CN112969667A - Glass article having three-dimensional shape and method for producing same, chemically strengthened glass article and method for producing same - Google Patents
Glass article having three-dimensional shape and method for producing same, chemically strengthened glass article and method for producing same Download PDFInfo
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- CN112969667A CN112969667A CN201980072502.6A CN201980072502A CN112969667A CN 112969667 A CN112969667 A CN 112969667A CN 201980072502 A CN201980072502 A CN 201980072502A CN 112969667 A CN112969667 A CN 112969667A
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- 239000011521 glass Substances 0.000 title claims abstract description 196
- 239000005345 chemically strengthened glass Substances 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000000203 mixture Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000000465 moulding Methods 0.000 claims abstract description 36
- 238000003426 chemical strengthening reaction Methods 0.000 claims abstract description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 13
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 13
- 239000005357 flat glass Substances 0.000 claims description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 239000006060 molten glass Substances 0.000 claims description 12
- 230000002093 peripheral effect Effects 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 229910001323 Li2O2 Inorganic materials 0.000 claims description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 7
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract description 7
- 238000005728 strengthening Methods 0.000 abstract description 4
- 238000005342 ion exchange Methods 0.000 description 17
- 238000002844 melting Methods 0.000 description 17
- 230000008018 melting Effects 0.000 description 17
- 238000012545 processing Methods 0.000 description 17
- 238000009826 distribution Methods 0.000 description 15
- 239000006059 cover glass Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 9
- 238000006124 Pilkington process Methods 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 238000004031 devitrification Methods 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000000156 glass melt Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 239000005358 alkali aluminosilicate glass Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000003280 down draw process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal 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
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 239000005407 aluminoborosilicate glass Substances 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000007723 die pressing method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 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
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B23/00—Re-forming shaped glass
- C03B23/02—Re-forming glass sheets
- C03B23/023—Re-forming glass sheets by bending
- C03B23/03—Re-forming glass sheets by bending by press-bending between shaping moulds
-
- 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
Abstract
The invention provides a glass article having a shape other than a flat plate and having a glass composition containing SiO in terms of mass% based on oxides2 60～70％、Al2O3 6～18％、Li2O 2～8％、Na2O 8～20％、K2O 0～1％、MgO 0～3％、CaO 1～6％、Fe2O30.01 to 0.2 percent. The glass composition is suitable for imparting a three-dimensional shape by a press molding method and for strengthening by a chemical strengthening treatment.
Description
Technical Field
The present invention relates to a glass article having a three-dimensional shape and containing an alkali aluminosilicate glass containing lithium, and a chemically strengthened glass article. In the present specification, the term "three-dimensional shape" refers to a shape other than a flat plate.
Background
In recent years, portable terminals equipped with a touch panel have been widely used, and in order to protect the display thereof, a cover glass is generally provided on the surface of the display. As the cover glass, for example, one obtained by chemically strengthening alkali aluminosilicate glass having a plate shape with a thickness of about 0.3mm to 1mm is used.
Further, recently, with the development of displays having a three-dimensional shape such as a curved shape, a cover glass having a three-dimensional shape is expected. In addition, in order to make the radio wave reception and transmission of the internal antenna of the portable terminal good, it is also expected that: by using a chemically strengthened glass case having a three-dimensional shape instead of a metal case, the radio wave reception and transmission of the built-in antenna of the portable terminal are made good. In order to solve these problems, cover glasses that are processed from a flat plate shape into a three-dimensional shape by hot working and further chemically strengthened have been proposed (patent documents 1 to 4).
As the three-dimensional shape, for example, patent document 1 discloses "a curved surface shape, an uneven shape, a wave shape, a stepped shape, and the like". In addition, patent document 2 exemplifies as "dish shape": a plate glass is bent at its peripheral edge portion to stand at a predetermined angle with respect to its main surface, and is referred to as a dish-like, plate (tray) -like, or box-like shape (fig. 1 and 2). Further, patent documents 4 and 5 exemplify shapes obtained by forming the entire body into a uniform curved surface shape.
As a method of forming a sheet glass into a three-dimensional shape, there are known: a self-weight forming method, a vacuum forming method (a sagging or suction method), or the like, in which a flat glass is heated and bent (for example, patent documents 5 and 6).
When a glass article having a three-dimensional shape with a curved portion which is not a uniform curved surface but is partially curved is formed (see fig. 1 and 2 of patent document 2), the press molding method is most suitable particularly when it is necessary to precisely control the shape and thickness distribution thereof (non-patent document 1). This is a method which is widely used for press molding of an aspherical lens, but it is also possible to perform a flat glass as a preform. Compared with other hot processing methods, the die pressing method has the following advantages: the degree of freedom in shape design of a three-dimensional shaped glass article is high; can be formed by precisely controlling the shape; further, a glass article having a smooth surface and a three-dimensional shape can be obtained, although the state of the mold surface varies.
The following problems are associated with the following problems in obtaining a three-dimensional shaped glass article by the above-described press method using a flat glass formed of a glass composition disclosed in patent documents 1 to 4 as a preform.
The degree of improvement in the strength of the glass article by chemical strengthening is greatly affected by the glass composition in the vicinity of the surface of the glass article, and therefore, the improvement in the strength of the glass article is generally adversely affected by the change in the glass composition in the vicinity of the surface of the glass article by thermal processing. From this point of view, the hot working at high temperature is also not preferable.
In order to solve this problem, a method of performing a thermal treatment after performing a chemical strengthening treatment on a sheet glass may be considered. In this case, stress relaxation occurs due to diffusion of ions introduced by ion exchange or the like, and the compressive stress applied to the surface of the glass article is reduced, so that it becomes difficult to apply the isothermal pressing method.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2010-168233
Patent document 2: japanese laid-open patent publication No. 2015-527277
Patent document 3: japanese laid-open patent publication No. 2015-527970
Patent document 4: japanese Kohyo publication 2017-506616
Patent document 5: international publication No. 2016/125713
Patent document 6: japanese patent publication No. 2011-526874
Non-patent document 1: shangen Zheng et al, Shuichang handbook, first edition, Kyoho Shuichi Shikou, 7/5/1999, and pages 419-422
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing a glass article having a glass composition suitable for imparting a three-dimensional shape by a press method and for increasing the strength by a subsequent chemical strengthening treatment, and the glass article being imparted with a three-dimensional shape. Another object of the present invention is to provide a glass article having such a glass composition, provided with a three-dimensional shape, and having a high strength by chemical strengthening treatment.
Means for solving the problems
The present invention provides a glass article having a first surface,
which has a three-dimensional shape, i.e. a shape other than a flat plate,
it contains, expressed in mass% on an oxide basis:
Al2 O 36% to 18% inclusive,
Li2O2% or more and 8% or less,
Na2O8% to 20%,
K2O is 0% to 1%,
MgO 0-3%,
CaO in an amount of 1 to 6%,
Fe2O30.01% or more and 0.2% or less.
