Crystallized glass, optical element, and optical device

Abstract

The problem of glass potentially deteriorating or breaking even when used in an environment where temperature changes occur can be solved. In brief, an oxide glass having a low thermal expansion coefficient and exhibiting fluorescence is provided. Provided is a crystallized glass characterized by containing SiO2 40-90 mol%, Al2O3 5-30 mol%, Li2O 1-15 mol%, SnO2 0-20 mol%, ZrO2 0-5 mol%, MgO 0-10 mol%, CaO 0-10 mol%, SrO 0-10 mol%, BaO 0-10 mol%, Na2O 0-10 mol%, K2O 0-10 mol%, P2O5 0-10 mol%, TiO2 0-4 mol%, and Ln2O3 (Ln is at least one selected from Ce, Nd, Yb, Er, Pr, Sm, Eu, Tb, Dy, Ho, and Tm) 0.01-10 mol%, in which Li2O / (MgO+CaO+SrO+BaO+Na2O+K2O) is 8 or less by molar ratio.

Description

Glass-ceramics, optical elements and optical devices

[0001] The present invention relates to rare earth metal element-containing crystallized glass that exhibits fluorescence, an optical element using the glass, and an optical device using the optical element.

[0002] Fluorescent materials using rare earth metal elements have been widely used in the past. For example, Patent Document 1 discloses a Tb- or Eu-containing fluorophosphate fluorescent glass that exhibits strong fluorescence in the visible range when irradiated with ultraviolet light such as an excimer laser.

[0003] Japanese Patent Application Publication No. 8-133780

[0004] However, although the fluorophosphate glass of Patent Document 1 can contain a large amount of rare earth metal elements, which are fluorescent components, it has low heat resistance and mechanical strength and a high thermal expansion coefficient, which can cause problems such as deterioration or breakage of the glass when used in high-temperature environments or environments with severe temperature changes.In addition, the temperature of the glass can rise due to heat from a high-power excitation light source or heat emitted from the fluorescent components in the glass irradiated with excitation light, which can cause problems such as deterioration or breakage of the glass.

[0005] The object of the present invention is to provide rare earth metal element-containing crystallized glass that exhibits fluorescence and has a low thermal expansion coefficient that can suppress deterioration or breakage of glass when excitation light is irradiated onto glass in a high-temperature environment or an environment with drastic temperature changes, or when high-power excitation light is irradiated onto glass; an optical element using said glass; and an optical device using said optical element.

[0006] As a result of extensive research, the present inventors have found that by appropriately designing the glass composition, it is possible to obtain oxide crystallized glass that exhibits fluorescence, has high thermal durability and glass strength, has a low thermal expansion coefficient, and is suitable for use even in environments where temperature changes occur.

[0007] The crystallized glass according to the first aspect of the present invention is ２ 40 to 90 mol%, Al ２ O ３ 5 to 30 mol %, Li ２ O 1 to 15 mol%, SnO２ 0 to 20 mol% ZrO ２ 0-5 mol%, MgO 0-10 mol%, CaO 0-10 mol%, SrO 0-10 mol%, BaO 0-10 mol%, Na ２ O 0 to 10 mol%, K ２ O 0 to 10 mol%, P ２ O ５ 0 to 10 mol% TiO ２ 0 to 4 mol%, Ln ２ O ３ (Ln is at least one selected from Ce, Nd, Yb, Er, Pr, Sm, Eu, Tb, Dy, Ho, and Tm) 0.01 to 10 mol % in a molar ratio of Li ２ O / (MgO+CaO+SrO+BaO+Na ２ O+K ２ O) is 8 or less. ２ O / (MgO+CaO+SrO+BaO+Na ２ O+K ２ O) means Li ２ The O content is MgO, CaO, SrO, BaO, Na ２ O and K ２ It is the value obtained by dividing by the total amount of O content.

[0008] The crystallized glass according to the second aspect is the same as that according to the first aspect, except that Ln ２ O ３ (Ln is at least one element selected from Ce, Nd, Yb, Er, Pr, Sm, Eu, Tb, Dy, Ho and Tm) It is preferable that it contains 1 to 10 mol %.

[0009] The crystallized glass according to the third aspect is the glass-ceramic according to either the first or second aspect, further comprising Nd ２ O ３ It is preferable that the content is 1 to 10 mol %.

[0010] The crystallized glass according to aspect 4 is the glass-ceramic of any one of aspects 1 to 3, further comprising 0 to 10 mol % of ZnO, B ２ O ３ The content is preferably 0 to 10 mol %.

[0011] The crystallized glass according to aspect 5 is the glass-ceramics of any one of aspects 1 to 4, further comprising Fe２ O ３ The content is preferably 0.10 mol % or less.

[0012] The crystallized glass according to Aspect 6 is the glass-ceramic of any one of Aspects 1 to 5, wherein the molar ratio is MgO / (Li ２ It is preferable that "MgO / (LiO+MgO)" is 0.08 or more. ２ "O + MgO" means that the content of MgO is ２ The value is obtained by dividing the content by the total content of O and MgO.

[0013] The crystallized glass according to aspect 7 is the glass-ceramic of any one of aspects 1 to 6, which contains MgO+CaO+SrO+BaO+Na ２ O+K ２ It is preferable that the composition of "MgO + CaO + SrO + BaO + Na ２ O+K ２ "O" refers to MgO, CaO, SrO, BaO, Na ２ O and K ２ The total content of O is

[0014] The crystallized glass according to aspect 8 is the glass-ceramic according to any one of aspects 1 to 7, further comprising ZrO ２ + TiO ２ It is preferable that the content of ZrO is 0.5 to 5.3 mol %. ２ + TiO ２ " means ZrO ２ , and TiO ２ The total content of

[0015] The crystallized glass according to Aspect 9 is the glass-ceramics of any one of Aspects 1 to 8, wherein the molar ratio is (SiO ２ +Al ２ O ３ +Li ２ O) / SiO ２ is preferably less than 1.41. ２ +Al ２ O ３ +Li ２ O) / SiO ２ " means SiO ２ , Al ２ O ３ , and Li ２The total content of O is SiO ２ The value is divided by the content of

[0016] The crystallized glass according to Aspect 10 is the glass-ceramics of any one of Aspects 1 to 9, wherein the molar ratio is (SiO ２ +Al ２ O ３ +Li ２ O) / Al ２ O ３ It is preferable that "(SiO ２ +Al ２ O ３ +Li ２ O) / Al ２ O ３ " means SiO ２ , Al ２ O ３ , and Li ２ The total content of O is Al ２ O ３ The value is divided by the content of

[0017] The crystallized glass according to an eleventh aspect of the present invention is the glass-ceramics of any one of the first to tenth aspects, which contains, in a molar ratio, ZrO ２ / Li ２ It is preferable that O is 0.01 or more. ２ / Li ２ "O" means ZrO ２ The content of Li ２ This is the value divided by the O content.

