Glass, chemically strengthened glass, method for producing glass, and method for producing chemically strengthened glass

Abstract

The present invention relates to a glass comprising, in mole percentage on an oxide basis, 60.0 to 75.0% of SiO2, 2.0 to 20.0% of Al2O3, 20.0 to 30.0% of Li2O, 0.0 to 10.0% of MgO, 0.0 to 10.0% of CaO, 2.00 to 10.00% of ZrO2, and 0.50 to 5.00% of P2O5, substantially free of Y2O3, wherein the value of X represented by X = ([TiO2] + [P2O5]) / [ZrO2] is 0.70 or less. Herein, the brackets [ ] denote the contents of each component within the parentheses in mole percentage on an oxide basis.

Description

Glass, chemically strengthened glass, method for manufacturing glass, and method for manufacturing chemically strengthened glass

[0001] The present invention relates to glass, chemically strengthened glass, a method for producing glass, and a method for producing chemically strengthened glass. The present invention also relates to a display device, an electronic device product, and a solar cell module that include the glass or chemically strengthened glass.

[0002] Chemically strengthened glass-based materials are sometimes used in electronic devices such as mobile phones, smartphones, and tablet terminals, electronic devices such as car navigation systems installed in vehicles such as automobiles, window glass, etc. In particular, in recent years, "glass ceramics" containing microcrystals have attracted attention as a mother glass for obtaining high-strength chemically strengthened glass.

[0003] By increasing the crystallization rate of the crystallized glass, the strength of the chemically strengthened glass obtained by using the crystallized glass as a mother glass can be increased. In order to increase the crystallization rate of the crystallized glass, glass compositions containing large amounts of elements such as Li ions that form crystals and Zr that form crystal nuclei have been developed.

[0004] For example, Patent Document 1 discloses a method for producing a glass-ceramic containing ZrO ２ 1.5 to 6 mol %, Li ２ Glass-ceramics containing 12 to 22 mol % of O are disclosed.

[0005] International Publication No. 2021 / 135992

[0006] As a component of a melting furnace used to melt glass raw materials, Al ２ O ３ High alumina bricks, which have a high content of ZrO ２In this case, high-zirconia bricks, which are bricks with a high Li and Zr content, are used. Here, the glass with a high Li and Zr content in the composition described above is subject to a large amount of corrosion at high temperatures compared to the high-alumina bricks and high-zirconia bricks. This makes the bricks more susceptible to corrosion during melting of the glass raw materials, shortening the service life of the melting furnace. Furthermore, the brick particles liberated by corrosion become crystal nuclei, making the resulting glass more susceptible to devitrification defects.

[0007] Therefore, an object of the present invention is to provide a glass with low brick corrosion resistance and a method for manufacturing the same. Another object of the present invention is to provide a chemically strengthened glass using the above glass as a mother glass and a method for manufacturing the same. A further object of the present invention is to provide a display device, an electronic device product, and a solar cell module that include the above glass or the chemically strengthened glass.

[0008] To solve the above problem, the present inventors have discovered a new glass composition that exhibits excellent brick corrosion properties, i.e., low brick corrosion properties.

[0009] One aspect of the present invention is a composition comprising, in mole percentage on an oxide basis, SiO ２ 60.0 to 75.0% of Al ２ O ３ 2.0 to 20.0%, Li ２ O 20.0 to 30.0%, MgO 0.0 to 10.0%, CaO 0.0 to 10.0%, ZrO ２ 2.00 to 10.00% and P ２ O ５ Contains 0.50 to 5.00% of Y ２ O ３ and wherein the value of X represented by the following formula (1) is 0.70 or less: X=([TiO ２ ]+[P ２ O ５ ]) / [ZrO ２ ] Formula (1) Here, [ ] means the content of each component in the brackets expressed as mole percentage based on the oxide.

[0010] In another aspect of the present invention, the composition of the central portion in the thickness direction is expressed in mole percentage based on oxides as follows: SiO ２60.0 to 75.0% of Al ２ O ３ 2.0 to 20.0%, Li ２ O 20.0 to 30.0%, MgO 0.0 to 10.0%, CaO 0.0 to 10.0%, ZrO ２ 2.00 to 10.00% and P ２ O ５ Contains 0.50 to 5.00% of Y ２ O ３ and wherein the value of X represented by the following formula (1) is 0.70 or less: X=([TiO ２ ]+[P ２ O ５ ]) / [ZrO ２ ] Formula (1) Here, [ ] means the content of each component in the brackets expressed as mole percentage on an oxide basis at the center in the thickness direction.

[0011] Another aspect of the present invention is a method for producing glass, comprising heating and melting glass raw materials in a melting furnace, wherein the melting furnace contains Al, expressed as a mass percentage on an oxide basis, ２ O ３ The glass contains, in mole percentage on an oxide basis, 85 mass % or more of: SiO ２ 60.0 to 75.0% of Al ２ O ３ 2.0 to 20.0%, Li ２ O 20.0 to 30.0%, MgO 0.0 to 10.0%, CaO 0.0 to 10.0%, ZrO ２ 2.00 to 10.00% and P ２ O ５ Contains 0.50 to 5.00% of Y ２ O ３ and the value of X represented by the following formula (1) is 0.70 or less: X=([TiO ２ ]+[P ２ O ５ ]) / [ZrO ２ ] Formula (1) Here, [ ] means the content of each component in the brackets expressed as mole percentage based on the oxide.

[0012] Another aspect of the present invention relates to a method for producing chemically strengthened glass, which includes chemically strengthening the above-mentioned glass.

[0013] Another aspect of the present invention relates to a display device having the above-mentioned chemically strengthened glass and a display.

[0014] Another aspect of the present invention relates to an electronic device product having the above-mentioned chemically strengthened glass as a part of its constituent members.

[0015] Another aspect of the present invention relates to a solar cell module having the above-mentioned chemically strengthened glass.

[0016] According to the present invention, a glass having a new composition with low brick corrosion resistance and a method for producing the same can be obtained. Furthermore, by chemically strengthening this glass, high-strength chemically strengthened glass can be obtained. The glass or chemically strengthened glass of the present invention can be suitably used in, for example, display devices, electronic device products, and solar cell modules.

[0017] The present invention will be described in detail below based on embodiments, but the present invention is not limited to the following embodiments and can be implemented in any modified form within the scope that does not deviate from the gist of the present invention.

[0018] In this specification, glass compositions are expressed in mole percentages based on oxides, and mole percent is sometimes simply referred to as percent. The symbol "to" indicating a range of values ​​is used to mean that the values ​​before and after it are included as the lower and upper limits.

[0019] In a glass composition, "substantially not contained" means that it is not contained except for unavoidable impurities contained in raw materials, etc., that is, it is not intentionally contained. In this specification, unless otherwise specified, "substantially not contained" in a glass composition means, for example, that the content in the glass composition is less than 0.05 mol%.

[0020] <<Glass>> The glass of this embodiment may be amorphous glass that does not contain a crystalline phase, or may be crystallized glass that contains a crystalline phase. The glass of this embodiment is preferably crystallized glass, as described below.

