CN115385571A - Chemically strengthened glass and glass for chemical strengthening - Google Patents
Chemically strengthened glass and glass for chemical strengthening Download PDFInfo
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- CN115385571A CN115385571A CN202211102763.8A CN202211102763A CN115385571A CN 115385571 A CN115385571 A CN 115385571A CN 202211102763 A CN202211102763 A CN 202211102763A CN 115385571 A CN115385571 A CN 115385571A
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- 239000011521 glass Substances 0.000 title claims abstract description 139
- 239000005345 chemically strengthened glass Substances 0.000 title claims abstract description 87
- 238000003426 chemical strengthening reaction Methods 0.000 title claims abstract description 69
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 8
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 238000012886 linear function Methods 0.000 claims description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 239000012634 fragment Substances 0.000 description 31
- 238000000034 method Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 238000005342 ion exchange Methods 0.000 description 12
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 10
- 238000004031 devitrification Methods 0.000 description 9
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- 229910001415 sodium ion Inorganic materials 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000006124 Pilkington process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- 230000010349 pulsation Effects 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 3
- 239000006103 coloring component Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000003280 down draw process Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000006872 improvement 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
- 239000006060 molten glass Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000005498 polishing 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
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- HEZMWWAKWCSUCB-PHDIDXHHSA-N (3R,4R)-3,4-dihydroxycyclohexa-1,5-diene-1-carboxylic acid Chemical compound O[C@@H]1C=CC(C(O)=O)=C[C@H]1O HEZMWWAKWCSUCB-PHDIDXHHSA-N 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 230000001535 kindling effect Effects 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
- 238000010309 melting process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 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
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
-
- 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
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- 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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- 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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
Abstract
The present invention relates to a chemically strengthened glass and a glass for chemical strengthening. The invention aims to provide chemically strengthened glass with improved strength and scratch resistance. The present invention relates to a chemically strengthened glass comprising: 38 to 75 percent of SiO 2 1 to 30 percent of Al 2 O 3 3 to 20 percent of MgO and more than 0 percent and less than or equal to 20 percent of Li 2 O, more than 0% and not more than 20% of Y 2 O 3 、0％～5% of B 2 O 3 0 to 6 percent of P 2 O 5 0 to 8 percent of Na 2 O, 0 to 10 percent of K 2 O, caO 0-20%, srO 0-20%, baO 0-15%, znO 0-10%, tiO 0-1% 2 And 0% to 8% of ZrO 2 And the chemically strengthened glass has a Young's modulus, a Vickers hardness, CS and CS of a predetermined value or more 50 。
Description
The application is a divisional application of Chinese patent application with the application date of 2018, 4 and 23 and the application number of 201880027496.8.
Technical Field
The present invention relates to a chemically strengthened glass and a glass for chemical strengthening.
Background
In recent years, protective glass including chemically strengthened glass has been used for the protection and the improvement of the appearance of display devices of mobile devices such as mobile phones, smart phones, personal Digital Assistants (PDAs), and tablet terminals.
In a glass after chemical strengthening (so-called chemically strengthened glass), the higher the surface Compressive Stress (CS) and the depth of layer (DOL) of the compressive stress, the higher the strength tends to be. On the other hand, in order to maintain a balance with the surface compressive stress, internal tensile stress (CT) is generated inside the glass, and therefore, the larger CS and DOL, the larger CT. When the glass having a large CT is broken, the glass is broken vigorously with a large number of fragments, and the fragments are easily scattered.
Therefore, for example, patent document 1 discloses an equation (10) representing an allowable limit of an internal tensile stress of a chemically strengthened glass, and by adjusting CT' described below, a chemically strengthened glass with less scattering of fragments can be obtained even if the strength of the chemically strengthened glass is increased. The internal tensile stress CT 'described in patent document 1 is derived from the following equation (11) using the measured values of CS and DOL'.
CT’≤-38.7×ln(t)+48.2 (10)
CS×DOL’＝(t-2×DOL’)×CT' (11)
Here, DOL' corresponds to the depth of the ion exchange layer.
Documents of the prior art
Patent document
Patent document 1: specification of U.S. Pat. No. 8075999
Disclosure of Invention
Problems to be solved by the invention
However, in the method described in patent document 1, the strength of the chemically strengthened glass may be insufficient. The reason is considered to be that: the influence of the glass composition is not sufficiently considered; in the above equation for CT' calculation, the stress distribution is linearly approximated; the point where the stress is zero is assumed to be equal to the ion diffusion layer depth. The method described in patent document 1 only mentions strength against breakage of chemically strengthened glass, and is not sufficient for measures against scratch resistance, which is important in practical use.
Accordingly, an object of the present invention is to provide a chemically strengthened glass and a glass for chemical strengthening, which have improved strength and scratch resistance.
Means for solving the problems
The present inventors have conducted extensive studies and, as a result, have found that the above problems can be solved by limiting the glass composition and physical properties, and have completed the present invention.
That is, the present invention relates to the following <1> to <5>.
<1> a glass for chemical strengthening, which comprises, in terms of mole percent based on oxides:
38 to 75 percent of SiO 2 、
1 to 30 percent of Al 2 O 3 、
3 to 20 percent of MgO,
Greater than 0% and not more than 20% Li 2 O、
More than 0% and not more than 20% of Y 2 O 3 、
0% -5% of B 2 O 3 、
0 to 6 percent of P 2 O 5 、
0 to 8 percent of Na 2 O、
0 to 10 percent of K 2 O、
0 to 20 percent of CaO,
0 to 20 percent of SrO,
0 to 15 percent of BaO,
0 to 10 percent of ZnO,
0 to 1 percent of TiO 2 And, and
0 to 8 percent of ZrO 2 And is and
the glass for chemical strengthening has a Young's modulus of 90GPa or more and a Vickers hardness of 650kgf/mm 2 The above.
