TEMPERED GLASS AND GLASS TO BE TEMPERED

Abstract

A tempered glass of the present invention includes as a glass composition, in terms of mass %, 40% to 60% of SiO.sub.2, 15% to 25% of Al.sub.2O.sub.3, 0% to 13.5% of B.sub.2O.sub.3, 12% to 24% of Na.sub.2O, and 0% to less than 3% of MgO.

Claims

1. A tempered glass, comprising as a glass composition, in terms of mass %, 40% to 60% of SiO.sub.2, 15% to 25% of Al.sub.2O.sub.3, 0% to 13.5% of B203, 12% to 24% of Na.sub.2O, and 0% to less than 3% of MgO.

2. The tempered glass according to claim 1, comprising as a glass composition, in terms of mass %, 40% to 53% of SiO.sub.2, 15% to 21% of Al.sub.2O.sub.3, 4% to 13.5% of B203, 17% to 24% of Na.sub.2O, and 0.1% to less than 3% of MgO.

3. The tempered glass according to claim 1, comprising as a glass composition, in terms of mass %, 50% to 60% of SiO.sub.2, 21% to 25% of Al.sub.2O.sub.3, 0% to 4% of B203, 3% to 6% of Li.sub.2O, 12% to 17% of Na.sub.2O, 0% to less than 3% of MgO, 0.1% to 3.5% of P.sub.2O.sub.5, and 0.1% to 5% of ZnO.

4. The tempered glass according to claim 1, further comprising 0.01 mass % to 0.1 mass % of ZrO.sub.2, 0.001 mass % to 0.01 mass % of K.sub.2O, and 0.01 mass % to 0.1 mass % of CaO.

5. The tempered glass according to claim 1, wherein the tempered glass has a bending processed portion.

6. The tempered glass according to claim 1, wherein the tempered glass has a compressive stress value CS of a compressive stress layer of 500 MPa or more and a depth of layer DOL of the compressive stress layer of 15 μm or more.

7. The tempered glass according to claim 1, wherein the tempered glass has a softening point of 750° C. or less.

8. The tempered glass according to claim 1, wherein the tempered glass has an annealing point of 600° C. or less.

9. The tempered glass according to claim 1, wherein the tempered glass has a strain point of 500° C. or more.

10. The tempered glass according to claim 1, wherein the tempered glass has a temperature at a viscosity at high temperature of 10.sup.4.0 dPa.Math.s of 1,100° C. or less.

11. The tempered glass according to claim 1, wherein the tempered glass has a value represented by (temperature at a viscosity at high temperature of 10.sup.4.0 dPa.Math.s)−(softening point) of 300° C. or more.

12. The tempered glass according to claim 1, wherein the tempered glass has a liquidus temperature of 1,050° C. or less.

13. The tempered glass according to claim 1, wherein the tempered glass has a liquidus viscosity of 10.sup.4.3 dPa.Math.s or more.

14. The tempered glass according to claim 1, wherein the tempered glass has a thermal expansion coefficient of from 80×10.sup.−7/° C. to 110×10.sup.−7/° C.

15. A glass to be tempered, which is to be subjected to ion exchange treatment, the glass to be tempered comprising as a glass composition, in terms of mass %, 40% to 60% of SiO.sub.2, 15% to 25% of Al.sub.2O.sub.3, 0% to 13.5% of B.sub.2O.sub.3, 12% to 24% of Na.sub.2O, and 0% to less than 3% of MgO.

16. The glass to be tempered according to claim 15, comprising as a glass composition, in terms of mass %, 40% to 53% of SiO.sub.2, 15% to 21% of Al.sub.2O.sub.3, 4% to 13.5% of B.sub.2O.sub.3, 17% to 24% of Na.sub.2O, and 0.1% to less than 3% of MgO.

17. The glass to be tempered according to claim 15, comprising as a glass composition, in terms of mass %, 50% to 60% of SiO.sub.2, 21% to 25% of Al.sub.2O.sub.3, 0% to 4% of B203, 3% to 6% of Li.sub.2O, 12% to 17% of Na.sub.2O, 0% to less than 3% of MgO, 0.1% to 3.5% of P.sub.2O.sub.5, and 0.1% to 5% of ZnO.

18. The tempered glass according to claim 2, further comprising 0.01 mass % to 0.1 mass % of ZrO.sub.2, 0.001 mass % to 0.01 mass % of K.sub.2O, and 0.01 mass % to 0.1 mass % of CaO.

19. The tempered glass according to claim 3, further comprising 0.01 mass % to 0.1 mass % of ZrO.sub.2, 0.001 mass % to 0.01 mass % of K.sub.2O, and 0.01 mass % to 0.1 mass % of CaO.

Description

DESCRIPTION OF EMBODIMENTS

[0033] A tempered glass of the present invention comprises as a glass composition, in terms of mass %, 40% to 60% of SiO.sub.2, 15% to 25% of Al.sub.2O.sub.3, 0% to 13.5% of B.sub.2O.sub.3, 12% to 24% of Na.sub.2O, and 0% to less than 3% of MgO. The reasons why the contents of the components are restricted within the above-mentioned ranges are described below. In the descriptions of the ranges of the contents of the components, the expression “%” represents “mass %” unless otherwise stated.

[0034] SiO.sub.2 is a component which forms a glass network. The upper limit of the content range of SiO.sub.2 is preferably 40% or more, 42% or more, 44% or more, 45% or more, 46% or more, 48% or more, or 49% or more, particularly preferably 50% or more, and the lower limit thereof is preferably 60% or less, 55% or less, 53% or less, 52% or less, 51% or less, 50% or less, or less than 50%, particularly preferably 49% or less. When the content of SiO.sub.2 is too small, it becomes difficult to cause vitrification. In addition, a thermal expansion coefficient is excessively increased, with the result that thermal shock resistance is liable to be reduced. Meanwhile, when the content of SiO.sub.2 is too large, meltability, formability, and bending processability are liable to be reduced.