Further, the present invention provides a method for manufacturing a glass article, including:
forming a sheet glass having the following glass composition from the molten glass raw material; and
forming the plate glass into a glass article having a shape other than a plate by press molding,
the glass composition is represented by mass% based on oxides and includes the above components at the above content ratios.
In addition, the present invention provides a chemically strengthened glass article,
it has a shape other than a flat plate,
a compressive stress layer is provided on the surface,
at least the portion other than the compressive stress layer is represented by mass% based on oxide, and contains the components at the above content ratios.
Further, the present invention provides a method for producing a chemically strengthened glass article, including:
forming a sheet glass having the following glass composition from the molten glass raw material;
forming the plate glass into a glass article having a shape other than a plate by press molding; and
the glass article is subjected to a chemical strengthening treatment,
the glass composition is represented by mass% based on oxides and includes the above components at the above content ratios.
The present invention also provides a mobile terminal including the glass article according to the present invention.
The present invention also provides a display device mounted on a vehicle, which includes the glass article according to the present invention.
Effects of the invention
According to the present invention, a glass article having a glass composition suitable for imparting a three-dimensional shape by a press molding method and for strengthening by a subsequent chemical strengthening treatment, and imparted with a three-dimensional shape, can be provided. Further, according to the present invention, there can be provided a glass article having such a glass composition, provided with a three-dimensional shape, and strengthened by a chemical strengthening treatment.
The glass compositions specified in the present invention can be formed by press molding at relatively low temperatures. The press molding method at a relatively low temperature is advantageous in terms of suppressing problems that may occur with the press molding method, such as a decrease in transmittance of the glass article due to devitrification, roughening of the surface of the glass article, and wear of a mold used for molding. The glass composition defined in the present invention can be subjected to chemical strengthening treatment after forming, and is suitable for realizing a high-strength glass article having a three-dimensional shape. In the present invention, the molding temperature by the press molding method may be set to a higher temperature as necessary. The molding at a higher temperature is preferably applied to a case where the plate glass is molded into a predetermined shape, for example, a shape in which the side plate portion is thicker than the bottom plate portion. The glass composition specified in the present invention can provide the following advantages: forming into such glass articles of varying thickness can also be carried out at lower temperatures.
Drawings
Fig. 1 is a plan view showing an example of the shape of a glass article having a three-dimensional shape.
FIG. 2 is a sectional view II-II of FIG. 1.
Fig. 3 is a sectional view III-III of fig. 1.
Fig. 4 is a plan view showing another example of the shape of a glass article having a three-dimensional shape.
Fig. 5 is a V-V sectional view of fig. 4.
Fig. 6 is a sectional view VI-VI of fig. 4.
Fig. 7 is a plan view showing still another example of the shape of a glass article having a three-dimensional shape.
Fig. 8 is a sectional view VIII-VIII of fig. 7.
Fig. 9 is a cross-sectional view IX-IX of fig. 7.
Fig. 10 is a plan view showing still another example of the shape of a glass article having a three-dimensional shape.
FIG. 11 is a graph showing temperature-viscosity curves of the glass compositions of examples 1 to 3.
Fig. 12 is a graph showing the compressive stress distribution in the depth direction of a chemically strengthened glass article formed from the glass composition of example 1.
Fig. 13 is an enlarged view of a part of fig. 12.
Fig. 14 is a graph showing the depth-direction concentration distribution of sodium ions in the vicinity of the surface of a chemically strengthened glass article formed from the glass composition of example 1.
Detailed Description
The present invention will be described below with reference to the accompanying drawings as appropriate, but the following description does not limit the present invention to a specific form.
[ three-dimensional shape of glass article ]
The glass article has a shape other than a flat plate, i.e., a three-dimensional shape. The three-dimensional shape is, for example, a shape including a bottom plate portion, a bent portion, and a side plate portion, and the side plate portion is connected to a peripheral edge of the bottom plate portion via the bent portion.
Fig. 1 to 3 show an example of the above shape. The glass article 10 has a shape in which the side plate 2 is connected to the entire periphery of the bottom plate 1 via the bent portion 3. The bottom plate 1 is substantially quadrangular in plan view, and is precisely rectangular with rounded corners. The bottom plate 1 is a flat plate, and its main surface 1f is a flat surface. The side plate portions 2 rise from the bent portion 3 to the same height as viewed from the main surface 1f of the bottom plate portion 1. The side plate 2 extends in a direction away from the bottom surface of the bottom plate 1, i.e., the main surface 1 f. The surfaces of the side plate portions 2 and the curved portion 3 are both curved surfaces (see fig. 2 and 3), and the surface of the curved portion 3 has a larger curvature than the surface of the side plate portion 2.
Fig. 4 to 6 show another example of the above shape. The bottom plate portion 1 of the glass article 20 includes: the peripheral edge of the side plate 2 and the peripheral edge of the unconnected side plate 2 are connected via the bent portion 3. The bottom plate portion 1 is substantially quadrangular in plan view, more specifically, rectangular. The side plate 2 stands up from the peripheral edge of the bottom plate 1 corresponding to the pair of opposing sides of the rectangle, and the end face of the bottom plate 1 is exposed at the peripheral edge corresponding to the remaining opposing sides of the bottom plate 1 via the bent portion 3.
Fig. 7 to 9 show still another example of the above shape. In the glass article 30, the bottom plate portion 1 also has a peripheral edge to which the side plate portion 2 is connected via the bent portion 3, and a peripheral edge to which the side plate portion 2 is not connected. However, unlike the glass article 20, in the glass article 30, the side plate portion 2 is raised from the peripheral edge corresponding to the long side of the main surface of the bottom plate portion 1 via the bent portion 3, rather than from the peripheral edge corresponding to the short side. In addition, unlike the glass articles 10 and 20, the bottom plate portion 1 of the glass article 30 is a curved plate whose main surface 1c is a curved surface (see fig. 9).
The shapes shown in fig. 1 to 9 may be referred to as dish-like shapes, plate (tray) shapes, and the like. Further, if the side plate 2 is extended from the shape shown in fig. 1 to 3, the shape can be called a box shape. Thus, the glass article may have a shape corresponding to at least one selected from a dish shape, a flat plate shape, and a box shape. However, the shape of the glass article is not limited to the examples shown in fig. 1 to 9. For example, the bottom plate 1 is not limited to a square shape in a plan view, and may have other shapes such as a circular shape and an elliptical shape. The side plate 2 may be a flat plate, or may be erected in a direction orthogonal to the main surface of the bottom plate 1. The side plate portion 2 may be provided with a notch, a hole, or the like for connecting a connector or the like to the portable terminal. A hole or the like may be formed in the bottom plate portion 1. The shape of the glass article is not limited to the shape having the bottom plate portion, the bent portion, and the side plate portion. For example, in the glass article 40 shown in fig. 10, the side plate portion 2 having a certain curvature is directly connected to the peripheral edge of the bottom plate portion 1 which is a flat plate in a cross-sectional view, and does not have a portion which can be regarded as a curved portion.