<2> a chemically strengthened glass, wherein the chemically strengthened glass comprises, in terms of mole percent based on oxides:
38 to 75 percent of SiO 2 、
1 to 30 percent of Al 2 O 3 、
3 to 20 percent of MgO,
More than 0% and not more than 20% of Li 2 O、
More than 0% and not more than 20% of Y 2 O 3 、
0% -5% of B 2 O 3 、
0 to 6 percent of P 2 O 5 、
0 to 8 percent of Na 2 O、
0 to 10 percent of K 2 O、
0 to 20 percent of CaO,
0 to 20 percent of SrO,
0 to 15 percent of BaO,
0 to 10 percent of ZnO,
0 to 1 percent of TiO 2 And, and
0 to 8 percent of ZrO 2 And is and
the chemically strengthened glass has a Young's modulus of 90GPa or more and a Vickers hardness of 700kgf/mm 2 Above, and
the chemically strengthened glass has a Compressive Stress (CS) value (CS) of a portion having a surface Compressive Stress (CS) of 300MPa or more and a depth of 50 [ mu ] m from the surface of the glass 50 ) Is 30MPa or more.
<3>As described above<2>The chemically strengthened glass, wherein the chemically strengthened glass has a compressive stress value (CS) of a portion having a depth of 90 μm from a surface of the glass 90 ) Is 25MPa or more.
<4>As described above<2>Or<3>The chemically strengthened glass, wherein the surface compressive stress and the compressive stressForce value (CS) 50 ) The relationship between them is represented by at least 2 different functions.
<5> the chemically strengthened glass according to <4> above, wherein the 2 different functions are a linear function indicating the 1 st region and a linear function indicating the 2 nd region in a 1 st region from a glass surface to a predetermined depth and a 2 nd region from the 1 st region to a depth at which the surface compressive stress is 0, and wherein a slope of the linear function indicating the 1 st region is larger than a slope of the linear function indicating the 2 nd region.
Effects of the invention
According to the present invention, a chemically strengthened glass and a glass for chemical strengthening having improved strength and scratch resistance can be provided.
Drawings
Fig. 1 is a graph showing the results of the scratch test of the present invention.
Detailed Description
The chemically strengthened glass and the glass for chemical strengthening of the present invention will be described in detail below, but the present invention is not limited to the following embodiments, and can be implemented by being arbitrarily modified within a range not departing from the gist of the present invention.
In the present specification, the glass composition of the glass for chemical strengthening is sometimes referred to as the basic composition of the chemically strengthened glass. "to" indicating a numerical range is used to include numerical values described before and after the range as a lower limit value and an upper limit value.
< glass composition >
When the thickness of the chemically strengthened glass is sufficiently large, a portion having a tensile stress (hereinafter also referred to as a tensile stress portion) of the chemically strengthened glass is not ion-exchanged, and therefore the tensile stress portion of the chemically strengthened glass has the same composition as that of the glass before chemical strengthening. In this case, the composition of the tensile stress portion of the chemically strengthened glass can be regarded as the basic composition of the chemically strengthened glass.
The composition of the glass can be measured by a wet analysis method such as ICP emission analysis. The content of the glass raw material is calculated from the amount of the glass raw material to be used, except for the case where a large amount of components that are particularly easily volatilized at the time of melting are contained.
Unless otherwise specified, the contents of the respective components are shown in terms of mole percentages based on oxides.
The chemically strengthened glass of the present invention contains, as expressed in mole percentage based on oxides: 38 to 75 percent of SiO 2 1 to 30 percent of Al 2 O 3 3 to 20 percent of MgO and more than 0 percent and less than or equal to 20 percent of Li 2 O, more than 0% and not more than 20% of Y 2 O 3 0 to 5 percent of B 2 O 3 0 to 6 percent of P 2 O 5 0 to 8 percent of Na 2 O, 0 to 10 percent of K 2 O, caO 0-20%, srO 0-20%, baO 0-15%, znO 0-10%, tiO 0-1% 2 And 0% to 8% of ZrO 2 And the chemically strengthened glass has a Young's modulus of 90GPa or more and a Vickers hardness of 700kgf/mm 2 The chemically strengthened glass has a compressive stress value (CS) of a portion having a surface Compressive Stress (CS) of 300MPa or more and a depth of 50 [ mu ] m from the surface of the glass 50 ) Is 30MPa or more.
The composition of the chemically strengthened glass of the present invention (the basic composition of the chemically strengthened glass of the present invention) comprises, in terms of mole percentage based on oxides: 38% -75% of SiO 2 1 to 30 percent of Al 2 O 3 3 to 20 percent of MgO and more than 0 percent and less than or equal to 20 percent of Li 2 O, more than 0% and not more than 20% of Y 2 O 3 0 to 5 percent of B 2 O 3 0 to 6 percent of P 2 O 5 0 to 8 percent of Na 2 O, 0 to 10 percent of K 2 O, caO 0-20%, srO 0-20%, baO 0-15%, znO 0-10%, tiO 0-1% 2 And 0% to 8% of ZrO 2 And the glass for chemical strengthening has a Young's modulus of 90GPa or more and a Vickers hardness of 650kgf/mm 2 The above.
The chemically strengthened glass and the chemically strengthened glass of the present invention will be described below with respect to their respective compositions.
SiO 2 Is a component constituting the skeleton of the glass and is a component for improving chemical durability. In addition, in order to reduce the occurrence of cracks when scratches (indentations) are generated on the glass surface, siO is used 2 The content of (b) is preferably 38% or more. SiO 2 2 More preferably, the content of (c) is gradually: more than 42%, more than 46%, more than 50%, more than 54%, more than 58% and more than 62%.
On the other hand, siO is used for improving the meltability of glass 2 The content of (b) is 75% or less, more preferably 72% or less, still more preferably 70% or less, particularly preferably 68% or less, most preferably 66% or less.