[0035] Al.sub.2O.sub.3 is a component which improves ion exchange performance, and is also a component which increases a strain point and a Young's modulus. The content of Al.sub.2O.sub.3 is from 15% to 25%. A suitable upper limit of the content range of Al.sub.2O.sub.3 is 23% or less, 21% or less, 20% or less, or 19% or less, particularly 18.7% or less. A suitable lower limit of the content range of Al.sub.2O.sub.3 is 16% or more, 17% or more, or 18% or more, particularly 18.5% or more. When the ion exchange performance is preferentially improved over devitrification resistance, a suitable lower limit of the content range of Al.sub.2O.sub.3 is 19% or more, 20% or more, or 21% or more, particularly 22% or more. When the content of Al.sub.2O.sub.3 is too small, there is a risk in that the ion exchange performance cannot be exhibited sufficiently. Meanwhile, when the content of Al.sub.2O.sub.3 is too large, the meltability, the formability, and the bending processability are liable to be reduced. Further, a devitrified crystal is liable to be precipitated in the glass, and in particular, it becomes difficult to form a glass sheet by an overflow down-draw method or the like.

[0036] B.sub.2O.sub.3 is a component which reduces the softening point, and is also a component which reduces a liquidus temperature, a viscosity at high temperature, and a density. The content of B.sub.2O.sub.3 is from 0% to 13.5%. A suitable upper limit of the content range of B.sub.2O.sub.3 is 13% or less or 12.5% or less, particularly 12% or less. When the ion exchange performance is preferentially improved over a reduction in softening point, a suitable upper limit of the content range of B.sub.2O.sub.3 is 8% or less or 6% or less, particularly 4% or less. A suitable lower limit of the content range of B.sub.2O.sub.3 is 4% or more, 6% or more, 7.5% or more, 8% or more, 8.4% or more, 9% or more, 10% or more, or 11% or more, particularly 12% or more. When the content of B.sub.2O.sub.3 is too small, it becomes difficult to obtain the above-mentioned effects. Meanwhile, when the content of B.sub.2O.sub.3 is too large, the ion exchange performance, water resistance, a liquidus viscosity, the strain point, and the like are liable to be reduced.

[0037] The content of Al.sub.2O.sub.3+B.sub.2O.sub.3 is preferably from 25% to 35%, from 26% to 34%, or from 27% to 33%, particularly preferably from 28% to 32%. When the content of Al.sub.2O.sub.3+B.sub.2O.sub.3 is outside the above-mentioned ranges, it becomes difficult to achieve both the ion exchange performance and the bending processability. The “Al.sub.2O.sub.3+B.sub.2O.sub.3” refers to the total content of Al.sub.2O.sub.3 and B.sub.2O.sub.3.

[0038] Na.sub.2O is a component which improves the ion exchange performance, and is also a component which improves the meltability, the formability, and the bending processability. Further, Na.sub.2O is a component which improves the devitrification resistance. The content of Na.sub.2O is from 12% to 24%. A suitable upper limit of the content range of Na.sub.2O is 23% or less, 22.5% or less, 22% or less, 21.5% or less, or 21% or less, particularly 20.5% or less. When the strain point and the thermal shock resistance are preferentially maintained at the expense of the bending processability, a suitable upper limit of the content range of Na.sub.2O is 20% or less, 19% or less, or 18% or less, particularly 17% or less. A suitable lower limit of the content range of Na.sub.2O is 14% or more, 16% or more, 17% or more, 17.5% or more, 18% or more, 18.5% or more, 19% or more, or 19.5% or more, particularly 20% or more. When the content of Na.sub.2O is too small, it becomes difficult to obtain the above-mentioned effects. Meanwhile, when the content of Na.sub.2O is too large, the strain point tends to be reduced, and a component balance of the glass composition tends to be lost, with the result that the devitrification resistance is reduced contrarily. Further, the thermal expansion coefficient is excessively increased, with the result that the thermal shock resistance is reduced, and it becomes difficult to match the thermal expansion coefficient with those of peripheral materials.

[0039] From the viewpoint of expanding the range of selection of manufacturing conditions of thermal bending processing, the content of B.sub.2O.sub.3+Na.sub.2O is preferably from 25% to 33%, from 26% to 32%, or from 27% to 31%, particularly preferably from 28% to 30%. When the content of B.sub.2O.sub.3+Na.sub.2O is too small, the bending processability is liable to be reduced. Meanwhile, when the content of B.sub.2O.sub.3+Na.sub.2O is too large, the liquidus viscosity and the strain point are liable to be reduced. The “B.sub.2O.sub.3+Na.sub.2O” refers to the total content of B.sub.2O.sub.3 and Na.sub.2O.

[0040] The content of Al.sub.2O.sub.3+B.sub.2O.sub.3+Na.sub.2O is preferably 34% or more, 37% or more, 40% or more, 43% or more, 45% or more, or 47% or more, particularly preferably from 49% to 57%. With this, both the ion exchange performance and the bending processability are easily achieved. Herein, the “Al.sub.2O.sub.3+B.sub.2O.sub.3+Na.sub.2O” refers to the total content of Al.sub.2O.sub.3, B.sub.2O.sub.3, and Na.sub.2O.