[0021] The glass of this embodiment contains, in terms of mole percentage based on oxides, SiO ２ 60.0 to 75.0%, Al ２ O ３ 2.0 to 20.0%, Li ２ O 20.0 to 30.0%, MgO 0.0 to 10.0%, CaO 0.0 to 10.0%, ZrO ２ 2.00 to 10.00% and P ２ O ５ Contains 0.50 to 5.00% of Y ２ O ３ It is substantially free of

[0022] SiO ２ is a component that forms the network structure of the glass and is an essential component of the glass of this embodiment. It is also a component that increases chemical durability and is a constituent of lithium silicate crystals and lithium aluminosilicate crystals. In the glass of this embodiment, SiO ２ The content of SiO is 60.0 to 75.0%. ２ The content of SiO is 60.0% or more, preferably 62.0% or more, more preferably 64.0% or more, and even more preferably 66.0% or more. ２ The content is 75.0% or less, preferably 73.0% or less, more preferably 72.0% or less, and even more preferably 70.0% or less.

[0023] Al ２ O ３ is a component that increases the surface compressive stress due to chemical strengthening, and is an essential component of the glass of this embodiment. ２ O ３ The content of Al is 2.0 to 20.0%. ２ O ３The content of Al is 2.0% or more, preferably 2.4% or more, more preferably 3.0% or more, and even more preferably 4.0% or more. ２ O ３ The content is 20.0% or less, preferably 15.0% or less, more preferably 10.0% or less, and even more preferably 8.0% or less.

[0024] Li ２ O is ZrO contained in the brick ２ It is a component that suppresses the elution of Li and reduces the brick corrosion of glass. ２ O is a component that forms surface compressive stress by ion exchange, and is also a constituent of lithium silicate crystals, lithium aluminosilicate crystals, and lithium phosphate crystals. ２ The content of O is 20.0 to 30.0%. ２ The O content is 20.0% or more, preferably 22.0% or more, more preferably 24.0% or more, and even more preferably 26.0% or more. ２ The O content is 30.0% or less, preferably 29.0% or less, more preferably 28.0% or less, and even more preferably 27.0% or less.

[0025] MgO is not essential, but ZrO contained in the brick ２ MgO is a component that suppresses the elution of MgO and reduces the brick erosion of the glass, and may be contained. MgO is also a component that improves the meltability of the glass. In the glass of this embodiment, the MgO content is 0.0 to 10.0%. When the glass of this embodiment contains MgO, the content is preferably 0.5% or more, more preferably 1.5% or more, and even more preferably 2.0% or more, from the above-mentioned viewpoints. From the viewpoint of suppressing a decrease in the ion exchange rate, the MgO content is 10.0% or less, preferably 7.0% or less, more preferably 5.0% or less, and even more preferably 3.0% or less.

[0026] CaO is not essential, but ZrO contained in the brick ２CaO is a component that suppresses the elution of CaO and reduces the brick erosion of the glass, and may be contained. CaO is also a component that improves the meltability of the glass. In the glass of this embodiment, the CaO content is 0.0 to 10.0%. When the glass of this embodiment contains CaO, the content is preferably 0.5% or more, more preferably 0.8% or more, and even more preferably 1.0% or more, from the above-mentioned viewpoints. From the viewpoint of suppressing a decrease in the ion exchange rate, the CaO content is 10.0% or less, preferably 7.0% or less, more preferably 5.0% or less, and even more preferably 3.0% or less.

[0027] ZrO ２ is the ZrO contained in the brick ２ and Al ２ O ３ This component suppresses the elution of ZrO and reduces the brick corrosion of the glass, and is an essential component of the glass of this embodiment. ２ is also a component that can form crystal nuclei during the crystallization treatment to obtain crystallized glass. ２ The content of ZrO is 2.00 to 10.00%. ２ The content of ZrO is 2.00% or more, preferably 2.80% or more, more preferably 3.00% or more, and even more preferably 4.00% or more. ２ The content is 10.00% or less, preferably 8.00% or less, more preferably 7.00% or less, and even more preferably 6.00% or less.

[0028] P ２ O ５ is the ZrO contained in the brick ２ and Al ２ O ３ It is a component that suppresses the elution of P and reduces the brick corrosion of the glass, and is an essential component of the glass of this embodiment. ２ O ５ is a component that promotes phase separation of the glass and promotes crystallization, and is also a component that constitutes lithium phosphate crystals. ２ O ５ The content of P is 0.50 to 5.00%. ２ O５ The content of P is 0.50% or more, preferably 0.70% or more, more preferably 0.80% or more, even more preferably 0.90% or more, particularly preferably more than 0.90%, and most preferably 1.20% or more. ２ O ５ The content is 5.00% or less, preferably 4.00% or less, more preferably 3.00% or less, even more preferably 2.00% or less, particularly preferably 1.60% or less, and most preferably 1.40% or less.

[0029] Y ２ O ３ is the Al contained in the bricks ２ O ３ Therefore, from the viewpoint of reducing the brick corrosion of the glass, the glass of this embodiment is ２ O ３ Substantially does not contain Y ２ O ３ The term "substantially free of Y" means that the glass composition does not contain Y. ２ O ３ This means that the content of is less than 0.05%.

[0030] TiO ２ is not essential, but is a component that can form crystal nuclei during the crystallization treatment to obtain crystallized glass, and may be contained. ２ is the Al contained in the bricks ２ O ３ In the glass of this embodiment, TiO is a component that suppresses the elution of TiO and reduces the corrosiveness of the glass, particularly against high-alumina bricks. ２ The content of is preferably 0.00 to 0.10%. ２ When TiO is contained, the content may be 0.05% or more, or 0.06% or more, from the above-mentioned viewpoint. ２ is ZrO contained in the brick ２ In order to promote the elution of TiO, particularly from the viewpoint of reducing the corrosion of glass against high zirconia bricks, ２The content of is preferably 0.10% or less, more preferably 0.09% or less, and even more preferably 0.08% or less, and the lower the content the better. ２ It is most preferable that the material does not substantially contain TiO. ２ The term "substantially not containing TiO" means that the glass composition does not contain TiO ２ This means that the content of is less than 0.05%.

[0031] In the glass of this embodiment, the value of X represented by the following formula (1) is 0.70 or less: X=([TiO ２ ]+[P ２ O ５ ]) / [ZrO ２ ] Formula (1) Here, [ ] means the content of each component in the brackets expressed as mole percentage based on the oxide.

[0032] When the value of X is 0.70 or less, a glass with low brick erosion can be more suitably obtained. The value of X is preferably 0.66 or less, more preferably 0.60 or less, and even more preferably 0.40 or less. The lower limit of the value of X is not particularly limited, but may be 0.05 or more, may be greater than 0.09, or may be 0.15 or more. The value of X is, for example, 0.05 to 0.70.

[0033] In the glass of this embodiment, ZrO ２ and P ２ O ５ and TiO ２ The total content ([ZrO ２ ]+[P ２ O ５ ]+[TiO ２ ]) is preferably 3.00% or more. ２ ]+[P ２ O ５ ]+[TiO ２ When the [ZrO ] is 3.00% or more, a glass with low brick corrosion resistance can be more suitably obtained. ２ ]+[P ２ O ５ ]+[TiO ２ ] is preferably 3.00% or more, more preferably 3.30% or more, and is preferably 7.00% or less, more preferably 6.50% or less.２ ]+[P ２ O ５ ]+[TiO ２ ] is, for example, 3.00 to 7.00%.

[0034] Na ２ O is not essential, but is a component that lowers the melting temperature of the glass and improves the meltability of the glass, and may be contained. ２ When O is contained, the content is preferably 0.50% or more, more preferably 1.00% or more, still more preferably 2.00% or more, and particularly preferably 2.50% or more, from the viewpoint of improving the meltability of the glass. ２ The O content is preferably 6.00% or less, more preferably 4.00% or less, further preferably 3.50% or less, particularly preferably 3.00% or less, and most preferably 2.70% or less.