Al 2 O 3 The component is a component for reducing the number of fragments at the time of breakage of the chemically strengthened glass and suppressing scattering of the fragments. In addition, in order to improve ion exchange performance at the time of chemical strengthening and to increase surface compressive stress after strengthening, al 2 O 3 The content of (a) is 1% or more, preferably in the following steps: more than 3%, more than 5%, more than 7%, more than 8%, more than 9%, more than 10%, more than 11%, more than 12%, more than 13%.
On the other hand, al is added to improve the acid resistance of glass or to lower the devitrification temperature 2 O 3 The content of (b) is preferably 30% or less, more preferably 25% or less, further preferably 20% or less, particularly preferably 18% or less, most preferably 15% or less. Al (Al) 2 O 3 When the content (c) is large, the melting temperature of the glass increases, and the productivity decreases. For improving productivity, al 2 O 3 The content of (b) is preferably 11% or less, preferably in steps of: less than 10%, less than 9%, less than 8%, less than 7%.
MgO is a component that increases the surface compressive stress of chemically strengthened glass. In order to reduce the number of fragments at the time of breakage of the chemically strengthened glass and suppress scattering of the fragments, the content of MgO is preferably 3% or more, and more preferably, the following steps are performed: more than 4%, more than 5%, more than 6%, more than 7% and more than 8%.
On the other hand, in order to suppress devitrification at the time of glass melting, the content of MgO is preferably 20% or less, more preferably, the following steps are performed: 18% or less, 15% or less, 14% or less, 13% or less, 12% or less, 11% or less, and 10% or less.
Li 2 O is a component for forming a surface compressive stress layer by ion exchange, and is a component for reducing the number of fragments at the time of breakage of the chemically strengthened glass and suppressing scattering of the fragments. The Li ions on the glass surface are exchanged with Na ions so that the CS is present 90 When chemical strengthening treatment is performed so as to reach 30MPa or more, li 2 The content of O is preferably more than 0%, more preferably 4% or more, further preferably 5% or more, further preferably 6% or more, and particularly preferably 7% or more.
On the other hand, in order to maintain acid resistance of glass, li 2 The content of O is preferably 20% or less, more preferably 18% or less, further preferably 16% or less, particularly preferably 15% or less, and most preferably 13% or less.
Y 2 O 3 The component is a component for improving the Young's modulus and improving the chipping resistance without excessively increasing the density. Y is 2 O 3 The content of (b) is more than 0%, preferably 1% or more, more preferably 1.5% or more, further preferably 3% or more, particularly preferably 5% or more, and most preferably 7.5% or more.
On the other hand, when Y 2 O 3 When the content (b) is excessively large, the acid resistance of the glass decreases or the devitrification temperature increases, and therefore, it is preferably 20% or less, more preferably 15% or less, further preferably 12% or less, and particularly preferably 9% or less.
B 2 O 3 The component is a component for improving the chipping resistance and the meltability of the chemically strengthened glass. B is 2 O 3 Is not an essential component, but contains B 2 O 3 In the case of (B), in order to improve the meltability, B 2 O 3 The content of (b) is preferably 0.5% or more, more preferably 1% or more, and further preferably 2% or more.
On the other hand, in order to maintain acid resistance of the glass, B 2 O 3 The content of (b) is preferably 5% or less. B is 2 O 3 The content of (b) is more preferably 4% or less, still more preferably 3% or less, and particularly preferably 1% or less. In order to prevent the formation of pulsation (pulsation) during melting, it is preferable that B is not substantially contained 2 O 3 。
P 2 O 5 Is a component for improving ion exchange performance and chipping resistance. May not contain P 2 O 5 But in the presence of P 2 O 5 In the case of (1), P 2 O 5 The content of (b) is preferably 0.5% or more, more preferably 1% or more, and further preferably 2% or more.
On the other hand, P is for reducing the number of fragments at the time of breakage of the chemically strengthened glass and suppressing scattering of the fragments 2 O 5 The content of (b) is 6% or less, preferably 4% or less, more preferably 3% or less, further preferably 2% or less, and particularly preferably 1% or less. In order to prevent the formation of pulsation (pulsation) during melting, it is preferable that substantially no P is contained 2 O 5 。
Na 2 O is a component that forms a surface compressive stress layer by ion exchange and improves the meltability of the glass. May not contain Na 2 O, while Li ions on the glass surface are exchanged with Na ions, na is contained 2 In the case of O, na 2 The content of O is preferably 1% or more. Na (Na) 2 The content of O is more preferably 2% or more, and still more preferably 3% or more.
On the other hand, when Na 2 When the content of O is excessive, the surface compressive stress formed by ion exchange is significantly reduced. Na (Na) 2 The content of O is preferably 8% or less, more preferably 7% or less, further preferably 6% or less, particularly preferably 5% or less, and most preferably 4% or less.
By immersing in a molten salt mixture of potassium nitrate and sodium nitrate, or the like, in the case where Li ions and Na ions on the glass surface and Na ions and K ions on the glass surface are ion-exchanged simultaneously, na ions are formed 2 The content of O is more preferably 7% or less, particularly preferably 6% or less, and most preferably 5% or less. In addition, na 2 The content of O is preferably 2% or more, more preferably 3% or more, and further preferablyMore than 4 percent is selected.
K may be contained for the purpose of improving ion exchange performance or the like 2 And O. In the presence of K 2 In the case of O, K 2 The content of O is preferably 0.5% or more, more preferably 1% or more, further preferably 2% or more, and particularly preferably 3% or more.
On the other hand, when K 2 When the content of O is excessive, the number of fragments may be large, and the fragments may be easily scattered. K for reducing the number of fragments at the time of breakage of the chemically strengthened glass and suppressing scattering of the fragments 2 The content of O is preferably 10% or less. K 2 The content of O is more preferably 8% or less, further preferably 6% or less, particularly preferably 4% or less, and most preferably 2% or less.
