CN111747661B - Method for producing chemically strengthened glass, molten salt composition, and method for prolonging life of molten salt composition - Google Patents
Method for producing chemically strengthened glass, molten salt composition, and method for prolonging life of molten salt composition Download PDFInfo
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- CN111747661B CN111747661B CN202010221883.4A CN202010221883A CN111747661B CN 111747661 B CN111747661 B CN 111747661B CN 202010221883 A CN202010221883 A CN 202010221883A CN 111747661 B CN111747661 B CN 111747661B
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- molten salt
- salt composition
- nitrate
- glass
- chemically strengthened
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- 150000003839 salts Chemical class 0.000 title claims abstract description 171
- 239000000203 mixture Substances 0.000 title claims abstract description 166
- 239000005345 chemically strengthened glass Substances 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000011521 glass Substances 0.000 claims abstract description 96
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 60
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052796 boron Inorganic materials 0.000 claims abstract description 54
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 38
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 32
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 30
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 30
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 29
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 29
- 239000012535 impurity Substances 0.000 claims abstract description 27
- 238000005728 strengthening Methods 0.000 claims abstract description 18
- 238000003426 chemical strengthening reaction Methods 0.000 claims description 49
- -1 anion compound Chemical class 0.000 claims description 25
- 150000001450 anions Chemical class 0.000 claims description 10
- 150000001449 anionic compounds Chemical class 0.000 claims description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 33
- 238000011282 treatment Methods 0.000 description 12
- 238000005342 ion exchange Methods 0.000 description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 8
- 239000004327 boric acid Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 230000006866 deterioration Effects 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 230000002035 prolonged effect Effects 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 102100033973 Anaphase-promoting complex subunit 10 Human genes 0.000 description 4
- OAUWKHSGCCPXOD-UHFFFAOYSA-N DOC1 Natural products C1=CC(O)=C2C(CC(=O)NCCCCCNCCCNCCCNCCCN)=CNC2=C1 OAUWKHSGCCPXOD-UHFFFAOYSA-N 0.000 description 4
- 101000779315 Homo sapiens Anaphase-promoting complex subunit 10 Proteins 0.000 description 4
- 101000737813 Homo sapiens Cyclin-dependent kinase 2-associated protein 1 Proteins 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- 238000006124 Pilkington process Methods 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003280 down draw process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 102100035353 Cyclin-dependent kinase 2-associated protein 1 Human genes 0.000 description 1
- 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 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000005407 aluminoborosilicate glass Substances 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000005355 lead glass 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
- 238000003754 machining Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate 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
- 238000005096 rolling process Methods 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
- 239000005361 soda-lime glass Substances 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
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 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
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container 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 method for producing chemically strengthened glass, a molten salt composition, and a method for prolonging the life of a molten salt composition. The method for producing chemically strengthened glass according to the present invention comprises: and chemically strengthening the lithium-containing glass using a molten salt composition containing boron as an impurity, and at least one of potassium nitrate and sodium nitrate, wherein the molten salt composition further contains nitrate of a metal having a valence of 2.
Description
Technical Field
The present invention relates to a method for producing chemically strengthened glass, a molten salt composition, and a method for prolonging the life of a molten salt composition.
Background
A chemically strengthened glass (hereinafter referred to as chemically strengthened glass) treated by ion exchange or the like is used for a cover glass for display devices such as digital cameras, cellular phones, and PDAs (Personal Digital Assistants: portable information terminals) and a glass substrate for use as a display. Chemically strengthened glass used for these applications requires high strength on both the surface and the end face in order to meet the purpose.
The chemical strengthening treatment by ion exchange is a treatment of replacing alkali metal ions having a small ionic radius existing in the vicinity of the surface of the glass plate with alkali metal ions having a larger ionic radius by ion exchange at a temperature equal to or lower than the glass transition temperature. Thus, compressive stress remains on the surface of the glass, and the strength of the glass is improved.
A glass containing Li (hereinafter referred to as a lithium-containing glass) is a glass material capable of obtaining a deep depth of layer of compressive stress (hereinafter referred to as DOL) by high-speed ion exchange (for example, substitution of Li ions with Na ions or K ions). Accordingly, the desire to develop chemical strengthening treatments for lithium-containing glasses has increased in recent years.
The chemical strengthening treatment of lithium-containing glass differs from the chemical strengthening treatment of glass that does not contain Li ions, for example, li ions are eluted into the molten salt composition; etc. In the chemical strengthening treatment of lithium-containing glass, there is a strong tendency that the life of a molten salt composition used for the chemical strengthening treatment becomes shorter, particularly due to a decrease in the expansion ratio of the glass before and after the chemical strengthening treatment, a decrease in stress (CT) of the chemical strengthening glass, and a deterioration in the appearance of the chemical strengthening glass (an increase in haze value). This is a major problem in managing the chemical strengthening treatment of lithium-containing glass.