The glass article typically has a shape that can be imparted by deforming a plate-like glass article, i.e., a flat glass, having a pair of main surfaces that are both flat by press molding. The glass article preferably has the bottom plate portion 1 as a main portion thereof, specifically, the bottom plate portion 1 preferably has a flat plate shape or a curved surface shape as an excess portion of the entire glass article on a mass basis. The curved surface shape of the bottom plate portion 1 is preferably a gentle curved surface having a minimum radius of curvature of 5cm or more. The shape of the bottom plate portion of the flat plate or the curved plate having a small curvature is suitable for use as, for example, a front surface portion disposed on the front surface of a display of a mobile terminal or the like, or a bottom portion of a glass case of a mobile terminal or the like.
The thickness t1 of the bottom plate portion 1 is, for example, 0.3mm or more and 2mm or less, and particularly 0.3mm or more and 1mm or less. This thickness is suitable for use as a cover glass or a glass case for a mobile terminal. However, the bottom plate portion 1 may have a thickness suitable for a display device other than a mobile terminal.
The thickness t2 of the side plate 2 may be, for example, 0.3mm or more and 2mm or less, and particularly may be 0.5mm or more and 2mm or less. In addition, the thickness t2 may be substantially the same as the thickness t1 of the bottom plate portion 1. In the glass article, the thickness may be substantially the same over all regions of the bottom plate 1 and the side plate 2. In the present specification, the thickness "substantially the same" means: the difference in thickness is 0.1mm or less, and further 0.05mm or less.
However, without being limited thereto, the thickness t2 may be substantially different from the thickness t1 and larger than the thickness t 1. In this case, the difference (t2-t1) may be, for example, 0.3mm or more, particularly 0.4 to 1 mm. By making the side plate portions 2 thicker than the bottom plate portion 1, the following advantages can be obtained: the weight increase of the entire glass article is suppressed, and 1) the strength against the weight of the bottom plate portion 1 itself and the pressure applied to the bottom plate portion 1, for example, the pressure applied to the display by a finger or the like is easily maintained, and 2) the strength of the side plate portion 2 is easily maintained even if a notch, a hole or the like is provided in the side plate portion 2. To sufficiently obtain such an effect, the thickness t2 may be 2 times or more the thickness t 1.
The thickness t2 of the side plate 2 may be locally thicker than the thickness t1 of the bottom plate 1. For example, in order to obtain the effect of 1), only 1 or 2 or more columnar portions extending from the connection portion with the bent portion 3 to the end face of the side plate portion 2 may be locally thickened, and a support portion may be provided in the side plate portion 2. In addition, for example, in order to obtain the effect of 2), a portion where the notch is provided may be locally thickened. In these cases, it is preferable to set the difference (t2p-t1) between the thickness t2p and the thickness t1 of the locally thickened portion to the above-described range with respect to the difference (t2-t 1).
As described later, if the conditions of the press method are appropriately selected, not only can a glass article having a side plate portion 2 having a thickness substantially equal to that of the bottom plate portion 1 be produced from a sheet glass having a substantially equal thickness, but also a glass article having a side plate portion 2 thicker than the bottom plate portion 1 can be formed from the sheet glass.
The surface of the glass article can have high smoothness after the molding method and the chemical strengthening treatment are applied. The arithmetic average roughness Ra of the surface is, for example, 1nm or less, and further 0.8nm or less. In addition, the glass article can have a high light transmittance after at least the press molding and the chemical strengthening treatment are applied to the bottom plate portion 1. When compared with a flat glass sheet as a preform before application of press molding and chemical strengthening treatment, the change in light transmittance is within 2% and further within 1% as represented by an average transmittance in a wavelength region of 400 to 1200 nm.
[ glass composition ]
The glass composition of the glass article is such that it comprises lithium oxide (Li)2O) alkali aluminosilicate glass. Hereinafter, the expression "percentage of the component representing the glass composition" means the mass% based on oxides. In the present specification, "substantially not containing" means: the content of this component is 0.05% or less, preferably 0.01% or less. There are cases where impurities are inevitably mixed in industrial mass production of glass articles. "substantially" means that a trace amount of impurities is allowed to be inevitably mixed.
Each component (SiO) of glass composition constituting the glass article2、Al2O3、Li2O、Na2O、K2O、MgO、CaO、Fe2O3) The preferable range of the content of (b) is as described above.
The glass article may further contain, for example, the following ingredients as a coloring agent, a clarifying agent, and the like.
SO30% to 1%,
As2 O 30% to 1%,
Sb2O30% or more and 1% or less
However, As2O3And Sb2O3Preferably substantially free. Other optional components will be described later.
Hereinafter, preferred content ratios of the respective components will be described in more detail.
(SiO2)
If SiO2If the content of (b) is too low, the chemical durability such as water resistance and heat resistance of the glass are deteriorated. On the other hand, if SiO2When the content of (2) is too high, the viscosity of the glass composition at high temperature becomes high, and melting and molding become difficult. Thus, SiO2The content of (b) is in the range of 60 to 70%, preferably 60 to 68%, more preferably 62 to 66%, most preferably 64 to 66%.
(Al2O3)
Al2O3The component is a component for improving chemical durability such as water resistance, and increasing the surface compressive stress after chemical strengthening by facilitating the movement of alkali metal ions in the glass, and for increasing the depth of a stress layer. When the ratio is less than 6%, the effect is insufficient. On the other hand, if it exceeds 18%, the viscosity of the glass melt increases, making melting or molding difficult and the coefficient of expansion becomes too small. Thus, Al2O3The content of (b) is in the range of 6 to 18%, preferably 10 to 18%, and more preferably 14 to 17%.
(Li2O)
Li2O is a component for ion exchange and a component for improving meltability. When the ratio is less than 2%, the surface compressive stress after ion exchange cannot be sufficiently obtained, and the meltability is also poor. On the other hand, if it exceeds 8%, the water resistance after ion exchange is deteriorated, and the liquid phase temperature is increased, making the formation difficult. Thus, Li2The content of O is in the range of 2 to 8%, preferably 2 to 6.1%, more preferably 2.6 to E6%, and more preferably 3 to 5%.
(Na2O)
Na2O is a component for improving the meltability. When the ratio is less than 8%, the effect is insufficient. On the other hand, if it exceeds 20%, the water resistance after ion exchange is deteriorated. Thus, Na2The content of O is in the range of 8 to 20%, preferably 10 to 16%, more preferably 10 to 14%, most preferably 11 to 13%.