[0018] The crystallized glass according to aspect 12 is the glass-ceramic of any one of aspects 1 to 11, which contains, in a molar ratio, SnO ２ / (SnO ２ + TiO ２ ) is preferably 0.1 or more. ２ / (SnO ２ + TiO ２ ")" refers to SnO ２ The content of SnO ２ , and TiO ２ The value is obtained by dividing the total content of the above by the total content of the above.

[0019] In the crystallized glass according to Aspect 13, in any one of Aspects 1 to 12, it is preferable that the molar ratio of ZnO / (ZnO+MgO) is 0.9 or less, where "ZnO / (ZnO+MgO)" is the value obtained by dividing the ZnO content by the combined amount of ZnO and MgO.

[0020] The crystallized glass according to Aspect 14 is the glass-ceramics of any one of Aspects 1 to 13, wherein the glass-ceramics contains, in a molar ratio, Al ２ O ３ / (SnO ２ + ZrO ２ ) is preferably greater than 5.5. ２ O ３ / (SnO ２ + ZrO ２ ")" means Al ２ O ３ The content of SnO ２ , and ZrO ２ The value is obtained by dividing the total content of the above by the total content of the above.

[0021] The crystallized glass according to Aspect 15 is the glass-ceramics of any one of Aspects 1 to 14, wherein the molar ratio is: (Li ２ O + Na ２ O+K ２ O) / ZrO ２ is preferably 9.0 or less. ２ O + Na ２ O+K ２ O) / ZrO ２ " means Li ２ O, Na ２ O and K ２ The total content of O is ZrO ２ The value is divided by the content of

[0022] The crystallized glass according to Aspect 16 is the glass-ceramic of any one of Aspects 1 to 15, wherein the molar ratio of TiO ２ / (TiO ２ +Fe ２ O ３ ) is preferably 0.09 or less. ２ / (TiO ２ +Fe ２ O ３ )) is TiO ２ The content of TiO ２, and Fe ２ O ３ The value is obtained by dividing the total content of the above by the total content of the above.

[0023] The crystallized glass according to Aspect 17, in any one of Aspects 1 to 16, preferably contains 6000 mol ppm or less of Pt.

[0024] The crystallized glass according to Aspect 18, in any one of Aspects 1 to 17, preferably contains 5000 mol ppm or less of Rh.

[0025] An optical element according to a nineteenth aspect of the present invention is characterized by comprising the crystallized glass of any one of the first to eighteenth aspects.

[0026] An optical device according to Aspect 20 of the present invention is characterized by including the optical element according to Aspect 19.

[0027] According to the present invention, it is possible to provide rare earth metal element-containing crystallized glass that exhibits fluorescence and has a low thermal expansion coefficient that can suppress deterioration or breakage of glass when excitation light is irradiated onto glass in a high-temperature environment or an environment with drastic temperature changes, or when high-power excitation light is irradiated onto glass, an optical element using this glass, and an optical device using this optical element.

[0028] Fig. 1 is a schematic diagram showing a light-emitting device according to one embodiment of the present invention. Fig. 2 is a schematic diagram showing a light-emitting device according to another embodiment of the present invention. Fig. 3 is a schematic diagram showing a light-emitting device according to another embodiment of the present invention. Fig. 4 is a diagram showing the fluorescence spectrum of sample No. 13. Fig. 5 is a diagram showing the relationship between temperature and fluorescence intensity and thermal expansion coefficient for sample No. 13. Fig. 6 is a diagram showing the relationship between temperature and fluorescence intensity and thermal expansion coefficient for sample No. 42.

[0029] The crystallized glass of the present invention (hereinafter also simply referred to as "crystallized glass") is a glass containing SiO ２ 40 to 90 mol%, Al ２ O ３ 5 to 30 mol %, Li ２ O 1 to 15 mol%, SnO ２ 0 to 20 mol% ZrO ２0-5 mol%, MgO 0-10 mol%, CaO 0-10 mol%, SrO 0-10 mol%, BaO 0-10 mol%, Na ２ O 0 to 10 mol%, K ２ O 0 to 10 mol%, P ２ O ５ 0 to 10 mol% TiO ２ 0 to 4 mol%, Ln ２ O ３ (Ln is at least one selected from Ce, Nd, Yb, Er, Pr, Sm, Eu, Tb, Dy, Ho, and Tm) 0.01 to 10 mol % in a molar ratio of Li ２ O / (MgO+CaO+SrO+BaO+Na ２ O+K ２ O) is not more than 8. The reasons for limiting the glass composition as above are as follows.

[0030] SiO ２ forms the skeleton of the glass and the precipitated crystals are Li ２ O-Al ２ O ３ -SiO ２ In the case of a Li-based crystal, ２ O-Al ２ O ３ -SiO ２ It is a component that constitutes the SiO crystal. ２ If the content of SiO is too low, the thermal expansion coefficient tends to be high, making it difficult to obtain crystallized glass with excellent thermal shock resistance. Also, the chemical durability tends to be reduced. ２ The lower limit of the content of SiO is 40 mol% or more, and is preferably 50 mol% or more, 52 mol% or more, 55 mol% or more, 58 mol% or more, 61 mol% or more, 64 mol% or more, 66 mol% or more, 67 mol% or more, 68 mol% or more, and particularly preferably 69 mol% or more. ２ If the content of SiO is too high, the meltability of the glass decreases, the viscosity of the glass melt increases, making it difficult to clarify the glass and to mold the glass, which tends to reduce productivity. Also, crystals of cristobalite and tridymite tend to precipitate, causing the glass to devitrify, and the crystallized glass becomes more susceptible to breakage. Furthermore, the time required for crystallization increases, which tends to reduce productivity. Therefore, SiO２ The upper limit of the content is 90 mol% or less, preferably 85 mol% or less, 83 mol% or less, 80 mol% or less, 75 mol% or less, 74 mol% or less, 73 mol% or less, particularly preferably 72 mol% or less.