[0041] The mass ratio Al.sub.2O.sub.3/Na.sub.2O is preferably from 0.7 to 1.15, from 0.75 to 1.1, or from 0.8 to 1.05, particularly preferably from 0.85 to 1.0 from the viewpoint of expanding the range of selection of manufacturing conditions of thermal bending processing, and is preferably from 1.4 to 2.3, from 1.5 to 2.2, or from 1.6 to 2.1, particularly preferably from 1.7 to 2.0 from the viewpoints of increasing the Young's modulus and the specific Young's modulus. The mass ratio (Al.sub.2O.sub.3+B.sub.2O.sub.3)/(B.sub.2O.sub.3+Na.sub.2O) is preferably from 0.7 to 1.15, from 0.75 to 1.1, or from 0.8 to 1.05, particularly preferably from 0.85 to 1.0 from the viewpoint of expanding the range of selection of manufacturing conditions of thermal bending processing, and is preferably from 1.4 to 2.2, from 1.5 to 2.1, or from 1.6 to 2.0, particularly preferably from 1.7 to 1.9 from the viewpoints of increasing the Young's modulus and the specific Young's modulus. The “Al.sub.2O.sub.3/Na.sub.2O” refers to a value obtained by dividing the content of Al.sub.2O.sub.3 by the content of Na.sub.2O. The “(Al.sub.2O.sub.3+B.sub.2O.sub.3)/(B.sub.2O.sub.3+Na.sub.2O)” refers to a value obtained by dividing the total content of Al.sub.2O.sub.3 and B.sub.2O.sub.3 by the total content of B.sub.2O.sub.3 and Na.sub.2O.

[0042] MgO is a component which improves the meltability, the formability, the bending processability, and the Young's modulus. However, when the content of MgO is too large, the glass is liable to be devitrified at the time of forming and bending processing. In addition, the ion exchange performance is liable to be reduced. Therefore, the content of MgO is from 0% to less than 3%, preferably from 0.1% to less than 3%, from 0.5% to 2.6%, from 1% to 2.4%, or from 1.5% to 2.2%, particularly preferably from 1.7% to less than 20.

[0043] In addition to the above-mentioned components, for example, the following components may be introduced.

[0044] Li.sub.2O is a component which improves the ion exchange performance, and is also a component which improves the meltability, the formability, and the bending processability. However, when the content of Li.sub.2O is too large, the liquidus viscosity is reduced, and the glass is liable to be devitrified at the time of forming and bending processing. Therefore, the content of Li.sub.2O is preferably from 0% to 10%, from 0% to 8%, from 0% to 6%, from 0% to 4%, from 0% to 3%, from 0% to 2%, from 0% to 1%, or from 0% to 0.5%, particularly preferably from 0% to 0.1%. The glass is desirably substantially free of Li.sub.2O (less than 0.01%). When the ion exchange performance and the bending processability are preferentially improved over the devitrification resistance, the content of Li.sub.2O is preferably from 0.1% to 10%, from 1% to 8%, or from 2% to 7%, particularly preferably from 3% to 6%.

[0045] K.sub.2O is a component which improves the ion exchange performance, and is also a component which has a high increasing effect on a depth of layer among alkali metal oxides. In addition, K.sub.2O is a component which improves the meltability, the formability, and the bending processability. However, when the content of K.sub.2O is too large, the strain point and the devitrification resistance are liable to be reduced. Therefore, a suitable upper limit of the content range of K.sub.2O is 3% or less, 2% or less, 1% or less, 0.1% or less, 0.01% or less, 0.009% or less, or 0.008% or less, particularly 0.007% or less, and a suitable lower limit thereof is 0% or more, 0.001% or more, 0.003% or more, or 0.004% or more, particularly 0.005% or more.

[0046] Li.sub.2O, Na.sub.2O, and K.sub.2O are each a component which improves the ion exchange performance, the meltability, the formability, and the bending processability. However, when the content of Li.sub.2O+Na.sub.2O+K.sub.2O is too large, the strain point and the devitrification resistance are liable to be reduced. Therefore, a suitable lower limit of the content range of Li.sub.2O+Na.sub.2O+K.sub.2O is 17% or more, 18% or more, or 19% or more, particularly 20% or more, and a suitable upper limit thereof is 27% or less or 25% or less, particularly 23% or less. The “Li.sub.2O+Na.sub.2O+K.sub.2O” refers to the total content of Li.sub.2O, Na.sub.2O, and K.sub.2O.

[0047] CaO is a component which improves the meltability, the formability, the bending processability, and the Young's modulus. However, when the content of CaO is too large, the density and the thermal expansion coefficient are excessively increased, the glass is liable to be devitrified, and the ion exchange performance is liable to be reduced. Therefore, the content of CaO is preferably from 0% to 0.5%, from 0.01% to 0.1%, from 0.02% to 0.09%, from 0.03% to 0.08%, or from 0.04% to 0.07%, particularly preferably from 0.05% to 0.06%.

[0048] SrO and BaO are each a component which improves the meltability, the formability, and the bending processability. When the content of SrO and BaO is too large, the ion exchange performance and the devitrification resistance are liable to be reduced. In addition, the density and the thermal expansion coefficient are excessively increased. Therefore, the total content of SrO and BaO (content of SrO+BaO) is preferably 3% or less, 2% or less, 1% or less, 0.8% or less, or 0.5% or less, particularly preferably 0.1% or less. The contents of SrO and BaO are each preferably 2% or less, 1% or less, 0.8% or less, or 0.5% or less, particularly preferably 0.1% or less.

[0049] When the content of MgO+CaO+SrO+BaO is too small, the meltability, the formability, the bending processability, and the Young's modulus are liable to be reduced. Meanwhile, when the content of MgO+CaO+SrO+BaO is too large, the ion exchange performance and the devitrification resistance are liable to be reduced. In addition, the density and the thermal expansion coefficient are excessively increased. Therefore, the content of MgO+CaO+SrO+BaO is preferably from 0.1% to less than 3%, from 0.5% to 2.6%, from 1% to 2.4%, or from 1.5% to 2.2%, particularly preferably from 1.7% to less than 2%. The “MgO+CaO+SrO+BaO” refers to the total content of MgO, CaO, SrO, and BaO.