In the chemical strengthening of lithium-containing glass, as a means for excluding the influence of Li ions, a method of adding sodium metasilicate as a heterogeneous anion compound to a molten salt composition in advance is used. According to this method, the sodium metasilicate adsorbs Li ions in the molten salt composition, so that the strengthening performance of the molten salt composition can be recovered and CT of the obtained chemically strengthened glass can be improved.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 61-178004
Disclosure of Invention
Problems to be solved by the invention
The inventors of the present invention have found that, when boron is contained as an impurity in a molten salt composition containing a heterogeneous anion compound, the appearance of the obtained chemically strengthened glass is deteriorated and the life of the molten salt composition is shortened in the chemical strengthening treatment of lithium-containing glass.
The following mechanism is considered as a reason why the appearance of chemically strengthened glass is deteriorated due to boron. By adding the heterogeneous anionic compound, the pH of the molten salt composition is raised and boron exists as boric acid at a pH of 9 or more. The etching of the glass is promoted by boric acid, and lithium-containing crystals are formed on the surface and surface layer of the glass, so that the surface of the glass is embrittled and the crystals fall off, thereby causing defects and deteriorating the appearance.
Accordingly, an object of the present invention is to provide a method for producing a chemically strengthened glass, which comprises a step of chemically strengthening a lithium-containing glass using a molten salt composition containing at least one of potassium nitrate and sodium nitrate, a heterogeneous anion compound, and boron as an impurity, wherein deterioration in the appearance of the chemically strengthened glass due to the incorporation of boron can be suppressed, and the life of the molten salt composition can be prolonged.
Means for solving the problems
The present inventors have found that the above problems can be solved by adding nitrate of a metal having a valence of 2 to a molten salt composition in a method for producing a chemically strengthened glass, the method comprising a step of chemically strengthening a lithium-containing glass using a molten salt composition containing at least one of potassium nitrate and sodium nitrate, a heterogeneous anion compound, and boron as an impurity, and have completed the present invention.
That is, the present invention provides a method for producing chemically strengthened glass, comprising: and chemically strengthening the lithium-containing glass using a molten salt composition containing boron as an impurity, and at least one of potassium nitrate and sodium nitrate, wherein the molten salt composition further contains nitrate of a metal having a valence of 2.
Further, the present invention provides a molten salt composition for chemical strengthening of lithium-containing glass, which contains at least one of potassium nitrate and sodium nitrate, a heteroanion compound, and boron as an impurity, wherein the molten salt composition further contains nitrate of a 2-valent metal.
The present invention also provides a method for prolonging the life of a molten salt composition for chemically strengthening a lithium-containing glass, wherein a nitrate of a metal having a valence of 2 is mixed with a molten salt composition containing at least one of potassium nitrate and sodium nitrate, a heterogeneous anion compound, and boron as an impurity.
Effects of the invention
In the method for producing a chemically strengthened glass of the present invention, a molten salt composition containing a heterogeneous anion compound and boron as an impurity is caused to contain nitrate of a metal having a valence of 2. In so doing, the 2-valent metal ion allows boric acid to settle, and inhibits etching of the glass by boric acid, so that deterioration in appearance of the chemically strengthened glass due to mixing of boron can be suppressed, and the life of the molten salt composition can be prolonged.
Drawings
FIG. 1A shows the addition or non-addition of Ca (NO) to a molten salt composition 3 ) 2 ·4H 2 Graph of the relationship between the treated area in the case of O and DOC1 of chemically strengthened glass. FIG. 1 (B) shows the addition or non-addition of Ca (NO) 3 ) 2 ·4H 2 Graph of the relationship between the treatment area in the case of O and CT of chemically strengthened glass. FIG. 1 (C) shows the addition or non-addition of Ca (NO) 3 ) 2 ·4H 2 Graph of the relationship between DOL in the case of O and CS of chemically strengthened glass.
FIG. 2 is a schematic view showing addition of Ca (NO) to a molten salt composition 3 ) 2 ·4H 2 Graph of the relationship between the treatment area and CS of the chemically strengthened glass in the case of O (example 1).
Detailed Description
The present invention will be described in detail below, but the present invention is not limited to the following embodiments, and may be implemented with any modifications within the scope of the present invention.
One embodiment of the method for producing chemically strengthened glass according to the present invention will be described below, but the present invention is not limited thereto.