[0035] K ２ O is not essential, but is a component that lowers the melting temperature of the glass and improves the meltability of the glass, and may be contained. ２ When O is contained, the content thereof is preferably 0.10% or more, more preferably 0.20% or more, still more preferably 0.30% or more, and particularly preferably 0.60% or more, from the viewpoint of improving the meltability of the glass. ２ The O content is preferably 6.00% or less, more preferably 4.00% or less, further preferably 3.50% or less, particularly preferably 3.00% or less, and most preferably 2.50% or less.

[0036] SnO ２ Although not essential, SnO has the effect of promoting the formation of crystal nuclei and may be contained. ２ When SnO is contained, the content is preferably 0.1% or more, more preferably 0.3% or more, further preferably 1% or more, and particularly preferably 2% or more. ２ The content is preferably 6% or less, more preferably 5% or less, even more preferably 4% or less, and particularly preferably 3% or less.

[0037] B ２ O ３ Although not essential, B is a component that improves the chipping resistance and melting property of the glass or chemically strengthened glass, and may be contained. ２ O ３ When B is contained, the content is preferably 0.5% or more, more preferably 1% or more, and even more preferably 2% or more in order to improve the melting property. ２ O ３ The content of B is preferably 5% or less in order to prevent the occurrence of striae during melting and the deterioration of the glass quality. ２ O ３ The content is more preferably 4% or less, further preferably 3% or less, and particularly preferably 2% or less.

[0038] Although BaO, SrO, and ZnO are not essential, they are components that improve the meltability of the glass and may be contained. They also improve the refractive index of the amorphous phase of the crystallized glass, bringing it closer to the crystalline phase, thereby improving the transmittance of the crystallized glass and reducing the haze value. When the glass of this embodiment contains at least one of BaO, SrO, and ZnO, the total content ([BaO] + [SrO] + [ZnO]) is preferably 0.3% or more, more preferably 0.5% or more, even more preferably 0.7% or more, and particularly preferably 1% or more. On the other hand, these components may reduce the ion exchange rate. To improve chemical strengthening properties, [BaO] + [SrO] + [ZnO] is preferably 2.5% or less, more preferably 2% or less, even more preferably 1.7% or less, and particularly preferably 1.5% or less.

[0039] CeO ２ Although not essential, it is a component that oxidizes the glass and may suppress coloring, and may be contained. ２ When CeO is contained, the content is preferably 0.03% or more, more preferably 0.05% or more, and even more preferably 0.07% or more. ２ When used as an oxidizing agent, CeO ２ The content of is preferably 1.5% or less, more preferably 1.0% or less, in order to increase the transparency of the glass.

[0040] When the glass is used in a colored state, a coloring component may be added to the glass in a range that does not impede the achievement of the desired chemical strengthening properties. ３ O ４ , MnO ２ , Fe ２ O ３ , NiO, CuO, Cr ２ O ３ , V ２ O ５ , Bi ２ O ３ , SeO ２ , Er ２ O ３ and Nd ２ O ３ are preferred examples.

[0041] The total content of coloring components is preferably in the range of 1% or less. If a higher visible light transmittance of the glass is desired, it is preferable that these components are substantially not contained.

[0042] In addition, SO is used as a fining agent when melting glass. ３ The glass of this embodiment may contain As, chloride, fluoride, etc. ２ O ３ It is preferable that the glass of this embodiment does not contain Sb. ２ O ３ When Sb is contained, its content is preferably 0.3% or less, more preferably 0.1% or less. ２ O ３ It is most preferred that it does not contain

[0043] The glass of this embodiment has an Al content expressed as a mass percentage based on oxides, measured by a finger test method under the following conditions: ２ O ３ The erosion rate of the electroformed brick containing 85% by mass or more of the glass is preferably 0.090 mm / day or less. ２ The glass is heated to a temperature T2 at which the viscosity of the glass becomes 10 dPa s and melted. ３．５The glass is cooled to a temperature of T3.5, where the viscosity becomes dPa s. A test piece of electroformed brick is immersed in the obtained glass and held at T3.5 for 48 hours. The glass is then cooled to below 20°C. The test piece is removed from the crucible together with the surrounding glass, and the test piece is cut on a plane perpendicular to the contact surface between the glass and the test piece, horizontally ground, and mirror-polished. The maximum erosion amount of the test piece is measured for the obtained cross section using a projector.

[0044] The electroformed bricks used in the finger test method contain Al in terms of mass percentage based on oxides. ２ O ３ The glass of this embodiment is a high-alumina brick containing 85 mass % or more of the above. In the glass of this embodiment, the erosion amount of the high-alumina brick measured by the finger test method is preferably 0.090 mm / day or less, more preferably 0.085 mm / day or less, and even more preferably 0.080 mm / day or less, with the smaller the better. The erosion amount is an indicator of the erosion resistance of the glass to the high-alumina brick, and can be adjusted by the composition of the glass.

[0045] The glass of this embodiment has a mass percentage of ZrO expressed on an oxide basis, measured by a finger test method under the following conditions: ２ The corrosion rate of the electroformed brick containing 80% by mass or more of the glass is preferably 0.20 mm / day or less. ２ A test piece of electroformed brick is immersed in molten glass heated to a temperature T2 where the viscosity is dPa s and held at T2 for 48 hours. The glass is then cooled to 20°C or below. The test piece is removed from the crucible along with the surrounding glass, cut on a plane perpendicular to the contact surface between the glass and the test piece, horizontally ground, and mirror-polished. The maximum erosion amount of the test piece is measured for the resulting cross section using a projector.

[0046] The electroformed bricks used in the finger test method are ZrO in terms of mass percentage based on oxides. ２The glass of this embodiment is a high-zirconia brick containing 80 mass % or more of the above. The erosion amount of the high-zirconia brick measured by the finger test method is preferably 0.20 mm / day or less, more preferably 0.15 mm / day or less, and even more preferably 0.13 mm / day or less, with the smaller the better. The erosion amount is an indicator of the erosion resistance of the glass to the high-zirconia brick, and can be adjusted by the composition of the glass.

[0047] The glass transition temperature Tg of the glass of this embodiment is preferably 390°C or higher, more preferably 410°C or higher, and even more preferably 420°C or higher. If the glass transition temperature Tg is high, stress relaxation during chemical strengthening treatment is less likely to occur, making it easier to obtain high strength. On the other hand, from the viewpoint of glass formability, etc., Tg is preferably 650°C or lower, more preferably 600°C or lower. The Tg may be, for example, 390 to 650°C.

[0048] The average thermal expansion coefficient of the glass of this embodiment at 50°C to 350°C is 90 x 10 －７ / °C or more, preferably 100 x 10 －７ / °C or more is more preferable, and 110 x 10 －７ / °C or more is more preferable. On the other hand, in order to prevent the glass from cracking during molding, the average thermal expansion coefficient is 150 × 10 －７ / °C or less, and 140 x 10 －７ / °C or less. The average thermal expansion coefficient is, for example, 90 x 10 －７ / ℃~150×10 －７ / °C.

[0049] The glass of this embodiment is crushed, and the glass transition temperature (Tg ＤＳＣ The difference between the crystallization peak temperature (Tc) appearing in the lowest temperature range on the DSC curve is defined as (Tc - Tg). The (Tc - Tg) of the glass of this embodiment is preferably 80°C or higher, more preferably 85°C or higher, even more preferably 90°C or higher, and particularly preferably 95°C or higher. When (Tc - Tg) is large, the glass is easily heated and bent, etc. (Tc - Tg) is preferably 150°C or lower, more preferably 140°C or lower. The above (Tc - Tg) may be, for example, 80 to 150°C.