[0050] When a value of the mass ratio (MgO+CaO+SrO+BaO)/(Li.sub.2O+Na.sub.2O+K.sub.2O) is too large, the devitrification resistance tends to be reduced. Therefore, the value of the mass ratio (MgO+CaO+SrO+BaO)/(Li.sub.2O+Na.sub.2O+K.sub.2O) is preferably 0.2 or less or 0.15 or less, particularly preferably 0.1 or less. The “(MgO+CaO+SrO+BaO)/(Li.sub.2O+Na.sub.2O+K.sub.2O)” refers to a value obtained by dividing the total content of MgO, CaO, SrO, and BaO by the total content of Li.sub.2O, Na.sub.2O, and K.sub.2O.

[0051] ZnO is a component which improves the ion exchange performance. In particular, ZnO is a component which increases a compressive stress value. In addition, ZnO is a component which reduces the viscosity at high temperature without reducing a viscosity at low temperature. However, when the content of ZnO is too large, the glass manifests phase separation, the devitrification resistance is reduced, and the density is liable to be increased. The content of ZnO is preferably from 0% to 5%, from 0.1% to 5%, from 0.1% to 3%, or from 0.1% to 2%, particularly preferably from 0.5% to 1%.

[0052] ZrO.sub.2 is a component which improves the ion exchange performance, the strain point, and the liquidus viscosity. However, when the content of ZrO.sub.2 is too large, the devitrification resistance may be excessively reduced. Therefore, the content of ZrO.sub.2 is preferably from 0% to 0.5%, from 0.01% to 0.1%, from 0.02% to 0.09%, from 0.03% to 0.08%, or from 0.04% to 0.07%, particularly preferably from 0.05% to 0.08%.

[0053] TiO.sub.2 is a component which improves the ion exchange performance, and is also a component which reduces the viscosity at high temperature. However, when the content of TiO.sub.2 is too large, the glass is colored and the devitrification resistance is liable to be reduced. Therefore, the content of TiO.sub.2 is preferably from 0% to 1% or from 0% to 0.5%, particularly preferably from 0% to 0.1%.

[0054] P.sub.2O.sub.5 is a component which improves the ion exchange performance. In particular, P.sub.2O.sub.5 is a component which increases the depth of layer. However, when the content of P.sub.2O.sub.5 is too large, the glass manifests phase separation and the water resistance is liable to be reduced. Therefore, the content of P.sub.2O.sub.5 is preferably 8% or less, 5% or less, 4% or less, 2% or less, 1% or less, 0.5% or less, or 0.2% or less, particularly preferably 0.1% or less. When the depth of layer is preferentially increased at the expense of the water resistance, the content of P.sub.2O.sub.5 is preferably from 0.1% to 5%, from 0.1% to 3.5%, from 0.3% to 3.5%, or from 0.2% to 3%, particularly preferably from 0.5% to 2%.

[0055] As a fining agent, one kind or two or more kinds selected from the group consisting of As.sub.2O.sub.3, Sb.sub.2O.sub.3, CeO.sub.2, SnO.sub.2, F, Cl, and SO.sub.3 may be introduced in an amount of from 0% to 2%. It is preferred to use As.sub.2O.sub.3, Sb.sub.2O.sub.3, and F in an amount as small as possible from the environmental viewpoints, and each content thereof is preferably less than 0.1%. The fining agent is preferably one kind or two or more kinds selected from the group consisting of SnO.sub.2, SO.sub.3, and Cl, particularly preferably SnO.sub.2. The content of SnO.sub.2 is preferably from 0% to 1% or from 0.01% to 0.5%, particularly preferably from 0.1% to 0.6%. When the content of SnO.sub.2 is too large, the devitrification resistance is liable to be reduced. The content of SO.sub.3 is preferably from 0% to 0.1%, from 0.0001% to 0.1%, from 0.0003% to 0.08%, or from 0.0005% to 0.05%, particularly preferably from 0.001% to 0.03%. When the content of SO.sub.3 is too large, SO.sub.3 reboils at the time of melting, with the result that bubble quality is liable to be reduced. The content of Cl is preferably from 0% to 0.5%, from 0% to 0.1%, from 0% to 0.09%, or from 0% to 0.05%, particularly preferably from 0.001% to 0.03%. When the content of Cl is too large, metal wiring is liable to be eroded at the time of forming a metal wiring pattern or the like on the tempered glass.

[0056] Transition metal oxides, such as CoO.sub.3 and NiO, are components which cause intense coloration of glass to reduce a transmittance. Therefore, the content of the transition metal oxides is preferably 0.5% or less or 0.1% or less, particularly preferably 0.05% or less in terms of a total content. It is desired to control the amount of impurities in raw materials and/or cullet of the glass so that the content of the transition metal oxides falls within such ranges.

[0057] Rare earth oxides, such as Nd.sub.2O.sub.3 and La.sub.2O.sub.3, are components which increase the Young's modulus. However, the cost of the raw material itself is high, and when the rare earth oxides are contained in a large amount, the devitrification resistance is liable to be reduced. Therefore, the content of the rare earth oxides is preferably 3% or less, 2% or less, 1% or less, or 0.5% or less, particularly preferably 0.1% or less in terms of a total content.

[0058] It is preferred to use PbO and Bi.sub.2O.sub.3 in an amount as small as possible from the environmental viewpoints, and the contents thereof are each preferably less than 0.1%.

[0059] Components other than the above-mentioned components may be introduced, and the total content thereof is preferably 3% or less, particularly preferably 1% or less.

