Crystal phase–containing glass

Abstract

Crystal phase–containing glass which contains, in mass% in terms of oxides, 30% to 85% of an SiO2 component, and which has a yield point of 840°C or lower and an average transmittance of 30% or lower at a thickness of 1 mm in a wavelength range of 380 nm to 830 nm.

Description

Glass containing a crystalline phase

[0001] This invention relates to a glass containing a crystalline phase.

[0002] In recent years, there has been a growing demand for the use of glass as the casing (exterior) of electronic devices such as smartphones and tablet PCs. Furthermore, glass used in these applications is required to have sufficient strength to withstand harsh use. In addition, when using glass as the casing of electronic devices, light-shielding properties are required to prevent light from leaking from internal components to the outside. For example, Patent Documents 1 and 2 disclose white, opaque crystallized glass as a high-strength glass used as the casing of electronic devices. In crystallized glass, a white color with high light-shielding properties can generally be achieved by further crystallization to a state close to ceramic, and such glass tends to exhibit very high thermal properties such as strain point.

[0003] On the other hand, these glasses require high mass production capabilities due to the increasing demand for electronic devices such as smartphones. Furthermore, in recent years, attempts have been made to employ processing methods that involve reheating and bending the glass after crystallization. For example, in recent years, the importance of recycling has increased from the perspective of reducing carbon dioxide emissions, and there is a demand for glass with excellent bendability, which is made by reheating and bending glass components recovered from used electronic devices. However, with conventional technology, it has been difficult to realize glass that satisfies all of the characteristics of excellent light shielding in the visible light range, bendability, and mass production capability.

[0004] Japanese Patent Publication No. 2018-150230 Japanese Patent Publication No. 2014-148641

[0005] The objective of the present invention is to provide glass that exhibits excellent light-shielding properties in the visible light range, is easy to bend with heat, and is easy to mass-produce.

[0006] The present invention provides glass and the like containing the following crystalline phases: (Configuration 1) By mass % on an oxide basis, SiO ２Glass containing 30% to 85% of a component, having a yield point of 840 °C or lower, and having an average transmittance of 30% or lower at a thickness of 1 mm in the wavelength range of 380 nm to 830 nm, and containing a crystal phase. (Configuration 2) From the reflection spectrum including regular reflection measured under the following conditions by a spectrophotometer, in the CIE Lab color space coordinates obtained using CIE light source D65 at an observer angle of 10°, a* is in the range of -10.00 to 5.00, b* is in the range of -20.00 to 5.00, and L* is in the range of 50.00 or more. The glass containing a crystal phase according to Configuration 1. (Reflection spectrum measurement conditions) Sample thickness: 1 mm Light receiving angle with respect to the normal of the sample surface: 8° (Configuration 3) In mass% in terms of oxide, P ２ O ５ The component is 0% to 10.0%, and the ZrO ２ The component contains 0% to 20.0%. The glass containing a crystal phase according to Configuration 1 or 2. (Configuration 4) In mass% in terms of oxide, [the content ratio (%) of the TiO ２ component + the content ratio (%) of the ZrO ２ component] is more than 0, and [(the content ratio (%) of the P ２ O ５ component + the content ratio (%) of the Al ２ O ３ component) / (the content ratio (%) of the TiO<​​​​​​​​​​​​​​​​​​​​​​O component 0% to 10.0%, MgO component 0% to 10.0%, CaO component 0% to 10.0%, SrO component 0% to 10.0%, BaO component 0% to 10.0%, ZnO component 0% to 15.0%, TiO ２ The ingredients are 0% to 10.0%, ZrO ２ The ingredients are 0% to 15.0%, Nb ２ O ５ The ingredients are 0% to 10.0%, Sb ２ O ３ A glass containing the crystalline phase described in composition 4, with the component present in 0% to 5%. (Composition 6) In terms of mass % on an oxide basis, TiO ２ Contains more than 0% of the component, [SiO ２ Percentage of component content (%) / TiO ２ A glass containing the crystalline phase described in composition 1 or 2, wherein the content ratio (%) of the component is less than 5.0. (Composition 7) In terms of mass %, SiO ２ The ingredients are 30.0% to 50.0%, Al ２ O ３ Ingredients in 0% to 10.0%, B ２ O ３ The ingredients are 0% to 10.0%, P ２ O ５ Ingredients: 0% to 10.0%, Li ２ O component 0% to 10.0%, Na ２ Component O: 5% to 20.0%, K ２ O component 0% to 15.0%, MgO component 0% to 10.0%, CaO component 0% to 10.0%, SrO component 0% to 10.0%, BaO component 0% to 10.0%, ZnO component 0% to 10.0%, TiO ２ The ingredients are 15% to 35.0%, ZrO ２ The ingredients are 0% to 10.0%, Nb ２ O ５ The ingredients are 0% to 15.0%, Sb ２ O ３ A glass containing the crystalline phase described in composition 6, containing 0% to 5.0% of the component. (Composition 8) Contains more than 0% of the ZnO component by mass percentage on an oxide basis, and [SiO ２A glass containing the crystalline phase described in composition 1 or 2, wherein the ratio of component content (%) / ZnO component content (%) is less than 20. (Composition 9) In terms of mass %, SiO ２ The ingredients are 30.0% to 70.0%, Al ２ O ３ The ingredients are 5.0% to 20.0%, B ２ O ３ The ingredients are 0% to 10.0%, P ２ O ５ Ingredients: 0% to 10.0%, Li ２ O component is greater than 0% and less than or equal to 20.0%, Na ２ O component 0% to 10.0%, K ２ O component 0% to 10.0%, MgO component 0% to 10.0%, CaO component 0% to 10.0%, SrO component 0% to 10.0%, BaO component 0% to 10.0%, ZnO component 5% to 35.0%, TiO ２ The ingredients are 0% to 10.0%, ZrO ２ The ingredients are 0% to 10.0%, Nb ２ O ５ The ingredients are 0% to 10.0%, Sb ２ O ３ A glass containing the crystalline phase described in composition 8, with the component present in an amount of 0% to 5.0%.

[0007] According to the present invention, it is possible to provide glass that has excellent light-shielding properties in the visible light range, is easy to bend with heat, and is also easy to mass-produce.

[0008] The following describes in detail embodiments and examples of the glass containing the crystalline phase of the present invention. However, the present invention is not limited in any way to the following embodiments and examples, and can be implemented with appropriate modifications within the scope of the object of the present invention.

[0009] [Glass containing a crystalline phase] A glass containing a crystalline phase according to one aspect of the present invention (hereinafter also simply referred to as "glass containing a crystalline phase" or "glass") contains, in terms of mass % on an oxide basis, SiO ２ It contains 30% to 85% of the component, has a refractory point of 840°C or lower, and an average transmittance of 30% or less at a thickness of 1 mm in the wavelength range of 380 nm to 830 nm.

[0010] The above-mentioned glass has a low light transmittance in the visible light range, resulting in excellent light shielding properties that prevent light from internal components from leaking to the outside when used as a housing. Furthermore, its low bending point allows for bending at relatively low temperatures without requiring extremely high temperatures, resulting in excellent bendability. The low bending point also leads to reduced energy consumption during thermal bending, which can contribute to improved mass productivity. In addition, there is a concern that thermal bending may not be possible with glass that has a high bending point due to the load on production equipment. Moreover, because the above-mentioned glass has a low crystallization temperature, the thermal bending process can be easily incorporated into existing glass product production lines, which also contributes to excellent mass productivity. The above-mentioned glass can be manufactured by appropriately adjusting the raw material composition and manufacturing conditions of each embodiment described below, following the manufacturing method and examples described later.

[0011] <Various physical properties>

[0012] (Average Transmittance) The glass containing the crystalline phase has an average transmittance of 30% or less at a thickness of 1 mm in the wavelength range of 380 nm to 830 nm, and may be 29% or less, 28% or less, or 27.5% or less. Having such an average transmittance provides excellent light shielding in the visible light range. There is no particular lower limit to the average transmittance, but for example, it is 0.1% or more. The average transmittance may be 0%. The average transmittance refers to the value calculated from the visible light transmittance spectrum obtained by measurement in the wavelength range of 380 nm to 830 nm, and is measured and calculated by the method described in "(6) Average Transmittance" of the Examples.

[0013] (Fracture Point (At)) Glass containing a crystalline phase has a fracture point of 840°C or lower, and may be 830°C or lower, 820°C or lower, 810°C or lower, or 800°C or lower. Having such a fracture point allows for excellent bendability and mass productivity. There is no particular lower limit to the fracture point, but for example, it is 400°C or higher. The fracture point is measured by the method described in "(7) Fracture Point (At)" of the Examples.

[0014] (Chromaticity) For glass containing a crystalline phase, the chromaticity may be in the range of -10.00 to 5.00, b* in the range of -20.00 to 5.00, and L* in the range of 50.0 or higher, obtained from the reflection spectrum including specular reflection measured by a spectrophotometer under the following conditions using a CIE light source D65 at an observer angle of 10°, from a*, b*, and L*. When a*, b*, and L* show values ​​within the above ranges, the crystallized glass exhibits good whiteness with high light-shielding properties. (Reflection spectrum measurement conditions) Sample thickness: 1 mm Receiving angle relative to the normal of the sample surface: 8° a*, b*, and L* are measured by the method described in "(4) Chromaticity (black background)" or "(5) Chromaticity (no background)" of the Examples.

[0015] a* may be between -8.00 and 3.00, or between -6.00 and 1.00. b* may be between -18.00 and 3.00, or between -16.00 and 1.00. L* may be between 55.0 and 99.0, or between 60.0 and 97.0.

[0016] <Glass containing a crystalline phase> Glass containing a crystalline phase is a glass material that has both a crystalline phase and a glass phase, and is distinguished from amorphous materials. The crystalline phase of glass containing a crystalline phase is determined using the angle of the peak that appears in the X-ray diffraction pattern of X-ray diffraction analysis. Glass containing a crystalline phase is, for example, crystallized glass. Crystallized glass, also called glass ceramics, is a material in which crystals are precipitated inside the glass by heat treatment. Glass containing a crystalline phase may be partially phase-separated. Phase separation refers to the phase separation of glass phases with different constituent components, or the state in which such phase separation occurs.

[0017] (Crystalline phase) Glass containing a crystalline phase may include, for example, lithium silicate (Li ２ O・nSiO ２ ), lithium monosilicate, lithium disilicate (Li ２ Si ２ O ５ ), cristobalite (e.g., α-cristobalite), quartz, burgilite, tridymite, petalite, lithium zinc phosphate (Li４ Zn(PO ４ ), lithium zinc silicate (Li ２ ), sodium titanate, lithium aluminosilicate (LiAlSi ２ SiO ４ ), and lithium silicate phosphate, keatite, high quartz mixed crystal, beta spodumene (β - spodumene), α - quartz solid solution, β - quartz solid solution, tetragonal ZrO ３ O ８ ), MgTa ２ O ２ O ６ ), mullite, cordierite, and (Mg ｘ Zn １－ｘ Al ２ O ４ (where x is less than 1), and may contain one or more selected from the crystal phases represented. The crystal phase includes solid solutions. The method for confirming the crystal phase is as described in “(3) Confirmation of Crystal Phase” in the Examples.

[0018] In one aspect, the glass containing the crystal phase of the present invention is lithium silicate (Li ２ O·nSiO ２ ), lithium monosilicate, lithium disilicate (Li ２ Si ２ O ５ ), cristobalite (e.g., α - cristobalite), quartz, vermiculite, tridymite (scaly quartz), petalite (leaf feldspar), lithium zinc phosphate (Li ４ Zn(PO ４ ), lithium zinc silicate (Li ２ ZnSiO ２ ), sodium titanate, lithium aluminosilicate (LiAlSi ４ O ３ O<96>), and contains only one or more crystal phases selected from the group consisting of lithium silicate phosphate, and does not substantially contain other crystal phases.

[0019] In one aspect, the glass containing a crystal phase may not substantially contain keatite as the crystal phase. In one aspect, the glass containing a crystal phase may not substantially contain high quartz mixed crystal as the crystal phase. In one aspect, the glass containing a crystal phase may not substantially contain β-lithium pyroxene (β-lithium pyroxene) as the crystal phase. In one aspect, the glass containing a crystal phase may not substantially contain β-quartz solid solution as the crystal phase. In one aspect, the glass containing a crystal phase may not substantially contain, as the crystal phase, a crystal phase represented by (Mg ｘ Zn １－ｘ )Al ２ O ４ (where x is less than 1). In one aspect, the glass containing a crystal phase may not substantially contain at least one selected from the group consisting of tetragonal ZrO ２ , MgTa ２ O ６ , mullite and cordierite as the crystal phase. When the glass containing a crystal phase "substantially does not contain a predetermined crystal phase", it means that no diffraction peak indicating the presence of the crystal phase is confirmed when the method for confirming the crystal phase described in the examples ("(3) Confirmation of crystal phase") is carried out.

[0020] (Component) The components of the glass containing a crystal phase will be described. In this specification, the content of each component is expressed in mass% in terms of oxide, unless otherwise specified. Here, "in terms of oxide" means the amount of the oxide of each component contained in the glass containing a crystal phase, expressed in mass%, when it is assumed that all the glass components containing a crystal phase are decomposed and changed into oxides and the total mass of the oxides is 100 mass%. In this specification, A% to B% represents A% or more and B% or less.

[0021] The glass containing a crystal phase according to one aspect of the present invention contains 30% to 85% of the SiO ２ component in terms of mass% in terms of oxide.

[0022] In one aspect, the glass containing a crystal phase contains the following components in the following composition in terms of mass% in terms of oxide. P ２ O ５Component content 0% to 10.0% ZrO ２ Ingredient content: 0% to 20.0%

[0023] The following describes the glass containing a crystalline phase according to the first embodiment (hereinafter also referred to as "glass containing a crystalline phase 1"), which is included in the glass containing a crystalline phase of the present invention.

[0024] [Glass containing a crystalline phase 1] Glass containing a crystalline phase 1 has a mass percentage of [TiO] in terms of oxide. ２ Percentage of component content (%) + ZrO ２ The percentage of the component contained (%) is greater than 0, and [(P ２ O ５ Percentage of ingredient content (%) + Al ２ O ３ Percentage of component content (%) / (TiO ２ Percentage of component content (%) + ZrO ２ The percentage of the component contained is 4.0 or less.

[0025] In one embodiment, the glass 1 containing the crystalline phase contains the following components in the following composition, in terms of mass percent on an oxide basis: SiO ２ Ingredient content: 45.0% to 85.0% Al ２ O ３ Ingredient content: Over 0% and up to 20.0% B ２ O ３ Ingredient content: 0% to 10.0% P ２ O ５ Ingredient content: 0% to 10.0% Li ２ Content of component O: greater than 0% and less than or equal to 20.0% Na ２ Content of component O: 0% to 10.0% K ２ O content 0% to 10.0% MgO content 0% to 10.0% CaO content 0% to 10.0% SrO content 0% to 10.0% BaO content 0% to 10.0% ZnO content 0% to 15.0% TiO ２ Component content 0% to 10.0% ZrO ２ Ingredient content: 0% to 15.0% Nb ２ O ５ Ingredient content: 0% to 10.0% Sb ２ O ３Ingredient content: 0% to 5%

[0026] The glass 1 containing the crystalline phase may have any of the following compositions, or it may have a composition in which any of the following compositions are appropriately combined.

[0027] SiO ２ The component is an essential component for forming the glass network structure of crystallized glass. SiO ２ If the component content is 85.0% or less, excessive viscosity increases and deterioration of melting properties can be suppressed. If it is 45.0% or more, devitrification can be suppressed. Preferably, the upper limit is 83.0% or less, 80.0% or less, 78.0% or less, or 76.0% or less. Preferably, the lower limit is 48.0% or more, 50.0% or more, or 53.0% or more.

[0028] Al ２ O ３ The components are suitable for improving the mechanical strength of crystallized glass. Al ２ O ３ If the component content is 20.0% or less, deterioration of melting and devitrification can be suppressed. Also, if it is greater than 0%, the effect of improving mechanical strength is excellent. Preferably, the upper limit can be less than 19.0%, 18.0% or less, less than 18.0%, 16.0% or less, less than 16.0%, 14.0% or less, or 13.0% or less. The upper limit may also be less than 11.0%. Also, the lower limit can be 0.5% or more, 1.0% or more, 1.5% or more, 2.0% or more, or 2.5% or more. Also, Al ２ O ３ The upper limit for the content of each component may be less than 10.5% in mol% on an oxide basis.

[0029] B ２ O ３ The components are suitable for lowering the glass transition temperature of crystallized glass and improving its meltability, but when the amount is 10.0% or less, it exhibits excellent chemical durability. Preferably, the upper limit is 8.0% or less, 7.0% or less, 5.0% or less, or 4.0% or less. B ２ O ３ The lower limit of the component can be 0% or more. Also, B ２ O ３The lower limit of the component may be greater than 0%, 0.001% or more, 0.01% or more, 0.05% or more, 0.10% or more, or 0.30% or more.

[0030] P ２ O ５ The components are optional ingredients that can be added to act as nucleating agents or phase-separating agents for glass crystals. ２ O ５ By limiting the amount of the component to 10.0% or less, devitrification of the glass can be suppressed. Preferably, the upper limit is 9.0% or less, 8.0% or less, 7.0% or less, or 6.0% or less. ２ O ５ The lower limit of the component can be 0% or more, 0.5% or more, 0.8% or more, or 1.0% or more.

[0031] Li ２ Component O is a component that improves the fusion properties of the raw glass. Also, Li ２ Component O is a component involved in chemical strengthening. When its amount is greater than 0%, it can improve the meltability of the raw glass. Also, Li ２ By keeping the amount of O component below 20.0%, devitrification of the glass can be suppressed. The lower limit can preferably be greater than 0%, 0.5% or more, 1.0% or more, 3.0% or more, 5.0% or more, greater than 5.0%, greater than 6.0%, greater than 6.5%, or 7.0% or more. ２ The lower limit of the O component content may be greater than 9.0% in mol% on an oxide basis. Preferably, the upper limit is 18.0% or less, 16.0% or less, 14.0% or less, 12.0% or less, or 10.0% or less.

[0032] Na ２ Component O is an optional component that participates in chemical strengthening when present in amounts greater than 0%. ２ By keeping the O component below 10.0%, excellent chemical durability is achieved. ２ The upper limit of component O can preferably be 8.0% or less, 6.0% or less, less than 5.0%, more preferably 4.0% or less, and even more preferably 2.0% or less. ２ The lower limit for component O can be set to 0% or higher.

[0033] K ２Component O is an optional component that participates in chemical strengthening when present in amounts greater than 0%. ２ The lower limit of component O can be 0% or more, greater than 0%, 0.1% or more, 0.3% or more, or 0.5% or more. Also, K ２ By keeping the O component below 10.0%, excellent chemical durability is achieved. Therefore, K ２ The upper limit of component O can preferably be 9.0% or less, 8.0% or less, 6.0% or less, or 5.0% or less.

[0034] The MgO component is an optional component that improves low-temperature meltability when present in amounts exceeding 0%, and can be included within a range that does not impair the effects of the present invention. On the other hand, by limiting the MgO content to 10.0% or less, the deterioration of devitrification can be suppressed. Therefore, the upper limit of the MgO component can preferably be 8.0% or less, 6.0% or less, 4.0% or less, or 2.0% or less. The lower limit of the MgO component can be 0% or more. The lower limit of the MgO component may also be greater than 0%, 0.3% or more, or 0.4% or more.

[0035] The CaO component is an optional component that improves low-temperature meltability when present in amounts exceeding 0%, and can be included within a range that does not impair the effects of the present invention. On the other hand, by limiting the CaO component to 10.0% or less, the deterioration of devitrification can be suppressed. Preferably, the upper limit of the CaO component can be 8.0% or less, 6.0% or less, 4.0% or less, or 2.0% or less. The lower limit of the CaO component can be 0% or more.

[0036] The SrO component is an optional component that improves low-temperature meltability when present in amounts exceeding 0%, and can be included within a range that does not impair the effects of the present invention. Preferably, the upper limit of the SrO component can be 10.0% or less, 6.0% or less, 4.0% or less, 3.0% or less, or 2.0% or less. The lower limit of the SrO component can be 0% or more.

[0037] The BaO component is an optional component that improves low-temperature meltability when present in amounts exceeding 0%, and can be included within a range that does not impair the effects of the present invention. Preferably, the upper limit of the BaO component can be 10.0% or less, 6.0% or less, 4.0% or less, 3.0% or less, 2.5% or less, or 2.0% or less. The lower limit of the BaO component can be 0% or more.

[0038] The ZnO component is an optional component that improves low-temperature meltability when present in amounts exceeding 0%, and can be included within a range that does not impair the effects of the present invention. On the other hand, by limiting the ZnO component content to 15.0% or less, the deterioration of devitrification can be suppressed. Preferably, the upper limit of the ZnO component can be 13.0% or less, 10.0% or less, 8.0% or less, 6.0% or less, or 5.0% or less. Also, preferably, the lower limit of the ZnO component can be 0% or more, greater than 0%, 0.1% or more, or 0.3% or more.

[0039] ZrO ２ The component is one that can improve mechanical strength. On the other hand, if its amount is 15.0% or less, deterioration of melting properties can be suppressed. Preferably, the upper limit is 14.0% or less, 13.5% or less, 13.0% or less, or 12.0% or less. Preferably, the lower limit can be 0% or more, greater than 0%, 1.0% or more, 1.5% or more, 2.0% or more, greater than 2.5%, greater than 3%, or greater than 3.5%.

[0040] TiO ２ The component is an optional component that improves the chemical durability of crystallized glass when present in amounts greater than 0%. On the other hand, TiO ２ By reducing the component content to 10.0% or less, the deterioration of devitrification can be suppressed. Preferably, the upper limit can be 8.0% or less, 6.0% or less, or 4.0% or less. TiO ２ The lower limit for the concentration of an ingredient can be 0% or higher.

[0041] Nb ２ O ５ The component is an optional component that improves the mechanical strength of the crystallized glass when present in amounts exceeding 0%. Preferably, the upper limit can be 10.0% or less, 8.0% or less, 6.0% or less, 4.0% or less, or 2.0% or less. Nb ２ O ５ The lower limit for the concentration of an ingredient can be 0% or higher.

[0042] Ta ２ O ５ The component is an optional component that improves the mechanical strength of the crystallized glass when present in amounts exceeding 0%. Preferably, the upper limit can be 6.0% or less, 5.5% or less, 5.0% or less, or 4.0% or less. ２ O５ The lower limit for the concentration of an ingredient can be 0% or higher.

[0043] From the viewpoint of achieving both the desired light transmittance and the inflection point, [TiO ２ Percentage of component content (%) + ZrO ２ The lower limit of the component content (%) is greater than 0, and may be 0.5 or higher, 1.0 or higher, 2.0 or higher, or 3.0 or higher. Also, [TiO ２ Percentage of component content (%) + ZrO ２ The upper limit for the percentage of the component content may be 25.0% or less, 23.0% or less, 20.0% or less, 18.0% or less, or 15.0% or less.

[0044] From the viewpoint of achieving both the desired light transmittance and the inflection point, [TiO ２ Percentage of component content (%) + ZrO ２ When the percentage of the component content (%) is greater than 0, [(P ２ O ５ Percentage of ingredient content (%) + Al ２ O ３ Percentage of component content (%) / (TiO ２ Percentage of component content (%) + ZrO ２ The upper limit of the percentage of the component content may be 4.0 or less, 3.5 or less, 3.0 or less, or 2.8 or less. Also, [(P ２ O ５ Percentage of ingredient content (%) + Al ２ O ３ Percentage of component content (%) / (TiO ２ Percentage of component content (%) + ZrO ２ The lower limit of the percentage of the component content may be 0.1 or higher, 0.2 or higher, 0.3 or higher, or 0.4 or higher.

[0045] Li in mol% on an oxide basis ２ Content of component O, Na ２ Content of component O, K ２ O content, MgO content, ZnO content, Al ２ O ３ The content of the ingredients, and B ２ O ３ [(Li ２ Content of component O + Na ２ Content of component O + K２ (Content of O component + Content of MgO component + Content of ZnO component) / (Al ２ O ３ Ingredient content + B ２ O ３ The content of the component may exceed 1.5.

[0046] Furthermore, the crystallized glass contains La to the extent that it does not impair the effects of the present invention. ２ O ３ Ingredients, Gd ２ O ３ Ingredients, Y ２ O ３ Ingredients, WO ３ Ingredients, TeO ２ Ingredients, Bi ２ O ３ The product may contain each of these ingredients, or it may not contain them at all. If these ingredients are included, their respective amounts may be 0% to 2.0%, 0% to less than 2.0%, or 0% to 1.0%.

[0047] Furthermore, the crystallized glass may or may not contain other components not mentioned above, as long as they do not impair the properties of the crystallized glass of the present invention. For example, it may contain a component (e.g., a metal oxide) containing at least one metal element selected from the group consisting of Yb, Lu, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Nd, and Mo, or it may substantially not contain a component containing at least one metal element selected from the group.

[0048] Glass containing a crystalline phase may contain Fe to the extent that it does not impair the effects of the present invention. ２ O ３ It may or may not contain the ingredient. Fe ２ O ３ If the product contains the active ingredient, the upper limit may be 5.0% or less, 2.0% or less, or less than 1.0%, and may also be less than 700 ppm.

[0049] Glass containing a crystalline phase may be Co to the extent that it does not impair the effects of the present invention. ３ O ４ It may or may not contain the ingredients. ３ O ４If the substance contains an ingredient, the upper limit may be 100 ppm or less, or less than 20 ppm.

[0050] Glass containing a crystalline phase is MoO ３ It may or may not contain the ingredients. MoO ３ If the component is present, the upper limit may be 0.5% or less, 0.1% or less, or less than 0.003%. Glass containing a crystalline phase is WO ３ Ingredients and MoO ３ The content of one or more components selected from the ingredients may be less than 0.35% in mol% on an oxide basis.

[0051] The glass containing the crystalline phase may contain at least one component selected from the group consisting of metal elements Co, Mn, Fe, Ni, Cu, Cr, V, Bi, Er, Sn, Ce, Pr, Eu, Nd, and Ag in an amount of less than 0.1% in mol% on an oxide basis.

[0052] Sb as a glass clarifying agent ２ O ３ It may contain the component. On the other hand, Sb ２ O ３ By limiting the component content to 5.0% or less, it is possible to suppress the deterioration of transmittance in the short-wavelength region of the visible light spectrum. Therefore, the upper limit can preferably be 3.0% or less, more preferably 2.0% or less, more preferably 1.0% or less, and even more preferably 0.6% or less. Sb ２ O ３ The lower limit for the concentration of an ingredient can be 0% or higher.

[0053] Also, as a glass clarifying agent, Sb ２ O ３ In addition to the components, SnO ２ Ingredients, CeO ２ Ingredients, As ２ O ３ Ingredients, F, NO ｘ and SO ｘ (For example, SO ３ It may contain one or more selected from the group consisting of ), or it may not contain any. However, the content of the clarifying agent can preferably be limited to an upper limit of 2.0%, more preferably 1.0%, and most preferably 0.6%. CeO２ If an ingredient is present, the upper limit of its content may be less than 1000 ppm.

[0054] On the other hand, since Pb, Th, Tl, Os, Be, Cl, and Se are components that have recently been used less frequently due to their harmful chemical properties, it is preferable that the product is substantially free of these elements.

[0055] The following describes a glass having a crystalline phase according to a second embodiment (hereinafter also referred to as "glass containing a crystalline phase 2") which is included in the glass having a crystalline phase of the present invention.

[0056] [Glass containing crystalline phase 2] Glass containing crystalline phase 2 has a mass percentage of TiO in terms of oxide. ２ Contains more than 0% of the component, [SiO ２ Percentage of component content (%) / TiO ２ The percentage of the ingredient is less than 5.0.

[0057] In one embodiment, the glass 2 containing the crystalline phase contains the following components in the following composition, in terms of mass percent on an oxide basis: SiO ２ Ingredient content: 30.0% to 50.0% Al ２ O ３ Ingredient content: 0% to 10.0% B ２ O ３ Ingredient content: 0% to 10.0% P ２ O ５ Ingredient content: 0% to 10.0% Li ２ Content of component O: 0% to 10.0% Na ２ Content of component O: 5% to 20.0% K ２ O content 0% to 15.0% MgO content 0% to 10.0% CaO content 0% to 10.0% SrO content 0% to 10.0% BaO content 0% to 10.0% ZnO content 0% to 10.0% TiO ２ Component content: 15% to 35.0% ZrO ２ Ingredient content: 0% to 10.0% Nb ２ O ５ Ingredient content: 0% to 15.0% Sb ２ O ３ Ingredient content: 0% to 5.0%

[0058] The glass 2 containing the crystalline phase may have any of the following compositions, or it may have a composition that is an appropriate combination of any of the following compositions.

[0059] SiO ２ The component is an essential component for forming the glass network structure of crystallized glass. SiO ２ If the component content is 50.0% or less, excessive viscosity increases and deterioration of solubility can be suppressed. Also, if it is 30.0% or more, devitrification can be suppressed. Preferably, the upper limit is 48.0% or less, 46.0% or less, 43.0% or less, or 40.0% or less. Also preferably, the lower limit is 31.0% or more, 32.0% or more, or 33.0% or more. Also, SiO ２ The upper limit for the content of each component may be less than 62.0% in mol% on an oxide basis.

[0060] Al ２ O ３ The components are suitable for improving the mechanical strength of crystallized glass. Al ２ O ３ By limiting the component content to 10.0% or less, deterioration of melting and devitrification can be suppressed. Furthermore, if the content exceeds 0%, the effect of improving mechanical strength is excellent. Preferably, the upper limit is 8.0% or less, 6.0% or less, 4.0% or less, or 2.0% or less. Al ２ O ３ The lower limit of the component can be 0% or higher. ２ O ３ The lower limit of the component may be greater than 0%, 0.001% or more, or 0.01% or more.

[0061] B ２ O ３ The components are suitable for lowering the glass transition temperature of crystallized glass and improving its meltability. Also, B ２ O ３ When the amount of the component is 10.0% or less, it exhibits excellent chemical durability. Preferably, the upper limit is 8.0% or less, 6.0% or less, 4.0% or less, or 2.0% or less. B ２ O ３ The lower limit of the component can be 0% or higher. B２ O ３ The lower limit of the component may be greater than 0%, 0.001% or more, 0.01% or more, 0.05% or more, 0.10% or more, or 0.30% or more.

[0062] P ２ O ５ The components are optional ingredients that can be added to act as nucleating agents or phase-separating agents for glass crystals. ２ O ５ By limiting the amount of the component to 10.0% or less, devitrification of the glass can be suppressed. Preferably, the upper limit is 8.0% or less, 6.0% or less, 4.0% or less, or 2.0% or less. ２ O ５ The lower limit of the component can be 0% or higher. ２ O ５ The lower limit of the component may be greater than 0%, 0.5% or more, 1.0% or more, or 1.5% or more.

[0063] Li ２ Component O is a component that improves the fusion properties of the raw glass. Also, Li ２ Component O is a component involved in chemical strengthening. When its amount is greater than 0%, it can improve the meltability of the raw glass. Also, Li ２ By limiting the amount of O component to 10.0% or less, devitrification of the glass can be suppressed. Preferably, the upper limit is 8.0% or less, 6.0% or less, 4.0% or less, less than 3.2%, 2.0% or less, or 1.0% or less. Li ２ The lower limit of the O component can be set to 0% or higher. Li ２ The lower limit of component O may be greater than 0%, 0.001% or more, or 0.01% or more.

[0064] Na ２ Component O is a component involved in chemical strengthening. Also, Na ２ By keeping the O component below 20.0%, excellent chemical durability is achieved. ２ The upper limit of the O component can preferably be 18.0% or less, 16.0% or less, more preferably 14.0% or less, and even more preferably 13.0% or less. ２ The lower limit of component O can preferably be 5.0% or more, 6.0% or more, 6.5% or more, or 7.0% or more.

[0065] K ２ Component O is an optional component that participates in chemical strengthening when present in amounts greater than 0%. ２ The lower limit of component O can be 0% or more, greater than 0%, 0.5% or more, 1.0% or more, greater than 1.5%, 3.0% or more, or 4.0% or more. Also, K ２ By keeping the O component at 15.0% or less, excellent chemical durability is achieved. Therefore, K ２ The upper limit of component O can preferably be 14.0% or less, 13.0% or less, 11.0% or less, or 10.0% or less.

[0066] The MgO component is an optional component that improves low-temperature meltability when present in amounts exceeding 0%, and can be included within a range that does not impair the effects of the present invention. On the other hand, by limiting the MgO content to 10.0% or less, the deterioration of devitrification can be suppressed. Therefore, the upper limit of the MgO component can preferably be 8.0% or less, 7.0% or less, 6.0% or less, or 5.0% or less. Furthermore, the lower limit of the MgO component may be 0% or more, greater than 0%, 0.5% or more, 1.0% or more, 1.5% or more, 2.0% or more, or 2.3% or more.

[0067] The CaO component is an optional component that improves low-temperature meltability when present in amounts exceeding 0%, and can be included within a range that does not impair the effects of the present invention. On the other hand, by limiting the CaO component to 10.0% or less, the deterioration of devitrification can be suppressed. Preferably, the upper limit of the CaO component can be 8.0% or less, 6.0% or less, 4.0% or less, or 2.0% or less. The lower limit of the CaO component can be 0% or more.

[0068] The SrO component is an optional component that improves low-temperature meltability when present in amounts exceeding 0%, and can be included within a range that does not impair the effects of the present invention. Preferably, the upper limit of the SrO component can be 10.0% or less, 6.0% or less, 4.0% or less, 3.0% or less, 2.5% or less, or 2.0% or less. The lower limit of the SrO component can be 0% or more.

[0069] The BaO component is an optional component that improves low-temperature meltability when present in amounts exceeding 0%, and can be included within a range that does not impair the effects of the present invention. Preferably, the upper limit of the BaO component can be 10.0% or less, 6.0% or less, 4.0% or less, 3.0% or less, 2.5% or less, or 2.0% or less. The lower limit of the BaO component can be 0% or more.

[0070] The ZnO component is an optional component that improves low-temperature meltability when present in amounts exceeding 0%, and can be included within a range that does not impair the effects of the present invention. On the other hand, by limiting the ZnO component content to 10.0% or less, the deterioration of devitrification can be suppressed. Preferably, the upper limit of the ZnO component can be 8.0% or less, 6.0% or less, 4.0% or less, 2.0% or less, or 1.9% or less. The lower limit of the ZnO component can be 0% or more. The lower limit of the ZnO component may also be greater than 0%, 0.5% or more, or 1.0% or more.

[0071] ZrO ２ The component is one that can improve mechanical strength. On the other hand, if its amount is 10.0% or less, deterioration of meltable properties can be suppressed. Preferably, the upper limit is 9.0% or less, 7.0% or less, 6.0% or less, or 5.0% or less. Preferably, the lower limit can be 0% or more, greater than 0%, 1.0% or more, 1.5% or more, 2.0% or more, 2.6% or more, or greater than 3%.

[0072] TiO ２ The components are those that improve the chemical durability of crystallized glass. On the other hand, TiO ２ By reducing the component content to 35.0% or less, the deterioration of devitrification can be suppressed. Preferably, the upper limit can be 34.0% or less, 33.0% or less, 31.0% or less, or 30.0% or less. Also, TiO ２ The lower limit of the component can be 15% or more, 17.0% or more, 19.0% or more, or 21.0% or more. Also, TiO ２ The lower limit of the component content may be greater than 4.5% in mol% on an oxide basis.

[0073] Nb ２ O ５The component is an optional component that improves the mechanical strength of the crystallized glass when present in amounts greater than 0%. Preferably, the upper limit can be 15.0% or less, 14.0% or less, 13.0% or less, 12.0% or less, or 11.0% or less. Also, Nb ２ O ５ The lower limit of the component can be 0%, 1.0%, 3.0%, 5.0%, or 6.0% or higher.

[0074] Ta ２ O ５ The component is an optional component that improves the mechanical strength of the crystallized glass when present in amounts exceeding 0%. Preferably, the upper limit can be 6.0% or less, 5.5% or less, 5.0% or less, or 4.0% or less. ２ O ５ The lower limit for the concentration of an ingredient can be 0% or higher.

[0075] From the perspective of achieving both the desired light transmittance and the inflection point, TiO ２ When the component is present in a quantity greater than 0%, [SiO ２ Percentage of component content (%) / TiO ２ The upper limit of the component content (%) may be less than 5.0, 4.8 or less, 4.5 or less, 4.0 or less, 3.5 or less, 3.0 or less, 2.5 or less, or 2.0 or less. Also, [SiO ２ Percentage of component content (%) / TiO ２ The lower limit of the component content (%) may be 0.5 or higher, 0.8 or higher, 1.0 or higher, or 1.1 or higher.

[0076] Furthermore, the crystallized glass contains La to the extent that it does not impair the effects of the present invention. ２ O ３ Ingredients, Gd ２ O ３ Ingredients, Y ２ O ３ Ingredients, WO ３ Ingredients, TeO ２ Ingredients, Bi ２ O ３ The product may contain each of these ingredients, or it may not contain them at all. If these ingredients are included, their respective amounts may be 0% to 2.0%, 0% to less than 2.0%, or 0% to 1.0%.

[0077] Furthermore, the crystallized glass may or may not contain other components not mentioned above, as long as they do not impair the properties of the crystallized glass of the present invention. For example, it may contain a component (e.g., a metal oxide) containing at least one metal element selected from the group consisting of Yb, Lu, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Nd, and Mo, or it may substantially not contain a component containing at least one metal element selected from the group.

[0078] Glass containing a crystalline phase may contain Fe to the extent that it does not impair the effects of the present invention. ２ O ３ It may or may not contain the ingredient. Fe ２ O ３ If the product contains the active ingredient, the upper limit may be 5.0% or less, 2.0% or less, or less than 1.0%, and may also be less than 700 ppm.

[0079] Glass containing a crystalline phase may be Co to the extent that it does not impair the effects of the present invention. ３ O ４ It may or may not contain the ingredients. ３ O ４ If the substance contains an ingredient, the upper limit may be 100 ppm or less, or less than 20 ppm.

[0080] Glass containing a crystalline phase is MoO ３ It may or may not contain the ingredients. MoO ３ If the component is present, the upper limit may be 0.5% or less, 0.1% or less, or less than 0.003%. Glass containing a crystalline phase is WO ３ Ingredients and MoO ３ The content of one or more components selected from the ingredients may be less than 0.35% in mol% on an oxide basis.

[0081] The glass containing the crystalline phase may contain at least one component selected from the group consisting of metal elements Co, Mn, Fe, Ni, Cu, Cr, V, Bi, Er, Sn, Ce, Pr, Eu, Nd, and Ag in an amount of less than 0.1% in mol% on an oxide basis.

[0082] Sb as a glass clarifying agent ２ O ３It may contain the component. On the other hand, Sb ２ O ３ By limiting the component content to 5.0% or less, it is possible to suppress the deterioration of transmittance in the short-wavelength region of the visible light spectrum. Therefore, the upper limit can preferably be 3.0% or less, more preferably 2.0% or less, more preferably 1.0% or less, and even more preferably 0.6% or less. Sb ２ O ３ The lower limit for the concentration of an ingredient can be 0% or higher.

[0083] Also, as a glass clarifying agent, Sb ２ O ３ In addition to the components, SnO ２ Ingredients, CeO ２ Ingredients, As ２ O ３ Ingredients, F, NO ｘ and SO ｘ (For example, SO ３ It may contain one or more selected from the group consisting of ), or it may not contain any. However, the content of the clarifying agent can preferably be limited to an upper limit of 2.0%, more preferably 1.0%, and most preferably 0.6%. CeO ２ If an ingredient is present, the upper limit of its content may be less than 1000 ppm.

[0084] On the other hand, since Pb, Th, Tl, Os, Be, Cl, and Se are components that have recently been used less frequently due to their harmful chemical properties, it is preferable that the product is substantially free of these elements.

[0085] The following describes a glass having a crystalline phase according to a third embodiment, which is included in the glass having a crystalline phase of the present invention (hereinafter also referred to as "glass containing a crystalline phase 3").

[0086] [Glass containing a crystalline phase 3] Glass containing a crystalline phase 3 contains more than 0% of the ZnO component by mass percentage on an oxide basis, and [SiO ２ The ratio of component content (%) / ZnO component content (%) is less than 20.

[0087] In one embodiment, the glass 3 containing the crystalline phase contains the following components in the following composition, in terms of mass percent on an oxide basis: SiO ２Ingredient content: 30.0% to 70.0% Al ２ O ３ Ingredient content: 5.0% to 20.0% B ２ O ３ Ingredient content: 0% to 10.0% P ２ O ５ Ingredient content: 0% to 10.0% Li ２ Content of component O: greater than 0% and less than or equal to 20.0% Na ２ Content of component O: 0% to 10.0% K ２ O content 0% to 10.0% MgO content 0% to 10.0% CaO content 0% to 10.0% SrO content 0% to 10.0% BaO content 0% to 10.0% ZnO content 5% to 35.0% TiO ２ Component content 0% to 10.0% ZrO ２ Ingredient content: 0% to 10.0% Nb ２ O ５ Ingredient content: 0% to 10.0% Sb ２ O ３ Ingredient content: 0% to 5.0%

[0088] The glass 3 containing the crystalline phase may have any of the following compositions, or it may have a composition in which any of the following compositions are appropriately combined.

[0089] SiO ２ The component is an essential component for forming the glass network structure of crystallized glass. SiO ２ If the component content is 70.0% or less, excessive viscosity increases and deterioration of melting properties can be suppressed. If it is 30.0% or more, devitrification can be suppressed. Preferably, the upper limit is 68.0% or less, 64.0% or less, 61.0% or less, or 58.0% or less. Preferably, the lower limit is 33.0% or more, 35.0% or more, 40.0% or more, or 42.0% or more.

[0090] Al ２ O ３ The components are suitable for improving the mechanical strength of crystallized glass. Al ２ O ３If the component content is 20.0% or less, deterioration of melting and devitrification can be suppressed. Furthermore, if it is 5.0% or more, the effect of improving mechanical strength is excellent. Preferably, the upper limit is less than 19.0%, 18.0% or less, less than 17.0%, or 16.0% or less. Al ２ O ３ The upper limit of the component may be 15.0% or less, or 14.0% or less. The lower limit may be 7.0% or more, 9.0% or more, 10.0% or more, 10.5% or more, or 11.0% or more.

[0091] B ２ O ３ The components are suitable for lowering the glass transition temperature of crystallized glass and improving its meltability, but when the amount is 10.0% or less, it exhibits excellent chemical durability. Preferably, the upper limit is 8.0% or less, 6.0% or less, 4.0% or less, 2.0% or less, or less than 2.0%. B ２ O ３ The lower limit of the component can be 0% or more. Also, B ２ O ３ The lower limit of the component may be greater than 0%, 0.001% or more, 0.01% or more, 0.05% or more, 0.10% or more, or 0.30% or more.

[0092] P ２ O ５ The components are optional ingredients that can be added to act as nucleating agents or phase-separating agents for glass crystals. ２ O ５ By keeping the amount of the component to 10.0% or less, devitrification of the glass can be suppressed. Preferably, the upper limit is 9.0% or less, 8.0% or less, 6.0% or less, or 4.0% or less. The lower limit can be 0% or more, 0.5% or more, 1.0% or more, or 1.5% or more.

[0093] Li ２ Component O is a component that improves the fusion properties of the raw glass. Also, Li ２ Component O is a component involved in chemical strengthening. When its amount is greater than 0%, it can improve the meltability of the raw glass. Also, Li ２By keeping the amount of O component below 20.0%, the devitrification of the glass can be suppressed. The lower limit can preferably be greater than 0%, 0.5% or more, 1.0% or more, 3.0% or more, 5.0% or more, greater than 5.0%, greater than 6.0%, or 7.0% or more. ２ The lower limit of the O component content may be greater than 6.0% or greater than 9.0% in mol% on an oxide basis. Preferably, the upper limit can be 18.0% or less, 16.0% or less, 15.0% or less, 14.0% or less, or 12.0% or less.

[0094] Na ２ Component O is an optional component that participates in chemical strengthening when present in amounts greater than 0%. ２ By keeping the O component below 10.0%, excellent chemical durability is achieved. ２ The upper limit of component O can preferably be 8.0% or less, 6.0% or less, less than 5.0%, more preferably 4.0% or less, and even more preferably 2.0% or less. ２ The lower limit for component O can be set to 0% or higher.

[0095] K ２ Component O is an optional component that participates in chemical strengthening when present in amounts greater than 0%. ２ The lower limit of component O can be 0% or more, greater than 0%, 0.1% or more, 0.5% or more, 1.0% or more, or greater than 1.0%. Also, K ２ By keeping the O component below 10.0%, excellent chemical durability is achieved. Therefore, K ２ The upper limit of component O can preferably be 9.0% or less, 8.0% or less, 6.0% or less, or 4.0% or less.

[0096] The MgO component is an optional component that improves low-temperature meltability when present in amounts exceeding 0%, and can be included within a range that does not impair the effects of the present invention. On the other hand, by limiting the MgO content to 10.0% or less, the deterioration of devitrification can be suppressed. Therefore, the upper limit of the MgO component can preferably be 8.0% or less, 6.0% or less, 4.0% or less, or 2.0% or less. The lower limit of the MgO component can be 0% or more. The lower limit of the MgO component may also be greater than 0%, 0.3% or more, or 0.4% or more.

[0097] The CaO component is an optional component that improves low-temperature meltability when present in amounts exceeding 0%, and can be included within a range that does not impair the effects of the present invention. On the other hand, by limiting the CaO component to 10.0% or less, the deterioration of devitrification can be suppressed. Preferably, the upper limit of the CaO component can be 8.0% or less, 6.0% or less, 4.0% or less, or 2.0% or less. The lower limit of the CaO component can be 0% or more.

[0098] The SrO component is an optional component that improves low-temperature meltability when present in amounts exceeding 0%, and can be included within a range that does not impair the effects of the present invention. Preferably, the upper limit of the SrO component can be 10.0% or less, 6.0% or less, 4.0% or less, 3.0% or less, 2.5% or less, or 2.0% or less. The lower limit of the SrO component can be 0% or more.

[0099] The BaO component is an optional component that improves low-temperature meltability when present in amounts exceeding 0%, and can be included within a range that does not impair the effects of the present invention. Preferably, the upper limit of the BaO component can be 10.0% or less, 6.0% or less, 4.0% or less, 3.0% or less, 2.5% or less, or 2.0% or less. The lower limit of the BaO component can be 0% or more.

[0100] The ZnO component is suitable for improving low-temperature meltability. On the other hand, by limiting the ZnO content to 35.0% or less, the deterioration of devitrification can be suppressed. Preferably, the upper limit of the ZnO component can be 33.0% or less, 30.0% or less, 28.0% or less, 26.0% or less, or 24.0% or less. Preferably, the lower limit of the ZnO component can be 5% or more, 6.0% or more, 8.0% or more, or 10.0% or more. Furthermore, the lower limit of the ZnO content may be greater than 4.0% in mol% on an oxide basis.

[0101] ZrO ２ The component is one that can improve mechanical strength. On the other hand, if its amount is 10.0% or less, deterioration of meltable properties can be suppressed. Preferably, the upper limit is 9.0% or less, 7.0% or less, 5.0% or less, or 3.0% or less. ZrO ２ The lower limit of the component can be 0% or more. ZrO ２The lower limit of the component may be greater than 0%, 1.0% or more, 1.5% or more, or 2.0% or more.

[0102] TiO ２ The component is an optional component that improves the chemical durability of crystallized glass when present in amounts greater than 0%. On the other hand, TiO ２ By reducing the component content to 10.0% or less, the deterioration of devitrification can be suppressed. Preferably, the upper limit can be 8.0% or less, 6.0% or less, 4.0% or less, or less than 0.5%. TiO ２ The lower limit for the concentration of an ingredient can be 0% or higher.

[0103] Nb ２ O ５ The component is an optional component that improves the mechanical strength of the crystallized glass when present in amounts exceeding 0%. Preferably, the upper limit can be 10.0% or less, 8.0% or less, 6.0% or less, 4.0% or less, or 2.0% or less. Nb ２ O ５ The lower limit for the concentration of an ingredient can be 0% or higher.

[0104] Ta ２ O ５ The component is an optional component that improves the mechanical strength of the crystallized glass when present in amounts exceeding 0%. Preferably, the upper limit can be 6.0% or less, 5.5% or less, 5.0% or less, or 4.0% or less. ２ O ５ The lower limit for the concentration of an ingredient can be 0% or higher.

[0105] From the viewpoint of achieving both the desired light transmittance and inflection point, when the ZnO component is greater than 0%, [SiO ２ The upper limit of the component content ratio (%) / ZnO component content ratio (%) may be less than 20, 18.0 or less, 15.0 or less, 13.0 or less, 10.0 or less, 8.0 or less, 6.0 or less, or 5.0 or less. Also, [SiO ２ The lower limit of the ratio of component content (%) / ZnO component content (%) may be 0.5 or higher, 0.8 or higher, 1.0 or higher, 1.5 or higher, 1.8 or higher, or 2.0 or higher.

[0106] Li in mol% on an oxide basis ２ Content of component O, Na ２ Content of component O, K ２O content, MgO content, ZnO content, Al ２ O ３ The content of the ingredients, and B ２ O ３ [(Li ２ Content of component O + Na ２ Content of component O + K ２ (Content of O component + Content of MgO component + Content of ZnO component) / (Al ２ O ３ Ingredient content + B ２ O ３ The content of the component may exceed 1.5.

[0107] Furthermore, the crystallized glass contains La to the extent that it does not impair the effects of the present invention. ２ O ３ Ingredients, Gd ２ O ３ Ingredients, Y ２ O ３ Ingredients, WO ３ Ingredients, TeO ２ Ingredients, Bi ２ O ３ The product may contain each of these ingredients, or it may not contain them at all. If these ingredients are included, their respective amounts may be 0% to 2.0%, 0% to less than 2.0%, or 0% to 1.0%.

[0108] Furthermore, the crystallized glass may or may not contain other components not mentioned above, as long as they do not impair the properties of the crystallized glass of the present invention. For example, it may contain a component (e.g., a metal oxide) containing at least one metal element selected from the group consisting of Yb, Lu, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Nd, and Mo, or it may substantially not contain a component containing at least one metal element selected from the group.

[0109] Glass containing a crystalline phase may contain Fe to the extent that it does not impair the effects of the present invention. ２ O ３ It may or may not contain the ingredient. Fe ２ O ３ If the product contains the active ingredient, the upper limit may be 5.0% or less, 2.0% or less, or less than 1.0%, and may also be less than 700 ppm.

[0110] Glass containing a crystalline phase may be Co to the extent that it does not impair the effects of the present invention. ３ O ４ It may or may not contain the ingredients. ３ O ４ If the substance contains an ingredient, the upper limit may be 100 ppm or less, or less than 20 ppm.

[0111] Glass containing a crystalline phase is MoO ３ It may or may not contain the ingredients. MoO ３ If the component is present, the upper limit may be 0.5% or less, 0.1% or less, or less than 0.003%. Glass containing a crystalline phase is WO ３ Ingredients and MoO ３ The content of one or more components selected from the ingredients may be less than 0.35% in mol% on an oxide basis.

[0112] The glass containing the crystalline phase may contain at least one component selected from the group consisting of metal elements Co, Mn, Fe, Ni, Cu, Cr, V, Bi, Er, Sn, Ce, Pr, Eu, Nd, and Ag in an amount of less than 0.1% in mol% on an oxide basis.

[0113] Sb as a glass clarifying agent ２ O ３ It may contain the component. On the other hand, Sb ２ O ３ By limiting the component content to 5.0% or less, it is possible to suppress the deterioration of transmittance in the short-wavelength region of the visible light spectrum. Therefore, the upper limit can preferably be 3.0% or less, more preferably 2.0% or less, more preferably 1.0% or less, and even more preferably 0.6% or less. Sb ２ O ３ The lower limit for the concentration of an ingredient can be 0% or higher.

[0114] Also, as a glass clarifying agent, Sb ２ O ３ In addition to the components, SnO ２ Ingredients, CeO ２ Ingredients, As ２ O ３ Ingredients, F, NO ｘ and SO ｘ (For example, SO３ It may contain one or more selected from the group consisting of ), or it may not contain any. However, the content of the clarifying agent can preferably be limited to an upper limit of 2.0%, more preferably 1.0%, and most preferably 0.6%. CeO ２ If an ingredient is present, the upper limit of its content may be less than 1000 ppm.

[0115] On the other hand, since Pb, Th, Tl, Os, Be, Cl, and Se are components that have recently been used less frequently due to their harmful chemical properties, it is preferable that the product is substantially free of these elements.

[0116] (Manufacturing Method) Crystallized glass according to one aspect of the present invention can be produced by the following method. That is, raw materials are uniformly mixed so that each of the above components is within a predetermined content range, and raw glass is produced by melting and molding. Next, this raw glass is crystallized to produce crystallized glass.

[0117] The raw glass is heat-treated to precipitate crystals inside the glass. The heat treatment may be performed in one stage or in two stages at different temperatures. In the two-stage heat treatment, a nucleation process is performed by first heat treatment at a first temperature, and after this nucleation process, a crystal growth process is performed by heat treatment at a second temperature higher than the nucleation process. The first temperature in the two-stage heat treatment is preferably 500°C to 750°C, and more preferably 520°C to 700°C. The holding time at the first temperature is preferably 30 minutes to 2000 minutes, and more preferably 180 minutes to 1440 minutes. The second temperature in the two-stage heat treatment is preferably 550°C to 850°C, and more preferably 580°C to 800°C. The holding time at the second temperature is preferably 30 minutes to 600 minutes, and more preferably 60 minutes to 400 minutes.

[0118] In a one-stage heat treatment, the nucleation process and the crystal growth process are carried out continuously at a single temperature. Typically, the temperature is raised to a predetermined heat treatment temperature, held for a certain period of time after reaching that temperature, and then cooled down. When performing heat treatment at a single temperature, the heat treatment temperature is preferably 580°C to 800°C, and more preferably 590°C to 770°C. The holding time at the heat treatment temperature is preferably 30 minutes to 500 minutes, and more preferably 60 minutes to 400 minutes.

[0119] A molded body may be produced from crystallized glass using methods such as grinding and polishing, and then further processed into a thin plate. Furthermore, the molded body processed into a thin plate may be shaped to suit applications such as housings.

[0120] (Strengthening Method) Crystallized glass may be strengthened by various strengthening methods to form a compressive stress layer on its surface.

[0121] One method for strengthening crystallized glass to form a compressive stress layer on its surface is chemical strengthening, which involves exchanging alkaline components present in the surface layer of crystallized glass with alkaline components having a larger ionic radius, thereby forming a compressive stress layer on the surface.

[0122] Chemical strengthening can be carried out, for example, by the following steps: Crystallized glass is strengthened with a salt containing potassium or sodium, such as potassium nitrate (KNO). ３ ), sodium nitrate (NaNO ３ ) or a molten salt of a mixed salt or complex salt thereof, which is then brought into contact with or immersed in. This treatment of contact with or immersion in the molten salt (chemical strengthening treatment) may be carried out in one or two stages.

[0123] The strengthening method for crystallized glass is not limited to chemical strengthening; for example, thermal strengthening or ion implantation may also be used.

[0124] [Applications] Crystallized glass according to one aspect of the present invention can be suitably used as a component of various devices such as smartphones, tablet PCs and other portable electronic devices, optical devices, building components, and automotive components. For example, it can be suitably used as a housing for various devices such as portable electronic devices and optical devices.

[0125] Examples 1-15, Comparative Examples 1-3 (1) Preparation of raw materials As raw materials for each component of the glass containing the crystalline phase, corresponding raw materials such as oxides, hydroxides, carbonates, nitrates, fluorides, chlorides, and metaphosphate compounds were selected, and these raw materials were weighed and uniformly mixed to the compositions shown in Tables 1 to 4.

[0126] (2) Production of glass containing the crystalline phase Next, the mixed raw materials were placed in a platinum crucible and melted in an electric furnace at 1100°C to 1600°C for 2 to 24 hours, depending on the difficulty of melting the glass composition. The molten glass was stirred to homogenize it, the temperature was lowered, and then it was poured into a mold and slowly cooled to produce raw glass. The obtained raw glass was heat-treated under the crystallization conditions of the nucleation process and crystal growth process shown in Tables 1 to 4 to produce glass containing the crystalline phase. The glass shown in Table 1 corresponds to "Glass containing the crystalline phase 1" above, the glass shown in Table 2 corresponds to "Glass containing the crystalline phase 2" above, and the glass shown in Table 3 corresponds to "Glass containing the crystalline phase 3" above.

[0127] (3) Confirmation of crystalline phase The crystalline phase contained in the glass containing the crystalline phase obtained in (2) was identified from the angle of the diffraction peaks appearing in the X-ray diffraction pattern measured using an X-ray diffraction analyzer (Bruker, D8 Discover). The confirmed crystalline phases are shown in Tables 1 to 4. Note that in the table, "Lithium Silicate" refers to lithium silicate (Li ２ O・nSiO ２ It is an abbreviation for "Lithium disilicate" (Li ２ Si ２ O ５ ) is an abbreviation for, "Cristobalite" is an abbreviation for cristobalite, "Quartz" is an abbreviation for quartz, "Virgilite" is an abbreviation for virgilite, "Tridymite" is an abbreviation for tridymite (silicate), "Sodium Titanium Oxide" is an abbreviation for sodium titanate, "Petalite" is an abbreviation for petalite (feldspar), and "Lithium Zinc Phosphate" is lithium zinc phosphate (Li ４ Zn(PO ４ ) ２ It is an abbreviation for "Lithium Zinc Silicate" (Li ２ ZnSiO ４ It is an abbreviation for "Lithium Aluminum Silicate" (LiAlSi). ３ O ８) is an abbreviation for ), and "Lithium Silicate Phosphate" is an abbreviation for lithium silicate phosphate.

[0128] (4) Chromaticity (black background) For the glass containing the crystalline phase obtained in (2), the reflectance spectrum including specular reflection at a direction of 8° with respect to the normal to the normal of the sample surface of the sample used for chromaticity measurement was measured using a spectrophotometer (Konica Minolta, CM-26dG). The thickness of the sample was 1 mm. The reflection spectrum was measured with a black glass plate (chromaticity: L* 26.4, a* 0.05, b* -0.60, thickness: 1 mmt) placed on the back of the sample (opposite the glass surface to which the light source was irradiated). From the obtained reflection spectrum, the chromaticity L*, a*, and b* (black background) were determined using a CIE light source D65 at an observer angle of 10°. The chromaticity L*, a*, and b* (black background) of the crystallized glass are shown in Tables 1 to 4.

[0129] (5) Chromaticity (without background) The chromaticity L*, a*, and b* (without background) of the glass containing the crystalline phase obtained in (2) were determined in the same manner as described in "(4) Chromaticity (black background)," except that the reflection spectrum was measured without placing a black glass plate on the back side of the sample (the side opposite to the glass surface illuminated by the light source).

[0130] (6) Average transmittance The glass containing the crystalline phase obtained in (2) was polished to a thickness of 1 mm to measure the transmittance of the sample. The visible light transmittance, including the reflection loss at wavelengths of 380 to 830 nm, was measured using a spectrophotometer (Hitachi High Technology, U-4000 model), and the average transmittance was calculated from the obtained visible light transmittance spectrum. The results are shown in Tables 1 to 4. In addition, the wavelengths λ1 at which the transmittance is 1% and λ5 at which the transmittance is 5% in the visible light transmittance spectrum are shown in Tables 1 to 4, respectively.

[0131] (7) Bending point (At) A round bar-shaped sample for measuring the bending point was prepared from the glass containing the crystalline phase obtained in (2), with a length of 50 mm and a diameter of 4 ± 0.5 mm. The temperature and elongation of the sample were measured using a high-temperature thermal expansion meter (Bruker AX Corporation, TD5000SA) in accordance with the Nippon Optical Glass Manufacturers Association standard JOGIS08-2003 "Method for measuring thermal expansion of optical glass". The elongation of the sample was measured by applying a load of 10 gf in the longitudinal direction of the sample. The temperature at which the sample softened and began to contract after expanding due to the load was defined as the bending point.

[0132]

[0133]

[0134]

[0135]

[0136] Tables 1-3 show that the glass of the present invention has a low light transmittance of 30% or less, exhibiting excellent light-shielding properties for visible light, and a low flexing point of 840°C or less, resulting in excellent bendability and mass-producibility. Furthermore, its ability to crystallize at relatively low temperatures also contributes to its excellent mass-producibility. On the other hand, Table 4 shows that the glasses of Comparative Examples 1-3 had high flexing points and were inferior in terms of bendability and mass-producibility.

[0137] Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will find it easy to make many modifications to these exemplary embodiments and / or examples without substantially departing from the novel teachings and effects of the present invention. Accordingly, many of these modifications fall within the scope of the present invention. All references to the documents described in this specification and the contents of the application on which the priority claim under the Paris Convention of this application is based are incorporated herein by reference.

Claims

1. In terms of mass percentage on an oxide basis, SiO ２ A crystalline glass containing 30% to 85% of a component, with a refractory point of 840°C or lower, and an average transmittance of 30% or less at a thickness of 1 mm in the wavelength range of 380 nm to 830 nm.

2. A glass containing a crystalline phase as described in claim 1, wherein, from a reflection spectrum including specular reflection measured by a spectrophotometer under the following conditions, the CIELAB color space coordinates obtained using a CIE light source D65 at an observer angle of 10° are such that a* is in the range of -10.00 to 5.00, b* is in the range of -20.00 to 5.00, and L* is in the range of 50.00 or higher. (Reflection spectrum measurement conditions) Sample thickness: 1 mm Receiving angle relative to the normal of the sample surface: 8° 3. In terms of mass percentage on an oxide basis, P ２ O ５ The ingredients are 0% to 10.0%, ZrO ２ A glass comprising the crystalline phase according to claim 1 or 2, containing 0% to 20.0% of the component.

4. In terms of mass% in terms of oxide, [TiO ２ content ratio (%) of the component + ZrO ２ content ratio (%) of the component] is more than 0, and [(P ２ O ５ content ratio (%) of the component + Al ２ O ３ content ratio (%) of the component) / (TiO ２ content ratio (%) of the component + ZrO ２ content ratio (%) of the component)] is 4.0 or less. The glass containing the crystal phase according to claim 1 or 2.

5. In terms of mass percentage on an oxide basis, SiO ２ The ingredients are 45.0% to 85.0%, Al ２ O ３ Ingredients in amounts greater than 0% and less than or equal to 20.0%, B ２ O ３ The ingredients are 0% to 10.0%, P ２ O ５ Ingredients: 0% to 10.0%, Li ２ O component is greater than 0% and less than or equal to 20.0%, Na ２ O component 0% to 10.0%, K ２ O component 0% to 10.0%, MgO component 0% to 10.0%, CaO component 0% to 10.0%, SrO component 0% to 10.0%, BaO component 0% to 10.0%, ZnO component 0% to 15.0%, TiO ２ The ingredients are 0% to 10.0%, ZrO ２ The ingredients are 0% to 15.0%, Nb ２ O ５ The ingredients are 0% to 10.0%, Sb ２ O ３ A glass comprising the crystalline phase described in claim 4, containing 0% to 5% of the component.

6. TiO ２ Contains more than 0% of the component, [SiO ２ Percentage of component content (%) / TiO ２ A glass comprising the crystalline phase according to claim 1 or 2, wherein the content ratio (%) of the component is less than 5.

0.

7. In terms of mass percentage on an oxide basis, SiO ２ The ingredients are 30.0% to 50.0%, Al ２ O ３ Ingredients in 0% to 10.0%, B ２ O ３ The ingredients are 0% to 10.0%, P ２ O ５ Ingredients: 0% to 10.0%, Li ２ O component 0% to 10.0%, Na ２ Component O: 5% to 20.0%, K ２ O component 0% to 15.0%, MgO component 0% to 10.0%, CaO component 0% to 10.0%, SrO component 0% to 10.0%, BaO component 0% to 10.0%, ZnO component 0% to 10.0%, TiO ２ The ingredients are 15% to 35.0%, ZrO ２ The ingredients are 0% to 10.0%, Nb ２ O ５ The ingredients are 0% to 15.0%, Sb ２ O ３ A glass comprising the crystalline phase described in claim 6, containing 0% to 5.0% of the component.

8. Contains more than 0% ZnO component by mass percentage on an oxide basis, [SiO ２ A glass comprising the crystalline phase according to claim 1 or 2, wherein the ratio of component content (%) / ZnO component content (%) is less than 20.

9. In terms of mass percentage on an oxide basis, SiO ２ The ingredients are 30.0% to 70.0%, Al ２ O ３ The ingredients are 5.0% to 20.0%, B ２ O ３ The ingredients are 0% to 10.0%, P ２ O ５ Ingredients: 0% to 10.0%, Li ２ O component is greater than 0% and less than or equal to 20.0%, Na ２ O component 0% to 10.0%, K ２ O component 0% to 10.0%, MgO component 0% to 10.0%, CaO component 0% to 10.0%, SrO component 0% to 10.0%, BaO component 0% to 10.0%, ZnO component 5% to 35.0%, TiO ２ The ingredients are 0% to 10.0%, ZrO ２ The ingredients are 0% to 10.0%, Nb ２ O ５ The ingredients are 0% to 10.0%, Sb ２ O ３ A glass containing the crystalline phase described in claim 8, which contains 0% to 5.0% of the component.

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