(K2O)
K2O is a component for improving the meltability, but is not necessarily required because the surface compressive stress after ion exchange may be reduced. Thus, K2The content of O is in the range of 0 to 2%, preferably 0 to 1%, more preferably 0 to 0.5%, most preferably 0.3 to 0.5%.
(MgO)
MgO is a component for improving the meltability, but if it exceeds 3%, the liquid phase temperature rises, and the molding becomes difficult. Therefore, the content of MgO is in the range of 0 to 3%, preferably 0 to 2%, more preferably 0.5 to 2%, and most preferably 0.5 to 1.5%.
(CaO)
CaO is a component for improving meltability and is an essential component for adjusting an ion exchange rate. When the ratio is less than 1%, the effect is insufficient. On the other hand, if it exceeds 6%, the liquid phase temperature rises and the molding becomes difficult. Therefore, the CaO content is in the range of 1 to 6%, preferably 1 to 4%, and most preferably 2 to 4%.
(Fe2O3)
Usually Fe as Fe2+Or Fe3+The state of (2) is present in the glass and functions as a colorant. Fe3+Is a component for improving the ultraviolet absorption property of the glass, Fe2+Is a component for improving the heat ray absorption property. When the glass article is used as a cover glass of a display, it is required that coloring is not conspicuous, and therefore, the Fe content is preferably low. However, Fe is inevitably mixed in most of the industrial raw materials. Therefore, in the case of manufacturing a cover glass for a display, it is preferable: conversion to Fe2O3The content of iron oxide (b) is 0.2% or less, preferably 0.15% or less, more preferably 0.1% or less, and even more preferably 0.05% or less, but may not be completely excluded, and may be 0.01% or more.
On the other hand, when a chemically strengthened glass article having a three-dimensional shape is used as the glass housing, it is sometimes preferable to: will be converted into Fe2O3The content of iron oxide (b) is 0.1% or more, and more preferably 0.5% or more.
(other Components)
SrO and BaO are components that improve the meltability and are effective for lowering the liquidus temperature. However, the density of the glass becomes high and the raw material cost increases. The content of SrO and BaO is in the range of 0 to 1%, preferably 0 to 0.5%, and more preferably 0 to 0.1%. Most preferably, the glass article is substantially free of SrO and BaO.
B2O3Is an ingredient that reduces the viscosity and improves the meltability of the glass composition. However, if B2O3When the content of (2) is too high, the phase separation of the glass composition is likely to occur, and the water resistance of the glass composition is lowered. In addition, B2O3Compounds formed with the alkali metal oxides volatilize and may damage the refractory of the glass melting chamber. In addition, B2O3The content (2) makes the depth of the compressive stress layer shallow during chemical strengthening. Thus, B2O3The content of (b) is preferably 0.5% or less, more preferably 0.1% or less. Most preferably, the glass article is substantially free of B2O3. In addition, regarding P2O5Its volatility and the like also become problems, and therefore, P2O5The content of (b) is preferably 0.5% or less, more preferably 0.1% or less.
The glass article may contain other components, such as components derived from colorants, fining agents, within the range of chemical strengthening without affecting the conditions of thermal processing. For example, when used as cover glass having high transmittance, TiO is suitable for use2、SO3、SnO、CeO2、As2O3、Sb2O3The content ratios of (a) and (b) are each 1% or less, preferably 0.5% or less, and further the total content ratio of these components is preferably 1% or less, preferably 0.5% or less, more preferably 0.3% or less, and still more preferably 0.1% or less. Wherein, As2O3And Sb2O3It is preferably substantially free of impurities because of adverse effects on the environment. It is also preferable that the other components are not substantially contained.
The glass article may further comprise ZrO2、PbO、La2O3、Y2O3、MoO3、WO3、Nb2O5、CoO、Cr2O3Each of the amounts is 0.5% or less, and preferably 0.1% or less. The glass article may contain 0.5% or less of each of noble metal elements such as Au, Ag, Pt, Rh, and Os and halogen elements such as Cl and F. However, from ZrO2To Cr2O3It is also preferable that the components listed above, noble metal elements and halogen elements are each substantially not contained. For example, ZrO2This causes erosion of the heat-resistant bricks of the melting furnace. TiO described in the above list2The total content of the components up to F is preferably 1% or less, more preferably 0.5% or less, particularly preferably 0.1% or less.
[ Properties of glass composition ]
Hereinafter, preferred characteristics of the glass composition constituting the glass article will be described.
The glass composition described above for the composition may have characteristics suitable for forming a three-dimensional shape by a press molding method performed at a relatively low temperature, and specifically, may have a yield point, a glass transition point, and a thermal expansion coefficient. These characteristics are as follows.
(yield point At)
The upper limit of the yield point is suitably 580 c, preferably 560 c, depending on the conditions of the processing temperature of the moulding process. On the other hand, the lower limit of the yield point is suitably 420 ℃, preferably 450 ℃, and more preferably 500 ℃.
(glass transition temperature Tg)
The upper limit of the glass transition temperature is suitably 530 c, preferably 500 c, depending on the conditions of the release temperature of the molding method. On the other hand, the lower limit of the glass transition temperature is suitably 330 ℃, preferably 400 ℃, and more preferably 430 ℃.
(coefficient of thermal expansion α)
In the press molding method, when the thermal expansion coefficient of the glass composition is too large, it may be difficult to design the shape of a mold for obtaining a desired glass shape. Therefore, the coefficient of thermal expansion α (unit: 10)-7/DEG C) is suitably from 80 to 120, preferably from 80 to 100, as an average value from 50 ℃ to 350 ℃.
The glass composition preferably has a melting point, an operating point, and a liquidus temperature suitable for producing a sheet glass as a preform. Various methods such as a float method and a downdraw method are available as methods for producing flat glass, but a float method, which is a method for producing large-area flat glass with good productivity, is preferable.
In the case of obtaining a flat glass by the float method, the melting point T of the glass composition is preferably2Operating point T4Liquid phase temperature TLAs follows.
(melting Point T)2)
When the melting point is low, the energy required for melting the glass raw material can be suppressed, and the glass raw material is more easily melted to promote defoaming and fining of the glass melt. The melting point is 1580 ℃ or lower, preferably 1550 ℃ or lower, and more preferably 1500 ℃ or lower. The melting point T is2For glass to have a viscosity of up to 102The temperature of dPa · s may be represented by T based on the viscosity2. The numerical values described below together with T correspond to the viscosity of the glass at that temperature.
(operating Point T)4)
In the case of producing a flat glass by the float method, when a molten glass is caused to flow from a melting furnace into a float furnace, the temperature of the molten glass is adjusted so that the viscosity η of the molten glass becomes 104Approximately dpas. Preferably, the viscosity of the molten glass is 104Temperature at dPa · s (operating point)) The operating point is suitably 1300 ℃ or lower, preferably 1200 ℃ or lower, and more preferably 1100 ℃ or lower, for example, in order to thinly form the glass into a cover glass for a display or the like. The lower limit of the operating point is not particularly limited, and may be, for example, 800 ℃.