[0031] Al ２ O ３ forms the skeleton of the glass and the precipitated crystals are Li ２ O-Al ２ O ３ -SiO ２ In the case of a Li-based crystal, ２ O-Al ２ O ３ -SiO ２ It is a component that constitutes the Al-based crystal. ２ O ３ If the content of Al is too low, the thermal expansion coefficient tends to be high, making it difficult to obtain crystallized glass with excellent thermal shock resistance. In addition, the rare earth metal element is not sufficiently dispersed in the glass, which causes concentration quenching and makes it easy for the intensity of light emitted by fluorescence to decrease. In addition, chemical durability tends to decrease. Therefore, Al ２ O ３ The lower limit of the content of Al is 5 mol% or more, and is preferably 7 mol% or more, 8 mol% or more, 9 mol% or more, 10 mol% or more, 11 mol% or more, 12 mol% or more, 13 mol% or more, and particularly preferably 13.5 mol% or more. ２ O ３ If the content of Al is too high, the meltability of the glass will decrease, the viscosity of the glass melt will increase, making it difficult to refine the glass and to mold the glass, which will tend to reduce productivity. In addition, corundum and mullite crystals will precipitate, causing the glass to devitrify, and the crystallized glass will be easily broken. Therefore, Al ２ O ３ The upper limit of the content is 30 mol% or less, and is preferably 25 mol% or less, 23 mol% or less, 22 mol% or less, 21 mol% or less, 20 mol% or less, 19 mol% or less, 18 mol% or less, 17 mol% or less, 16 mol% or less, 15.8 mol% or less, 15.5 mol% or less, and particularly preferably 15 mol% or less.

[0032] Li ２ O is the precipitated crystals of Li ２O-Al ２ O ３ -SiO ２ In the case of a Li-based crystal, ２ O-Al ２ O ３ -SiO ２ Li is a component that constitutes the crystalline structure and has a significant effect on the crystallinity, as well as lowering the viscosity of the glass and improving the meltability and formability of the glass. ２ If the O content is too low, mullite crystals tend to precipitate and the glass tends to devitrify. ２ O-Al ２ O ３ -SiO ２ The precipitation of Li-based crystals becomes difficult, making it difficult to obtain crystallized glass having excellent thermal shock resistance. Furthermore, the meltability of the glass decreases, the viscosity of the glass melt increases, making it difficult to refine the glass and to mold the glass, which tends to reduce productivity. ２ The lower limit of the O content is 1 mol% or more, and is preferably 2 mol% or more, 3 mol% or more, 4 mol% or more, 4.5 mol% or more, 5.0 mol% or more, 5.3 mol% or more, 5.5 mol% or more, 6 mol% or more, 6.5 mol% or more, 7.0 mol% or more, particularly preferably 7.5 mol% or more. ２ If the O content is too high, the crystallinity becomes too strong, and the glass tends to be easily devitrified, and the crystallized glass becomes easily broken. ２ The upper limit of the O content is 15 mol% or less, and is preferably 13 mol% or less, 11 mol% or less, 10 mol% or less, 9.5 mol% or less, 9.0 mol% or less, 8.5 mol% or less, 8.3 mol% or less, 8.2 mol% or less, or 8.1 mol% or less, and particularly preferably 8.0 mol% or less.

[0033] (SiO ２ +Al ２ O ３ +Li ２ O) / SiO ２ (SiO ２ , Al ２ O ３ , and Li ２ The total content of O is SiO ２(value divided by the content of SiO ２ +Al ２ O ３ +Li ２ O) / Al ２ O ３ (SiO ２ , Al ２ O ３ , and Li ２ The total content of O is ２ O ３ By adjusting the content of SiO (the value obtained by dividing by the content of SiO), it is possible to make it difficult for the above-mentioned crystals such as cristobalite, tridymite, corundum, and mullite to precipitate, and to suppress devitrification of the glass. ２ +Al ２ O ３ +Li ２ O) / SiO ２ The upper limit of is preferably less than 1.41, and is preferably 1.4 or less, 1.39 or less, 1.38 or less, 1.37 or less, 1.365 or less, 1.36 or less, 1.355 or less, 1.35 or less, 1.345 or less, 1.34 or less, 1.335 or less, 1.33 or less, 1.325 or less, 1.32 or less, 1.315 or less, 1.31 or less, particularly preferably 1.28 or less. ２ +Al ２ O ３ +Li ２ O) / Al ２ O ３ The lower limit is preferably 6.0 or more, 6.3 or more, 6.5 or more, more than 6.6, 6.61 or more, 6.62 or more, 6.63 or more, 6.64 or more, 6.65 or more, 6.66 or more, 6.67 or more, 6.675 or more, 6.68 or more, 6.685 or more, 6.69 or more, 6.695 or more, 6.7 or more, 6.9 or more, 7.1 or more, particularly preferably 7.3 or more.

[0034] SnO ２ is a component that acts as a clarifier. It is also a nucleation component for precipitating crystals in the crystallization process. On the other hand, if contained in large amounts, it is also a component that significantly intensifies the coloring of the crystallized glass. Therefore, SnO ２The upper limit of the content of SnO is 20 mol% or less, and is preferably 10 mol% or less, 8 mol% or less, 5 mol% or less, 4 mol% or less, 3 mol% or less, 2.5 mol% or less, 2 mol% or less, 1.5 mol% or less, 1.3 mol% or less, 1.2 mol% or less, 1 mol% or less, 0.8 mol% or less, 0.7 mol% or less, and particularly preferably 0.6 mol% or less. ２ The lower limit of the content is preferably more than 0 mol %, more preferably 0.01 mol % or more, 0.05 mol % or more, 0.07 mol % or more, 0.1 mol % or more, particularly preferably 0.3 mol % or more.

[0035] ZrO ２ is a nucleation component for precipitating crystals in the crystallization step. ２ If the content is too high, coarse ZrO ２ Crystals are precipitated, the glass becomes easily devitrified, and the crystallized glass becomes easily broken. ２ The upper limit of the content of is 5 mol% or less, and is preferably 4.5 mol% or less, 4 mol% or less, 3.5 mol% or less, 3 mol% or less, 2.9 mol% or less, 2.7 mol% or less, 2.5 mol% or less, 2.3 mol% or less, 2.1 mol% or less, 1.9 mol% or less, 1.7 mol% or less, 1.65 mol% or less, and particularly preferably 1.6 mol% or less. ２ The lower limit of the content is preferably more than 0 mol%, and is preferably 0.1 mol% or more, 0.2 mol% or more, 0.3 mol% or more, 0.4 mol% or more, 0.5 mol% or more, 0.6 mol% or more, 0.7 mol% or more, particularly preferably 0.8 mol% or more.

[0036] MgO is a material in which the precipitated crystals are Li ２ O-Al ２ O ３ -SiO ２ In the case of Li-based crystals, ２ O-Al ２ O ３ -SiO ２ It is solid-dissolved in the system crystal, and Li ２ O-Al ２ O ３ -SiO ２It is a component that increases the thermal expansion coefficient of the glass-ceramic. If the MgO content is too high, the crystallinity becomes too strong, making it prone to devitrification and breakage of the crystallized glass. Furthermore, the thermal expansion coefficient tends to be too high. Therefore, the upper limit of the MgO content is 10 mol% or less, and preferably 8 mol% or less, 7 mol% or less, 5 mol% or less, 3.5 mol% or less, 3.0 mol% or less, 2.5 mol% or less, and particularly 2.0 mol% or less. Since MgO is easily mixed in as an impurity, attempting to completely remove MgO tends to increase the cost of the raw material batch and increase the manufacturing cost. In order to suppress the increase in manufacturing cost, the lower limit of the MgO content is preferably 0.00001 mol% or more, more preferably 0.00003 mol% or more, and particularly preferably 0.00005 mol% or more.

[0037] CaO is a component that reduces the viscosity of glass and improves the melting and molding properties of glass. It is also a component that adjusts the thermal expansion coefficient and refractive index of the crystallized glass. Furthermore, the precipitated crystals are ２ O-Al ２ O ３ -SiO ２ In the case of Li-based crystals, ２ O-Al ２ O ３ -SiO ２It is a component that can be solid-soluble in the system crystal. If the CaO content is too high, the glass is likely to devitrify, and the crystallized glass is likely to break. In addition, the ionic radius of Ca cations is larger than that of Li cations and Mg cations, which are the main crystal constituents, and is therefore difficult to incorporate into the crystal, so that the Ca cations tend to remain in the remaining glass after crystallization. Therefore, if the CaO content is too high, the refractive index difference between the crystal phase and the remaining glass is likely to occur, and the crystallized glass tends to become cloudy. Therefore, the upper limit of the CaO content is 10 mol% or less, and is preferably 9 mol% or less, 7 mol% or less, 5 mol% or less, 3 mol% or less, 1.5 mol% or less, 1 mol% or less, 0.1 mol% or less, 0.05 mol%, 0.03 mol% or less, 0.025 mol% or less, 0.02 mol% or less, 0.015 mol% or less, 0.01 mol% or less, particularly 0.001 mol% or less. Since CaO is easily mixed in as an impurity, attempting to completely remove CaO tends to increase the cost of the raw material batch and the manufacturing cost. In order to suppress the increase in manufacturing cost, the lower limit of the CaO content is preferably 0.00001 mol% or more, 0.00003 mol% or more, and particularly preferably 0.00005 mol% or more. The refractive index of the glass can be measured using a precision refractometer (KPR-2000 manufactured by Shimadzu Corporation).

[0038] SrO is a component that reduces the viscosity of glass and improves the melting and molding properties of glass. It is also a component that adjusts the thermal expansion coefficient and refractive index of glass-ceramics. Furthermore, the precipitated crystals are ２ O-Al ２ O ３ -SiO ２ In the case of Li-based crystals, ２ O-Al ２ O ３ -SiO ２It is a component that can be solid-soluble in the system crystal. If the SrO content is too high, the glass is likely to devitrify, and the crystallized glass is likely to break. In addition, the ionic radius of Sr cations is larger than that of Li cations and Mg cations, which are the main crystal constituents, and is therefore difficult to incorporate into the crystal, so the Sr cations tend to remain in the remaining glass after crystallization. Therefore, if the SrO content is too high, the refractive index difference between the crystal phase and the remaining glass is likely to occur, and the crystallized glass tends to become cloudy. Therefore, the upper limit of the SrO content is 10 mol% or less, and is preferably 9 mol% or less, 7 mol% or less, 5 mol% or less, 3 mol% or less, 1.5 mol% or less, 1 mol% or less, 0.1 mol% or less, 0.03 mol% or less, 0.025 mol% or less, 0.02 mol% or less, 0.015 mol% or less, 0.01 mol% or less, particularly 0.001 mol% or less. Since SrO is easily mixed in as an impurity, attempting to completely remove SrO tends to increase the cost of the raw material batch and the manufacturing cost. In order to suppress the increase in manufacturing cost, the lower limit of the SrO content is preferably 0.00001 mol% or more, 0.00003 mol% or more, and particularly preferably 0.00005 mol% or more.

[0039] BaO is a component that reduces the viscosity of glass and improves the melting and molding properties of glass. It is also a component that adjusts the thermal expansion coefficient and refractive index of glass-ceramics. Furthermore, the precipitated crystals are ２ O-Al ２ O ３ -SiO ２ In the case of Li-based crystals, ２ O-Al ２ O ３ -SiO ２It is a component that can be solid-solubilized in the system crystal. If the content of BaO is too high, crystals containing Ba will precipitate, making the glass prone to devitrification, and the crystallized glass prone to breakage. In addition, the ionic radius of Ba cation is larger than that of Li cation or Mg cation, which are the constituent components of the main crystal, and is difficult to be incorporated into the crystal, so the Ba cation is likely to remain in the remaining glass after crystallization. Therefore, if the content of BaO is too high, the refractive index difference between the crystal phase and the remaining glass is likely to occur, and the crystallized glass tends to become cloudy. Therefore, the upper limit of the BaO content is 10 mol% or less, and is preferably 9 mol% or less, 8 mol% or less, 7 mol% or less, 6 mol% or less, 5 mol% or less, 4 mol% or less, 3 mol% or less, 2 mol% or less, 1 mol% or less, 0.5 mol% or less, 0.1 mol% or less, 0.03 mol% or less, 0.025 mol% or less, 0.02 mol% or less, 0.015 mol% or less, 0.01 mol% or less, and particularly preferably 0.001 mol% or less. Since BaO is easily mixed in as an impurity, attempting to completely remove BaO tends to increase the cost of the raw material batch, resulting in an increase in production costs. To suppress increases in production costs, the lower limit of the BaO content is preferably 0.00001 mol% or more, 0.00003 mol% or more, and particularly preferably 0.00005 mol% or more.

[0040] Na ２ O is the precipitated crystals ２ O-Al ２ O ３ -SiO ２ In the case of Li-based crystals, ２ O-Al ２ O ３ -SiO ２ It is a component that can dissolve in the system crystal, has a significant effect on the crystallization, and reduces the viscosity of the glass, improving the melting and formability of the glass. It is also a component that adjusts the thermal expansion coefficient and refractive index of the crystallized glass. ２ If the O content is too high, the crystallinity becomes too strong, the glass becomes easily devitrified, and the crystallized glass becomes easily broken. In addition, the linear thermal expansion coefficient tends to increase. ２The upper limit of the O content is 10 mol% or less, and is preferably 9 mol% or less, 8 mol% or less, 7 mol% or less, 6 mol% or less, 5 mol% or less, 4 mol% or less, 3 mol% or less, 2 mol% or less, or 1 mol% or less, particularly preferably 0.5 mol% or less. ２ O is easily mixed in as an impurity, so Na ２ If an attempt is made to completely remove O, the raw material batch becomes expensive and the manufacturing cost tends to increase. ２ The lower limit of the O content is preferably 0.0003 mol % or more, 0.0005 mol % or more, particularly preferably 0.001 mol % or more, 0.01 mol % or more, or 0.1 mol % or more.

[0041] K ２ O is the precipitated crystals ２ O-Al ２ O ３ -SiO ２ In the case of Li-based crystals, ２ O-Al ２ O ３ -SiO ２ It is a component that can dissolve in the glass crystals, has a significant effect on the crystallization, and reduces the viscosity of the glass, improving the melting and formability of the glass. It is also a component that adjusts the thermal expansion coefficient and refractive index of the glass-ceramics. ２ If the O content is too high, the linear thermal expansion coefficient tends to be high. Also, the crystallinity becomes too strong, the glass tends to devitrify, and the crystallized glass tends to break. In addition, the ionic radius of K cations is larger than that of Li cations and Mg cations, which are the main crystal constituents, and they are difficult to incorporate into the crystals, so K cations tend to remain in the remaining glass after crystallization. For this reason, K ２ If the O content is too high, a difference in refractive index between the crystalline phase and the remaining glass is likely to occur, and the crystallized glass tends to become cloudy. ２The upper limit of the O content is 10 mol% or less, and is preferably 9 mol% or less, 8 mol% or less, 7 mol% or less, 6 mol% or less, 5 mol% or less, 4 mol% or less, 3 mol% or less, 2 mol% or less, 1 mol% or less, 0.5 mol% or less, 0.3 mol% or less, 0.1 mol% or less, 0.03 mol% or less, 0.025 mol% or less, 0.02 mol% or less, 0.01 mol% or less, 0.005 mol% or less, and particularly preferably 0.001 mol% or less. ２ O is easily mixed in as an impurity, so K ２ If an attempt is made to completely remove O, the raw material batch becomes expensive and the manufacturing cost tends to increase. ２ The lower limit of the O content is preferably 0.00001 mol % or more, 0.00003 mol % or more, and particularly preferably 0.00005 mol % or more.

[0042] In the case of crystallized glass, if there is a large difference in the thermal expansion coefficient between the crystalline phase after crystallization and the remaining glass phase, there is a risk of surface peeling or cracks from inside the sample. ２ O-Al ２ O ３ -SiO ２ In the case of Li-based crystals, ２ O-Al ２ O ３ -SiO ２ If the solid solubility of Li in the system crystal is too large, the amount of volume shrinkage during crystallization becomes large, and the thermal expansion coefficient of the crystalline phase after the crystallization is completed becomes too low, and a large difference in the thermal expansion coefficient between the crystalline phase and the remaining glass phase is likely to occur. As a result, the crystallized glass is likely to develop surface peeling and cracks. Therefore, MgO / (Li ２ The lower limit of the molar ratio of MgO / (LiO+MgO) is preferably 0.08 or more, more preferably 0.09 or more, 0.10 or more, 0.11 or more, 0.12 or more, 0.13 or more, 0.14 or more, 0.15 or more, 0.16 or more, 0.17 or more, 0.18 or more, particularly preferably 0.19 or more. ２ The upper limit of the molar ratio of LiO+MgO is preferably 5.0 or less, more preferably 3.0 or less, 1.0 or less, and particularly preferably 0.5 or less. ２ O / (MgO+CaO+SrO+BaO+Na２ O+K ２ The upper limit of the molar ratio of Li is 8 or less, and is preferably 7.5 or less, 7.0 or less, 6.5 or less, 6.0 or less, 5.5 or less, 5 or less, 4.9 or less, 4.8 or less, 4.7 or less, 4.6 or less, 4.5 or less, 4.4 or less, 4.3 or less, 4.2 or less, 4.1 or less, 4 or less, 3.95 or less, 3.9 or less, 3.85 or less, 3.8 or less, 3.75 or less, 3.7 or less, 3.65 or less, 3.6 or less, 3.55 or less, 3.5 or less, 3.45 or less, 3.4 or less, and particularly preferably 3.35 or less. ２ O / (MgO+CaO+SrO+BaO+Na ２ O+K ２ The lower limit of the molar ratio of O) is preferably 0.01 or more, more preferably 0.1 or more, 1.0 or more, and particularly preferably 3.0 or more.

[0043] Li ２ O, Na ２ O.K. ２ O is a component that improves the meltability and formability of the glass, but if the content of this component is too high, the low-temperature viscosity may decrease too much, and the glass may flow too much during crystallization. ２ O, Na ２ O.K. ２ O is a component that can deteriorate the chemical durability of the glass before crystallization. If the glass before crystallization is deteriorated by moisture or the like, the desired crystallization behavior and, ultimately, the desired properties may not be obtained. ２ is a component that functions as a nucleating agent, which crystallizes preferentially in the initial stage of crystallization and has the effect of suppressing the flow of the remaining glass. ２ is SiO ２ It efficiently fills the voids in the glass network, which is mainly composed of the skeleton, and has the effect of inhibiting the diffusion of protons and various chemical components within the glass network, thereby improving the weather resistance, water resistance, chemical resistance, etc. of the glass before crystallization. In order to obtain crystallized glass with the desired shape and properties, (Li ２ O + Na ２ O+K ２ O) / ZrO ２ should be suitably controlled. ２ O + Na ２ O+K２ O) / ZrO ２ The upper limit of the molar ratio is preferably 9.0 or less, and is preferably 8.8 or less, 8.6 or less, 8.4 or less, 8.2 or less, 8.0 or less, 7.8 or less, 7.6 or less, 7.4 or less, 7.2 or less, 7 or less, 6.8 or less, 6.6 or less, 6.4 or less, 6.2 or less, 6.0 or less, 5.8 or less, 5.6 or less, and particularly preferably 5.4 or less.

[0044] Also, MgO + CaO + SrO + BaO + Na ２ O+K ２ The lower limit of O is preferably 1.3 mol% or more, more preferably 1.4 mol% or more, 1.5 mol% or more, 1.6 mol% or more, 1.7 mol% or more, 1.8 mol% or more, 1.9 mol% or more, 2.0 mol% or more, 2.1 mol% or more, 2.2 mol% or more, 2.3 mol% or more, particularly preferably 2.35 mol% or more. ２ O+K ２ If the amount of O is too small, the thermal expansion coefficient of the crystallized glass tends to be too high or too low. ２ O+K ２ The upper limit of O is preferably 40 mol % or less.

[0045] ZrO ２ is a sparingly soluble nucleating agent, Li ２ O acts as a flux to promote melting, so ZrO ２ / Li ２ If O is small, ZrO ２ It can dissolve ZrO ２ / Li ２ If the O content is too small, the low-temperature viscosity will be too low, and the glass will be prone to flow during the nucleation step, which involves heat treatment at a relatively low temperature, causing deformation. Also, if the low-temperature viscosity is too low, the nucleation rate will be too fast, making it difficult to control the nucleation step. Therefore, ZrO ２ / Li ２The lower limit of O in terms of molar ratio is preferably 0.01 or more, more preferably 0.02 or more, 0.03 or more, 0.04 or more, 0.05 or more, 0.06 or more, 0.07 or more, 0.08 or more, 0.09 or more, 0.10 or more, 0.11 or more, 0.12 or more, 0.13 or more, 0.14 or more, 0.15 or more, 0.16 or more, 0.17 or more, particularly preferably 0.18 or more. ２ / Li ２ If O is too large, ZrO becomes insoluble. ２ However, ZrO tends to remain as devitrified particles. ２ / Li ２ The upper limit of O in terms of molar ratio is preferably 4 or less, more preferably 3 or less, 2 or less, 1 or less, 0.5 or less, and particularly preferably 0.25 or less.

[0046] Also, Al ２ O ３ / (SnO ２ + ZrO ２ ) is preferably more than 5.5 in molar ratio, and is preferably 5.6 or more, 5.7 or more, 5.8 or more, 5.9 or more, 6.0 or more, 6.1 or more, 6.2 or more, 6.3 or more, 6.4 or more, 6.5 or more, 6.6 or more, 6.7 or more, 6.8 or more, particularly preferably 6.9 or more. ２ O ３ / (SnO ２ + ZrO ２ If the ratio of TiO to TiO is too small, the crystal nuclei become large and the crystallized glass tends to become cloudy. ２ On the other hand, when the content of Al is 0.2 mol % or more, the above phenomenon is easily manifested. ２ O ３ / (SnO ２ + ZrO ２ If the Al 2 O 3 is too large, nucleation may not proceed efficiently, and crystallization may not proceed efficiently. ２ O ３ / (SnO ２ + ZrO ２ The upper limit of the molar ratio of ) is preferably 25 or less.

[0047] P ２ O ５ is a coarse ZrO ２It is a component that suppresses crystal precipitation. It may also be involved in the ease with which phase separation occurs during crystal nucleation. ２ O ５ If the content of P is too high, the amount of crystal precipitation tends to decrease and the thermal expansion coefficient tends to increase. ２ O ５ The upper limit of the content of is 10 mol% or less, and is preferably 9 mol% or less, 8 mol% or less, 7 mol% or less, 6 mol% or less, 5 mol% or less, 4 mol% or less, 3 mol% or less, 2.5 mol% or less, 2.0 mol% or less, 1.5 mol% or less, 1 mol% or less, and particularly preferably 0.7 mol% or less. ２ O ５ The lower limit of the content is preferably more than 0 mol%, and is preferably 0.1 mol% or more, 0.2 mol% or more, 0.3 mol% or more, 0.4 mol% or more, 0.5 mol% or more, 0.55 mol% or more, particularly preferably 0.6 mol% or more.

[0048] TiO ２ is a nucleation component for precipitating crystals in the crystallization process. On the other hand, if it is contained in a large amount, it significantly intensifies the coloring of the glass. ２ and TiO ２ The zirconia titanate crystals containing SiO act as crystal nuclei, but electrons transition from the valence band of the oxygen ligand to the conduction band of the central metals zirconia and titanium (LMCT transition), which contributes to the coloring of the crystallized glass. ２ An LMCT transition can occur from the valence band of the framework to the conduction band of tetravalent titanium in the residual glass phase. In addition, a dd transition occurs in the trivalent titanium in the residual glass phase, which contributes to the coloring of the glass-ceramic. Furthermore, when titanium and iron coexist, ilmenite (FeTiO ３ It is known that when titanium and tin coexist, the yellow color becomes stronger. ２ The upper limit of the content of TiO is 4 mol% or less, and is preferably 3.8 mol% or less, 3.6 mol% or less, 3.4 mol% or less, 3.2 mol% or less, 3 mol% or less, 2.5 mol% or less, and particularly preferably 2 mol% or less. ２The lower limit of the content is preferably more than 0 mol%, and is preferably 0.00001 mol% or more, 0.00003 mol% or more, 0.00005 mol% or more, 0.00007 mol% or more, 0.0001 mol% or more, 0.001 mol% or more, particularly preferably 0.01 mol% or more.

[0049] TiO ２ and ZrO ２ are components that can function as crystal nuclei. Ti and Zr are homologous elements, and have similar electronegativity and ionic radius. Therefore, they tend to take similar molecular conformations as oxides, and TiO ２ and ZrO ２ It has been found that in the presence of TiO, phase separation is likely to occur in the initial stage of crystallization. ２ and ZrO ２ Both of these may be contained. ２ / ZrO ２ If the value is too small, the raw material batch becomes expensive and the manufacturing cost increases. ２ / ZrO ２ The lower limit of the molar ratio is preferably 0.00001 or more, more preferably 0.00002 or more, 0.00003 or more, 0.00004 or more, 0.00005 or more, 0.00006 or more, 0.00007 or more, 0.00008 or more, 0.00009 or more, particularly preferably 0.0001 or more. ２ / ZrO ２ If is too large, the crystal nucleation rate will be slow, which may increase the production cost. ２ / ZrO ２ The upper limit of the molar ratio is preferably 5.0 or less, more preferably 4.0 or less, 3.0 or less, 2.5 or less, 2.0 or less, 1.54 or less, 1.51 or less, 1.48 or less, 1.45 or less, particularly preferably 1.42 or less.

[0050] In glass-ceramics, a phase separation region is formed in the glass sample prior to the formation of crystal nuclei, and ZrO ２ and TiO ２ Crystal nuclei are formed, consisting of ZrO ２ + TiO ２If the amount of ZrO is too small, it becomes difficult to form crystal nuclei, and crystallization does not proceed easily. ２ + TiO ２ The lower limit of ZrO is preferably 0.5 mol% or more, more preferably 0.6 mol% or more, 0.7 mol% or more, 0.8 mol% or more, 0.9 mol% or more, 1.0 mol% or more, 1.1 mol% or more, 1.15 mol% or more, 1.2 mol% or more, 1.25 mol% or more, 1.3 mol% or more, 1.35 mol% or more, 1.37 mol% or more, particularly preferably 1.4 mol% or more. ２ + TiO ２ If the amount is too large, the phase separation region becomes large and the crystallized glass tends to become cloudy. ２ + TiO ２ The upper limit is preferably 5.3 mol% or less, more preferably 5.0 mol% or less, 4.5 mol% or less, 4 mol% or less, 3.5 mol% or less, 3.0 mol% or less, 2.5 mol% or less, 2.2 mol% or less, particularly preferably 2.0 mol% or less.