[0050] The above Tg ＤＳＣ may not coincide with the glass transition point (Tg) determined from the thermal expansion curve. ＤＳＣ Since the glass is crushed and measured, the measurement error is likely to be large. However, in order to evaluate the relationship with the crystallization peak temperature, it is more important to use the Tg obtained by the same DSC measurement than the Tg obtained from the thermal expansion curve. ＤＳＣ It is appropriate to use

[0051] The Young's modulus of the glass of this embodiment is preferably 75 GPa or more, more preferably 80 GPa or more, and even more preferably 85 GPa or more, and is preferably 130 GPa or less, more preferably 125 GPa or less, and even more preferably 120 GPa or less. The Young's modulus may be, for example, 75 to 130 GPa.

[0052] The Vickers hardness of the glass of this embodiment is preferably 500 or more, more preferably 550 or more, and is preferably 1100 or less, more preferably 1050 or less, and even more preferably 1000 or less. The Vickers hardness may be, for example, 500 to 1100.

[0053] The thickness of the glass of this embodiment is, for example, 2000 μm or less, preferably 1500 μm or less, more preferably 1000 μm or less, even more preferably 900 μm or less, particularly preferably 800 μm or less, and most preferably 700 μm or less. Furthermore, in order to obtain sufficient strength, the thickness is, for example, 200 μm or more, preferably 400 μm or more, more preferably 500 μm or more, and even more preferably 600 μm or more. The thickness may be, for example, 200 to 2000 μm.

[0054] The shape of the glass of this embodiment may be plate-like or may be other shapes depending on the product to which it is applied, its intended use, etc. Furthermore, when the glass of this embodiment is plate-like glass, i.e., a glass plate, the glass plate may have a rim shape with a different thickness around the periphery, etc. Furthermore, the shape of the glass plate is not limited thereto; for example, the two main surfaces do not have to be parallel to each other, and one or both of the two main surfaces may be entirely or partially curved. More specifically, the glass plate may be, for example, a flat glass plate without warping, or a curved glass plate having a curved surface.

[0055] The glass of this embodiment can be used as a cover glass for mobile electronic devices such as mobile phones, smartphones, personal digital assistants (PDAs), tablet devices, etc. It is also useful as a cover glass for electronic devices that are not intended to be portable, such as televisions (TVs), personal computers (PCs), touch panels, etc. It is also useful as a building material such as window glass, a tabletop, the interior of automobiles and airplanes, etc., and as a cover glass for these materials.

[0056] The glass of this embodiment can be bent or formed into a shape other than a flat plate before or after chemical strengthening, and is therefore useful for applications such as housings having curved surfaces.

[0057] <Ceramics> The glass of this embodiment is preferably the crystallized glass that contains crystalline phase.Ceramics can be obtained by heating amorphous glass to crystallize it.The glass composition of the entire crystallized glass is consistent with the composition of the amorphous glass before crystallization, and the preferred embodiment of the composition of crystallized glass is the same as above.

[0058] In this specification, the term "crystallized glass containing a crystalline phase" refers to glass in which diffraction peaks indicating crystals are observed in an XRD pattern obtained by powder X-ray diffraction (XRD) method.

[0059] When the glass of this embodiment is glass-ceramics, the glass-ceramics may contain Li ２ Si ２ O ５ (lithium disilicate), LiAlSi ２ O ６(β-spodumene), LiAlSi ４ O １０ (Petalite), Li ３ P.O. ４ It is preferable that the glass-ceramics contain at least one crystal selected from the group consisting of (lithium phosphate) and β-quartz solid solution. When the glass-ceramics contain the above crystals, it is possible to more suitably obtain glass that exhibits high strength when chemically strengthened. The crystals contained in the glass-ceramics are Li ２ Si ２ O ５ , LiAlSi ２ O ６ , and LiAlSi ４ O １０ It is more preferable that the crystal is at least one selected from the group consisting of Li ２ Si ２ O ５ It is more preferable that the crystals contained in the glass-ceramics are contained in the above crystals. The presence of the crystals in the glass-ceramics can be confirmed by X-ray diffraction spectrum.

[0060] The crystallization rate of the glass of this embodiment is preferably 5% or more, more preferably 10% or more, even more preferably 15% or more, and particularly preferably 20% or more, in order to increase mechanical strength. The crystallization rate is preferably 80% or less, more preferably 70% or less, and particularly preferably 60% or less, in order to increase transparency. A small crystallization rate is also advantageous in that it is easy to heat and bend. The crystallization rate may be, for example, 5 to 80%.

[0061] The crystallinity can be calculated from the X-ray diffraction intensity by the Rietveld method, which is described in "Crystal Analysis Handbook" edited by the editorial committee of the Crystallographic Society of Japan (Kyoritsu Shuppan, 1999, pp. 492-499).

[0062] The average particle size of the precipitated crystals of the crystallized glass is preferably 80 nm or less, more preferably 60 nm or less, even more preferably 50 nm or less, particularly preferably 40 nm or less, and most preferably 30 nm or less.The lower limit of the average particle size is not particularly limited, but is usually, for example, 5 nm or more.The average particle size is determined from a transmission electron microscope (TEM) image.

[0063] When the glass of this embodiment is crystallized glass, the average thermal expansion coefficient of the crystallized glass at 50°C to 350°C is 90 x 10 －７ / °C or more, and more preferably 100 × 10 －７ / °C or more, more preferably 110 x 10 －７ / °C or more, particularly preferably 120 x 10 －７ / °C or more, most preferably 130 x 10 －７ In order to prevent cracks from occurring due to the difference in the thermal expansion coefficient during the chemical strengthening process, the average thermal expansion coefficient is preferably 160×10 ―７ / °C or less, more preferably 150 x 10 －７ / °C or less, more preferably 140 x 10 －７ / °C or less. The average thermal expansion coefficient is, for example, 90 x 10 －７ / ℃~160×10 ―７ / °C.

[0064] Since crystallized glass contains crystals, it has high hardness. Therefore, it is scratch-resistant and has excellent abrasion resistance. When the glass of this embodiment is crystallized glass, in order to increase abrasion resistance, the Vickers hardness is preferably 600 or more, more preferably 700 or more, even more preferably 730 or more, particularly preferably 750 or more, and most preferably 780 or more. From the viewpoint of processability, the Vickers hardness of the crystallized glass is preferably 1100 or less, more preferably 1050 or less, and even more preferably 1000 or less. The Vickers hardness may be, for example, 600 to 1100.

[0065] When the glass of this embodiment is crystallized glass, the Young's modulus of the crystallized glass is preferably 85 GPa or more, more preferably 90 GPa or more, even more preferably 95 GPa or more, and particularly preferably 100 GPa or more in order to suppress warping due to strengthening during chemical strengthening. The crystallized glass may be polished before use. For ease of polishing, the Young's modulus of the crystallized glass is preferably 130 GPa or less, more preferably 125 GPa or less, and even more preferably 120 GPa or less. The Young's modulus may be, for example, 85 to 130 GPa.

[0066] When the glass of this embodiment is glass-ceramics, the fracture toughness value of the glass-ceramics is preferably 0.8 MPa m １／２ More preferably, 0.85 MPa m １／２ More preferably, 0.9 MPa m １／２ This is because when the glass-ceramics is chemically strengthened, fragments are less likely to scatter when broken. The upper limit of the fracture toughness value is not particularly limited, but may be, for example, 2.0 MPa m １／２ The fracture toughness value is usually 0.8 to 2.0 MPa m １／２ It may be.