(liquidus temperature (devitrification temperature) TL)
When flat glass is produced by the float method, devitrification in forming the molten glass into a flat shape needs to be avoided. Namely, it is preferable that: the molten glass does not devitrify at the forming temperature (operating point), in other words, the difference between the operating point and the liquidus temperature is large. Difference (T) between operating point and liquid phase temperature4-TL) Suitably 10 ℃ or higher, preferably 50 ℃ or higher, and more preferably 100 ℃ or higher.
[ method for producing glass article ]
(Molding of plate glass)
The glass article can be obtained by melting a glass raw material to form a plate glass, molding the plate glass into a shape other than a plate by a press method, and further performing a chemical strengthening treatment as necessary. The sheet glass can be formed by a float method, a down-draw method, and other known methods. As described above, the float process is a preferable production method of flat glass. A method of forming a flat glass represented by a float process is well known to those skilled in the art, and therefore, a description thereof will be omitted.
(Molding method)
The glass sheet is press-formed by a press molding method using a forming mold. In this case, it is preferable to use an isothermal pressing method: the forming mold and the plate glass are heated to a prescribed temperature, and pressed at that temperature (processing temperature) to be a desired shape. After press forming, the glass article is cooled to a predetermined temperature, removed from the mold, and precision annealed.
In the isothermal pressing method, the mold is heated to a temperature for processing the sheet glass, and therefore, strength at a high temperature and reactivity with the sheet glass are required to be low. In general, it is preferred that: the surface of the cemented carbide is precisely processed, and a preform having a shape similar to a desired product shape is formed at a relatively low processing temperature using a mold having a surface coated with a release film such as a DLC (diamond like carbon) film. As the cemented carbide, tungsten carbide may be exemplified. If a mold obtained by processing a cemented carbide is used, surface polishing after molding is not required. On the other hand, in the case of processing glass in a molten and softened state, since the processing temperature is high, a carbon-based material can be used for the mold material, but the processing accuracy of the surface is inferior to that of cemented carbide, or the surface is roughened due to deterioration of a release film, and therefore polishing is easily required after pressing. Carbon-based materials are inferior to cemented carbide in strength and durability.
In the case of producing a glass article having a three-dimensional shape by the aforementioned press method using a sheet glass as a preform, it is preferable that: the mold and the plate glass are heated to a temperature exceeding the yield point, the plate glass is pressed by using a mold while maintaining a predetermined time (for example, 2 to 6 minutes, 5 minutes as an example) required for deformation, and then cooled to a temperature before and after the glass transition point. When a die for covering a DLC film on a cemented carbide is used, the pressing is preferably performed at a processing temperature of 650 ℃ or less, preferably 630 ℃ or less, in order to suppress the loss of the DLC film. This condition is suitable for a method of forming a glass article having a thickness t2 of the side panel portion 2 substantially the same as the thickness t1 of the bottom panel portion 1 from a flat glass sheet having a uniform thickness. On the other hand, in particular, when the shape change by hot working is large, if the working temperature is too low, the viscosity η of the glass becomes large, and the time (holding time) required for deformation becomes long, so that the working temperature is preferably 550 ℃ or more, preferably 580 ℃ or more, and more preferably 600 ℃ or more. When a glass article is molded so that the thickness t2 of the side plate part is larger than the thickness t1 of the bottom plate part, the processing temperature is preferably 680 to 720 ℃, and further 700 to 715 ℃. In order to prevent the cooling time from becoming too long, the difference between the processing temperature and the mold release temperature is preferably 150 ℃ or less, preferably 130 ℃ or less, more preferably 120 ℃ or less, and still more preferably 100 ℃ or less.
According to the press molding method, a mark or a pattern is engraved on a portion of the molding die which comes into contact with the sheet glass, whereby the mark or the like can be transferred to the surface of the glass article while the glass article is molded.
(chemical strengthening treatment)
Chemical strengthening is a technique of forming a compressive stress layer on the surface of a glass article by ion exchange in which alkali metal ions contained in the surface of the glass article are replaced with monovalent alkali metal ions having a larger radius. Chemical strengthening is mostly achieved by using sodium ions (Na +) to convert lithium ions (Li)+) The substitution is performed by substituting sodium ions with potassium ions (K +).
The ion exchange may be performed by bringing the glass article into contact with a molten salt containing alkali metal ions introduced to the surface of the glass article. Ion exchange can be carried out in two stages. For example, K may be further used+To replace with Li+Na introduced into the surface of the glass article by ion exchange+. Potassium nitrate is exemplified as the molten salt used for ion exchange. A mixed molten salt of potassium nitrate and sodium nitrate is also a preferred molten salt.
The temperature of the molten salt in contact with the glass article is preferably 360 to 450 ℃. The contact time of the glass article with the molten salt is preferably 2 to 6 hours. Note that the contact time is the time of each ion exchange.
[ chemically strengthened glass article ]
In the glass article having the above glass composition, the glass composition before ion exchange can be maintained in the inside thereof except for the surface affected by ion exchange. A compressive stress layer is generated on the surface so as to include a portion affected by ion exchange. Therefore, in the chemically strengthened glass article, the glass composition before chemical strengthening can be maintained at least in the inner portion other than the compressive stress layer. The entirety of the glass article may also have the above composition.
Surface compressive stress C of chemically strengthened glass articlesSIs 400MPa or more, preferably 600MPa or more, and more preferably 800MPa or more. The thickness doc (depth of compression) of the compressive stress layer is 60 μm or more, preferably 80 μm or more, and more preferably 100 μm or more. DOC is the depth at which the stress inside the glass changes from compression to tension, that is, the depth at which the stress becomes 0 MPa. The ion exchange depth DOL (depth of layer) is preferably 5 to 12 μm. DOL is a depth at which birefringence can be confirmed, and can be measured using a glass surface stress meter (FSM-6000, manufactured by FAMIA, for example).
The present invention will be described in more detail with reference to examples, but the following examples are not intended to limit the present invention.
[ example 1]
(production of glass)
Glass raw material batch was prepared by using silica sand, spodumene, alumina, lithium carbonate, sodium carbonate, potassium carbonate, dolomite, limestone, iron oxide, and the like, which are general glass raw materials, so as to have a glass composition shown in example 1 of table 2. The batch was melted by heating to 1550 ℃ in a platinum crucible, and after keeping this state for 4 hours, the molten glass was poured out onto an iron plate. The molten glass poured out of the iron plate was solidified within 100 seconds, and immediately after solidification, the glass was placed in an electric furnace set at 600 ℃. After 30 minutes, the electric furnace was turned off, left to cool to room temperature, and annealed to obtain glass.