CaO is a component for improving the meltability of glass, and is a component for reducing the number of fragments at the time of breakage of chemically strengthened glass and suppressing scattering of fragments, and may contain CaO. When CaO is contained, the content of CaO is preferably 0.5% or more, more preferably 1% or more, further preferably 2% or more, particularly preferably 3% or more, and most preferably 5% or more.
On the other hand, in order to improve the ion exchange performance, it is preferably 20% or less. The CaO content is more preferably 14% or less, and further preferably stepwise as follows: less than 10%, less than 8%, less than 6%, less than 3%, less than 1%.
SrO is a component for improving the meltability of glass, and is a component for reducing the number of fragments at the time of breakage of chemically strengthened glass and suppressing scattering of fragments, and may contain SrO. When SrO is contained, the SrO content is preferably 0.5% or more, more preferably 1% or more, further preferably 2% or more, particularly preferably 3% or more, and most preferably 5% or more.
On the other hand, in order to improve the ion exchange performance, it is preferably 20% or less. The SrO content is more preferably 14% or less, and further preferably gradually as follows: less than 10%, less than 8%, less than 6%, less than 3%, less than 1%.
BaO is a component for improving the meltability of the chemically strengthened glass, and is a component for reducing the number of fragments at the time of breakage of the chemically strengthened glass and suppressing scattering of the fragments, and BaO may be contained. When BaO is contained, the content of BaO is preferably 0.5% or more, more preferably 1% or more, further preferably 2% or more, particularly preferably 3% or more, and most preferably 5% or more.
On the other hand, in order to improve the ion exchange performance, the content of BaO is preferably 15% or less, more preferably, it is stepwise as follows: less than 10%, less than 8%, less than 6%, less than 3%, less than 1%. In order to improve chipping resistance, baO is preferably not contained.
ZnO is a component for improving the meltability of the glass, and may contain ZnO. When ZnO is contained, the content of ZnO is preferably 0.25% or more, more preferably 0.5% or more.
On the other hand, in order to maintain the weather resistance of the glass, the content of ZnO is preferably 10% or less, more preferably 7% or less, further preferably 5% or less, particularly preferably 2% or less, and most preferably 1% or less.
TiO 2 The component is a component for reducing the number of fragments and suppressing the scattering of the fragments when the chemically strengthened glass is broken, and may contain TiO 2 . In the presence of TiO 2 In the case of (2), tiO 2 The content of (b) is preferably 0.1% or more, more preferably 0.15% or more, and further preferably 0.2% or more.
On the other hand, tiO is used for suppressing devitrification at the time of melting 2 The content of (b) is preferably 1% or less, more preferably 0.5% or less, and further preferably 0.25% or less.
ZrO 2 Is a component which increases the surface compressive stress by ion exchange, has the effects of reducing the number of fragments at the time of breakage of the chemically strengthened glass and suppressing scattering of the fragments, and may contain ZrO 2 . In the presence of ZrO 2 In the case of (2), zrO 2 The content of (b) is preferably 0.5% or more, more preferably 1% or more.
On the other hand, zrO is less susceptible to devitrification when melted 2 The content of (b) is preferably 8% or less, more preferably 6% or less, further preferably 4% or less, particularly preferably 2% or less, and most preferably 1.2% or less.
La 2 O 3 、Nb 2 O 5 All of them are components for reducing the number of fragments at the time of breakage of the chemically strengthened glass and suppressing scattering of the fragments, and La may be contained 2 O 3 、Nb 2 O 5 . When these components are contained, the content of each component is preferably 0.5% or more, more preferably 1% or more, further preferably 1.5% or more, particularly preferably 2% or more, and most preferably 2.5% or more.
On the other hand, when La 2 O 3 、Nb 2 O 5 If the content is too large, the glass may be devitrified during melting, and the quality of the chemically strengthened glass may be degraded. La 2 O 3 、Nb 2 O 5 The content of (b) is preferably 8% or less, more preferably 6% or less, further preferably 5% or less, particularly preferably 4% or less, and most preferably 3% or less, respectively.
In order to reduce the number of fragments at the time of breakage of the chemically strengthened glass and to suppress scattering of the fragments, a small amount of Ta may be contained 2 O 5 、Gd 2 O 3 However, since the refractive index and reflectance are increased, the content is preferably 1% or less, more preferably 0.5% or less, and further preferably no Ta is contained 2 O 5 、Gd 2 O 3 。
Fe 2 O 3 Is a component for improving the meltability of the glass. Due to Fe 2 O 3 Is a component that absorbs heat rays, and therefore has the effects of promoting thermal convection of molten glass to increase homogeneity of the glass, preventing a bottom brick of a melting furnace from being heated to a high temperature to extend the life of the furnace, and the like, and in a melting process of plate-shaped glass using a large-sized furnace, it is preferable that Fe be contained in the composition of the plate-shaped glass 2 O 3 。Fe 2 O 3 The content of (b) is preferably 0.002% or more, more preferably 0.006% or more, further preferably 0.01% or more, and particularly preferably 0.02% or more.
On the other hand, when Fe is contained in excess 2 O 3 When is made of Fe 2 O 3 The resulting coloration becomes a problem. Fe known to be in an oxidized state 2 O 3 Coloring of yellow color is caused, coloring of blue color is caused by FeO in a reduced state, and it is known that the balance between bothThe glass is colored green. Fe 2 O 3 The content of (b) is preferably 0.3% or less, more preferably 0.04% or less, further preferably 0.03% or less, and particularly preferably 0.025% or less.
In addition, when the glass is colored, a coloring component may be added within a range that does not hinder achievement of the desired chemical strengthening property. The coloring component may be, for example, co 3 O 4 、MnO 2 、Fe 2 O 3 、NiO、CuO、Cr 2 O 3 、V 2 O 5 、Bi 2 O 3 、SeO 2 、TiO 2 、CeO 2 、Er 2 O 3 、Nd 2 O 3 And the like as appropriate components.