[0051] SnO ２ , TiO ２ All of these can be involved in nucleation. It is known that in the initial stage of nucleation of volume-ceramic glass, the nucleation components undergo phase separation prior to the precipitation of the nucleus crystals. Furthermore, phase separation is more likely to occur when multiple components are contained than when each component is contained alone. Therefore, SnO ２ / (SnO ２ + TiO ２ The lower limit of the molar ratio of SnO is preferably 0.1 or more, more preferably 0.3 or more, 0.5 or more, 0.7 or more, particularly preferably 0.9 or more. ２ / (SnO ２ + TiO ２ The upper limit of the molar ratio of ) is preferably less than 2.0.

[0052] Ln ２ O ３(Ln is at least one element selected from Ce, Nd, Yb, Er, Pr, Sm, Eu, Tb, Dy, Ho, and Tm) functions in glass as an ion that exhibits fluorescence. These elements can be used alone or in combination of two or more elements. From the viewpoint of obtaining glass with high transparency, Ln is preferably Nd. Nd acts as a complementary coloring agent to the coloring of iron contained in the raw materials of the glass, and has the advantage that if a heterogeneous phase (bubbles, uneven composition spots, devitrification particles, etc.) is present in the glass, the presence of the heterogeneous phase can be easily detected by visual inspection or various inspection devices. Ln ２ O ３ If the content of Ln is too low, the intensity of the light emitted by fluorescence will be very low. ２ O ３ The lower limit of the content of Ln is 0.01 mol% or more, and is preferably 0.03 mol% or more, 0.05 mol% or more, 0.1 mol% or more, 0.3 mol% or more, 0.5 mol% or more, 0.7 mol% or more, 1 mol% or more, 1.5 mol% or more, 2 mol% or more, 2.5 mol% or more, 3 mol% or more, 3.5 mol% or more, 4.5 mol% or more, particularly preferably 5 mol% or more. ２ O ３ If the content of Ln is too high, the glass is likely to devitrify and lose its translucency due to crystallization. In addition, the intensity of light emitted by fluorescence becomes very low due to concentration quenching. ２ O ３ The upper limit of the content is 10 mol% or less, and is preferably 9.5 mol% or less, 9 mol% or less, 8.5 mol% or less, 8 mol% or less, 7.5 mol% or less, 7.0 mol% or less, 6.5 mol% or less, and particularly preferably 6.0 mol% or less. Representative ranges of oscillation wavelengths for each ion that exhibits fluorescence are shown below, but are not limited thereto, and the oscillation wavelength may be in the ultraviolet region on the short wavelength side or the infrared region on the long wavelength side, rather than being limited to the visible light region of 380 to 780 nm.

[0053] Ce ２ O ３ is a component that emits light in the range of 300 nm to 500 nm by fluorescence. ２ O ３If the content of Ce is too low, the intensity of light emitted by fluorescence in the range of 300 nm to 500 nm will be low. ２ O ３ The lower limit of the content of Ce is preferably 0.01 mol% or more, more preferably 0.03 mol% or more, 0.05 mol% or more, 0.1 mol% or more, 0.2 mol% or more, 0.3 mol% or more, 0.4 mol% or more, 0.5 mol% or more, 0.7 mol% or more, 1 mol% or more, 2 mol% or more, 3 mol% or more, particularly preferably 5 mol% or more. ２ O ３ If the content of Ce is too high, the glass is likely to devitrify and lose its translucency due to crystallization. In addition, it becomes difficult to prevent a decrease in transmittance due to the glass turning yellow or orange. In addition, the intensity of light emitted by fluorescence becomes very low due to concentration quenching. Therefore, Ce ２ O ３ The upper limit of the content is preferably 10 mol% or less, more preferably 9.5 mol% or less, 9 mol% or less, 8.5 mol% or less, 8 mol% or less, 7.5 mol% or less, 7.0 mol% or less, 6.5 mol% or less, particularly preferably 6.0 mol% or less.

[0054] Nd ２ O ３ is a component that emits light in the range of 850 nm to 1400 nm by fluorescence. It is also a component that can suppress the coloring of iron contained in the raw materials of glass as a color complementing agent. Specifically, Nd ２ O ３ This is a technique that creates an achromatic color by overlaying blue coloring by Nd ２ O ３ If the content is too low, the intensity of the light emitted by fluorescence in the range of 850 nm to 1400 nm will be low. ２ O ３ The lower limit of the content of Nd is preferably 0.01 mol% or more, more preferably 0.03 mol% or more, 0.05 mol% or more, 0.1 mol% or more, 0.2 mol% or more, 0.3 mol% or more, 0.4 mol% or more, 0.5 mol% or more, 0.7 mol% or more, 1 mol% or more, 2 mol% or more, 3 mol% or more, particularly preferably 5 mol% or more. ２ O３ If the content of Nd is too high, the glass is likely to devitrify and lose its translucency due to crystallization. In addition, the intensity of light emitted by fluorescence becomes very low due to concentration quenching. ２ O ３ The upper limit of the content is preferably 10 mol% or less, more preferably 9.5 mol% or less, 9 mol% or less, 8.5 mol% or less, 8 mol% or less, 7.5 mol% or less, 7.0 mol% or less, 6.5 mol% or less, particularly preferably 6.0 mol% or less.

[0055] Yb ２ O ３ is a component that emits light in the vicinity of 925 nm to 1100 nm by fluorescence. ２ O ３ If the content of Yb is too low, the intensity of the light emitted by fluorescence in the range of 925 nm to 1100 nm will be low. ２ O ３ The lower limit of the content of Yb is preferably 0.01 mol% or more, more preferably 0.03 mol% or more, 0.05 mol% or more, 0.1 mol% or more, 0.2 mol% or more, 0.3 mol% or more, 0.4 mol% or more, 0.5 mol% or more, 0.7 mol% or more, 1 mol% or more, 2 mol% or more, 3 mol% or more, particularly preferably 5 mol% or more. ２ O ３ If the content of Yb is too high, the glass is likely to devitrify and lose its translucency due to crystallization. In addition, the intensity of light emitted by fluorescence becomes very low due to concentration quenching. ２ O ３ The upper limit of the content is preferably 10 mol% or less, more preferably 9.5 mol% or less, 9 mol% or less, 8.5 mol% or less, 8 mol% or less, 7.5 mol% or less, 7.0 mol% or less, 6.5 mol% or less, particularly preferably 6.0 mol% or less.