The method for producing chemically strengthened glass according to the present invention comprises: a step of chemically strengthening a lithium-containing glass using a molten salt composition containing boron as an impurity, and at least one of potassium nitrate and sodium nitrate, wherein the molten salt composition further contains a nitrate of a metal having a valence of 2.
(glass composition)
The glass used in the present invention may contain lithium, and may have various compositions as long as it has a composition that can be strengthened by a forming and chemical strengthening treatment. Specifically, examples thereof include: aluminosilicate glass, soda lime glass, borosilicate glass, lead glass, alkali barium glass, aluminoborosilicate glass, and the like.
The method for producing glass is not particularly limited, and can be produced by: the desired glass raw material is charged into a continuous melting furnace, the glass raw material is heated and melted at a temperature of preferably 1500 ℃ to 1600 ℃, clarified, then fed to a forming apparatus, and then the molten glass is formed into a plate shape and cooled slowly.
The glass may be formed by various methods. For example, various molding methods such as a downdraw method (for example, overflow downdraw method, flow hole downdraw method, and re-traction method), a float method, a roll method, and a press method can be employed. Among them, the float method is preferable from the viewpoint that cracks are easily generated in at least a part of the glass surface, and the effect of the present invention is more remarkably observed.
The thickness of the glass is not particularly limited, but is usually preferably 5mm or less, more preferably 3mm or less, further preferably 1mm or less, particularly preferably 0.7mm or less, in order to effectively perform the chemical strengthening treatment.
In addition, the shape of the glass used in the present invention is not particularly limited. For example, glass having a flat plate shape with a uniform plate thickness, a shape with at least one of a front surface and a back surface having a curved surface, a three-dimensional shape with a curved portion, or the like, and various shapes can be used. It is preferable that the glass is subjected to a shape processing according to the application, such as a machining process including cutting, end face processing, and hole forming, before the chemical strengthening treatment.
The content of lithium in the glass used in the present invention is preferably 0.1 to 20% in terms of mole percent based on the oxide.
The composition of the glass is not particularly limited, and examples thereof include the following.
Expressed as mole percent on an oxide basis, comprises 50% to 80% SiO 2 2 to 25 percent of Al 2 O 3 0.1 to 20 percent of Li 2 O, na 0.1-18% 2 O, 0-10% K 2 O, mgO 0-15%, caO 0-5% and P0-5% 2 O 5 0 to 5 percent of B 2 O 3 0 to 5 percent of Y 2 O 3 And 0% to 5% ZrO 2 Is composed of (1).
The chemically strengthened glass obtained by the production method of the present invention has a compressive stress layer on the glass surface, which is obtained by ion exchange. In the ion exchange method, the surface of glass is ion-exchanged to form a surface layer of residual compressive stress. Specifically, at a temperature equal to or lower than the glass transition temperature, alkali metal ions (typically Li ions, na ions) having a small ion radius on the surface of the glass plate are replaced with alkali metal ions having a larger ion radius (typically Na ions or K ions relative to the Li ions, and K ions relative to the Na ions) by ion exchange. Thus, compressive stress remains on the surface of the glass, and the strength of the glass is improved.
(molten salt composition)
In the production method of the present invention, the lithium-containing glass is chemically strengthened by contacting the glass with a molten salt composition containing at least one of potassium nitrate and sodium nitrate. Thereby, the Li ions on the glass surface are ion-exchanged with K ions and Na ions in the molten salt composition, thereby forming a high-density compressive stress layer. The method of bringing the glass into contact with the molten salt composition may be a method of applying a paste-like molten salt composition to the glass, a method of spraying the molten salt composition onto the glass, a method of immersing the glass in a salt bath of the molten salt composition heated to a melting point or higher, or the like, and among these, a method of immersing the glass in the molten salt composition is preferable.
The molten salt composition is preferably a molten salt composition having a melting point at or below the strain point (usually 500 to 600 ℃) of glass subjected to chemical strengthening, and in the present invention, is a molten salt composition containing at least one of potassium nitrate (melting point: 334 ℃) and sodium nitrate (melting point: 308 ℃). By containing at least one of potassium nitrate and sodium nitrate, the molten salt is in a molten state at or below the strain point of the glass, and is easy to handle in the operating temperature range (use temperature range), and is therefore preferable. The total content of potassium nitrate and sodium nitrate in the molten salt composition is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more.
The molten salt composition contains a xenogenic anionic compound. The heterogeneous anion compound is a compound containing an anion species different from anions constituting the molten salt. By containing the heterogeneous anion compound in the molten salt composition, the heterogeneous anion compound in the molten salt composition reacts with Li ions, and Li ions in the molten salt composition can be adsorbed. Examples of the heterogeneous anion compound include: sodium xenogeneic anions, potassium xenogeneic anions. Examples of the sodium anions include: sodium metasilicate, sodium orthosilicate, sodium sesquisilicate, sodium phosphate, sodium carbonate. Examples of the potassium anion include: potassium metasilicate, potassium phosphate, potassium carbonate. These hetero anion compounds may be used singly or in combination.