The total content of the coloring components is preferably 7% or less in terms of a molar percentage based on oxides. When it is more than 7%, the glass is liable to devitrify, and thus it is not preferable. The content is preferably 5% or less, more preferably 3% or less, and further preferably 1% or less. When priority is given to the visible light transmittance of the glass, it is preferable that these components are not substantially contained.
May suitably contain SO 3 And chlorides and fluorides as fining agents in glass melting. Preferably not containing As 2 O 3 . In the presence of Sb 2 O 3 In the case of (3), it is preferably 0.3% or less, more preferably 0.1% or less, and most preferably no Sb is contained 2 O 3 。
Further, the chemically strengthened glass or the glass for chemical strengthening of the present invention has silver ions on the surface, and therefore can impart antibacterial properties.
The fracture toughness value (K1 c) of the glass for chemical strengthening or the chemically strengthened glass of the present invention is preferably 0.7MPa · m 1/2 More preferably 0.75 MPa.m or more 1/2 More preferably 0.77MPa m 1/2 Above, particularly preferably 0.80MPa · m 1/2 Above and most preferably 0.82 MPa.m 1/2 The above. When the fracture toughness value (K1 c) is 0.7MPa · m 1 /2 In this case, the number of fragments generated when the glass is broken can be suppressed.
The fracture toughness value (K1 c) in the present specification is a value obtained by measuring a K1-v curve by a DCDC method (double clean drilled compression) and setting a crack propagation velocity v to 10 - 1 Stress expansion coefficient K1 (MPa. M) at m/sec 1/2 ) The fracture toughness value obtained in the form of (1).
In the present invention, it is preferable that the Young's modulus of the glass for chemical strengthening is 70GPa or more, and that the value of Compressive Stress (CS) of the outermost surface of the chemically strengthened glass and the value of Compressive Stress (CS) of a portion having a depth of 1 μm from the surface of the glass are set to be equal to or greater than 1 ) The difference is 50MPa or less. In this way, it is preferable to perform a polishing treatment of the glass surface after the chemical strengthening treatment because warpage is less likely to occur.
The Young's modulus (E) of the glass for chemical strengthening or the chemically strengthened glass is more preferably 90GPa or more, particularly preferably 95GPa or more, and still more preferably 100GPa or more. The upper limit of the Young's modulus is not particularly limited, but is, for example, 150GPa or less, preferably 145GPa or less, more preferably 135GPa or less, particularly preferably 125GPa or less, and most preferably 118GPa or less, in consideration of the acid resistance and devitrification properties of the glass. The Young's modulus can be measured by, for example, an ultrasonic pulse method.
The density (. Rho.) of the glass for chemical strengthening is preferably 3.2g/cm for the purpose of reducing the weight of the product and improving chipping resistance 3 Less than, more preferably 3.1g/cm 3 The concentration is preferably 3.0g/cm or less 3 The following. The lower limit of the density is not particularly limited, but is, for example, 2.3g/cm for maintaining chemical resistance such as acid resistance 3 At least, preferably 2.5g/cm 3 More preferably 2.7g/cm or more 3 The above.
In order to reduce the warpage after chemical strengthening, the average linear thermal expansion coefficient (linear expansion coefficient. Alpha.) of the glass for chemical strengthening at 50 ℃ to 350 ℃ is preferably 120X 10 -7 Lower than/° C, more preferably 100X 10 -7 Less than/° C, and more preferably 90X 10 -7 Lower than/° C, particularly preferably 80X 10 -7 Lower than/° C. Linear expansion coefficient exampleE.g. 45 x 10 -7 /. Degree.C.or more, preferably 55X 10 -7 Above/° c.
In order to reduce the warpage after chemical strengthening, the glass transition temperature (Tg) of the glass for chemical strengthening is preferably 550 ℃ or higher, more preferably 570 ℃ or higher, and still more preferably 590 ℃ or higher. On the other hand, when the glass transition temperature is more than 750 ℃, the members usable in sheet-like molding such as float molding are limited. Preferably 750 ℃ or lower, more preferably 720 ℃ or lower, further preferably 700 ℃ or lower, and particularly preferably 660 ℃ or lower.
The Vickers hardness (Hv) of the glass for chemical strengthening is preferably 650kgf/mm 2 Above, more preferably 700kgf/mm 2 The above. The upper limit of the Vickers hardness (Hv) of the glass for chemical strengthening is not particularly limited, but is, for example, 1000kgf/mm in consideration of the production characteristics of the glass 2 Preferably 900kgf/mm or less 2 Hereinafter, more preferably 800kgf/mm 2 The following.
The chemically strengthened glass preferably has a Vickers hardness (Hvct or Hv) of 700kgf/mm 2 More preferably 750kgf/mm 2 More preferably 800kgf/mm or more 2 The above. The upper limit of the Vickers hardness (Hvct) of the chemically strengthened glass is not particularly limited, but is, for example, 1100kgf/mm in consideration of the production characteristics of the glass 2 Hereinafter, preferably 1000kgf/mm 2 Hereinafter, more preferably 900kgf/mm 2 The following.
Compressive stress value (CS) of surface of chemically strengthened glass of the present invention 0 ) (hereinafter, also referred to as "surface compressive stress value" or simply as "CS") is preferably 300MPa or more, more preferably 350MPa or more, and still more preferably 400MPa or more. On the other hand, CS 0 The upper limit of (b) is not particularly limited, but is, for example, 1200MPa or less, preferably 1000MPa or less, and more preferably 800MPa or less.
The chemically strengthened glass of the present invention preferably has a depth of compressive stress layer (DOL) of 50 μm or more, more preferably 70 μm or more, still more preferably 90 μm or more, and particularly preferably 110 μm or more. On the other hand, if the DOL is larger than 200 μm, CT becomes large, and there is a risk that fragments are scattered at the time of fracture. DOL is preferably 200 μm or less, more preferably 160 μm or less.
The chemically strengthened glass of the present invention has a compressive stress value (CS) at a depth of 50 μm from the surface of the glass 50 ) Preferably 30MPa or more. More preferably 40MPa or more, still more preferably 50MPa or more, and particularly preferably 60MPa or more.