[0060] Suitable glass composition ranges can each be obtained by appropriately selecting suitable content ranges of the components. Of those, from the viewpoint of expanding the range of selection of manufacturing conditions of thermal bending processing, the glass preferably comprises as a glass composition, in terms of mass %, 40% to 53% of SiO.sub.2, 15% to 21% of Al.sub.2O.sub.3, 4% to 13.5% of B.sub.2O.sub.3, 17% to 24% of Na.sub.2O, and 0.1% to less than 3% of MgO. In addition, from the viewpoints of increasing the Young's modulus and the specific Young's modulus, the glass preferably comprises as a glass composition, in terms of mass %, 50% to 60% of SiO.sub.2, 21% to 25% of Al.sub.2O.sub.3, 0% to 4% of B.sub.2O.sub.3, 3% to 6% of Li.sub.2O, 12% to 17% of Na.sub.2O, 0% to less than 3% of MgO, 0.1% to 3.5% of P.sub.2O.sub.3, and 0.1% to 5% of ZnO.

[0061] In the tempered glass of the present invention, the compressive stress value of the compressive stress layer is preferably 500 MPa or more or 600 MPa or more, particularly preferably 700 MPa or more. As the compressive stress value becomes higher, the mechanical strength of the tempered glass becomes higher. Meanwhile, when an excessively large compressive stress is formed in the surface, micro cracks are generated on the surface, and the mechanical strength of the tempered glass may be reduced contrarily. Further, the formation of an excessively large compressive stress in the surface may cause an excessively high internal tensile stress. Therefore, the compressive stress value is preferably 1,300 MPa or less.

[0062] The depth of layer is preferably 15 μm or more or 20 μm or more, particularly preferably 30 μm or more. As the depth of layer becomes larger, the tempered glass is less liable to be broken even when the tempered glass has a deep flaw. Meanwhile, when the depth of layer is too large, there is a risk in that the internal tensile stress is excessively increased. Therefore, the depth of layer is preferably 100 μm or less or 80 μm or less, particularly preferably less than 50 μm.

[0063] The internal tensile stress is preferably 200 MPa or less, 150 MPa or less, or 100 MPa or less, particularly preferably 70 MPa or less. As the internal tensile stress becomes smaller, the probability that the tempered glass is broken owing to an internal defect becomes lower. However, when the internal tensile stress is extremely small, the compressive stress value and the depth of layer are liable to be reduced excessively. Therefore, the internal tensile stress is preferably 15 MPa or more or 20 MPa or more, particularly preferably 30 MPa or more. The internal tensile stress refers to a value calculated by the following mathematical formula.

Internal tensile stress=(compressive stress value×depth of layer)/(thickness of glass-depth of layer×2)

[0064] Internal tensile stress (MPa)

[0065] Compressive stress value (MPa)

[0066] Depth of layer (μm)

[0067] Thickness of glass (μm)

[0068] It is preferred that the tempered glass of the present invention have the following characteristics.

[0069] The density is preferably 2.52 g/cm.sup.3 or less, 2.50 g/cm.sup.3 or less, 2.49 g/cm.sup.3 or less, or 2.48 g/cm.sup.3 or less, particularly preferably 2.45 g/cm.sup.3 or less. As the density becomes lower, the weight of the glass can be made lighter. The “density” refers to a value measured by a well-known Archimedes method.

[0070] The strain point is preferably 500° C. or more, 510° C. or more, or 520° C. or more, particularly preferably 530° C. or more. As the strain point becomes higher, the compressive stress layer is less liable to disappear through heat treatment. In addition, when the strain point is high, stress relaxation is less liable to occur at the time of ion exchange, and hence a high compressive stress value is easily ensured.

[0071] The annealing point is preferably 580° C. or less, 570° C. or less, or 560° C. or less, particularly preferably 550° C. or less. As the annealing point becomes lower, an annealing time period and a cooling time period after the thermal bending processing can be shortened more.

[0072] The softening point is preferably 750° C. or less, 720° C. or less, or 710° C. or less, particularly preferably 700° C. or less. As the softening point becomes lower, the thermal bending processing can be performed at lower temperature. As a result, the annealing time and cooling time after the thermal bending processing can be shortened. In addition, as the softening point becomes lower, burden on a mold becomes smaller when press molding is performed. Deterioration of a mold is often caused by a reaction between a metal material to be used for a mold and oxygen in the air, that is, an oxidation reaction. Such oxidation reaction allows the formation of a reaction product on the surface of the mold. As a result, press molding does not provide a predetermined shape in some cases. In addition, when the oxidation reaction occurs, ions in the glass are reduced to produce bubbles in some cases. The degree of the oxidation reaction varies depending on the press molding temperature or the softening point. As the press molding temperature and the softening point become lower, the oxidation reaction can be suppressed more.

[0073] The temperature at a viscosity at high temperature of 10.sup.4.0 dPa.Math.s is preferably 1,100° C. or less or 1,080° C. or less, particularly preferably 1,050° C. or less. As the temperature at a viscosity at high temperature of 10.sup.4.0 dPa.Math.s becomes lower, a forming temperature is reduced more, and hence the manufacturing cost of the tempered glass can be reduced more.

[0074] A value represented by (temperature at a viscosity at high temperature of 10.sup.4.0 dPa.Math.s)−(softening point) is preferably 300° C. or more, 310° C. or more, 320° C. or more, or 330° C. or more, particularly preferably 340° C. or more. The thermal bending processing is performed in a temperature region between the temperature at a viscosity at high temperature of 10.sup.4.0 dPa.Math.s and the softening point. Therefore, when the value represented by (temperature at a viscosity at high temperature of 10.sup.4.0 dPa.Math.s)−(softening point) is too small, in the case where the thermal bending processing is performed in a high temperature region, a temperature range suitable for the thermal bending processing is narrowed, and hence the range of selection of manufacturing conditions of the thermal bending processing is narrowed.

