid was prepared in a tank made of resin, and the temperature was adjusted to 40 ℃ by a fluororesin-coated heater (KKS 14A; manufactured by Octon electric machine). The glass plate obtained in the ion exchange step was immersed in the adjusted nitric acid for 30 minutes, subjected to acid treatment, and then washed with pure water several times. The glass thus obtained is subjected to an alkali treatment.
Comparative example 2-1
In example 2-2, the same procedure as in example 2-2 was repeated except that the alkali treatment was not performed after the ion exchange step and only the flash treatment was performed.
Comparative examples 2 and 2
In examples 2 to 3, the same procedure as in examples 2 to 3 was repeated except that after the ion exchange step, the alkali treatment was not performed and only the acid treatment was performed.
The results of XPS analysis and wettability evaluation of the chemically strengthened glasses of the obtained examples and comparative examples are shown in table 2. In the wettability evaluation, the glass was treated, stored in a clean room for 4 days, and then measured.
[ Table 2]
| Example 2-1 | Examples 2 to 2 | Example 23 | Comparative example 21 | Comparative example 22 | |
| Flash processing | Is free of | Is provided with | Is free of | Is provided with | Is free of |
| Acid treatment | Is free of | Is free of | Is provided with | Is free of | Is provided with |
| Alkali treatment | Is provided with | Is provided with | Is provided with | Is free of | Is free of |
| Surface removal amount [ nm ]] | 65 | 2984 | 65 | 2903 | 48 |
| C1s | 2.08 | 2.28 | 1.17 | 0.64 | 0.34 |
| O1s | 3.05 | 2.88 | 2.78 | 2.49 | 2.43 |
| Na2s | 0.05 | 0.05 | 0.06 | 0.03 | 0.02 |
| Mg2s | 0.01 | 0.14 | 0.05 | 0.01 | 0.02 |
| A12p | 0.21 | 0.25 | 0.22 | 0.13 | 0.09 |
| |
1 | 1 | 1 | 1 | 1 |
| K2s | 0.13 | 0.1 | 0.13 | 0.05 | 0.04 |
| Amount of surface cations | 0.83 | 1.18 | 0.96 | 0.49 | 0.37 |
| Amount of surface silanol groups | 0.81 | 0.46 | 0.68 | 1.15 | 1.27 |
| Contact angle [ ° [ ]] | 14.3 | 16.3 | 15.5 | 8.2 | 7.7 |
As shown in Table 2, in examples 2-1 to 2-3 in which the alkali treatment was carried out, the amount of silanol groups on the glass surface was 1 or less and the contact angle was 14 ℃ or more, as compared with comparative examples 2-1 and 2-2 in which the alkali treatment was not carried out. From the results, it was found that: by alkali-treating the glass surface after the ion exchange step, the amount of silanol groups on the glass surface can be reduced, and the adhesion of contaminants to the glass surface can be suppressed.
The invention has been described in detail and with reference to specific embodiments thereof, but it will be apparent to one skilled in the art that: various changes and modifications can be made without departing from the spirit and scope of the invention.
The present application is based on Japanese patent application 2016-.
Claims (16)
1. A chemically strengthened glass having a compressive stress layer in a surface layer, wherein the chemically strengthened glass satisfies the following conditions (1) to (5):
(1) having abrasive damage on the surface;
(2) a texture direction index (Stdi) of 0.70 or more;
(3) the amount of surface silanol groups obtained by the following formula (i) is 1 or less,
(amount of surface silanol group) (amount of cation in glass) - (amount of cation on glass surface) … formula (i)
The amount of cations on the glass surface was determined by measuring the atomic concentration of each element on the glass surface by X-ray photoelectron spectroscopy and by the following formula (ii),
the amount of cations in the glass was determined by measuring the atomic concentration of each element in the glass by X-ray photoelectron spectroscopy after sputtering with C60 and by the following formula (ii),
(amount of cation) ═ K/Si + Na/Si +2 xmg/Si +3 × Al/Si … formula (ii);
(4) a hydrogen concentration C in a region having a depth X of 0.1 to 0.4 [ mu ] m from the outermost surface of the glass is less than 0.070 mol/L;
(5) the surface roughness (Ra) measured by AFM under the condition of 1 μm square is 0.35nm or less.
2. The chemically strengthened glass according to claim 1, wherein the chemically strengthened glass has a texture aspect ratio (Str20) of 0.5 or more.
3. The chemically strengthened glass according to claim 1 or 2, wherein the chemically strengthened glass has a core roughness depth (Sk) of 1nm or less.
4. The chemically strengthened glass according to claim 1 or 2, wherein the BOR average surface strength of the chemically strengthened glass is 800N or more.
5. The chemically strengthened glass according to claim 1 or 2, wherein the glass is an aluminosilicate glass, an aluminoborosilicate glass, or a soda lime glass.