For example, in the case of using sodium metasilicate as the heterogeneous anionic compound in the molten salt composition, the reaction formula of the heterogeneous anionic compound with Li ions in the molten salt composition is as follows.
Na 2 SiO 3 →NaSiO 3 - +Na +
NaSiO 3 - +Li + →LiNaSiO 3
SiO 3 2- +2Li + →Li 2 SiO 3
For the chemical strengthening treatment of lithium-containing glass, li ions are present in the glass surface layer due to the dissolution of Li ions into the molten salt composition, and ion exchange of Li ions in the glass with Na ions in the molten salt composition is hindered due to the presence of Li ions in the molten salt composition. The molten salt composition of the present invention contains the heterogeneous anion compound, whereby the Li ions in the molten salt composition are adsorbed by the heterogeneous anion compound, and this inhibition is suppressed, and the strengthening performance of the molten salt composition is stabilized, and the stress can be improved.
The content of the hetero anionic compound in the molten salt composition is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and still more preferably 1 mass% or more, relative to the entire molten salt composition. When the content of the heterogeneous anion compound in the molten salt composition is 1 mass% or more, li ions in the molten salt composition can be effectively adsorbed, and the strengthening performance of the molten salt composition can be stabilized. The content of the heterogeneous anionic compound in the molten salt composition is preferably 10 mass% or less, more preferably 7.5 mass% or less, and further preferably 5 mass% or less.
In the molten salt composition, the content of the hetero anionic compound is preferably 0.1 to 10 mol% with respect to the total content of potassium nitrate and sodium nitrate. By setting the amount of the heterogeneous anionic compound to the above range with respect to the total content of potassium nitrate and sodium nitrate, li ions in the molten salt composition can be effectively adsorbed, and the strengthening performance of the molten salt composition can be stabilized.
The content of boron contained as an impurity in the molten salt composition is preferably 100 mass ppm or less, more preferably 50 mass ppm or less, and further preferably 10 mass ppm or less. Further, the typical content of boron is 10 to 50 mass ppm. The inclusion of boron as an impurity means that boron is not intentionally added. For example, when boron is contained in impurities or the like of a raw material of the molten salt composition, boron can be mixed into the molten salt.
The molten salt composition contains nitrate of a metal of valence 2. Examples of the metal having a valence of 2 include: ca. Mg, ba, zn, cu, fe, pb, ni, mn, sn Ca, mg and Ba are preferable. The nitrate of the metal having a valence of 2 may be used singly or in combination.
Boron contained as an impurity in the molten salt composition exists in the form of boric acid under the condition of high pH, but by containing nitrate of a metal having valence 2 in the molten salt composition, it is possible to react a metal ion having valence 2 with boric acid to precipitate boric acid. This can suppress deterioration of the appearance of the chemically strengthened glass due to the mixing of boron and can prolong the life of the molten salt composition.
Specifically, the molten salt composition (1) contains Mg (NO 3 ) 2 Nitrate as a metal of valence 2; (2) The molten salt composition contains Ca (NO) 3 ) 2 In the case of nitrate of a metal having a valence of 2, the following reaction formula of boric acid and metal ions is shown.
In the molten salt composition, the boron content in each 1g of the whole molten salt composition was 3.7X10 -2 In the case of mass ppm or less, the content of nitrate of the metal having valence 2 is preferably 0.02 mol% or more. By setting the nitrate content of the metal having a valence of 2 in the above range, the nitrate content can react with boron contained in the molten salt composition as an impurity in an appropriate amount, and the influence of boron can be effectively eliminated, deterioration in the appearance of the chemically strengthened glass due to the incorporation of boron can be suppressed, and the life of the molten salt composition can be further prolonged. On the other hand, the boron content in each 1g of the total molten salt composition was 3.57X 10 -2 In the case of mass ppm or less, the content of nitrate of the metal having valence 2 is preferably 0.5 mol% or less, more preferably 0.3 mol% or less, and still more preferably 0.25 mol% or less. By making the nitrate content of the 2-valent metal within the above range, ion exchange is not hindered.