The chemically strengthened glass of the present invention has a compressive stress value (CS) at a portion having a depth of 90 μm from the surface of the glass 90 ) Preferably 25MPa or more. More preferably 30MPa or more, still more preferably 40MPa or more, and particularly preferably 50MPa or more.
Preferably the surface Compressive Stress (CS) and the compressive stress value (CS) 50 ) The relationship between them is represented by at least 2 different functions. For example, the 2 different functions are a function representing the 1 st region and a function representing the 2 nd region in the 1 st region from the glass surface to a predetermined depth and the 2 nd region from the 1 st region to a depth at which the surface compressive stress is 0. In this case, both the function indicating the 1 st region and the function indicating the 2 nd region are linear functions, and the slope of the linear function indicating the 1 st region is preferably larger than the slope of the linear function indicating the 2 nd region.
The chemically strengthened glass of the present invention can be produced, for example, as follows.
First, glass to be subjected to chemical strengthening treatment is prepared. The glass to be subjected to the chemical strengthening treatment is preferably the glass for chemical strengthening of the present invention. The glass subjected to the chemical strengthening treatment can be produced by a usual method. For example, raw materials for each component of glass are prepared and heated and melted in a glass melting furnace. Thereafter, the glass is homogenized by a known method, formed into a desired shape such as a glass plate, and gradually cooled.
Examples of the method for forming a glass sheet include: float process, press process, fusion process and downdraw process. Particularly preferred is a float process suitable for mass production. In addition, a continuous forming method other than the float method, that is, a fusion method and a downdraw method, is also preferable.
Thereafter, the formed glass is subjected to grinding and polishing treatments as needed to form a glass substrate. When the glass substrate is cut into a predetermined shape and size or subjected to chamfering, if the glass substrate is cut and chamfered before chemical strengthening treatment described later is performed, a compressive stress layer is also formed on the end face by the chemical strengthening treatment thereafter, which is preferable.
The chemically strengthened glass of the present invention can be produced by subjecting the resulting glass sheet to a chemical strengthening treatment, followed by cleaning and drying.
The chemical strengthening treatment can be performed by a conventionally known method. In the chemical strengthening treatment, a molten solution containing a metal salt (e.g., potassium nitrate) of a metal ion (typically, a K ion) having a large ionic radius is brought into contact with the glass sheet by immersion or the like, thereby replacing the metal ion (typically, a Na ion or a Li ion) having a small ionic radius in the glass sheet with the metal ion (typically, a K ion for a Na ion, or a Na ion or a K ion for a Li ion) having a large ionic radius.
The chemical strengthening treatment (ion exchange treatment) can be performed, for example, as follows: the glass plate is immersed in a molten salt such as potassium nitrate heated to 360 to 600 ℃ for 0.1 to 500 hours. The heating temperature of the molten salt is preferably 375 to 500 ℃, and the time for immersing the glass plate in the molten salt is preferably 0.3 to 200 hours.
Examples of the molten salt used for the chemical strengthening treatment include nitrates, sulfates, carbonates, chlorides, and the like. Among them, examples of the nitrate include lithium nitrate, sodium nitrate, potassium nitrate, cesium nitrate, and silver nitrate. Examples of the sulfate include lithium sulfate, sodium sulfate, potassium sulfate, cesium sulfate, and silver sulfate. Examples of the carbonate include lithium carbonate, sodium carbonate, and potassium carbonate. Examples of the chloride include lithium chloride, sodium chloride, potassium chloride, cesium chloride, and silver chloride. These molten salts may be used alone or in combination of two or more.
In the present invention, the conditions for the chemical strengthening treatment may be selected as appropriate in consideration of the characteristics and composition of the glass, the type of molten salt, and the chemical strengthening characteristics such as surface Compressive Stress (CS) and depth of compressive stress layer (DOL) desired for the finally obtained chemically strengthened glass.
In the present invention, the chemical strengthening treatment may be performed only once, or may be performed a plurality of times under different conditions of 2 or more (multi-stage strengthening). Here, for example, when the chemical strengthening treatment is performed under a condition of relatively low CS as the chemical strengthening treatment of the 1 St stage, and then the chemical strengthening treatment is performed under a condition of relatively high CS as the chemical strengthening treatment of the 2 nd stage, the CS of the outermost surface of the chemically strengthened glass can be increased while suppressing the internal tensile stress area (St), and as a result, the reduction of the internal tensile stress (CT) can be suppressed.
The chemically strengthened glass of the present invention is particularly useful as a cover glass for use in mobile devices such as mobile phones, smart phones, personal Digital Assistants (PDAs), and tablet terminals. Further, the present invention is useful for applications such as protective glass for display devices such as Television Sets (TVs), personal Computers (PCs), and touch panels, wall surfaces of elevators, wall surfaces of buildings such as houses and buildings (full-screen displays), building materials such as window glass, interior materials of desktops, automobiles, airplanes, and the like, or protective glass for these, and housings having curved surface shapes other than flat plate shapes by bending and processing.
For the glass for chemical strengthening of the present invention, the devitrification temperature T is preferably 10 degrees of viscosity 4 A temperature T4 at dPa · s or lower. This is because, when the devitrification temperature T is higher than T4, quality deterioration due to devitrification is likely to occur when a glass sheet is formed by a float process or the like.
In the glass for chemical strengthening of the present invention, naNO was applied to a glass having a thickness of 0.8mm 3 : surface compressive stress value (CS) after chemical strengthening at 100%, 500 ℃ for 15 hours g ) Preferably 300MPa or more, more preferably 350MPa or more, and still more preferably 400MPa or more. On the other hand, CS g The upper limit of (b) is not particularly limited,for example, 1200MPa or less, preferably 1000MPa or less, and more preferably 800MPa or less.