6. A chemically strengthened glass having a compressive stress layer in a surface layer, wherein the chemically strengthened glass satisfies the following conditions (1) to (3):
(1) a texture direction index (Stdi) of 0.70 or more;
(2) a hydrogen concentration C in a region having a depth X of 0.1 to 0.4 [ mu ] m from the outermost surface of the glass is less than 0.070 mol/L;
(3) the surface roughness (Ra) measured by AFM under the condition of 1 μm square is 0.35nm or less.
7. The chemically strengthened glass according to claim 6, wherein the chemically strengthened glass satisfies the following conditions:
conditions are as follows: the amount of surface silanol groups obtained by the following formula (i) is 1 or less,
(amount of surface silanol group) (amount of cation in glass) - (amount of cation on glass surface) … formula (i)
The amount of cations on the glass surface was determined by measuring the atomic concentration of each element on the glass surface by X-ray photoelectron spectroscopy and by the following formula (ii),
the amount of cations in the glass was determined by measuring the atomic concentration of each element in the glass by X-ray photoelectron spectroscopy after sputtering with C60 and by the following formula (ii),
(amount of cation) ═ K/Si + Na/Si +2 xmg/Si +3 × Al/Si … formula (ii).
8. The chemically strengthened glass as claimed in claim 6, which has abrasive damage on the surface.
9. The chemically strengthened glass according to claim 6 or 7, wherein the chemically strengthened glass has a texture aspect ratio (Str20) of 0.5 or more.
10. The chemically strengthened glass according to claim 6 or 7, wherein the chemically strengthened glass has a core roughness depth (Sk) of 1nm or less.
11. The chemically strengthened glass according to claim 6 or 7, wherein the BOR average surface strength of the chemically strengthened glass is 800N or more.
12. The chemically strengthened glass according to claim 6 or 7, wherein the glass is an aluminosilicate glass, an aluminoborosilicate glass, or a soda lime glass.
13. A method of making chemically strengthened glass, comprising:
an ion exchange step of forming a compressive stress layer on the surface layer of the glass by an ion exchange method, and
a glass surface treatment step of performing an alkali treatment after the ion exchange step,
wherein,
the surface treatment step is a surface treatment step of treating the glass surface so as to satisfy the following (a) to (c),
(a) a texture direction index (Stdi) of 0.70 or more;
(b) a hydrogen concentration C in a region having a depth X of 0.1 to 0.4 [ mu ] m from the outermost surface of the glass is less than 0.070 mol/L;
(c) the surface roughness (Ra) measured by AFM under the condition of scanning size of 1 μm × 1 μm is 0.35nm or less.
14. The method for producing chemically strengthened glass according to claim 13, wherein the surface treatment step is a surface treatment step of treating the glass surface so as to satisfy the following (d) as well,
(d) the amount of surface silanol groups obtained by the following formula (i) is 1 or less,
(amount of surface silanol group) (amount of cation in glass) - (amount of cation on glass surface) … formula (i)
The amount of cations on the glass surface was determined by measuring the atomic concentration of each element on the glass surface by X-ray photoelectron spectroscopy and by the following formula (ii),
the amount of cations in the glass was determined by measuring the atomic concentration of each element in the glass by X-ray photoelectron spectroscopy after sputtering with C60 and by the following formula (ii),
(amount of cation) ═ K/Si + Na/Si +2 xmg/Si +3 × Al/Si … formula (ii).
15. The method for producing chemically strengthened glass according to claim 13 or 14, wherein the production method comprises a sampling inspection that is determined to be suitable when a texture direction index (Stdi) obtained by AFM image analysis after the surface treatment step is 0.70 or more.