The content of the nitrate of the metal having valence 2 is preferably 0.5 mol or more, more preferably 1 mol or more, and still more preferably 2 mol or more, based on 1 mol of boron in the molten salt composition. The nitrate of the metal having a valence of 2 is added to boron in the above range, so that the influence of boron contained as an impurity in the molten salt composition can be effectively eliminated, deterioration of the appearance of the chemically strengthened glass due to the mixing of boron can be suppressed, and the life of the molten salt composition can be further prolonged. On the other hand, the content of nitrate of the metal having valence 2 is preferably 6.5 mol or less, more preferably 6 mol or less, with respect to 1 mol of boron. The content of nitrate by the 2-valent metal is within the above range, and ion exchange is not hindered.
The molten salt composition may contain other chemical substances in addition to potassium nitrate and sodium nitrate within a range that does not hinder the effects of the present invention, and examples thereof include: nitrate, sulfate, carbonate, chloride, etc. Examples of the nitrate include: lithium nitrate, cesium nitrate, silver nitrate, and the like. Examples of the sulfate include: lithium sulfate, sodium sulfate, potassium sulfate, cesium sulfate, silver sulfate, and the like. Examples of carbonates include: lithium carbonate, sodium carbonate, potassium carbonate, and the like. Examples of the chloride include: lithium chloride, sodium chloride, potassium chloride, cesium chloride, silver chloride, and the like. These molten salts may be used alone or in combination of two or more.
In the method for producing a chemically strengthened glass according to the present invention, a molten salt composition containing boron as an impurity and at least one of potassium nitrate and sodium nitrate is used to chemically strengthen a lithium-containing glass, and the glass is immersed in the molten salt composition at a temperature of about 350 to about 500 ℃ for 0.1 to 10 hours, for example.
The above-described step may be used as the first strengthening treatment, and after the above-described step, the second and subsequent strengthening treatments may be performed using a molten salt composition containing K ions (for example, a molten salt composition containing potassium nitrate). The cleaning step is preferably provided between the first strengthening treatment and the second strengthening treatment.
Specifically, for example, as the second strengthening treatment, the glass is immersed in a metal salt composition containing K ions (for example, a molten salt composition containing potassium nitrate) at a temperature of about 350 to about 500 ℃ for about 0.1 to about 10 hours. In the case of performing the second and subsequent chemical strengthening treatments, the total treatment time is preferably 10 hours or less, more preferably 5 hours or less, and even more preferably 3 hours or less from the viewpoint of productivity.
(method for prolonging the life of molten salt composition)
According to the present invention, by including the nitrate of the metal having valence 2 in the molten salt composition, even when boron is included as an impurity in the molten salt composition, the service life (lifetime) of the molten salt composition including the heterogeneous anionic compound and at least one of potassium nitrate and sodium nitrate for chemical strengthening of the lithium-containing glass can be prolonged.
Accordingly, as one embodiment of the present invention, there is exemplified a method for prolonging the life of a molten salt composition for chemical strengthening of lithium-containing glass, wherein nitrate of a metal having valence 2 is mixed with a molten salt composition containing at least one of potassium nitrate and sodium nitrate, a heterogeneous anion compound, and boron as an impurity.
In order to quantitatively evaluate the service life (lifetime) of the molten salt composition, as an index, stress (CT) of the chemically strengthened glass, expansion ratio of the glass before and after the chemical strengthening treatment, and appearance (haze) of the chemically strengthened glass may be used.
When the stress of the chemically strengthened glass is used as an index of the life of the molten salt composition, the CT value as an index is set as: the CT value obtained from the molten salt containing at least one of potassium nitrate and sodium nitrate in the initial state is set to a CT value of 100% or more of a desired value (%). Further, the Li ion concentration in the molten salt composition when the CT value as an index cannot be obtained in the chemical strengthening treatment, that is, when the value is smaller than the desired value (%) is taken as the life of the molten salt composition.
In the case where the stress of the chemically strengthened glass is used as an index of the life of the molten salt composition, specifically, for example, the life of the molten salt composition can be evaluated as follows. First, in order to simulate the production of a state in which the chemical strengthening treatment is repeated, a Li ion source is intentionally added to the molten salt composition. Then, the lithium-containing glass is subjected to a chemical strengthening treatment with the molten salt composition to which the Li ion source is added, and when the CT value of the treated glass is lower than the CT value as an index, the Li ion concentration is calculated from the amount of the Li ion source added, and this can be used as an index of the lifetime of the molten salt composition.
The expansion ratio is the expansion ratio of the glass after the chemical strengthening treatment relative to the glass before the chemical strengthening treatment. When the expansion ratio is used as an index of the life of the molten salt composition, the expansion ratio as an index is set as: the expansion ratio obtained from the molten salt containing at least one of potassium nitrate and sodium nitrate in the initial state is set to a desired value (%) or more when the expansion ratio is 100%. Further, the Li ion concentration in the molten salt composition when the expansion ratio as an index cannot be obtained in the chemical strengthening treatment, that is, when the expansion ratio is smaller than the desired value (%) is regarded as the service life of the molten salt composition.