[0067] Chemically strengthened glass of this embodiment has a composition at the center in the thickness direction, expressed in mole percentage based on oxides, of SiO ２ 60.0 to 75.0%, Al ２ O ３ 2.0 to 20.0%, Li ２ O 20.0 to 30.0%, MgO 0.0 to 10.0%, CaO 0.0 to 10.0%, ZrO ２ 2.00 to 10.00% and P ２ O ５ Contains 0.50 to 5.00% of Y ２ O ３ Furthermore, in the chemically strengthened glass of this embodiment, the value of X represented by the following formula (1) is 0.70 or less in the composition of the center portion in the thickness direction. X = ([TiO ２ ]+[P ２ O ５ ]) / [ZrO ２ ] Formula (1) Here, [ ] means the content of each component in the brackets expressed as mole percentage on an oxide basis at the center in the thickness direction.

[0068] The chemically strengthened glass of this embodiment refers to glass after chemical strengthening treatment. The chemically strengthened glass of this embodiment can be produced, for example, by chemically strengthening the glass of this embodiment described above.

[0069] In chemically strengthened glass, a compressive stress layer due to ion exchange is usually formed on the glass surface. Therefore, the glass composition of the non-ion-exchanged portion of the chemically strengthened glass, i.e., the center portion in the thickness direction, is consistent with the composition of the glass of this embodiment, which is the base composition of the chemically strengthened glass. Furthermore, even in the ion-exchanged portion, the concentrations of components other than alkali metal oxides basically do not change from the base composition. A preferred embodiment of the glass composition of the center portion in the thickness direction of the chemically strengthened glass of this embodiment is the same as that described above for the glass composition of this embodiment.

[0070] The chemically strengthened glass of this embodiment has a thickness t (unit: μm), a compressive stress layer depth (DOC) of 0.15t or more, and a compressive stress value (CS) at a depth of 50 μm from the glass surface. ５０ ) is 30 MPa or more, and the compressive stress value (CS １００ ) is preferably −10 MPa or more.

[0071] From the viewpoint of improving strength, the chemically strengthened glass of this embodiment preferably has a compressive stress layer depth (DOC) (unit: μm), which is the depth at which the compressive stress value (CS) becomes zero, of 0.15t or more. The DOC is preferably 0.15t or more, more preferably 0.15t + 5 or more, and even more preferably 0.15t + 10 or more. From the viewpoint of suppressing an increase in internal tensile stress (CT), the DOC is preferably 0.25t or less, more preferably 0.25t - 5 or less, and even more preferably 0.25t - 10 or less. The DOC may be, for example, 0.15t to 0.25t.

[0072] The chemically strengthened glass of this embodiment is made of CS from the viewpoint of improving drop strength against #180 sandpaper. ５０ is preferably 30 MPa or more. ５０ is more preferably 60 MPa or more, further preferably 90 MPa or more, and particularly preferably 120 MPa or more. ５０ is preferably 300 MPa or less, more preferably 250 MPa or less, and even more preferably 200 MPa or less. ５０may be, for example, 30 to 300 MPa.

[0073] The chemically strengthened glass of this embodiment is made of CS from the viewpoint of improving drop strength against #80 sandpaper. １００ is preferably -10 MPa or more. １００ is more preferably 0 MPa or more, further preferably 10 MPa or more, and particularly preferably 20 MPa or more. １００ is preferably 100 MPa or less, more preferably 80 MPa or less, and even more preferably 60 MPa or less. １００ may be, for example, −10 to 100 MPa. １００ If takes a negative value, the CS １００ means that it is a tensile stress.

[0074] The chemically strengthened glass of this embodiment has a DOC of 0.15t or more and a CS ５０ is 30 MPa or more, and CS １００ is preferably -10 MPa or more, DOC is 0.15t+5 or more, and CS ５０ is 60 MPa or more, and CS １００ It is more preferable that DOC is 0.15t+10 or more, and CS ５０ is 90 MPa or more, and CS １００ It is more preferable that the stress is 10 MPa or more.

[0075] In this specification, the above DOC, CS ５０ and C.S. １００ are the results obtained by measuring the stress value of chemically strengthened glass using a measuring instrument SLP-2000 manufactured by Orihara Seisakusho Co., Ltd.

[0076] Preferred aspects of the thickness (t), shape, and use of the chemically strengthened glass of this embodiment are the same as those described above for the glass of this embodiment.

[0077] <<Glass Manufacturing Method>> The glass manufacturing method of this embodiment includes heating and melting glass raw materials in a melting furnace. The melting furnace contains Al, in terms of mass percentage based on oxides, ２ O３ The electroformed brick contains 85 mass % or more of the above glass, expressed in mole percentage on an oxide basis, SiO ２ 60.0 to 75.0%, Al ２ O ３ 2.0 to 20.0%, Li ２ O 20.0 to 30.0%, MgO 0.0 to 10.0%, CaO 0.0 to 10.0%, ZrO ２ 2.00 to 10.00% and P ２ O ５ Contains 0.50 to 5.00% of Y ２ O ３ and the value of X represented by the following formula (1) is 0.70 or less: X=([TiO ２ ]+[P ２ O ５ ]) / [ZrO ２ ] Formula (1) Here, [ ] means the content of each component in the brackets expressed as mole percentage based on the oxide.

[0078] The melting furnace used in the glass manufacturing method of this embodiment is a furnace containing Al, expressed as a mass percentage based on oxides. ２ O ３ The high alumina brick is an electroformed brick containing 85 mass % or more of the above-mentioned high alumina brick. More specifically, at least a part of the furnace materials constituting the melting furnace contains the above-mentioned high alumina brick. The furnace materials containing the above-mentioned high alumina brick are preferably arranged at least in a region in the melting furnace that comes into contact with the heated and molten glass raw material, and are used to heat and melt the glass raw material so that the viscosity of the heated and molten glass raw material reaches 10 ３．５ Even when the furnace material of the melting furnace contains high alumina bricks, when producing the glass of this embodiment having a specific composition, it is possible to suppress erosion of the bricks during melting of the glass frits.

[0079] The melting furnace further contains ZrO ２Preferably, the furnace material contains high zirconia bricks, which are electroformed bricks containing 80 mass % or more of the above-mentioned high zirconia bricks. More specifically, at least a part of the furnace materials constituting the melting furnace preferably contains the above-mentioned high zirconia bricks. More preferably, the furnace material containing the high zirconia bricks is disposed at least in a region in the melting furnace that comes into contact with the glass raw material that has been heated and melted, and the high zirconia bricks are disposed at least in a region in the melting furnace that comes into contact with the glass raw material that has been heated and melted to a viscosity of 10 ２ Even when the furnace material of the melting furnace contains high-zirconia bricks, when producing the glass of this embodiment having a specific composition, erosion of the bricks can be suppressed during melting of the glass frits.

[0080] In the method for producing glass of this embodiment, glass raw materials are prepared so as to obtain glass of the above-mentioned predetermined composition, and then heated and melted in a glass melting furnace. Preferred aspects of the composition of the glass obtained by the method for producing glass of this embodiment are the same as those described above for the glass of this embodiment.