[0075] The temperature at a viscosity at high temperature of 10.sup.2.5 dPa.Math.s corresponds to a melting temperature, and is preferably 1,450° C. or less, 1,420° C. or less, 1,400° C. or less, 1,380° C. or less, or 1,350° C. or less, particularly preferably 1,320° C. or less. As the temperature at 10.sup.2.5 dPa.Math.s becomes lower, burden on a manufacturing facility, such as a melting furnace, becomes smaller at the time of melting, and bubble quality can be improved more. That is, as the temperature at 10.sup.2.5 dPa.Math.s becomes lower, the glass can be manufactured more inexpensively. The “temperature at a viscosity at high temperature of 10.sup.2.5 dPa.Math.s” refers to a value measured by a platinum sphere pull up method.

[0076] The thermal expansion coefficient is preferably from 80×10.sup.−7/° C. to 110×10.sup.−7/° C., particularly preferably from 85×10.sup.−7/° C. to 100×10.sup.−7/° C. When the thermal expansion coefficient falls within the above-mentioned ranges, it becomes easy to match the thermal expansion coefficient with that of a peripheral member, such as a metal or an organic adhesive, thereby making it possible to prevent the separation of the peripheral member.

[0077] The liquidus temperature is preferably 1,050° C. or less or 1,000° C. or less, particularly preferably 950° C. or less. When the liquidus temperature is high, a devitrified crystal is liable to be precipitated at the time of forming. The liquidus viscosity is preferably 10.sup.4.3 dPa.Math.s or more or 10.sup.4.5 dPa.Math.s or more, particularly preferably 10.sup.5.0 dPa.Math.s or more. When the liquidus viscosity is low, a devitrified crystal is liable to be precipitated at the time of forming.

[0078] The Young's modulus is preferably 70 GPa or more, 74 GPa or more, or from 75 GPa to 100 GPa, particularly preferably from 76 GPa to 90 GPa. The specific Young's modulus is preferably 28 GPa/g.Math.cm.sup.3 or more, 30 GPa/g.Math.cm.sup.3 or more, or from 31 GPa/g.Math.cm.sup.−3 to 35 GPa/g.Math.cm.sup.3, particularly preferably from 31.5 GPa/g.Math.cm.sup.3 to 34 GPa/g.Math.cm.sup.−3. When the Young's modulus or the specific Young's modulus is low, the glass is liable to be deflected when used as a cover glass. The “Young's modulus” may be calculated by a well-known resonance method, and the “specific Young's modulus” refers to a value obtained by dividing the Young's modulus by the density.

[0079] The thickness of the tempered glass (sheet thickness when the tempered glass has a sheet shape) is preferably 0.2 mm or more, 0.3 mm or more, or 0.5 mm or more, particularly preferably 0.7 mm or more. With this, the mechanical strength of the tempered glass can be maintained. Meanwhile, when the thickness of the tempered glass is large, the bending processability is liable to be reduced. Further, it becomes difficult to achieve weight saving of the tempered glass. Therefore, the thickness of the tempered glass is preferably 2.0 mm or less, 1.5 mm or less, or 1.0 mm or less, particularly preferably 0.85 mm or less.

[0080] It is preferred that the tempered glass of the present invention have an unpolished surface. It is particularly preferred that the entire effective surface except end edge areas be unpolished. In addition, the average surface roughness (Ra) of the unpolished surface is preferably 10 A or less or 5 A or less, particularly preferably 2 A or less. With this, an appropriate gloss can be imparted to the tempered glass. As a result, the tempered glass is easily applied to an exterior part. In addition, when the surface is unpolished, the tempered glass is less liable to be broken by a point impact. An unpolished glass sheet having high surface accuracy can be obtained when the molten glass is formed by an overflow down-draw method. Herein, the “average surface roughness (Ra)” refers to a value measured by a method in conformity with SEMI D7-97 “FPD Glass Substrate Surface Roughness Measurement Method.” In order to prevent a situation in which the glass is broken from an end surface (cut surface), an end edge region or the end surface is preferably subjected to chamfering processing.

[0081] The tempered glass of the present invention preferably has a bending processed portion, such as a bent portion or a curved portion. With this, the design property of an exterior part or the like can be improved.

[0082] The bent portion is formed preferably in at least one end edge area of the tempered glass having a rectangular shape, more preferably in opposing end edge areas. With this, when the tempered glass is applied to an exterior part or the like, its end surface is less liable to be exposed to an outside, and hence the design property of the exterior part or the like can be improved. Besides, a situation in which the tempered glass is broken from the end surface by a physical impact is easily prevented.

[0083] The tempered glass of the present invention preferably has a flat sheet portion and the bent portion. With this, when the tempered glass is applied to as an exterior part or the like, the flat sheet portion is allowed to correspond to an operating area of a touch panel, and the surface of the bent portion (excluding the end surface) is allowed to correspond to an external side surface. In addition, in the case of allowing the surface of the bent portion (excluding the end surface) to correspond to the external side surface, the end surface is less liable to be exposed to the outside, and a situation in which the tempered glass is broken from the end surface by a physical impact is easily prevented.

[0084] The curved portion is preferably formed in the overall width direction or in the overall length direction of the tempered glass. The curved portion is more preferably formed in the overall width direction and in the overall length direction of the tempered glass. With this, a stress is less liable to be concentrated in a specific portion, and when the tempered glass is applied to a window glass of an automobile or the like, the tempered glass is less liable to be broken by a physical impact. When the curved portion is formed in the overall width direction and in the overall length direction, it is preferred to set the degree of curve in the width direction and the degree of curve in the length direction to differ from each other. With this, the design property of the window glass of an automobile or the like can be improved.