(melting Point T)2Operating point T4)
The high-temperature viscosity of the glass was measured using a platinum ball pull-up type automatic viscosity measuring apparatus, and the viscosity (η, in dPa · s) of the glass melt was 102determining the melting point T at a temperature of dPa · s2. Likewise, the viscosity of the glass melt is 104determining the operating point T by the temperature of dPa · s4. The results are shown in Table 2.
(temperature of liquid phase TL)
The obtained glass was pulverized in an agate mortar, and the pulverized glass was passed through a screen having a mesh size of 2380 μm and left on a 1000 μm screenThe glass pellets were sieved, washed with ultrasonic waves in ethanol, and dried to prepare a sample for measuring the liquidus temperature. 25g of this sample was weighed, transferred to a platinum boat having a width of 12mm and a length of 200mm, held in a temperature gradient furnace for 2 hours and taken out, crystals (devitrification) formed in the glass were observed with an optical microscope, and the highest temperature at which the crystals were observed was regarded as the liquid phase temperature (devitrification temperature) TL. The results are shown in Table 2.
(Density p)
The obtained glass was cut into a size of 5 × 40 × 30mm, and each surface was mirror-polished to prepare a plate-like sample, and the density p of the glass was calculated from the weight of the sample. The results are shown in Table 2.
(coefficient of thermal expansion α)
A cylindrical sample having a diameter of 5mm and a length of 15mm was prepared, and the glass transition temperature, yield point and average linear expansion coefficient α of 50 to 350 ℃ were determined using a thermal dilatometer (thermomechanical analyzer TMA4110SA, manufactured by BRUKER AXS Co., Ltd.). The results are shown in Table 2.
(softening Point T)7.6Sag Point T10Annealing point T13Strain point T14.5And temperature-viscosity curve
The resulting glass was used as a sample, and the softening point T was measured by a fiber elongation method (sample size: round bar shape with a diameter of 10 mm. times.length of 200 mm) or a beam bending method (sample size: square bar sample with a diameter of 3 mm. times.3 mm. times.55 mm) as disclosed in non-patent document 47.6(η＝4.5×107dPa. s), sag Point T10(η＝1010dPa · s), annealing point T13(η＝1013dPa · s), strain point T14.5(η＝1014.5dPa · s). The results are shown in Table 5. Fig. 11 shows a temperature-viscosity curve created using the melting point, the operating point, and these values and the Fulcher equation.
(Hot working)
A glass plate having a size of 50 mm. times.100 mm. times.0.9 mm was produced from the glass thus obtained, and both surfaces were mirror-polished to produce a plate glass sample. The flat glass sample was subjected to hot working by press molding to obtain a glass sample having the same three-dimensional shape as that shown in FIGS. 1 to 3. A dish-like shape having a side plate portion and a bottom plate portion of substantially the same thickness and a depth of about 5mm was formed using a die obtained by coating a die made of cemented carbide with a DLC film. Specifically, the mold and the glass are heated by an infrared heater, and the temperature is raised to a processing temperature (a predetermined temperature ranging from 610 to 670 ℃) while measuring the temperature, and the pressure is applied and held for 5 minutes. Then, the mold was removed from the mold by cooling to a mold release temperature (500 ℃), annealed to 200 ℃ while cooling, and left to stand at room temperature. Further, the operation was performed in the same manner as described above, and a dish-like shape having a side plate portion thicker than the bottom plate portion and a depth of about 5mm was formed. The thicknesses of the bottom plate and the side plate of this sample were 0.6mm and 1.3mm, respectively. At this time, the sample was molded at a processing temperature of 710 ℃ and a holding time of 12 minutes. The average transmittance of the bottom plate portion in the wavelength region of 400 to 1200nm and the arithmetic average roughness Ra of the main surface corresponding to the bottom surface of the bottom plate portion of each of the obtained glass samples having three-dimensional shapes were measured. The results are shown in Table 1. The obtained glass sample having a three-dimensional shape was found to have no decrease in transmittance due to devitrification or the like, and the flatness of the bottom plate portion and the smoothness of the surface were ensured to such an extent that the glass sample could be used as the front surface portion of the display.
The average transmittance is determined by obtaining an average value of the transmittances measured at 5nm intervals in a wavelength range of 400 to 1200nm using a Spectrophotometer (Hitachi U-4100 Spectrophotometer). The arithmetic mean roughness Ra was determined by measuring each sample 2 times with a stylus gauge (Tencor Alpha-Step500) while setting the needle diameter to 5 μm, the needle pressure to 10mg, and the needle scanning speed to 50 μm/sec, and determining the average value.
(chemical strengthening treatment)
The obtained glass sample having a three-dimensional shape was subjected to two-stage chemical strengthening treatment to obtain a chemically strengthened glass sample having a three-dimensional shape. The first chemical strengthening treatment uses a chemical strengthening agent containing sodium nitrate (NaNO) in a weight ratio of 6: 43) And potassium nitrate (KNO)3) The mixed salt of (2) is melted at a temperature of 420 DEG CThe sample was immersed in the molten salt bath for 5 hours. Next, as a second chemical strengthening treatment, the sample was immersed in a molten potassium nitrate bath maintained at 370 ℃ for 3 hours. The sample was taken out, cooled to room temperature, washed and dried.
(measurement of stress distribution)
In order to confirm the effect of chemical strengthening by hot working, the compressive stress distribution of a chemically strengthened sample obtained by hot working at 670 ℃ was measured. Surface compressive stress C was measured using a stress distribution measuring apparatus (FSM-6000 and SLP-1000 manufactured by TOYO CORPORATION)S(unit: MPa), compressive stress layer thickness DOC (unit: μm), and compressive stress distribution in the depth direction from the surface. CS is 980MPa, and DOC is 120 μm. The obtained stress distribution curve is shown in fig. 12. As a comparative object, measurement results of a sample (ref. product) obtained by chemically strengthening a plate glass that has not been subjected to hot working under the same conditions are shown together. In the case of the scale of fig. 12, it was confirmed that the curve was repeated. Fig. 13 is a partially enlarged view. The difference was found to be slight.
(surface Na ion distribution)
The Na concentration distribution in the depth direction from the surface was evaluated using an X-ray microanalyzer having a sputter etching function. The sample was used for stress distribution measurement. The results are shown in FIG. 14. As a result, it was confirmed that almost no difference was observed in the stress distribution in the depth direction (fig. 12), and almost no difference was observed in the concentration distribution of Na ions in the depth direction.
From the evaluation results of the compressive stress distribution and the Na ion concentration distribution, it was confirmed that: the effect of the chemical strengthening treatment by hot working at 670 ℃ is slight.
[ examples 2 to 23]
Glass samples were prepared in the same manner as in example 1 with respect to the glass compositions of examples 2 to 23 in tables 2 to 4, and the measured density ρ, the thermal expansion coefficient α, the yield point At, the glass transition point Tg, and the melting point T were measured2Operating point T4Liquid phase temperature TLThe results are shown in tables 2 to 4.