16. The method for producing chemically strengthened glass according to claim 13 or 14, wherein the production method comprises a polishing step of polishing the glass surface after the ion exchange step and before the surface treatment step.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016036084A JP2017149628A (en) | 2016-02-26 | 2016-02-26 | Chemically strengthened glass and method for producing chemically strengthened glass |
| JP2016-036084 | 2016-02-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107129160A CN107129160A (en) | 2017-09-05 |
| CN107129160B true CN107129160B (en) | 2021-10-08 |
Family
ID=59720666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710102390.7A Active CN107129160B (en) | 2016-02-26 | 2017-02-24 | Chemically strengthened glass and method for producing chemically strengthened glass |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2017149628A (en) |
| CN (1) | CN107129160B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020142952A (en) * | 2019-03-06 | 2020-09-10 | 日本電気硝子株式会社 | Near-infrared absorbing glass plate |
| KR20220016088A (en) | 2019-05-30 | 2022-02-08 | 코닝 인코포레이티드 | Textured glass articles and methods of making them |
| CN114502515B (en) * | 2019-09-09 | 2024-03-26 | 康宁股份有限公司 | Textured, antiglare glass article and method of making same |
| CN112694260B (en) * | 2019-10-23 | 2021-12-07 | 比亚迪股份有限公司 | Glass piece and preparation method and device thereof |
| CN113443830A (en) * | 2020-03-27 | 2021-09-28 | Ａｇｃ株式会社 | Glass plate and method for producing same |
| US11759909B2 (en) * | 2020-06-19 | 2023-09-19 | Sk Enpulse Co., Ltd. | Polishing pad, preparation method thereof and method for preparing semiconductor device using same |
| JP7511105B2 (en) | 2021-03-26 | 2024-07-05 | Ａｇｃ株式会社 | Chemically strengthened glass and method for producing chemically strengthened glass |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012151459A1 (en) * | 2011-05-05 | 2012-11-08 | Corning Incorporated | Glass with high frictive damage resistance |
| CN103782152A (en) * | 2011-08-04 | 2014-05-07 | 旭硝子株式会社 | Method for impact-testing chemically strengthened glass, method for reproducing cracks in chemically strengthened glass, and method for manufacturing chemically strengthened glass |
| CN103946171A (en) * | 2011-11-18 | 2014-07-23 | 旭硝子株式会社 | Glass for chemical reinforcement and chemically reinforced glass |
| CN104350020A (en) * | 2012-05-25 | 2015-02-11 | 旭硝子株式会社 | Chemically strengthened glass plate, cover glass, chemically strengthened glass with touch sensor, and display device |
| CN104918898A (en) * | 2013-07-19 | 2015-09-16 | 旭硝子株式会社 | Chemically strengthened glass and method for manufacturing same |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6402851B1 (en) * | 2000-05-19 | 2002-06-11 | International Business Machines Corporation | Lanthanide oxide dissolution from glass surface |
| JP2002150547A (en) * | 2000-11-06 | 2002-05-24 | Nippon Sheet Glass Co Ltd | Method for manufacturing glass substrate for information recording medium |
| JP2010168270A (en) * | 2008-12-26 | 2010-08-05 | Hoya Corp | Glass substrate and method for manufacturing the same |
| JP5636022B2 (en) * | 2011-05-02 | 2014-12-03 | Hoya株式会社 | Glass substrate for cover glass for electronic equipment and method for manufacturing the same |
| JP2013040086A (en) * | 2011-08-19 | 2013-02-28 | Asahi Glass Co Ltd | Method for manufacturing tempered glass plate and cover glass, and cover glass |
| JP2015171956A (en) * | 2012-07-17 | 2015-10-01 | 旭硝子株式会社 | Production method of strengthened cover glass, and strengthened cover glass, as well as production method of strengthened cover glass integrated with touch sensor, and strengthened cover glass integrated with touch sensor |
| JP2015143160A (en) * | 2014-01-31 | 2015-08-06 | 日本電気硝子株式会社 | Method of tempered glass and tempered glass |
-
2016
- 2016-02-26 JP JP2016036084A patent/JP2017149628A/en active Pending
-
2017
- 2017-02-24 CN CN201710102390.7A patent/CN107129160B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012151459A1 (en) * | 2011-05-05 | 2012-11-08 | Corning Incorporated | Glass with high frictive damage resistance |
| CN103782152A (en) * | 2011-08-04 | 2014-05-07 | 旭硝子株式会社 | Method for impact-testing chemically strengthened glass, method for reproducing cracks in chemically strengthened glass, and method for manufacturing chemically strengthened glass |
| CN103946171A (en) * | 2011-11-18 | 2014-07-23 | 旭硝子株式会社 | Glass for chemical reinforcement and chemically reinforced glass |
| CN104350020A (en) * | 2012-05-25 | 2015-02-11 | 旭硝子株式会社 | Chemically strengthened glass plate, cover glass, chemically strengthened glass with touch sensor, and display device |
| CN104918898A (en) * | 2013-07-19 | 2015-09-16 | 旭硝子株式会社 | Chemically strengthened glass and method for manufacturing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107129160A (en) | 2017-09-05 |
| JP2017149628A (en) | 2017-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107129160B (en) | Chemically strengthened glass and method for producing chemically strengthened glass | |
| CN104918898B (en) | Chemically reinforced glass and manufacture method thereof | |
| CN107207334B (en) | Chemically strengthened glass and method for producing chemically strengthened glass | |
| CN107207333B (en) | Chemically strengthened glass and method for producing same | |
| JP7310966B2 (en) | chemically strengthened glass | |
| CN110914213B (en) | Chemically strengthened glass | |
| TW201536709A (en) | Chemically strengthened glass, and method for producing same | |
| CN107207311B (en) | Float glass | |
| CN109803938B (en) | Method for producing chemically strengthened glass | |
| CN111902378B (en) | Method for maximally reducing dent defects in chemically strengthened glass | |
| WO2014084096A1 (en) | Reinforced glass and method for manufacturing same | |
| CN111606573A (en) | Glass substrate with concave-convex shape and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| CB02 | Change of applicant information |
Address after: Tokyo, Japan Applicant after: AGC Corporation Address before: Tokyo, Japan Applicant before: Asahi Glass Co., Ltd. |
|
| CB02 | Change of applicant information | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |