Glass including crystalline phase

Abstract

Provided is a glass containing a crystalline phase, the raw glass comprising, in terms of the oxide mass%, 65.0% to 85.0% of an SiO2 component, 3.0% to 15.0% of an Al2O3 component, from greater than 0% to 5.0% of a P2O5 component, from greater than 5.0% to 15.0% of an Li2O component, 0% to 10.0% of a ZrO2 component, and 0% to 5.0% of an MgO component, and the raw glass satisfying the matter of a ratio of the [content of the SiO2 component / (the content of an Na2O component + the content of a K2O component)] being from 23.0 to 150.0. The light transmittance thereof at 550 nm is 70% or greater.

Description

Glass containing crystalline phase

[0001] The present invention relates to glasses that contain a crystalline phase.

[0002] Glass containing a crystalline phase is sometimes used as a cover glass for a smartphone, a glass component for a housing, etc. While glass containing a crystalline phase can increase strength, it has the problem of difficulty in ensuring transparency. Patent Documents 1 to 4 disclose glasses containing a crystalline phase with specific compositions and physical properties.

[0003] JP 2021-095333 A JP 2001-048584 A JP 2020-019659 A JP 2008-254984 A

[0004] It is an object of the present invention to provide a glass containing a crystalline phase that has high transparency.

[0005] The present inventors have conducted extensive research into the composition of glass containing a crystalline phase and have found that when specific compositional conditions are met, the glass exhibits high transparency, leading to the completion of the present invention.

[0006] The present invention provides the following: (Configuration 1) A raw glass containing, in mass % in terms of oxides, SiO ２ Component content 65.0% to 85.0%, Al ２ O ３ Ingredient content 3.0% to 15.0%, P ２ O ５ Component content: Over 0% to 5.0%, Li ２ O content: over 5.0% to 15.0%, ZrO ２ The content of the component is 0% to 10.0%, the content of the MgO component is 0% to 5.0%, and [SiO ２ Ingredient content / (Na ２ O component content + K ２ A glass containing a crystalline phase, wherein the base glass satisfies the following conditions: 23.0 to 150.0, and the light transmittance at 550 nm is 70% or more. (Configuration 2) The base glass contains, in mass % in terms of oxides, Li, ２ O component, P ２ O ５ component, and Al ２ O ３The total content of the components [Li ２ O component content + P ２ O ５ Ingredient content + Al ２ O ３ The glass containing a crystalline phase according to the first aspect of the present invention, wherein the base glass contains, in mass % in terms of oxides, 22.5 to 40.0% of Li. ２ SiO relative to the content of O component ２ The ratio of the content of the components [SiO ２ Component content / Li ２ The glass containing the crystalline phase according to the first or second aspect of the present invention, wherein the content of the O component in the raw glass is 4.0 to 8.0% by mass in terms of oxides. ２ O ５ SiO relative to the content of the component ２ The ratio of the content of the components [SiO ２ Ingredient content / P ２ O ５ (Configuration 5) A glass containing a crystalline phase according to any one of Configurations 1 to 3, wherein the base glass contains, in mass % in terms of oxides, Li ２ O component and P ２ O ５ The total content of the components [Li ２ O component content + P ２ O ５ A glass containing a crystalline phase according to any one of the first to fourth aspects, wherein the base glass contains, in mass % in terms of oxides, ZrO ２ SiO relative to the content of the component ２ The ratio of the content of the components [SiO ２ Component content / ZrO ２ A glass comprising a crystalline phase according to any one of configurations 1 to 5, which satisfies the following: [Content of component] 10.0 to 150.0. (Configuration 7) A glass comprising a crystalline phase according to any one of configurations 1 to 6, which contains one or more crystalline phases selected from vergielite, lithium disilicate, petalite, and β-quartz solid solution. (Configuration 8) A glass comprising a crystalline phase according to any one of configurations 1 to 7, which is glass-ceramics.

[0007] According to the present invention, a glass containing a crystalline phase and having high transparency can be provided.

[0008] Hereinafter, embodiments and examples of the glass containing a crystalline phase of the present invention will be described in detail, but the present invention is not limited to the following embodiments and examples, and can be practiced with appropriate modifications within the scope of the object of the present invention.

[0009] [Glass containing a crystalline phase] In the glass containing a crystalline phase of the present invention, the base glass satisfies the following conditions in terms of mass % of oxides: SiO ２ Component content 65.0% to 85.0%, Al ２ O ３ Ingredient content 3.0% to 15.0%, P ２ O ５ Component content: Over 0% to 5.0%, Li ２ O content: over 5.0% to 15.0%, ZrO ２ The content of the component is 0% to 10.0%, the content of the MgO component is 0% to 5.0%, and [SiO ２ Ingredient content / (Na ２ O component content + K ２ The glass of the present invention containing a crystalline phase has a transmittance of 70% or more at 550 nm. The transmittance is measured by the method described in the examples using a sample having a thickness of 10 mm.

[0010] Glasses containing the above-mentioned crystalline phases satisfy specific compositional conditions, and therefore exhibit high light transmittance and excellent transparency. Therefore, they can be used as components for smartphone cover glass and housings, components for portable electronic devices such as tablet PCs and wearable devices, and components for protective protectors and head-up display substrates used in transportation vehicles such as cars and airplanes, and the high transparency of the glass can improve the utility value of each of the above-mentioned devices. Hereinafter, each configuration of the glass containing the crystalline phase of the present invention will be described.

[0011] <Glass containing a crystalline phase> The glass containing a crystalline phase of the present invention is a glass material having a crystalline phase and a glass phase, and is distinguished from an amorphous material. The glass containing a crystalline phase of the present invention is, for example, crystallized glass. The glass containing a crystalline phase of the present invention can be produced by adjusting the raw material composition and production conditions according to the production method and examples described below. Furthermore, the glass containing a crystalline phase of the present invention can have a compressive stress layer formed on its surface by various strengthening methods (chemical strengthening, thermal strengthening, ion implantation, etc.).

[0012] In one embodiment, the glass (e.g., crystallized glass) containing a crystalline phase of the present invention has a light transmittance at 550 nm of 70% or more, 75% or more, or 80% or more.

[0013] In one embodiment, the glass (e.g., crystallized glass) containing a crystalline phase of the present invention has an average light transmittance of 70% or more, 75% or more, or 80% or more in the range of 400 to 800 nm, as measured using a 10 mm thick sample by the method described in the Examples.

[0014] (Glass-ceramics) Glass-ceramics, also known as glass ceramics, are materials in which crystals are precipitated inside the glass by heat-treating the glass. Glass-ceramics are materials that have a crystalline phase and a glass phase, and are distinguished from amorphous solids. Generally, the crystalline phase of glass-ceramics is determined by the angle of the peaks that appear in the X-ray diffraction pattern of X-ray diffraction analysis.

[0015] In one embodiment, the glass containing a crystalline phase (e.g., glass-ceramics) of the present invention contains one or more crystalline phases selected from vergielite, lithium disilicate (also called lithium disilicate or lithium disilicate), petalite, and β-quartz solid solution. The method for identifying the crystalline phase is as described in the Examples.

[0016] In one embodiment, the crystalline phase-containing glasses (e.g., glass-ceramics) of the present invention include a crystalline phase of vergielite, a crystalline phase of lithium disilicate (also known as lithium disilicate or lithium disilicate), and a crystalline phase of petalite.

[0017] Crystallized glass can be produced by the following method: raw materials are uniformly mixed so that each component falls within a predetermined content range, and then melt-molded to produce a base glass. This base glass is then crystallized to produce crystallized glass.

[0018] (Base Glass) The base glass satisfies the specific compositional conditions described above. In this specification, the content of each component is expressed in mass% converted to oxide unless otherwise specified. Here, "oxide converted" refers to the amount of oxide of each component contained in the crystallized glass, expressed in mass%, when the total mass of the oxides is 100 mass%, assuming that all the components constituting the crystallized glass are decomposed and converted to oxides. In this specification, A% to B% means A% or more and B% or less.

[0019] The base glass may have the following configuration in addition to the above compositional conditions in order to be easily deformed into a curved shape by thermal processing and to obtain a high visible light transmittance in the crystallized glass.

[0020] SiO ２ The component is a framework component that constitutes the glass containing a crystalline phase, and is a component that enhances stability and precipitates a desired crystalline phase. ２ When the content of the component is 85.0% or less, excessive increase in viscosity and deterioration of meltability can be suppressed, and when it is 65.0% or more, the stability of the glass containing a crystalline phase can be improved. Therefore, the upper limit is preferably 85.0% or less, more preferably 83.0% or less, and even more preferably 80.0% or less. The lower limit is preferably 65.0% or more, and may be 68.0% or more, or more than 70.0%.

[0021] Al ２ O ３ The Al component is a framework component that constitutes the inorganic composition part and is a component that enhances stability. ２ O ３When the content of the component is 15.0% or less, the deterioration of devitrification can be suppressed, and when it is 3.0% or more, the deterioration of stability can be suppressed. Therefore, the upper limit is preferably 15.0% or less, more preferably 13.0% or less, and may be less than 12.0%. Furthermore, the lower limit is preferably 3.0% or more, more preferably 4.0% or more, more preferably 5.0% or more, more preferably more than 7.0%, and more preferably more than 8.0%.

[0022] P ２ O ５ The component is an essential component that promotes crystal formation in glasses containing crystalline phases. ２ O ５ If the content of the component is 5.0% or less, phase separation of the glass can be suppressed. Therefore, the upper limit is preferably 5.0% or less, more preferably 4.5% or less, and even more preferably 4.0% or less. The lower limit is preferably more than 0%, more preferably 0.5% or more, and even more preferably 1.0% or more. ２ O ５ The content of the component may be 3.0% or less, 2.7% or less, or 2.5% or less. ２ O ５ The content of the component may be 1.5% or more, or 2.0% or more.

[0023] Li ２ The O component is a component that improves the meltability of the base glass and enhances manufacturability. ２ When the content of the O component is 15.0% or less, the deterioration of devitrification can be suppressed, and when it exceeds 5.0%, the deterioration of viscosity and meltability can be suppressed, and manufacturability can be improved. Therefore, the lower limit is preferably more than 5.0%, more preferably 6.0% or more, and even more preferably 7.0% or more. The upper limit is preferably 15.0% or less, more preferably 13.0% or less, and may be 12.0% or less.

[0024] ZrO ２ Although the glass containing the crystalline phase according to the present invention can be prepared even at 0% of this component, it is a component that acts as a nucleating agent for crystals when contained at more than 0%. ２When the content of this component is 10.0% or less, deterioration of meltability can be suppressed. Therefore, the upper limit is preferably 10.0% or less, more preferably 8.0% or less, more preferably 5.0% or less, and even more preferably 3.5% or less, and may be less than 2.5%. Furthermore, the lower limit is preferably 0% or more, more preferably 0.5% or more, more preferably 0.8% or more, more preferably 1.0% or more, and even more preferably more than 1.5%.

[0025] Although the MgO component can produce a glass containing the crystalline phase according to the present invention even at 0%, it is a component that improves low-temperature melting properties when contained in an amount exceeding 0%. When the MgO content is 5.0% or less, the glass is easily tempered during chemical tempering. Therefore, the upper limit is preferably 5.0% or less, more preferably 3.0% or less, and even more preferably less than 2.0%. The lower limit is preferably 0% or more, more preferably 0.1% or more, and even more preferably 0.2% or more.

[0026] Although the ZnO component can produce a glass containing the crystalline phase according to the present invention even at 0%, it is a component that improves low-temperature melting properties when contained in an amount exceeding 0%. When the ZnO content is 5.0% or less, strengthening is facilitated during chemical strengthening. Therefore, the upper limit is preferably 5.0% or less, more preferably 3.0% or less, and even more preferably less than 2.0%. The lower limit is preferably 0% or more, more preferably more than 0%, more preferably 0.1% or more, and even more preferably 0.2% or more.

[0027] Although the CaO component can produce a glass containing the crystalline phase according to the present invention even at 0%, it is a component that improves low-temperature melting property when contained in an amount exceeding 0%. If the CaO content is 5.0% or less, strengthening is facilitated during chemical strengthening. Therefore, the upper limit can be preferably set to 5.0% or less, more preferably 3.0% or less, and even more preferably less than 1.0%.

[0028] Although the glass according to the present invention can be produced even with 0% of the SrO component and the BaO component, when the content exceeds 0%, these components improve low-temperature melting property. When the content of each of the SrO component and the BaO component is 5.0% or less, strengthening is facilitated when chemical strengthening is performed. Therefore, the upper limit of each of the SrO component and the BaO component can be preferably set to 5.0% or less, more preferably 3.0% or less, and even more preferably 1.0% or less.

[0029] Gd ２ O ３ The glass according to the present invention can be produced even if the content of this component is 0%, but when it is contained in an amount exceeding 0%, it is a component that can increase the refractive index and decrease the partial dispersion ratio. ２ O ３ If the component is contained in a large amount, the liquidus temperature may decrease, causing the glass to devitrify. ２ O ３ By making the content of the component 10.0% or less, it is possible to reduce devitrification and coloring. ２ O ３ The upper limit of the content of the component is preferably 10.0% or less, more preferably 8.0% or less, even more preferably 5.0% or less, and most preferably 3.0% or less.

[0030] By setting the total content of CaO and MgO [CaO content + MgO content] to 5.0% or less, it is possible to prevent chemical strengthening from becoming difficult, and even at 0%, it is possible to produce a glass containing the crystalline phase according to the present invention. However, if the total content exceeds 0%, deterioration of meltability can be suppressed. Therefore, the upper limit of [CaO content + MgO content] is preferably 5.0% or less, more preferably 3.0% or less, more preferably less than 3.0%, even more preferably 2.0% or less, and may be 1.0% or less. Furthermore, the lower limit of [CaO content + MgO content] is preferably 0% or more, more preferably more than 0%, more preferably 0.1% or more, and even more preferably 0.2% or more.

[0031] K ２ O component, Na ２ The O component is a component that improves the meltability of the base glass and enhances manufacturability.２ O component, Na ２ When the content of each of the O components is 5.0% or less, the deterioration of devitrification can be suppressed. ２ O component, Na ２ Even if the O component is 0%, it is possible to prepare a glass containing a crystalline phase according to the present invention. However, when the O component is contained in an amount exceeding 0%, deterioration in viscosity and meltability can be suppressed, and manufacturability can be improved. ２ O component, Na ２ The lower limit of each of the O components is preferably 0% or more, more preferably 0.2% or more, and further preferably 0.3% or more. ２ O component, Na ２ The upper limit of each of the O components is preferably set to 5.0% or less, more preferably 4.0% or less, more preferably less than 3.0%, and even more preferably less than 2.0%.

[0032] Sb ２ O ３ The component functions as a fining agent when producing raw glass. ２ O ３ If the component is contained in excess, the transmittance in the short wavelength region of the visible light region may be deteriorated. Therefore, the upper limit can be preferably set to 2.0% or less, more preferably 1.0% or less, more preferably 0.6% or less, and even more preferably 0.5% or less. The lower limit can be preferably set to 0% or more, more preferably more than 0%, more preferably 0.001% or more, more preferably 0.01% or more, and more preferably 0.05% or more.

[0033] B ２ O ３ The component has the effect of lowering the viscosity of the raw glass. ２ O ３ When the content of the component is 10.0% or less, the deterioration of devitrification can be suppressed. ２ O ３Although a glass containing the crystalline phase according to the present invention can be produced even when the content of the component is 0%, a content of more than 0% can suppress deterioration in the viscosity and meltability of the base glass. Therefore, the upper limit can be preferably set to 10.0% or less, more preferably 8.0% or less, more preferably 7.0% or less, more preferably 5.0% or less, more preferably 4.0% or less, and even more preferably 3.0% or less. The lower limit can be preferably set to 0% or more, more preferably more than 0%, more preferably 0.001% or more, more preferably 0.01% or more, more preferably 0.05% or more, more preferably 0.10% or more, and even more preferably 0.30% or more.

[0034] Na ２ O content and K ２ SiO relative to the total content of O components ２ The ratio of the content of the components [SiO ２ Ingredient content / (Na ２ O component content + K ２ O component content)] is set to 23.0 to 150.0, excellent transmittance can be achieved. ２ Ingredient content / (Na ２ O component content + K ２ The upper limit of [SiO content] is preferably 150.0 or less, more preferably 130.0 or less, more preferably 120.0 or less, and even more preferably 110.0 or less. It may also be 100.0 or less, 90.0 or less, or 80.0 or less. ２ Ingredient content / (Na ２ O component content + K ２ The preferred lower limit of the [content of O component] is 23.0 or more, more preferably 25.0 or more, more preferably 30.0 or more, more preferably 35.0 or more, and may be 54.0 or more.

[0035] K ２ O component and Na ２ Total content of O components [K ２ O component content + Na ２Although the glass containing the crystalline phase according to the present invention can be produced even at a content of 0%, when the content exceeds 0%, the deterioration of viscosity can be suppressed and the increase in melting temperature can be suppressed. Furthermore, when the content is 5.0% or less, the deterioration of devitrification can be suppressed. Therefore, the content of [K ２ O component content + Na ２ The lower limit of the [content of O component] is preferably 0% or more, more preferably 0.1% or more, more preferably 0.2% or more, and even more preferably 0.3% or more, and the upper limit is preferably 5.0% or less, more preferably 4.0% or less, more preferably less than 4.0%, more preferably less than 3.0%, and even more preferably less than 2.0%.

[0036] The total content of MgO, CaO, SrO, BaO, and ZnO [MgO + CaO + SrO + BaO + ZnO] is 15.0% or less to facilitate chemical strengthening. Although a glass containing the crystalline phase according to the present invention can be produced even when [MgO + CaO + SrO + BaO + ZnO] is 0%, deterioration of meltability can be suppressed when the content exceeds 0%. Therefore, the lower limit of [MgO + CaO + SrO + BaO + ZnO] is preferably 0% or more, more preferably more than 0%, more preferably 0.3% or more, and may be 0.5% or more, or 1.0% or more. The upper limit is preferably 15.0% or less, more preferably 10.0% or less, more preferably 5.0% or less, and even more preferably 3.5% or less.

[0037] [Al ２ O ３ Ingredient content / K ２ By setting the [Al O content] to 100.0 or less, it is possible to suppress the deterioration of viscosity. Furthermore, by setting it to 0.6 or more, it is possible to suppress the deterioration of devitrification. ２ O ３ Ingredient content / K ２The upper limit of the [Al O component content] is preferably 100.0 or less, more preferably 80.0 or less, more preferably 60.0 or less, more preferably 40.0 or less, more preferably 20.0 or less, and even more preferably 15.0 or less. ２ O ３ Ingredient content / K ２ The lower limit of the [content of K component] is preferably 0.6 or more, more preferably 1.0 or more, more preferably 2.0 or more, more preferably 3.0 or more, and even more preferably 4.0 or more or 5.0 or more, and may be 5.7 or more. ２ The content of the O component can be set to 0.

[0038] [Al ２ O ３ Ingredient content / (K ２ If the [Al content + MgO content] is 20.0 or less, the deterioration of viscosity can be suppressed. If it is more than 0, the deterioration of devitrification can be suppressed. Therefore, the upper limit is preferably 20.0 or less, more preferably 18.0 or less, more preferably 16.0 or less, and even more preferably 15.0 or less. ２ O ３ Ingredient content / (K ２ The lower limit of the ratio [content of the O component + content of the MgO component] is preferably more than 0, more preferably 1.0 or more, more preferably 2.0 or more, and even more preferably 2.6 or more.

[0039] [Al ２ O ３ By setting the ratio [Al component content / (ZnO component content+MgO component content)] to 20.0 or less, it is possible to suppress deterioration of meltability, and by setting it to 3.0 or more, it is possible to suppress deterioration of devitrification. ２ O ３ The upper limit of the ratio [content of ZnO component + content of MgO component] is preferably 20.0 or less, more preferably 18.0 or less, even more preferably 17.0 or less, and may be 16.0 or less. The lower limit is preferably 3.0 or more, more preferably 4.0 or more, even more preferably 4.5 or more, and may be more than 5.0.

[0040] [Li ２By setting the ratio of [LiO component content / MgO component content] to 150.0 or less, it is possible to suppress deterioration of devitrification, and by setting it to 5.0 or more, it is possible to facilitate chemical strengthening. ２ The upper limit of the ratio of [LiO component content / MgO component content] is preferably 150.0 or less, more preferably 100.0 or less, more preferably 50.0 or less, more preferably 30.0 or less, and can be 25.0 or less, or 23.0 or less. Also, MgO can be 0. On the other hand, ２ The lower limit of the ratio [content of O component / content of MgO component] is preferably 5.0 or more, more preferably 6.0 or more, and can be 8.0 or more, 9.0 or more, 9.5 or more, 10.0 or more, or 10.6 or more.

[0041] [Li ２ O component content / (MgO component content + CaO component content + SrO component content + BaO component content + Na ２ O component content + K ２ By making the [Li content (Li content)] 50.0 or less, it is possible to improve the melting property and prevent the deterioration of devitrification. In addition, by making it 1.0 or more, it is possible to prevent the chemical strengthening from becoming difficult. ２ O component content / (MgO component content + CaO component content + SrO component content + BaO component content + Na ２ O component content + K ２ The upper limit of [LiO component content] can be set to 50.0 or less, more preferably 35.0 or less, more preferably 30.0 or less, more preferably 20.0 or less, more preferably 15.0 or less, more preferably 13.0 or less, and even more preferably 10.0 or less. ２ O component content / (MgO component content + CaO component content + SrO component content + BaO component content + Na ２ O component content + K ２ O content)] can be set to 0. ２ O component content / (MgO component content + CaO component content + SrO component content + BaO component content + Na ２ O component content + K ２The preferred lower limit of the [content of the O component] can be set to 1.0 or more, more preferably 2.0 or more, more preferably 3.0 or more, and even more preferably more than 3.0.

[0042] [MgO component content / (Li ２ By setting the value of [content of MgO component / (LiO component content + content of MgO component)] to 0.6 or less, it is possible to prevent chemical strengthening from becoming difficult and to prevent the deterioration of devitrification. Even if the lower limit is 0, it is possible to prepare a glass containing the crystalline phase according to the present invention. However, by setting the value of [content of MgO component / (LiO component content + content of MgO component content)] to more than 0, it is possible to improve the low-temperature melting property while maintaining the devitrification property. ２ The upper limit of [content of MgO component / (LiO component content + content of MgO component)] is preferably 0.6 or less, more preferably 0.3 or less, and even more preferably less than 0.15. ２ The lower limit of the ratio [content of the O component + content of the MgO component] can be set to 0 or more, more preferably 0.01 or more, more preferably 0.03 or more, and even more preferably 0.04 or more.

[0043] Li ２ O component, Na ２ O component and K ２ Total content of O components [Li ２ O component content + Na ２ O component content + K ２ The content of the LiO component increases meltability and is an index of the ease of producing a base glass. That is, by making the content 17.0% or less, it is possible to suppress the deterioration of devitrification, and by making the content 3.0% or more, it is possible to suppress the deterioration of viscosity and the increase in melting temperature. Therefore, [Li ２ O component content + Na ２ O component content + K ２ The upper limit of the [Li content] is preferably 17.0% or less, more preferably 15.0% or less, and even more preferably 14.0% or less. ２ O component content + Na ２ O component content + K ２ The lower limit of the [content of O component] can be set to preferably 3.0% or more, more preferably 5.0% or more, and even more preferably 8.0% or more.

[0044] Li２ O component and P ２ O ５ The total content of the components [Li ２ O component content + P ２ O ５ If the content of the [Li component] is 18.0% or less, the deterioration of devitrification can be suppressed. ２ O component content + P ２ O ５ The content of the component is, for example, 8.0% or more. ２ O component content + P ２ O ５ The upper limit of the [Li content] is preferably 18.0% or less, more preferably 17.0% or less, and may be 15.0% or less, 14.0% or less, or 13.8% or less. ２ O component content + P ２ O ５ The lower limit of the content of the component is preferably 8.0% or more, more preferably 9.0% or more, more preferably 10.0% or more, more preferably 11.5% or more, and even more preferably 12.01% or more.

[0045] Li ２ O component and P ２ O ５ Components and Al ２ Total content of O3 components [Li ２ O component content + P ２ O ５ Ingredient content + Al ２ If the [LiO3 content] is 40.0% or less, the deterioration of devitrification can be suppressed. ２ O component content + P ２ O ５ Ingredient content + Al ２ If the content of the LiO component is 22.5% or more, it is expected that the effect of promoting the precipitation of fine crystals will be achieved. ２ O component content + P ２ O ５ Ingredient content + Al ２ The upper limit of the [LiO3 content] is preferably 35.0% or less, more preferably 30.0% or less, and may be 27.0% or less, or 25.0% or less. ２ O component content + P２ O ５ Ingredient content + Al ２ The preferred lower limit of the O3 component content is 22.5% or more, and may be 22.8% or more.

[0046] [P ２ O ５ If the ratio [P component content / MgO component content] is 50.0 or less, deterioration of low-temperature melting properties can be suppressed. ２ O ５ The ratio of [P ２ O ５ The upper limit of the ratio [content of component / content of MgO component] is preferably 50.0 or less, more preferably 30.0 or less, more preferably 10.0 or less, more preferably 7.0 or less, and may be 5.0 or less, 4.1 or less, 4.0 or less, or 3.7 or less. The content of the MgO component may also be 0. ２ O ５ The lower limit of the ratio [content of component / content of MgO component] is preferably greater than 0, more preferably 0.02 or more, more preferably 0.1 or more, more preferably 0.15 or more, and even more preferably 0.5 or more, and may be 1.0 or more, or 2.4 or more.

[0047] [SiO ２ Component content / ZrO ２ The content of the [SiO ２ Component content / ZrO ２ The preferred upper limit of [content of SiO ２ Component content / ZrO ２ The preferred lower limit of the [content of component] is 10.0 or more, more preferably 15.0 or more, more preferably 17.0 or more, more preferably 18.0 or more, more preferably 19.6 or more, and even more preferably 20.0 or more, and may be 29.9 or more.

[0048] [SiO ２ Component content / Li２ By setting the [content of SiO component] to 8.0 or less, deterioration of low-temperature melting property can be suppressed. ２ Component content / Li ２ O content] is, for example, 4.0 or more. ２ Component content / Li ２ The upper limit of the [SiO content] is preferably 8.0 or less, more preferably 7.5 or less, and even more preferably 7.0 or less. ２ Component content / Li ２ The lower limit of the [content of O component] can be set to preferably 4.0 or more, more preferably 4.3 or more, and even more preferably 5.0 or more.

[0049] [SiO ２ Ingredient content / P ２ O ５ The content of the [SiO ２ Ingredient content / P ２ O ５ The upper limit of the [content of the SiO ２ Ingredient content / P ２ O ５ The preferred lower limit of the [content of component] is 13.0 or more, more preferably 17.0 or more, more preferably 20.0 or more, and may be 25.0 or more, 30.0 or more, or 33.0 or more.

[0050] [SiO ２ Ingredient content / (P ２ O ５ Component content + ZrO ２ The content of the [SiO ２ Ingredient content / (P ２ O ５ Component content + ZrO ２The upper limit of [SiO ２ Ingredient content / (P ２ O ５ Component content + ZrO ２ The preferred lower limit of [content of component (%)] is 4.3 or more, more preferably 10.0 or more, and may be 15.0 or more or 16.1 or more.

[0051] [ZnO component content / (Li ２ O component content + P ２ O ５ The ratio [content of ZnO component / (LiO content + content of MgO component)] is, for example, 1.0 or less, and even if the lower limit is 0, a glass containing a crystalline phase according to the present invention can be produced. However, by making the ratio exceed 0, it is possible to improve low-temperature melting property while maintaining devitrification property. ２ O component content + P ２ O ５ The upper limit of the ratio [content of ZnO component / (LiO component content + content of MgO component)] is preferably 1.0 or less, more preferably 0.09 or less, more preferably less than 0.06, and even more preferably 0.05 or less. ２ O component content + P ２ O ５ The lower limit of the ratio [(content of the component + content of the MgO component)] is preferably 0 or more, more preferably more than 0, more preferably 0.01 or more, more preferably 0.02 or more, and even more preferably 0.03 or more.

[0052] [(SiO ２ Ingredient content + Al ２ O ３ Ingredient content + P ２ O ５ Content of component) / (Li ２ O component content + Na ２ O component content + K ２ By setting the [(SiO content + MgO content)] to 9.0 or less, deterioration of low-temperature melting property can be suppressed, and by setting it to 0.7 or more, crystal precipitation can be promoted.２ Ingredient content + Al ２ O ３ Ingredient content + P ２ O ５ Content of component) / (Li ２ O component content + Na ２ O component content + K ２ The upper limit of [(SiO ２ Ingredient content + Al ２ O ３ Ingredient content + P ２ O ５ Content of component) / (Li ２ O component content + Na ２ O component content + K ２ The lower limit of the ratio [content of the O component + content of the MgO component] is preferably 0.7 or more, more preferably 4.0 or more, more preferably 5.0 or more, and even more preferably 5.5 or more, and may be 6.0 or more.

[0053] The glass containing the crystalline phase of the present invention may contain TiO within a range that does not impair the effects of the present invention. ２ , Bi ２ O ３ , Cr ２ O ３ , CuO, La ２ O ３ , MnO, MoO ３ , PbO, V ２ O ５ , W.O. ３ , Y ２ O ３ The absence of these components has the effect of preventing deterioration of transmittance.

[0054] Furthermore, the glass containing the crystalline phase of the present invention may or may not contain other components not mentioned above, as long as the properties of the crystallized glass of the present invention are not impaired. For example, metal components such as Yb, Lu, Fe, Co, Ni, and Ag (including oxides of these metals) may be contained.

[0055] As a glass fining agent, Sb ２ O３ In addition to the ingredients, SnO ２ Component, CeO ２ Component, As ２ O ３ The fining agent may contain one or more selected from the group consisting of F, NOx, and SOx, but the upper limit of the fining agent content is preferably 3.0% or less, more preferably 2.0% or less, more preferably 1.0% or less, and most preferably 0.6% or less.

[0056] On the other hand, since the use of Pb, Th, Tl, Os, Be, Cl, and Se has recently been discouraged as harmful chemical substances, it is preferable that these components are substantially free of these elements. "Substantially free of these elements" refers to the case where these elements are contained as unavoidable impurities or are not contained at all. The total amount of these elements is, for example, 0.1% or less.

[0057] (Method for manufacturing crystallized glass) The heat treatment for crystal precipitation may be a one-stage or two-stage heat treatment. In the two-stage heat treatment, a nucleation step is first performed by heat treatment at a first temperature, and after this nucleation step, a crystal growth step is performed by heat treatment at a second temperature higher than that of the nucleation step. The first temperature of the two-stage heat treatment is preferably 400°C to 750°C, more preferably 450°C to 720°C, and even more preferably 500°C to 680°C. It can also be 550°C to 650°C. The holding time at the first temperature is preferably 30 minutes to 2000 minutes, more preferably 180 minutes to 1440 minutes. The second temperature of the two-stage heat treatment is preferably 550°C to 850°C, more preferably 600°C to 800°C. It can also be 650°C to 750°C. The holding time at the second temperature is preferably 30 minutes to 600 minutes, more preferably 60 minutes to 400 minutes.

[0058] In one-stage heat treatment, the nucleation step and the crystal growth step are carried out continuously at a single temperature. Typically, the temperature is raised to a predetermined heat treatment temperature, and after reaching the heat treatment temperature, the temperature is maintained for a certain period of time, and then the temperature is lowered. In the case of one-stage heat treatment, the heat treatment temperature is preferably 600°C to 800°C, more preferably 630°C to 770°C. The holding time at the heat treatment temperature is preferably 30 minutes to 500 minutes, more preferably 60 minutes to 400 minutes.

[0059] Examples 1 to 64, Comparative Example 1 (1) Preparation of raw materials As raw materials for each component of the crystallized glass, raw materials of the corresponding oxides were selected, and these raw materials were weighed and mixed uniformly to obtain the compositions shown in Tables 1 to 5.

[0060] (2) Production of Crystallized Glass Next, the mixed raw materials were placed in a platinum crucible and melted in an electric furnace at 1300°C to 1600°C for 2 to 24 hours depending on the melting difficulty of the glass composition. The molten glass was then stirred to homogenize it, and the temperature was lowered to 1000°C to 1450°C, after which it was poured into a mold and slowly cooled to produce a base glass. The obtained base glass was heated under the nucleation conditions and nucleus growth (crystallization) conditions shown in Tables 6 to 10 to produce a crystallized glass.

[0061] (3) Confirmation of crystalline phase The crystalline phase contained in the crystallized glass obtained in (2) was determined from the angle of the diffraction peak and the intensity ratio of multiple diffraction peaks appearing in the X-ray diffraction pattern measured using an X-ray diffraction analyzer (D8Discover, manufactured by Bruker). The confirmed crystalline phases are shown in Tables 6 to 10.

[0062] (4) Measurement of light transmittance The crystallized glass obtained in (2) was polished to prepare a plate-shaped measurement sample having a thickness of 10 mm. The measurement sample was measured for light transmittance (%) at 550 nm and average light transmittance (%) at 400 to 800 nm using a spectrophotometer (Hitachi High-Technologies Corporation's "U-4100"). The results are shown in Tables 6 to 10.

[0063]

[0064] It can be seen from Tables 6 to 10 that the crystallized glasses of the examples that satisfy the specific compositions exhibit excellent light transmittance.

[0065] Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will readily be able to make numerous modifications to these exemplary embodiments and / or examples without substantially departing from the novel teachings and advantages of the present invention. Accordingly, these numerous modifications are within the scope of the present invention. The contents of all documents cited in this specification and of the applications from which this application claims priority under the Paris Convention are incorporated by reference in their entirety.

Claims

1. The mass percent of the raw glass is calculated as oxide, and is SiO ２ Content of components: 65.0% to 85.0%, Al ２ O ３ Content of ingredients: 3.0% to 15.0%, P ２ O ５ Content of ingredients: 0% to 5.0%, Li ２ O content: 5.0% to 15.0%, ZrO ２ The content of the component is 0% to 10.0%, the content of the MgO component is 0% to 5.0%, and [SiO ２ Content of ingredients / (Na ２ Content of O component + K ２ A glass containing a crystalline phase, which satisfies the above formula (1) below: [0025] 23.0 to 150.0, and has a light transmittance of 70% or more at 550 nm.

2. The raw glass contains, in mass % in terms of oxide, Li ２ O component, P ２ O ５ Component, and Al ２ O ３ The total content of the components [Li ２ Content of O component + P ２ O ５ Content of ingredients + Al ２ O ３ The glass containing the crystalline phase according to claim 1, which satisfies the following: [Content of component] 22.5 to 40.0%.

3. The raw glass contains, in mass % in terms of oxide, Li ２ SiO vs. O content ２ Ratio of component contents [SiO ２ Component content / Li ２ The glass containing the crystalline phase according to claim 1 or 2, wherein the content of O component is 4.0 to 8.

0.

4. The raw glass contains, in mass % oxide equivalent, P ２ O ５ SiO relative to component content ２ Ratio of component contents [SiO ２ Ingredient content / P ２ O ５ Component Content] 13.0 to 40.

0. The glass containing the crystalline phase according to claim 1 or 2.

5. The raw glass contains, in mass % in terms of oxide, Li ２ O component and P ２ O ５ The total content of the components [Li ２ Content of O component + P ２ O ５ The glass containing the crystalline phase according to claim 1 or 2, which satisfies the following: [Content of component] 8.0 to 18.0%.

6. The raw glass contains, in mass % in terms of oxide, ZrO ２ SiO relative to component content ２ Ratio of component contents [SiO ２ Component content / ZrO ２ Component Content] 10.0 to 150.

0. The glass containing the crystalline phase according to claim 1 or 2.

7. A glass comprising the crystalline phase of claim 1 or 2, comprising one or more crystalline phases selected from vergillite, lithium disilicate, petalite and β-quartz solid solution.

8. A glass comprising the crystalline phase according to claim 1 or 2, which is a crystallized glass.

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