For examples 2 and 3, the test was also conductedDefining a softening point T7.6And the like. The results are shown in Table 5. In addition, the temperature-viscosity curve is shown in fig. 11. In fig. 11, reference numerals 11, 12, and 13 show the measurement results of the glass compositions of examples 1, 2, and 3, respectively. Curves 11-13 are temperature-viscosity curves suitable for use in compression molding.
The glass composition (expressed in mass%) and various measurement results are shown in the table below.
[ Table 1]
[ Table 2]
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 | |
| SiO2 | 65.2 | 63.4 | 65.4 | 65.1 | 65.3 | 64.4 | 64.7 | 65.8 | 65.3 |
| Al2O3 | 15.9 | 16.4 | 16.3 | 16.5 | 15 | 13.5 | 12.6 | 8.7 | 7 |
| Li2O | 3.9 | 3.5 | 3.7 | 3.9 | 4.9 | 4.9 | 4.4 | 6.1 | 5.7 |
| Na2O | 11.4 | 10.4 | 8.7 | 11 | 11.4 | 14.7 | 16.3 | 13.8 | 12.9 |
| K2O | 0.4 | 0.4 | 0.4 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| |
1 | 1.9 | 1.8 | 1 | 1.3 | 0.8 | 0.4 | 1 | 2.5 |
| CaO | 2.1 | 3.9 | 3.6 | 1.9 | 1.5 | 1.1 | 1 | 4 | 6 |
| Fe2O3 | 0.1 | 0.1 | 0.1 | 0.09 | 0.08 | 0.1 | 0.1 | 0.1 | 0.1 |
| ρ(g/cm3) | 2.46 | 2.48 | 2.46 | 2.51 | 2.49 | 2.46 | 2.46 | 2.46 | 2.51 |
| α(×10-7/℃) | 93 | 89 | 86 | 92 | 96 | 104 | 106 | 108 | 106 |
| At(℃) | 551 | 551 | 564 | 563 | 528 | 501 | 506 | 474 | 494 |
| Tg(℃) | 495 | 511 | 520 | 478 | 437 | 410 | 418 | 390 | 425 |
| T2(℃) | 1541 | 1521 | 1592 | 1389 | 1360 | 1285 | 1264 | 1257 | 1265 |
| T4(℃) | 1037 | 1041 | 1084 | 1042 | 999 | 947 | 943 | 900 | 912 |
| TL(℃) | 901 | 1012 | 1038 | 948 | 901 | 872 | 840 | 780 | 876 |
[ Table 3]
| Example 10 | Example 11 | Example 12 | Example 13 | Example 14 | Example 15 | Example 16 | Example 17 | Example 18 | |
| SiO2 | 64.8 | 62.5 | 61.9 | 68.4 | 67 | 68.5 | 69.1 | 65.7 | 66.8 |
| Al2O3 | 6.9 | 16.3 | 15.2 | 13.4 | 12 | 13.6 | 9.9 | 11.7 | 11.6 |
| Li2O | 4.3 | 3.7 | 4.3 | 2.8 | 2.6 | 3.8 | 3.7 | 4.4 | 2.7 |
| Na2O | 19.7 | 10.6 | 11.6 | 11.3 | 11.2 | 11.1 | 11 | 10.9 | 9.8 |
| K2O | 0.5 | 0.3 | 1 | 0.3 | 0.3 | 0.3 | 0.3 | 0 | 3.1 |
| MgO | 1.1 | 2.1 | 2.8 | 2.5 | 2.3 | 0.9 | 1.9 | 1.3 | 1.9 |
| CaO | 2.6 | 4.4 | 3.1 | 1.2 | 4.5 | 1.7 | 4 | 5.9 | 4 |
| Fe2O3 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| ρ(g/cm3) | 2.45 | 2.47 | 2.47 | 2.47 | 2.47 | 2.61 | 2.46 | 2.49 | 2.46 |
| α(×10-7/℃) | 116 | 90 | 87 | 86 | 93 | 95 | 96 | 96 | 94 |
| At | 479 | - | - | - | - | - | - | - | - |
| Tg(℃) | 411 | - | - | - | - | - | - | - | - |
| T2(℃) | 1168 | 1579 | 1475 | 1548 | 1535 | 15f1 | 1539 | 1491 | 1551 |
| T4(℃) | 872 | 1068 | 1009 | 1052 | 1047 | 1008 | 1008 | 1002 | 1064 |
| TL(℃) | 740 | 1038 | 997 | 1020 | 1020 | 925 | 923 | 961 | 996 |
[ Table 4]
| Example 19 | Example 20 | Example 21 | Example 22 | Example 23 | |
| SiO2 | 68.2 | 66.2 | 66.3 | 66.7 | 67.8 |
| Al2O3 | 11.6 | 13.2 | 14.5 | 11.6 | 11.7 |
| Li2O | 4.3 | 3.6 | 4 | 3.7 | 3.7 |
| Na2O | 11.1 | 10.8 | 8.9 | 12.4 | 12 |
| K2O | 0 | 0.3 | 0 | 0 | 0 |
| MgO | 2.1 | 1.9 | 2 | 2.9 | 2.1 |
| CaO | 2.6 | 3.9 | 4.2 | 2.6 | 2.6 |
| Fe2O3 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| ρ(g/cm3) | 2.46 | 2.47 | 2.49 | 2.47 | 2.47 |
| α(×10-7/℃) | 93 | 92 | 88 | 98 | 96 |
| At | - | - | - | - | - |
| Tg(℃) | - | - | - | - | - |
| T2(℃) | 1546 | 1540 | 1535 | 1503 | 1532 |
| T4(℃) | 1005 | 1024 | 1046 | 1006 | 1012 |
| TL(℃) | 910 | 990 | 1003 | 945 | 924 |
[ Table 5]
| (℃) | Example 1 | Example 2 | Example 3 |
| T7.6 | 691 | 709 | 734 |
| T10 | 580 | 601 | 615 |
| T1a | 496 | 515 | 524 |
| T14.5 | 456 | 475 | 484 |
Industrial applicability
The glass article according to the present invention can be used for various applications, for example, a cover glass of a portable terminal represented by a smartphone or a smart watch, a glass case for housing a main body of the portable terminal, and the like. The glass article according to the present invention can be used as, for example, a display device for mounting on a vehicle, a digital signage device, or the like. The glass article is not limited to being colorless and transparent, and particularly in the case of being used as a glass housing, coloring may be carried out by adding a coloring component.
Claims (12)
1. A glass article having a shape other than a flat plate and having a glass composition,
the glass composition includes, expressed in mass% on an oxide basis:
SiO260% to 70% inclusive,
Al2O36% to 18% inclusive,
Li2O2% or more and 8% or less,
Na2O8% to 20%,
K2O is 0% to 1%,
MgO 0-3%,
CaO in an amount of 1 to 6%,
Fe2O30.01% or more and 0.2% or less.