In the case of using the expansion ratio as an index of the life of the molten salt composition, specifically, for example, the life of the molten salt composition can be evaluated as follows. First, in order to simulate the production of a state in which the chemical strengthening treatment is repeated, a Li ion source is intentionally added to the molten salt composition. Then, the lithium-containing glass is subjected to a chemical strengthening treatment with the molten salt composition to which the Li ion source is added, and when the expansion ratio of the treated glass is lower than the expansion ratio as an index, the Li ion concentration is calculated from the amount of the Li ion source added, and this can be used as an index of the life of the molten salt composition.
When the appearance (haze) of the chemically strengthened glass is used as an index of the life of the molten salt composition, for example, when the haze value obtained from the molten salt including at least one of potassium nitrate and sodium nitrate in the initial state is 0.1% to 0.2%, for example, the Li ion concentration in the molten salt composition when the haze value is increased to more than 1% (in the second state, 1% よ, up to date) is used as the life of the molten salt composition. "haze" is determined by JIS K7136:2000 (ISO 14782:1999). As a haze measurement, a haze meter (model NDH 7000) manufactured by Nippon electric color industry Co., ltd was used.
In the case of using the haze value as an index of the life of the molten salt composition, specifically, for example, the life of the molten salt composition can be evaluated as follows. First, in order to simulate the production of a state in which the chemical strengthening treatment is repeated, a Li ion source is intentionally added to the molten salt composition. Then, the lithium-containing glass is subjected to a chemical strengthening treatment with the molten salt composition to which the Li ion source is added, and when the haze value of the treated glass is larger than the haze value as an index, the Li ion concentration is calculated from the amount of the Li ion source added, and this can be used as an index of the life of the molten salt composition.
Examples (example)
Hereinafter, examples of the present invention will be specifically described, but the present invention is not limited thereto.
(glass composition)
As the glass to be chemically strengthened, a glass having the following composition in mol% based on oxides was used.
SiO 2 ：70％、Al 2 O 3 ：7.5％、Li 2 O：8.0％、Na 2 O：5.3％、K 2 O：1.0％、MgO：7.0％、CaO：0.2％、ZrO 2 ：1.0％
(evaluation method of glass)
(1) Stress of
As shown in the following formula, CT was obtained from the surface compressive stress value (CS, unit: MPa) and the depth of layer of compressive stress (DOC 1, unit: μm) at the time of CS being 0. The surface compressive stress value (in MPa), the compressive stress value (in MPa) at each depth, and the depth of the compressive stress layer (DOL, in μm) were measured using a surface stress meter (FSM-6000) manufactured by the manufacturing company of the primitive folder and a scattered light photoelastic stress meter (SLP-1000) manufactured by the manufacturing company of the primitive folder. Regarding the stress (CT) in table 1, the standard deviation σ of CT when nitrate of 2-valent metal was not added was evaluated as "no anomaly" when σ was equal to or smaller than 5.
CT=CS [ MPa ] DOC1[ mm ]/(glass thickness [ mm ] -2 x DOC1[ mm ])
(2) Appearance of
With respect to the appearance of the product,the boundary value (limit value) of the haze value was set to 1.4%, and evaluation was performed by using the processing area at the time of reaching the haze value. The "treated area" herein means the cumulative treated area (m 2 /kg). Haze (Hz) (%) A haze meter (manufacturer: japanese electric color industry Co., ltd., model: NDH 7000) was used and was used in accordance with JIS K7136:2000, the method specified in 2000.
(3) Expansion ratio
Regarding the expansion ratio of the glass, the length of any one side on the main surface of the glass before chemical strengthening is L 0 The length of the one side of the chemically strengthened glass is L, and is represented by the formula L-L 0 Calculation of L/l×100 (%). In addition, regarding the "expansion ratio" in table 1, when there was no significant difference from the nitrate to which no 2-valent metal was added, it was evaluated as "no abnormality".
Experimental example 1 analysis of the influence of cumulative chemical strengthening treatment on glass/molten salt compositions
The chemical strengthening treatment was performed cumulatively, and the effect of the addition of nitrate with the 2-valent metal on the molten salt composition and the glass was investigated.
Na as a material of the molten salt composition was added to SUS-made cup 2 SiO 3 B and Ca (NO) 3 ) 2 ·4H 2 O is set to the content shown in table 1. In addition, sodium nitrate was added and heated to 450 ℃ with a sheathed resistance heater to prepare a molten salt composition.