In addition, in the glass for chemical strengthening of the present invention, naNO was applied to a glass having a thickness of 0.8mm 3 : depth of compressive stress layer (DOL) after chemical strengthening at 100%, 500 ℃ for 15 hours g ) Preferably 30 μm or more, more preferably 40 μm or more, further preferably 50 μm or more, and particularly preferably 60 μm or more.
In the case where the chemically strengthened glass of the present invention has a plate shape (glass plate), the plate thickness (t) is, for example, 2mm or less, preferably 1.5mm or less, more preferably 1mm or less, further preferably 0.9mm or less, particularly preferably 0.8mm or less, and most preferably 0.7mm or less, in order to enhance the effect of chemical strengthening. The thickness is, for example, 0.1mm or more, preferably 0.2mm or more, more preferably 0.4mm or more, and further preferably 0.5mm or more, from the viewpoint of obtaining a sufficient strength improvement effect by the chemical strengthening treatment.
The chemically strengthened glass of the present invention may have a shape other than a plate shape depending on the product, application, and the like to which it is applied. The glass plate may have a frame shape with a different outer peripheral thickness. The glass plate may have 2 main surfaces and end surfaces adjacent to the main surfaces to form a plate thickness, and the 2 main surfaces may form flat surfaces parallel to each other. However, the form of the glass plate is not limited to this, and for example, the 2 main surfaces may not be parallel to each other, and one or both of the 2 main surfaces may be entirely or partially curved. More specifically, the glass plate may be, for example, a flat glass plate without warp, or may be a curved glass plate having a curved surface.
Examples
The present invention will be described below with reference to examples, but the present invention is not limited thereto. In the table, the blank column indicates that no measurement was performed for each measurement result.
(production of chemically strengthened glass)
Prepared by melting each glass composition in terms of mole percentage based on oxides shown in the table in a platinum crucibleA glass plate is produced. The glass raw material generally used, such as oxide, hydroxide, carbonate, or nitrate, is appropriately selected and weighed so as to be 1000g in glass. Subsequently, the mixed raw materials were charged into a platinum crucible, and placed in a resistance heating type electric furnace at 1500 to 1700 ℃, melted for about 3 hours, defoamed, and homogenized. The resulting molten glass was poured into a mold material, held at a temperature of glass transition temperature +50 ℃ for 1 hour, and then cooled to room temperature at a rate of 0.5 ℃/minute, to thereby obtain a glass gob. The obtained glass block was cut and ground, and finally both surfaces were mirror-finished to obtain plate-like glass (glass for chemical strengthening) having a length of 20mm, a width of 20mm and a thickness of 0.8 (mm). Fe in glass 2 O 3 The content is 0.0125%.
Subsequently, each glass was subjected to chemical strengthening treatment, thereby obtaining chemically strengthened glass. To obtain CS g 、DOL g The glasses of comparative examples 1 to 7 had a thickness of 0.8mm and NaNO 3 : the chemical strengthening treatment was performed at 100%, 500 ℃ for 15 hours. The results are shown in table 1. CS in examples 1 and 7 g 、DOL g The value of (d) is a calculated value.
In addition, as the glass used in the scratch test, the glass of example 1 was treated in 2 kinds of molten salts to have a thickness of 0.8mm, (first) NaNO 3 :100%, 450 ℃ for 4 hours; (second time) KNO 3 :100%, 450 ℃ for 6 hours. For the glasses of examples 2 to 6, 1 molten salt was used, with a plate thickness of 0.8mm and NaNO 3 : the chemical strengthening treatment was performed at 100%, 500 ℃ for 15 hours. The glass of example 7 was treated in 2 kinds of molten salts to have a thickness of 0.8mm and NaNO (first) 3 :100%, 450 ℃ and 3 hours; (second time) KNO 3 :100%, 450 ℃ for 1.5 hours.
< Density (ρ) >
The density measurement is carried out by the immersion weight method (JISZ 8807. The unit is g/cm 3 。
< Young's modulus (E) >
The Young's modulus E (unit: GPa) of the glass before chemical strengthening was measured by the ultrasonic pulse method (JIS R1602: 1995).
< Vickers hardness (Hv) >
Vickers hardness Hv (unit: kgf/mm) of glass before and after chemical strengthening 2 ) According to JIS Z2244: the measurement was performed with a load of 100gf in a method of 2009 "vickers hardness test-test method".
< glass transition temperature (Tg) >
The glass transition temperature Tg (unit:. Degree. C.) of the glass before chemical strengthening was measured by using a thermomechanical analyzer (TMA) according to the method prescribed in JIS R3103-3.
< coefficient of linear expansion α >
Linear expansion coefficient α and glass transition temperature Tg were measured according to JIS R3102: 1995 "test method of average Linear expansion coefficient of glass", an average linear expansion coefficient (. Alpha.) of 50 to 350 ℃ was measured 50～350 ) (unit: /° c).
<CS、DOL>
As the surface compressive stress CS (unit: MPa), CS was measured by a surface stress meter FSM-6000 manufactured by FANYAKU GYNOL. Thickness DOL (unit: mum), CS for compressive stress layer 50 、CS 90 、CS g And DOL g The glasses of examples 1 and 2 were measured by a method using Abrio-IM and a sheet sample, and the glasses of examples 3 to 7 were measured by a measuring device SLP1000 manufactured by kindling using scattered light photoelasticity.
< scratch test >
A sandpaper of #80 garnet was cut into about 1cm square, mounted on a friction wear tester (1248812521\124521246212450manufactured by new eastern science corporation, and subjected to rubbing with a load of 300 gf.
TABLE 1
TABLE 2
From the above results, it is understood that in examples 1 to 6, the Vickers hardness Hv after chemical strengthening was 700 (kgf/mm) 2 ) Above, therefore, the scratch resistance is excellent. It is found that the Vickers hardness Hv of examples 1 and 3 to 6 is 700 (kgf/mm) 2 ) Above, and DOL g 30 μm or more, excellent in scratch resistance and excellent in bending fracture resistance.