2. The glass article according to claim 1, comprising: a bottom plate portion, a side plate portion and a bent portion,
the side plate portion is connected to the peripheral edge of the bottom plate portion via the bent portion.
3. The glass article of claim 2, wherein the shape corresponds to at least one selected from the group consisting of a dish, a plate, and a box.
4. The glass article of claim 2 or 3, wherein the side plate portion is thicker than the bottom plate portion.
5. The glass article according to any one of claims 2 to 4, wherein the thickness of the bottom plate portion is 0.3mm or more and 2mm or less.
6. The glass article of any of claims 1-5, wherein Li in the glass composition2The content of O is 2% to 6.1%.
7. A method for manufacturing a glass article, comprising:
forming a sheet glass having the following glass composition from the molten glass raw material; and
the sheet glass is formed into a glass article having a shape other than a flat plate by press molding,
the glass composition includes, expressed in mass% on an oxide basis:
SiO260% to 70% inclusive,
Al2O36% to 18% inclusive,
Li2O2% or more and 8% or less,
Na2O8% to 20%,
K2O is 0% to 1%,
MgO 0-3%,
CaO in an amount of 1 to 6%,
Fe2O30.01% or more and 0.2% or less.
8. A chemically strengthened glass article having a shape other than a flat plate,
a compressive stress layer is provided on the surface,
at least the portion other than the compressive stress layer has the following glass composition,
the glass composition includes, expressed in mass% on an oxide basis:
SiO260% to 70% inclusive,
Al2O36% to 18% inclusive,
Li2O2% or more and 8% or less,
Na2O8% to 20%,
K2O is 0% to 1%,
MgO 0-3%,
CaO in an amount of 1 to 6%,
Fe2O30.01% or more and 0.2% or less.
9. The chemically strengthened glass article of claim 8 wherein the surface compressive stress is 400MPa or greater and the compressive stress layer has a thickness of 60 μm or greater.
10. A method for producing a chemically strengthened glass article, comprising:
forming a sheet glass having the following glass composition from the molten glass raw material;
forming the plate glass into a glass article having a shape other than a plate by press molding; and
the glass article is subjected to a chemical strengthening treatment,
the glass composition includes, expressed in mass% on an oxide basis:
SiO260% to 70% inclusive,
Al2O36% to 18% inclusive,
Li2O2% or more and 8% or less,
Na2O8% to 20%,
K2O is 0% to 1%,
MgO 0-3%,
CaO in an amount of 1 to 6%,
Fe2O30.01% or more and 0.2% or less.
11. A mobile terminal comprising the glass article according to claim 1 to 6, 8 or 9.
12. A display device mounted on a vehicle, comprising the glass article according to claim 1 to 6, 8 or 9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018207981 | 2018-11-05 | ||
| JP2018-207981 | 2018-11-05 | ||
| PCT/JP2019/041217 WO2020095660A1 (en) | 2018-11-05 | 2019-10-18 | Glass product which has three-dimensional shape and method for manufacturing same, and chemically strengthened glass product and method for manufacturing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112969667A true CN112969667A (en) | 2021-06-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980072502.6A Pending CN112969667A (en) | 2018-11-05 | 2019-10-18 | Glass article having three-dimensional shape and method for producing same, chemically strengthened glass article and method for producing same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2020095660A1 (en) |
| KR (1) | KR20210090616A (en) |
| CN (1) | CN112969667A (en) |
| TW (1) | TW202028139A (en) |
| WO (1) | WO2020095660A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113998873A (en) * | 2020-12-31 | 2022-02-01 | 安徽金龙浩光电科技有限公司 | Hot melting process for 3D glass with curved surfaces of different thicknesses |
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| WO2018074335A1 (en) * | 2016-10-18 | 2018-04-26 | 旭硝子株式会社 | Glass for chemical strengthening, chemically strengthened glass and method for manufacturing chemically strengthened glass |
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| JPH1160294A (en) * | 1997-06-10 | 1999-03-02 | Nippon Sheet Glass Co Ltd | Laminated glass for vehicle |
| US9010153B2 (en) | 2008-07-02 | 2015-04-21 | Corning Incorporated | Method of making shaped glass articles |
| JP5622069B2 (en) | 2009-01-21 | 2014-11-12 | 日本電気硝子株式会社 | Tempered glass, tempered glass and method for producing tempered glass |
| US9512029B2 (en) | 2012-05-31 | 2016-12-06 | Corning Incorporated | Cover glass article |
| EP3110769B1 (en) | 2014-02-27 | 2023-04-05 | Corning Incorporated | Ion exchangeable glass article for three-dimensional forming |
| JP6299888B2 (en) | 2015-02-05 | 2018-03-28 | 旭硝子株式会社 | Curved cover glass, manufacturing method thereof, and display member for vehicle |
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2019
- 2019-10-18 CN CN201980072502.6A patent/CN112969667A/en active Pending
- 2019-10-18 JP JP2020556738A patent/JPWO2020095660A1/en active Pending
- 2019-10-18 KR KR1020217012433A patent/KR20210090616A/en not_active Application Discontinuation
- 2019-10-18 WO PCT/JP2019/041217 patent/WO2020095660A1/en active Application Filing
- 2019-10-31 TW TW108139467A patent/TW202028139A/en unknown
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102167507A (en) * | 2010-02-26 | 2011-08-31 | 肖特玻璃科技(苏州)有限公司 | Thin lithium aluminosilicate glass for 3D tight mould pressing |
| US20130189486A1 (en) * | 2010-02-26 | 2013-07-25 | Schott Glass Technologies (Suzhou) Co., Ltd. | Thin lithium-aluminosilicate glass for three dimensional precision molding |
| JP2013028506A (en) * | 2011-07-29 | 2013-02-07 | Central Glass Co Ltd | Cover glass for display |
| JP2013125118A (en) * | 2011-12-14 | 2013-06-24 | Konica Minolta Advanced Layers Inc | Cover glass for display |
| US20150344351A1 (en) * | 2012-07-17 | 2015-12-03 | Corning Incorporated | Ion exchangeable li-containing glass compositions for 3-d forming |
| US20150368145A1 (en) * | 2013-02-07 | 2015-12-24 | Nippon Sheet Glass Company, Limited | Glass composition, glass composition for chemical strengthening, strengthened glass article, and cover glass for display |
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| CN113998873A (en) * | 2020-12-31 | 2022-02-01 | 安徽金龙浩光电科技有限公司 | Hot melting process for 3D glass with curved surfaces of different thicknesses |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20210090616A (en) | 2021-07-20 |
| JPWO2020095660A1 (en) | 2021-09-30 |
| WO2020095660A1 (en) | 2020-05-14 |
| TW202028139A (en) | 2020-08-01 |
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Application publication date: 20210615 |