[0081] In the glass manufacturing method of this embodiment, ZrO of the obtained glass ２ The content (unit: mole %) of the electroformed bricks contained in the melting furnace ２ O ３ The value of Y expressed by the following formula (2) using the content (unit: mol % expressed as a mole percentage on an oxide basis) is preferably 0.02 to 0.10. The electrocast bricks referred to here are those which are contained in at least a part of the furnace materials constituting the melting furnace and are arranged at least in the region in the melting furnace that comes into contact with the heated and melted glass raw material. ２ O ３ The electroformed bricks include those containing 85% by mass or more of Al. ２ O ３ When a plurality of electroformed bricks with different contents of ZrO are included, it is preferable that the value of Y is 0.02 to 0.10 for at least some of the plurality of electroformed bricks, and it is more preferable that the value of Y is 0.02 to 0.10 for all of the plurality of electroformed bricks. ２ content) / (Al content of electroformed brick２ O ３ Content) Formula (2)

[0082] When the value of Y is 0.02 to 0.10, the effect of suppressing brick erosion in the glass manufacturing method of this embodiment is more preferably achieved. The value of Y is more preferably 0.03 or more, and even more preferably 0.04 or more. The value of Y is more preferably 0.09 or less, and even more preferably 0.08 or less.

[0083] Other manufacturing steps and conditions may be those conventionally known. For example, after the glass raw materials are heated and melted in a melting furnace as described above, the molten glass may be homogenized by bubbling, stirring, adding a fining agent, etc., formed into a desired shape such as a glass plate, and slowly cooled. Alternatively, the molten glass may be formed into a plate by forming it into a block, slowly cooling it, and then cutting it.

[0084] Examples of glass forming methods include float method, press method, fusion method and down-draw method. In particular, when producing a large glass plate, the float method is preferred. In addition, continuous forming methods other than the float method, such as the fusion method and down-draw method, are also preferred.

[0085] The molded glass is then subjected to grinding and polishing as necessary. The obtained glass may be subjected to the chemical strengthening treatment described below to obtain chemically strengthened glass. In this case, it is preferable to cut the glass to a predetermined shape and size or to chamfer the glass before performing the chemical strengthening treatment. This is because a compressive stress layer is also formed on the end surface by the subsequent chemical strengthening treatment.

[0086] <Method for producing crystallized glass> When the glass of this embodiment is crystallized glass, the amorphous glass obtained by the above procedure is subjected to a heat treatment to obtain crystallized glass.

[0087] The heat treatment is preferably a two-stage heat treatment in which the temperature is raised from room temperature to a first treatment temperature and maintained for a certain period of time, and then the temperature is maintained at a second treatment temperature higher than the first treatment temperature for a certain period of time.

[0088] In the case of two-stage heat treatment, the first treatment temperature is preferably in a temperature range where the crystal nucleation rate is high in the glass composition, and the second treatment temperature is preferably in a temperature range where the crystal growth rate is high in the glass composition. In addition, the holding time at the first treatment temperature is preferably long enough to generate a sufficient number of crystal nuclei. By generating a large number of crystal nuclei, the size of each crystal becomes small, and highly transparent crystallized glass can be obtained.

[0089] The first treatment temperature is, for example, 450°C to 700°C, the second treatment temperature is, for example, 600°C to 800°C, the holding time at the first treatment temperature is, for example, 1 hour to 6 hours, and the holding time at the second treatment temperature is, for example, 1 hour to 6 hours.

[0090] <<Method for producing chemically strengthened glass>> The chemically strengthened glass of this embodiment is produced by chemically strengthening the amorphous glass or crystallized glass described above. That is, the method for producing chemically strengthened glass of this embodiment includes chemically strengthening the glass or crystallized glass of this embodiment.

[0091] In the method for producing chemically strengthened glass of this embodiment, the chemical strengthening is preferably performed using a molten salt composition containing sodium and having a potassium content of less than 5 mass%. In the method for producing chemically strengthened glass of this embodiment, the chemical strengthening treatment may be performed in two or more stages, but one stage of strengthening is preferred to increase productivity.

[0092] The chemical strengthening treatment is carried out, for example, by immersing the glass for 0.1 to 500 hours in a molten salt composition such as sodium nitrate heated to 360 to 600° C. The heating temperature of the molten salt composition is more preferably 375 to 500° C., and the immersion time of the glass in the molten salt composition is more preferably 0.3 to 200 hours.

[0093] The molten salt composition used in the method for producing chemically strengthened glass of this embodiment preferably contains sodium and has a potassium content of less than 5 mass% in terms of potassium nitrate. The potassium content is more preferably less than 2 mass% in terms of potassium nitrate, and the molten salt composition is even more preferably substantially free of potassium. "Substantially free of potassium" means that the composition does not contain any potassium, or may contain potassium as an impurity that is unavoidably mixed in during production.

[0094] Examples of the reinforcing salt contained in the molten salt composition include nitrates, sulfates, carbonates, and chlorides. Among these, examples of the nitrates include lithium nitrate and sodium nitrate. Examples of the sulfates include lithium sulfate and sodium sulfate. Examples of the carbonates include lithium carbonate and sodium carbonate. Examples of the chlorides include lithium chloride, sodium chloride, cesium chloride, and silver chloride. These reinforcing salts may be used alone or in combination.

[0095] Appropriate conditions for the chemical strengthening treatment may be selected in consideration of the composition (characteristics) of the glass, the type of strengthening salt, and the desired chemical strengthening characteristics.

[0096] Display Device, Electronic Device Product, and Solar Cell Module The display device of this embodiment includes the glass or chemically strengthened glass of this embodiment and a display. Such a display device may be used in electronic devices such as mobile phones, smartphones, and tablet terminals, as well as electronic devices such as car navigation systems installed in vehicles such as automobiles.

[0097] The electronic device product of this embodiment has the glass or chemically strengthened glass of this embodiment as a part of its constituent parts. Such electronic device products may be, for example, electronic devices such as mobile phones, smartphones, and tablet terminals, or electronic devices such as car navigation systems installed in vehicles such as automobiles.

[0098] The solar cell module of this embodiment includes the glass or chemically strengthened glass of this embodiment. The glass or chemically strengthened glass can be used, for example, as a transparent cover member for the light-receiving surface of the solar cell module.