The present 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 therein without departing from the spirit and scope thereof. The present application is based on the japanese patent application (japanese patent application 2017-089984) proposed on 28/4/2017, the content of which is incorporated herein by reference.
Claims (11)
1. A glass for chemical strengthening, which comprises, in terms of mole percent based on oxides:
62 to 75 percent of SiO 2 、
10 to 15 percent of Al 2 O 3 、
3 to 20 percent of MgO,
7 to 20% or less of Li 2 O、
Y of more than 0% and not more than 20% 2 O 3 、
0 to 1 percent of B 2 O 3 、
0 to 2 percent of P 2 O 5 、
1 to 6 percent of Na 2 O、
0.5 to 4 percent of K 2 O、
0 to 3 percent of CaO,
0 to 20 percent of SrO,
0 to 15 percent of BaO,
0 to 10 percent of ZnO,
0 to 1 percent of TiO 2 And, and
0 to 2 percent of ZrO 2 And are each and every
The Young's modulus of the glass for chemical strengthening is 70GPa or more.
2. A chemically strengthened glass, wherein the chemically strengthened glass comprises, in mole percent on an oxide basis:
62 to 75 percent of SiO 2 、
10 to 15 percent of Al 2 O 3 、
3 to 20 percent of MgO,
7 to 20% or less of Li 2 O、
Y of more than 0% and not more than 20% 2 O 3 、
0 to 1 percent of B 2 O 3 、
0 to 2 percent of P 2 O 5 、
1 to 6 percent of Na 2 O、
0.5 to 4 percent of K 2 O、
0 to 3 percent of CaO,
0 to 20 percent of SrO,
0 to 15 percent of BaO,
0 to 10 percent of ZnO,
0 to 1 percent of TiO 2 And, and
0 to 2 percent of ZrO 2 And are each and every
The chemically strengthened glass has a Young's modulus of 70GPa or more, and
the chemically strengthened glass has a surface Compressive Stress (CS) of 300MPa or more and a compressive stress value (CS) of a portion having a depth of 50 [ mu ] m from the surface of the glass 50 ) Is 30MPa or more.
3. The chemically strengthened glass according to claim 2, wherein the chemically strengthened glass has a compressive stress value (CS) of a portion having a depth of 90 μm from a surface of the glass 90 ) Is composed ofAbove 25 MPa.
4. The chemically strengthened glass as claimed in claim 2 or 3, wherein the surface compressive stress and the compressive stress value (CS) 50 ) The relationship between them is represented by at least 2 different functions.
5. The chemically strengthened glass according to claim 4, wherein the 2 different functions are such that, in a case where a linear function representing the 1 st region and a linear function representing the 2 nd region are present in a 1 st region from a glass surface to a predetermined depth and a 2 nd region from the 1 st region to a depth at which the surface compressive stress is 0, a slope of the linear function representing the 1 st region is larger than a slope of the linear function representing the 2 nd region.
6. The glass for chemical strengthening according to claim 1, wherein the glass for chemical strengthening contains 3% to 6% of MgO.
7. The chemically strengthened glass according to claim 2 or 3, wherein the chemically strengthened glass contains 3% to 6% of MgO.
8. The glass for chemical strengthening as claimed in claim 1 or 6, wherein the glass for chemical strengthening contains 0% to 1% of TiO 2 But not 0%.
9. The chemically strengthened glass as claimed in claim 2 or 3, wherein the chemically strengthened glass contains 0% to 1% TiO 2 But not 0%.
10. The glass for chemical strengthening as claimed in claim 1 or 6, wherein the glass for chemical strengthening has a fracture toughness value (K1 c) of 0.75 MPa-m 1/2 The above.
11. The chemically strengthened glass as claimed in claim 2 or 3, wherein the chemically strengthened glass isHas a fracture toughness value (K1 c) of 0.75MPa · m 1/2 As described above.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017089984 | 2017-04-28 | ||
| JP2017-089984 | 2017-04-28 | ||
| PCT/JP2018/016505 WO2018199046A1 (en) | 2017-04-28 | 2018-04-23 | Chemically strengthened glass, and glass for chemical strengthening purposes |
| CN201880027496.8A CN110546115B (en) | 2017-04-28 | 2018-04-23 | Chemically strengthened glass and glass for chemical strengthening |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880027496.8A Division CN110546115B (en) | 2017-04-28 | 2018-04-23 | Chemically strengthened glass and glass for chemical strengthening |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115385571A true CN115385571A (en) | 2022-11-25 |
| CN115385571B CN115385571B (en) | 2024-05-03 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001172043A (en) * | 1999-12-20 | 2001-06-26 | Asahi Glass Co Ltd | Glass used for substrate of data recording medium, and glass substrate of data recording medium |
| US20080213495A1 (en) * | 2007-02-19 | 2008-09-04 | Nippon Sheet Glass Company, Limited | Mother glass composition for gradient-index lens, gradient-index lens, manufacturing method thereof, optical product, and optical device |
| CN106232540A (en) * | 2014-04-24 | 2016-12-14 | 日本板硝子株式会社 | Glass composition, chemical enhanced glass plate, strengthening glass sheets and display hardened glass substrate |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001172043A (en) * | 1999-12-20 | 2001-06-26 | Asahi Glass Co Ltd | Glass used for substrate of data recording medium, and glass substrate of data recording medium |
| US20080213495A1 (en) * | 2007-02-19 | 2008-09-04 | Nippon Sheet Glass Company, Limited | Mother glass composition for gradient-index lens, gradient-index lens, manufacturing method thereof, optical product, and optical device |
| CN106232540A (en) * | 2014-04-24 | 2016-12-14 | 日本板硝子株式会社 | Glass composition, chemical enhanced glass plate, strengthening glass sheets and display hardened glass substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110546115A (en) | 2019-12-06 |
| CN110546115B (en) | 2022-10-04 |
| WO2018199046A1 (en) | 2018-11-01 |
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