Glass having the above composition and cut to a thickness of 0.65mm and 50mm×50mm was prepared, preheated to 350 to 400 ℃, then immersed in a molten salt composition as a chemical strengthening treatment, treated at 410 ℃ for 4 hours, then cooled to around room temperature, subjected to a first chemical strengthening treatment, and then the attached salt was washed with water.
Next, the glass is preheated to 350-400 ℃, and then the glass is immersed in 100 wt% KNO 3 Is treated at 440 ℃ for 1 hour and then cooledCooling to room temperature, performing a second chemical strengthening treatment, and then washing the attached salt with water. Thereafter, the combination of the first chemical strengthening treatment and the second chemical strengthening treatment is cumulatively repeated.
The chemically strengthened glass obtained by the second chemical strengthening treatment was evaluated for stress, appearance, and expansion ratio, and the results thereof and the influence caused by the addition of salt are shown in table 1.
Fig. 1 (a) to (C) show the influence of the cumulative chemical strengthening treatment on the stress in the glass deep layer portion. FIG. 1A shows Ca (NO) added to a molten salt composition 3 ) 2 ·4H 2 O (example 1) or Ca (NO) 3 ) 2 ·4H 2 Graph of the relationship between the treatment area and DOC1 of chemically strengthened glass in the case of O (comparative example 2). FIG. 1 (B) shows the addition of Ca (NO) to a molten salt composition 3 ) 2 ·4H 2 O (example 1) or Ca (NO) 3 ) 2 ·4H 2 Graph of the relationship between the treatment area and CT of chemically strengthened glass in the case of O (comparative example 2). FIG. 1 (C) shows addition of Ca (NO) to a molten salt composition 3 ) 2 ·4H 2 O (example 1) or Ca (NO) 3 ) 2 ·4H 2 Graph of CS relationship between DOL and chemically strengthened glass in the case of O (comparative example 2).
As an influence on the stress in the surface layer portion of the glass, ca (NO 3 ) 2 ·4H 2 The relationship between the treatment area in the case of O (example 1) and CS of the chemically strengthened glass is shown in FIG. 2.
As shown in Table 1, a molten salt composition containing sodium nitrate, sodium metasilicate and boron as impurities was used, in which Ca (NO 3 ) 2 ·4H 2 Example 1, which was treated with the composition of O to chemically strengthen the lithium-containing glass, showed the same appearance and appearance as those of comparative example 1, which contained no boron in the molten salt compositionStress. In addition, the method uses boron as an impurity and Ca (NO 3 ) 2 ·4H 2 The molten salt composition of O showed equivalent stress and expansion ratio and excellent appearance compared with comparative example 2 after chemical strengthening.
As shown in fig. 1 (a) to (C), it is understood that by using a catalyst containing sodium nitrate, sodium metasilicate and boron as impurities, ca (NO 3 ) 2 ·4H 2 O-containing molten salt composition for chemically strengthening lithium-containing glass, and Ca (NO 3 ) 2 ·4H 2 The comparative example of O shows equivalent stress, and the chemical strengthening property is not hindered. As shown in fig. 2, ca (NO) was added to the solution using boron containing sodium nitrate, sodium metasilicate and impurities 3 ) 2 ·4H 2 Stress value of the molten salt composition of O after the lithium-containing glass is chemically strengthened is equal to that of the glass to which Ca (NO 3 ) 2 ·4H 2 The case of O is equivalent, and the chemical strengthening property is not hindered.
Therefore, it is found that by chemically strengthening a lithium-containing glass with a composition in which nitrate of a metal having valence 2 is added to a molten salt composition containing at least one of potassium nitrate and sodium nitrate, a heterogeneous anion compound, and boron as an impurity, deterioration in appearance due to the incorporation of boron can be suppressed, and the life of the molten salt composition can be prolonged.
Test example 2 liquid phase observation and elemental analysis of molten salt composition
Used in a composition comprising 50 mass ppm of boron and 1.15 mass ppm of Na 2 SiO 3 Ca (NO) was added to 450℃sodium nitrate 3 ) 2 ·4H 2 The molten salt composition of O was subjected to a chemical strengthening treatment in a cumulative manner as in test example 1. The results obtained by measuring the element concentration (mass ppm) in the molten salt composition are shown in table 2. The determination of the element concentration was carried out by ICP PS3520 UVDDII.
TABLE 2
As shown in table 2, it was found that the concentration of boron in the molten salt composition can be reduced by adding nitrate of a metal having valence 2 to the molten salt composition containing at least one of potassium nitrate and sodium nitrate, a heterogeneous anion compound, and boron as an impurity.