[0099] As described above, the present specification discloses the following configurations: <1> In terms of mole percentage based on oxides, SiO ２ 60.0 to 75.0% of Al ２ O ３ 2.0 to 20.0%, Li ２ O 20.0 to 30.0%, MgO 0.0 to 10.0%, CaO 0.0 to 10.0%, ZrO ２ 2.00 to 10.00% and P ２ O ５ Contains 0.50 to 5.00% of Y ２ O ３ A glass that is substantially free of TiO and has a value of X represented by the following formula (1) of 0.70 or less: X=([TiO ２ ]+[P ２ O ５ ]) / [ZrO ２ ] Formula (1) where [ ] means the content of each component in the brackets expressed as mole percentage based on oxide. <2> In mole percentage based on oxide, ２ Contains 3.00 to 10.00% of TiO ２ <3> The glass according to <1>, containing 0.00 to 0.10% of ZrO ２ and P ２ O ５ and TiO ２ <4> The glass according to <1> or <2>, wherein the total content of Li is 3.00% or more. ２ Si ２ O ５ (lithium disilicate), LiAlSi ２ O ６ (β-spodumene), LiAlSi ４ O １０ (Petalite), Li ３ P.O. ４<5> The glass according to any one of <1> to <3>, which contains at least one crystal selected from the group consisting of Al (lithium phosphate) and β-quartz solid solution. <6> The glass according to any one of <1> to <3>, which contains at least one crystal selected from the group consisting of Al (lithium phosphate) and β-quartz solid solution, expressed as a mass percentage based on oxides, measured by a finger test method under the following conditions: ２ O ３ The glass according to any one of <1> to <4>, wherein the erosion rate of an electroformed brick containing 85 mass % or more of the above is 0.090 mm / day or less. (Condition) When the viscosity of the glass in a crucible is 10 ２ The glass is heated to a temperature T2 at which the viscosity of the glass becomes 10 dPa s and melted. ３．５ The glass is cooled to a temperature T3.5 where the viscosity becomes dPa s. A test piece of electroformed brick is immersed in the obtained glass and kept at T3.5 for 48 hours. The glass is then cooled to 20°C or below. The test piece is removed from the crucible together with the surrounding glass, and the test piece is cut on a plane perpendicular to the contact surface between the glass and the test piece, horizontally ground, and mirror-polished. The maximum erosion amount of the test piece is measured for the obtained cross section using a projector. <6> ZrO, expressed as a mass percentage based on oxides, measured under the following conditions using the finger test method. ２ The glass according to any one of <1> to <5>, wherein the erosion rate of an electroformed brick containing 80 mass % or more of the above is 0.20 mm / day or less. (Condition) When the viscosity of the glass in a crucible is 10 ２ A test piece of electroformed brick is immersed in the molten glass heated to a temperature T2 where the viscosity becomes dPa s, and is held at T2 for 48 hours. The glass is then cooled to 20°C or below. The test piece is removed from the crucible together with the surrounding glass, cut on a plane perpendicular to the contact surface between the glass and the test piece, horizontally ground, and mirror-polished. The maximum erosion amount of the obtained cross section is measured using a projector. <7> The composition at the center in the thickness direction is expressed in mole percentage based on oxides, and is SiO ２ 60.0 to 75.0% of Al ２ O ３ 2.0 to 20.0%, Li ２ O 20.0 to 30.0%, MgO 0.0 to 10.0%, CaO 0.0 to 10.0%, ZrO ２ 2.00 to 10.00% and P ２ O ５Contains 0.50 to 5.00% of Y ２ O ３ Chemically strengthened glass that is substantially free of TiO and has a value of X represented by the following formula (1) of 0.70 or less: X=([TiO ２ ]+[P ２ O ５ ]) / [ZrO ２ ] Formula (1) where [ ] means the content of each component in the brackets at the center in the thickness direction, expressed as a mole percentage based on oxide. <8> The composition at the center in the thickness direction is expressed as a mole percentage based on oxide, and ２ Contains 3.00 to 10.00% of TiO ２ <9> The chemically strengthened glass according to <7>, containing 0.00 to 0.10% of <10>. <11> The chemically strengthened glass according to <7>, wherein the thickness is t (unit: μm), the depth of compressive stress layer (DOC) is 0.15t or more, and the compressive stress value (CS) at a depth of 50 μm from the glass surface is ５０ ) is 30 MPa or more, and the compressive stress value (CS) at a depth of 100 μm from the glass surface １００ <10> A method for producing glass, comprising heating and melting glass raw materials in a melting furnace, wherein the melting furnace contains Al, in terms of mass percentage on an oxide basis, ２ O ３ The glass contains, in mole percentage on an oxide basis, 85 mass % or more of: SiO ２ 60.0 to 75.0% of Al ２ O ３ 2.0 to 20.0%, Li ２ O 20.0 to 30.0%, MgO 0.0 to 10.0%, CaO 0.0 to 10.0%, ZrO ２ 2.00 to 10.00% and P ２ O ５ Contains 0.50 to 5.00% of Y ２ O ３ and the value of X represented by the following formula (1) is 0.70 or less. X=([TiO ２ ]+[P ２ O ５]) / [ZrO ２ ] Formula (1) where [ ] means the content of each component in the brackets expressed as a mole percentage based on oxide. <11> The glass contains, expressed as a mole percentage based on oxide, ２ Contains 3.00 to 10.00% of TiO ２ <12> The method for producing glass according to <10>, wherein the glass contains 0.00 to 0.10% of ZrO. ２ content (unit: mole % expressed as mole percentage on oxide basis), and the Al content of the electroformed brick ２ O ３ The method for producing glass according to <10> or <11>, wherein the value of Y, which is represented by the following formula (2) using the content (unit: mol % expressed as mole percentage based on oxide), is 0.02 to 0.10: Y=(ZrO ２ content) / (Al content of electroformed brick ２ O ３ <13> The melting furnace further contains ZrO in terms of mass percentage on an oxide basis. ２ <14> A method for producing chemically strengthened glass, comprising chemically strengthening the glass according to any one of <1> to <6>. <15> A method for producing chemically strengthened glass according to <14>, wherein the chemical strengthening is performed using a molten salt composition containing sodium and less than 5 mass% of potassium. <16> A display device comprising the glass according to any one of <1> to <6> or the chemically strengthened glass according to any one of <7> to <9>, and a display. <17> An electronic device product comprising the glass according to any one of <1> to <6> or the chemically strengthened glass according to any one of <7> to <9> as a part of a constituent member. <18> A solar cell module comprising the glass according to any one of <1> to <6> or the chemically strengthened glass according to any one of <7> to <9>.

[0100] The present invention will be described in detail below with reference to examples. However, the present invention is not limited to the following descriptions. Examples 1 to 6 are working examples, and Examples 7 to 12 are comparative examples.

[0101] [Glass production and brick erosion measurement] Glass was produced and brick erosion was measured by finger test. Glass raw materials were mixed to obtain the glass composition shown in Table 1 in terms of oxide-based mole percentage, and 190 ml of cullet was prepared. The glass raw materials were placed in a 300 ml platinum crucible. ２ The temperature was raised at a rate of 300° C. / hour to a temperature T2 at which the viscosity of the glass reached 10 dPa·s, and the temperature was maintained for 6 hours to melt the glass. ３．５ The mixture was cooled to a temperature T3.5 where the viscosity of the mixture was dPa·s. ２ O ３ A test specimen was prepared from an electroformed brick ("MB-G" manufactured by AGC Ceramics Co., Ltd.) containing 95% by mass of ZnO and measuring 25 mm x 15 mm x 73 mm. The test specimen was immersed in the molten glass at T3.5 for at least 65% of its long side length (73 mm) and held at T3.5 for 48 hours. The glass was then cooled to 20 °C at a rate of 300 °C / hour. The test specimen, together with the surrounding glass, was removed from the crucible, cut on a plane perpendicular to the contact surface between the glass and the test specimen, horizontally ground, and mirror-polished. The maximum erosion of the resulting cross section was measured using a projector ("V12BDC" manufactured by Nikon Corporation). The measurement results are shown in Table 1 as "High-Alumina Brick Erosion Amount."

[0102] Furthermore, as a test piece, ZrO ２ The erosion amount of the brick was measured in the same manner as above, except that electroformed bricks containing 94.5 mass% of zirconia ("ZB-X9510" manufactured by AGC Ceramics Co., Ltd.) were used, and the molten glass was not cooled to T3.5, but the test specimens were immersed in the molten glass at T2 and held at T2 for 48 hours. The measurement results are shown in Table 1 as "High-zirconia brick erosion amount."

[0103] From the glass compositions listed in Table 1, the value of X and ZrO ２ and P ２ O ５ and TiO ２ The total content of ZrO was calculated. These are shown in Table 1 as "X value" and "[ZrO ２ ]+[P ２ O５ ]+[TiO ２ ]”.