[0085] A glass to be tempered of the present invention is a glass to be tempered, which is to be subjected to ion exchange treatment, the glass to be tempered comprising as a glass composition, in terms of mass %, 40% to 60% of SiO.sub.2, 15% to 25% of Al.sub.2O.sub.3, 0% to 13.5% of B.sub.2O.sub.3, 12% to 24% of Na.sub.2O, and 0% to less than 3% of MgO. With this, both the ion exchange performance and the bending processability can be achieved. In addition, the glass to be tempered of the present invention has technical features (suitable glass composition range, suitable characteristics, and the like) similar to those of the tempered glass of the present invention. Therefore, a detailed description of the glass to be tempered of the present invention is omitted for convenience.

[0086] The glass to be tempered of the present invention may be produced by placing a glass batch which is prepared to have a predetermined glass composition in a continuous melting furnace, melting the glass batch at from 1,500° C. to 1,650° C., fining the resultant, feeding the resultant to a forming apparatus, and forming the molten glass, and annealing the glass.

[0087] Various forming methods may be adopted as a forming method. For example, there may be adopted forming methods, such as down-draw methods (e.g., an overflow down-draw method, a slot down method, and a re-draw method), a float method, and a roll out method. In addition, the molten glass may be directly formed into a predetermined shape by press molding.

[0088] The glass to be tempered of the present invention is preferably formed by an overflow down-draw method. With this, a glass which is unpolished and has improved surface quality can be produced. This is because in the case of adopting the overflow down-draw method, a surface to be the surface of the glass sheet does not come into contact with a trough-shaped refractory, and is formed in the form of a free surface. Herein, the overflow down-draw method is a method in which a molten glass is allowed to overflow from both sides of a heat-resistant trough-shaped structure, and the overflown molten glasses are down-drawn downwardly while combining them at the lower end of the trough-shaped structure, to thereby produce a glass to be tempered having a flat sheet shape.

[0089] The tempered glass can be obtained by subjecting the glass to be tempered to ion exchange treatment. The ion exchange treatment may be performed by, for example, immersing the glass to be tempered in a KNO.sub.3 molten salt at from 400° C. to 550° C. for from 1 hour to 8 hours. The conditions of the ion exchange treatment may be optimally selected in consideration of the viscosity characteristics, applications, thickness, internal tensile stress, or the like of the glass.

[0090] The thermal bending processing is preferably performed on a glass to be tempered before the ion exchange treatment, and also the grinding and/or polishing of the end surface is preferably performed on the glass to be tempered before the ion exchange treatment. Further, it is also preferred to perform the grinding and/or polishing of the end surface after the thermal bending processing in order to remove the dimensional error or the like after the thermal bending processing.

[0091] The thermal bending processing is preferably performed on a glass to be tempered having a flat sheet shape. In addition, as a preferred thermal bending processing method, there is given a method involving subjecting the glass to be tempered having a flat sheet shape to press molding with a mold. With this, the dimensional accuracy of the glass to be tempered can be increased after the thermal bending processing.

[0092] In addition, as another preferred thermal bending processing method, there is given a method involving sandwiching the glass to be tempered having a flat sheet shape in a sheet thickness direction with a certain mold to support the glass to be tempered, to thereby allow elastic deformation of the glass to be tempered into a curved state, and then, while keeping this state, subjecting the glass to be tempered, which has been elastically deformed, to heat treatment, to thereby obtain a glass to be tempered having a curved portion (particularly a glass to be tempered having a curved portion in which the entire glass is curved in an arc in a sheet width direction). By such method, a flaw to be caused on the surface of the glass to be tempered owing to displacement or the like in association with the operation of allowing the elastic deformation can be suitably avoided. As a result, a defect or a flaw can be prevented on the surface of the curved portion as much as possible.

[0093] A temperature of the thermal bending processing is preferably (annealing point−10°) C. or more, (annealing point−5)° C. or more, or (annealing point+5)° C. or more, particularly preferably (annealing point+20)° C. or more. With this, the thermal bending processing can be performed in a short time period. Meanwhile, the temperature of the thermal bending processing is preferably (softening point−5)° C. or less, (softening point−15)° C. or less, or (softening point−20)° C. or less, particularly preferably (softening point−30)° C. or less. With this, surface smoothness is less liable to be impaired through the thermal bending processing, and dimensional accuracy after the thermal bending processing can be improved as well.

EXAMPLES

Example 1

[0094] Now, the present invention is described in detail based on Examples. The following Examples are merely illustrative. The present invention is by no means limited to the following Examples.

[0095] Examples of the present invention (Nos. 1 to 10) are shown in Table 1.