In addition, regarding the processing area (0 m 2 Per kg) of molten salt composition, ca (NO) is added 3 ) 2 ·4H 2 O, and then the state of the liquid phase was observed after 2 hours, 6 hours, 25 hours have elapsed. As a result, it was found that the liquid phase became cloudy immediately after the addition, and cloudiness remained in the liquid phase of the molten salt composition after the addition for 2 hours, but the cloudiness was improved after the addition for 6 hours, and the cloudiness of the liquid phase disappeared after the lapse of 25 hours.
Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications and alterations can be made without departing from the spirit and scope of the invention.
The present application is based on japanese patent application No. 2019-059039, filed on 3 months 26 in 2019, the contents of which are incorporated herein by reference.
Claims (10)
1. A method of manufacturing chemically strengthened glass, the method comprising: a step of chemically strengthening a lithium-containing glass using a molten salt composition containing boron as an impurity and at least one of potassium nitrate and sodium nitrate, a heterogeneous anion compound,
the heterogeneous anionic compound is a compound containing an anion species different from anions constituting the molten salt,
the molten salt composition also contains nitrate of a metal of valence 2,
in the molten salt composition, the nitrate content of the metal having valence 2 is 0.5 mol or more with respect to 1 mol of the boron.
2. The method for producing chemically strengthened glass according to claim 1, wherein the metal having valence 2 is at least one selected from the group consisting of Ca, mg, and Ba.
3. The method for producing chemically strengthened glass according to claim 1, wherein the metal having valence 2 is Ca.
4. The method for producing chemically strengthened glass according to any one of claims 1 to 3, wherein the content of boron in the molten salt composition is not less than 0 mass ppm and not more than 100 mass ppm.
5. The method for producing chemically strengthened glass according to any one of claims 1 to 3, wherein the content of the heterogeneous anionic compound in the molten salt composition is 0.1 to 10 mol% based on the total content of the potassium nitrate and the sodium nitrate.
6. The method for producing a chemically strengthened glass according to any one of claims 1 to 3, wherein the heteroanionic compound is sodium metasilicate or sodium phosphate.
7. The method for producing a chemically strengthened glass according to any one of claims 1 to 3, wherein the method for producing a chemically strengthened glass further comprises: and a step of performing a second-stage chemical strengthening using a molten salt composition containing potassium nitrate.
8. The method for producing chemically strengthened glass according to any one of claims 1 to 3, wherein the content of nitrate of the metal having valence 2 is 6.5 mol or less based on 1 mol of boron in the molten salt composition.
9. A molten salt composition for chemical strengthening of lithium-containing glass, which contains at least one of potassium nitrate and sodium nitrate, a heteroanionic compound, and boron as an impurity, wherein,
the heterogeneous anion compound is a compound containing an anion species different from anions constituting a molten salt, and the molten salt composition further contains a nitrate of a metal having a valence of 2, wherein the content of the nitrate of the metal having a valence of 2 is 0.5 mol or more with respect to 1 mol of the boron in the molten salt composition.
10. A method for prolonging the life of a molten salt composition, which is a method for prolonging the life of a molten salt composition for chemical strengthening of lithium-containing glass, wherein,
nitrate of a metal having a valence of 2 is mixed with a molten salt composition containing at least one of potassium nitrate and sodium nitrate, a heterogeneous anion compound that is a compound containing an anion different from anions constituting the molten salt, and boron as an impurity, wherein the content of nitrate of the metal having a valence of 2 is 0.5 mol or more with respect to 1 mol of boron in the molten salt composition.
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| GB1215722A (en) * | 1967-04-24 | 1970-12-16 | Glaverbel | Processes for tempering glass and vitro-crystalline materials |
| WO2012086544A1 (en) * | 2010-12-20 | 2012-06-28 | 三菱化学株式会社 | Silicon preparation method and preparation apparatus, silicon wafer, and solar cell panel |
| CN103781739A (en) * | 2011-09-09 | 2014-05-07 | Hoya株式会社 | Process for producing cover glass for potable appliance |
| JP2015129063A (en) * | 2014-01-07 | 2015-07-16 | 旭硝子株式会社 | Regeneration method of molten salt for toughening glass, and production method of toughened glass |
| JP2016188166A (en) * | 2015-03-27 | 2016-11-04 | 旭硝子株式会社 | Method for manufacturing chemically strengthened glass |
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| GB1215722A (en) * | 1967-04-24 | 1970-12-16 | Glaverbel | Processes for tempering glass and vitro-crystalline materials |
| WO2012086544A1 (en) * | 2010-12-20 | 2012-06-28 | 三菱化学株式会社 | Silicon preparation method and preparation apparatus, silicon wafer, and solar cell panel |
| CN103781739A (en) * | 2011-09-09 | 2014-05-07 | Hoya株式会社 | Process for producing cover glass for potable appliance |
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