[0104] In addition, the ZrO ２ The Al content (unit: mole % expressed as mole percentage based on oxides) of the electroformed bricks used in measuring the amount of brick erosion was ２ O ３ The value of Y' expressed by the following formula (3) was calculated using the content (unit: mol % expressed as mole percentage based on oxide; 93.03 mol %). This is shown as "Y' value" in Table 1. The value of Y' corresponds to the value of Y expressed by the above formula (2) when the electroformed bricks used in the above brick erosion measurement are used as at least a part of the furnace material of a melting furnace. Y' = (ZrO ２ content) / (Al content of electroformed brick ２ O ３ Content) Formula (3)

[0105]

[0106] As shown in Table 1, the glass of this embodiment was found to have low corrosion resistance against high-alumina bricks. In particular, the glasses of Examples 1 to 3 were found to have low corrosion resistance against high-zirconia bricks.

[0107] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on Japanese patent applications filed on June 7, 2024 (Patent Application No. 2024-092882), January 14, 2025 (Patent Application No. 2025-004715), and February 17, 2025 (Patent Application No. 2025-023654), the contents of which are incorporated herein by reference.

[0108] The glass according to this embodiment has low brick corrosion resistance, and therefore can be suitably produced in a melting furnace made of furnace materials including bricks.

Claims

1. In terms of mole percentage based on oxide, SiO ２ 60.0 to 75.0% of Al ２ O ３ 2.0 to 20.0%, Li ２ O 20.0 to 30.0%, MgO 0.0 to 10.0%, CaO 0.0 to 10.0%, ZrO ２ 2.00 to 10.00% and P ２ O ５ Contains 0.50 to 5.00% of Y ２ O ３ A glass that is substantially free of TiO and has a value of X represented by the following formula (1) of 0.70 or less: X=([TiO ２ ]+[P ２ O ５ ]) / [ZrO ２ ] Formula (1) Here, [ ] means the content of each component in the brackets expressed as mole percentage based on the oxide.

2. In terms of mole percentage based on oxide, the ZrO ２ Contains 3.00 to 10.00% of TiO ２ The glass according to claim 1, containing 0.00 to 0.10% of 3. In terms of mole percentage based on oxide, ZrO ２ and P ２ O ５ and TiO ２ The glass according to claim 1 or 2, wherein the total content of is 3.00% or more.

4. Crystallized glass containing Li ２ Si ２ O ５ (lithium disilicate), LiAlSi ２ O ６ (β-spodumene), LiAlSi ４ O １０ (Petalite), Li ３ P.O. ４ 3. The glass according to claim 1, comprising at least one crystal selected from the group consisting of (lithium phosphate) and β-quartz solid solution.

5. Al mass percentage based on oxides measured under the following conditions using the finger test method ２ O ３ The glass according to claim 1 or 2, wherein the erosion rate of an electroformed brick containing 85 mass % or more of the glass is 0.090 mm / day or less. ２ The glass is heated to a temperature T2 at which the viscosity of the glass becomes 10 dPa s and melted. ３．５ The glass is cooled to a temperature of T3.5, where the viscosity becomes dPa s. A test piece of electroformed brick is immersed in the obtained glass and held at T3.5 for 48 hours. The glass is then cooled to below 20°C. The test piece is removed from the crucible together with the surrounding glass, and the test piece is cut on a plane perpendicular to the contact surface between the glass and the test piece, horizontally ground, and mirror-polished. The maximum erosion amount of the test piece is measured for the obtained cross section using a projector.

6. ZrO, expressed as a mass percentage based on oxides, measured under the following conditions using the finger test method ２ The glass according to claim 5, wherein the erosion rate of an electroformed brick containing 80 mass % or more of the glass is 0.20 mm / day or less. ２ A test piece of electroformed brick is immersed in molten glass heated to a temperature T2 where the viscosity is dPa s and held at T2 for 48 hours. The glass is then cooled to 20°C or below. The test piece is removed from the crucible along with the surrounding glass, cut on a plane perpendicular to the contact surface between the glass and the test piece, horizontally ground, and mirror-polished. The maximum erosion amount of the test piece is measured for the resulting cross section using a projector.

7. The composition of the center of the thickness direction is expressed as mole percentage based on oxides: SiO ２ 60.0 to 75.0% of Al ２ O ３ 2.0 to 20.0%, Li ２ O 20.0 to 30.0%, MgO 0.0 to 10.0%, CaO 0.0 to 10.0%, ZrO ２ 2.00 to 10.00% and P ２ O ５ Contains 0.50 to 5.00% of Y ２ O ３ Chemically strengthened glass that is substantially free of TiO and has a value of X represented by the following formula (1) of 0.70 or less: X=([TiO ２ ]+[P ２ O ５ ]) / [ZrO ２ ] Formula (1) Here, [ ] means the content of each component in the brackets expressed as mole percentage on an oxide basis at the center in the thickness direction.

8. The composition of the center portion in the thickness direction is expressed in mole percentage on an oxide basis, and the ZrO ２ Contains 3.00 to 10.00% of TiO ２ The chemically strengthened glass according to claim 7, containing 0.00 to 0.10%.

9. The thickness is t (unit: μm), the depth of the compressive stress layer (DOC) is 0.15t or more, and the compressive stress value (CS) at a depth of 50 μm from the glass surface ５０ ) is 30 MPa or more, and the compressive stress value (CS) at a depth of 100 μm from the glass surface １００ 9. The chemically strengthened glass according to claim 7 or 8, wherein the compressive strength (S) of the glass is −10 MPa or more.

10. A method for producing glass, comprising heating and melting glass raw materials in a melting furnace, wherein the melting furnace contains Al, expressed as a mass percentage on an oxide basis. ２ O ３ The glass contains, in mole percentage on an oxide basis, 85 mass % or more of: SiO ２ 60.0 to 75.0% of Al ２ O ３ 2.0 to 20.0%, Li ２ O 20.0 to 30.0%, MgO 0.0 to 10.0%, CaO 0.0 to 10.0%, ZrO ２ 2.00 to 10.00% and P ２ O ５ Contains 0.50 to 5.00% of Y ２ O ３ and the value of X represented by the following formula (1) is 0.70 or less. X=([TiO ２ ]+[P ２ O ５ ]) / [ZrO ２ ] Formula (1) Here, [ ] means the content of each component in the brackets expressed as mole percentage based on the oxide.

11. The glass contains, in mole percentage on an oxide basis, ZrO ２ Contains 3.00 to 10.00% of TiO ２ The method for producing glass according to claim 10, wherein the glass contains 0.00 to 0.10% of 12. ZrO of the glass ２ content (unit: mole % expressed as mole percentage on oxide basis), and the Al content of the electroformed brick ２ O ３ The method for producing glass according to claim 10 or 11, wherein the value of Y, expressed by the following formula (2) using the content (unit: mol % expressed as mole percentage on an oxide basis), is 0.02 to 0.

10. Y=(ZrO ２ content) / (Al content of electroformed brick ２ O ３ Content) Formula (2) 13. The melting furnace further contains ZrO ２ The method for producing glass according to claim 10 or 11, comprising electroformed bricks containing 80 mass % or more of the above.

14. A method for producing chemically strengthened glass, comprising chemically strengthening the glass of claim 1 or 2.

15. A method for producing chemically strengthened glass according to claim 14, wherein the chemical strengthening is performed using a molten salt composition containing sodium and having a potassium content of less than 5 mass %.

16. A display device comprising the chemically strengthened glass according to claim 7 or 8 and a display.

17. An electronic device product having the chemically strengthened glass according to claim 7 or 8 as part of its constituent parts.

18. A solar cell module comprising the chemically strengthened glass according to claim 7 or 8.

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