TABLE-US-00001 TABLE 1 Glass composition [mass %] No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 No. 9 No. 10 SiO.sub.2 50.25 47.98 44.23 52.57 48.60 52.07 58.98 56.93 57.47 54.36 Al.sub.2O.sub.3 15.59 18.56 18.45 18.59 18.48 18.67 21.91 21.85 22.05 24.69 B.sub.2O.sub.3 12.78 8.45 12.60 8.46 12.62 4.25 0.00 2.16 0.00 2.13 P.sub.2O.sub.5 0.00 0.00 0.00 0.00 0.00 0.00 1.04 1.04 1.04 1.02 Li.sub.2O 0.00 0.00 0.00 0.00 0.00 0.00 3.88 3.87 3.90 3.82 Na.sub.2O 18.96 22.57 22.44 18.08 17.97 22.70 12.63 12.60 12.71 12.44 K.sub.2O 0.002 0.010 0.004 0.000 0.001 0.000 0.004 0.003 0.002 0.001 MgO 1.85 1.83 1.82 1.84 1.83 1.85 0.00 0.00 1.26 0.00 CaO 0.10 0.07 0.00 0.00 0.03 0.00 0.00 0.00 0.00 0.00 ZnO 0.00 0.00 0.00 0.00 0.00 0.00 1.47 1.46 1.48 1.45 ZrO.sub.2 0.01 0.07 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 SnO.sub.2 0.46 0.46 0.46 0.46 0.46 0.46 0.09 0.09 0.09 0.09 Density [g/cm.sup.3] 2.44 2.48 2.47 2.46 2.45 2.45 2.46 2.46 2.48 2.46 Strain point [° C.] 530 522 525 520 511 515 486 478 489 494 Annealing point [° C.] 567 558 561 555 545 552 528 518 530 535 Softening point [° C.] 740 735 736 721 700 736 738 718 738 743 10.sup.4.0 dPa .Math. s [° C.] 1,073 1,081 1,069 1,039 1,001 1,074 1,118 1,100 1,100 1,125 10.sup.3.0 dPa .Math. s [° C.] 1,270 1,275 1,257 1,232 1,180 1,266 1,329 1,309 1,298 1,325 10.sup.2.5 dPa .Math. s [° C.] 1,400 1,403 1,381 1,357 1,301 1,392 1,461 1,441 1,423 1,449 10.sup.4.0 dPa .Math. s-softening 334 346 334 318 302 339 380 383 362 383 point [° C.] Thermal expansion coefficient 87 101 97 93 92 104 94 91 96 92 [×10.sup.−7/° C.] (30° C.-380° C.) Young's modulus [GPa] 70 70 69 70 69 70 78 79 80 79 Specific Young's modulus 28.5 28.3 28.1 28.4 28.0 28.6 31.7 32.1 32.3 32.1 [GPa/(g/cm.sup.3)] Liquidus temperature [° C.] 938 1,023 991 973 951 1,025 Not Not 902 904 measured measured Liquidus viscosity [dPa .Math. s] 5.0 4.4 4.6 4.5 4.4 4.3 Not Not 5.5 5.6 measured measured Compressive stress value 793 718 783 752 735 587 711 702 905 932 [MPa] Depth of layer [μm] 21 31 26 22 18 37 16 13 15 14

[0096] Each sample was prepared as described below. First, glass raw materials were blended so as to achieve the glass composition shown in the table, and the resultant was melted at 1,600° C. for 8 hours by using a platinum pot. Next, the molten glass was poured onto a carbon sheet and formed into a flat sheet shape. Various properties of the resultant glass sheet were evaluated.

[0097] The density is a value measured by a well-known Archimedes method.

[0098] The strain point and the annealing point are values measured based on a method of ASTM C336. The softening point is a value measured based on a method of ASTM C338.

[0099] The temperatures at viscosities at high temperature of 10.sup.4.0 dPa.Math.s, 10.sup.3.0 dPa.Math.s, and 10.sup.2.5 dPa.Math.s are values measured by a platinum sphere pull up method.

[0100] The thermal expansion coefficient is a value measured with a dilatometer and is an average value in the temperature range of from 30° C. to 380° C.

[0101] The Young's modulus is a value measured by a flexural resonance method. In addition, the specific Young's modulus is a value obtained by dividing the Young's modulus by the density.

[0102] The liquidus temperature is a value obtained as follows: the glass is pulverized; then glass powder that passes through a standard 30-mesh sieve (sieve opening: 500 μm) and remains on a 50-mesh sieve (sieve opening: 300 μm) is placed in a platinum boat and kept for 24 hours in a gradient heating furnace; and a temperature at which a crystal is deposited is measured. The liquidus viscosity is a value obtained by measuring the viscosity of glass at a liquidus temperature by a platinum ball pull up method.

[0103] The samples were each immersed in a KNO.sub.3 bath kept at 430° C. for 4 hours to be subjected to ion exchange treatment, to thereby obtain tempered glasses. In each of the tempered glasses, the compressive stress value and depth of layer of the compressive stress layer were measured by observing the number of interference fringes and the intervals of the interference fringes using a surface stress meter (FSM-6000 manufactured by Orihara Industrial Co., Ltd.). At the time of measurement, a refractive index was set to 1.52 and an optical elastic constant was set to 30 [(nm/cm)/MPa] for each sample.

[0104] In preparing each sample in the table, a molten glass was flown, formed into a flat sheet shape, and then the resultant was optically polished before the ion exchange treatment, for convenience of description of the present invention. When the tempered glass is manufactured on an industrial scale, the following procedure is preferred: the glass is formed into a flat sheet shape by an overflow down-draw method or the like, and cut processed into a rectangular shape; and then the glass in a state in which its surface is unpolished is subjected to ion exchange treatment, to thereby produce the tempered glass.

[0105] As apparent from Table 1, Sample Nos. 1 to 10, in each of which the glass composition was restricted to the predetermined range, had a compressive stress value of 587 MPa or more and a softening point of 743° C. or less. Therefore, Sample Nos. 1 to 10 each have satisfactory ion exchange performance and satisfactory bending processability.

Example 2

[0106] With regard to Sample Nos. 1 to 10, a glass sheet having a thickness of 0.7 mm was produced by an overflow down-draw method, and press molded using a mold made of mullite at a temperature lower than the softening point by 30° C. Further, the glass sheet having been removed from the mold was immersed in a KNO.sub.3 bath kept at 430° C. for 4 hours to be subjected to ion exchange treatment. Thus, tempered glasses each having a bending processed portion were produced.

INDUSTRIAL APPLICABILITY

[0107] While the tempered glass of the present invention is suitable for, for example, a cover glass for a mobile phone, exterior parts for a mobile PC and the like, and window glasses for an automobile, a train, a ship, and the like, the tempered glass of the present invention is also suitable for a substrate for a magnetic disk, a substrate for a flat panel display, a substrate and a cover glass for a solar cell, a cover glass for a solid state image sensor, tableware, and an ampoule tube for medical purposes in addition to the above-mentioned applications.