[0056] Er ２ O ３ is a component that emits light in the vicinity of 1530 nm to 1620 nm by fluorescence. ２ O ３ If the content of Er is too low, the intensity of the light emitted by fluorescence in the range of 1530 nm to 1620 nm will be low.２ O ３ The lower limit of the content of Er is preferably 0.01 mol% or more, more preferably 0.03 mol% or more, 0.05 mol% or more, 0.1 mol% or more, 0.2 mol% or more, 0.3 mol% or more, 0.4 mol% or more, 0.5 mol% or more, 0.7 mol% or more, 1 mol% or more, 2 mol% or more, 3 mol% or more, particularly preferably 5 mol% or more. ２ O ３ If the content of Er is too high, the glass is likely to devitrify and lose its translucency due to crystallization. In addition, the intensity of light emitted by fluorescence becomes very low due to concentration quenching. ２ O ３ The upper limit of the content is preferably 10 mol% or less, more preferably 9.5 mol% or less, 9 mol% or less, 8.5 mol% or less, 8 mol% or less, 7.5 mol% or less, 7.0 mol% or less, 6.5 mol% or less, particularly preferably 6.0 mol% or less.

[0057] Pr ２ O ３ is a component that emits light in the vicinity of 630 nm to 670 nm by fluorescence. ２ O ３ If the content of Pr is too low, the intensity of light emitted by fluorescence in the range of 630 nm to 670 nm will be low. In addition, the intensity of light emitted by fluorescence will be very low due to concentration quenching. ２ O ３ The lower limit of the content of Pr is preferably 0.01 mol% or more, more preferably 0.03 mol% or more, 0.05 mol% or more, 0.1 mol% or more, 0.2 mol% or more, 0.3 mol% or more, 0.4 mol% or more, 0.5 mol% or more, 0.7 mol% or more, 1 mol% or more, 2 mol% or more, 3 mol% or more, particularly preferably 5 mol% or more. ２ O ３ If the content of Pr is too high, the glass is likely to devitrify and lose its translucency due to crystallization. In addition, the intensity of light emitted by fluorescence becomes very low due to concentration quenching. ２ O ３The upper limit of the content is preferably 10 mol% or less, more preferably 9.5 mol% or less, 9 mol% or less, 8.5 mol% or less, 8 mol% or less, 7.5 mol% or less, 7.0 mol% or less, 6.5 mol% or less, particularly preferably 6.0 mol% or less.

[0058] Sm ２ O ３ is a component that emits light in the range of 500 nm to 700 nm by fluorescence. ２ O ３ If the content of Sm is too low, the intensity of the light emitted by fluorescence in the range of 500 nm to 700 nm will be low. ２ O ３ The lower limit of the content of Sm is preferably 0.01 mol% or more, more preferably 0.03 mol% or more, 0.05 mol% or more, 0.1 mol% or more, 0.2 mol% or more, 0.3 mol% or more, 0.4 mol% or more, 0.5 mol% or more, 0.7 mol% or more, 1 mol% or more, 2 mol% or more, 3 mol% or more, particularly preferably 5 mol% or more. ２ O ３ If the content of Sm is too high, the glass is likely to devitrify and lose its translucency due to crystallization. In addition, the intensity of light emitted by fluorescence becomes very low due to concentration quenching. ２ O ３ The upper limit of the content is preferably 10 mol% or less, more preferably 9.5 mol% or less, 9 mol% or less, 8.5 mol% or less, 8 mol% or less, 7.5 mol% or less, 7.0 mol% or less, 6.5 mol% or less, particularly preferably 6.0 mol% or less.

[0059] EU ２ O ３ is a component that emits light in the vicinity of 550 nm to 650 nm by fluorescence. ２ O ３ If the content of Eu is too low, the intensity of the light emitted by fluorescence in the range of 550 nm to 650 nm will be low. ２ O ３The lower limit of the content of Eu is preferably 0.01 mol% or more, more preferably 0.03 mol% or more, 0.05 mol% or more, 0.1 mol% or more, 0.2 mol% or more, 0.3 mol% or more, 0.4 mol% or more, 0.5 mol% or more, 0.7 mol% or more, 1 mol% or more, 2 mol% or more, 3 mol% or more, particularly preferably 5 mol% or more. ２ O ３ If the content of Eu is too high, the glass is likely to devitrify and lose its translucency due to crystallization. In addition, the intensity of light emitted by fluorescence becomes very low due to concentration quenching. ２ O ３ The upper limit of the content is preferably 10 mol% or less, more preferably 9.5 mol% or less, 9 mol% or less, 8.5 mol% or less, 8 mol% or less, 7.5 mol% or less, 7.0 mol% or less, 6.5 mol% or less, particularly preferably 6.0 mol% or less.

[0060] Tb ２ O ３ is a component that emits light in the range of 350 nm to 600 nm by fluorescence. ２ O ３ If the content of Tb is too low, the intensity of the light emitted by fluorescence in the range of 350 nm to 600 nm will be low. ２ O ３ The lower limit of the content of Tb is preferably 0.01 mol% or more, more preferably 0.03 mol% or more, 0.05 mol% or more, 0.1 mol% or more, 0.2 mol% or more, 0.3 mol% or more, 0.4 mol% or more, 0.5 mol% or more, 0.7 mol% or more, 1 mol% or more, 2 mol% or more, 3 mol% or more, particularly preferably 5 mol% or more. ２ O ３ If the content of Tb is too high, the glass is likely to devitrify and lose its translucency due to crystallization. In addition, the intensity of light emitted by fluorescence becomes very low due to concentration quenching. ２ O ３ The upper limit of the content is preferably 10 mol% or less, more preferably 9.5 mol% or less, 9 mol% or less, 8.5 mol% or less, 8 mol% or less, 7.5 mol% or less, 7.0 mol% or less, 6.5 mol% or less, particularly preferably 6.0 mol% or less.

[0061] Dy ２ O ３ is a component that emits light in the range of 250 nm to 600 nm by fluorescence. ２ O ３ If the content of Dy is too low, the intensity of light emitted by fluorescence in the range of 250 nm to 600 nm will be low. In addition, the intensity of light emitted by fluorescence will be very low due to concentration quenching. ２ O ３ The lower limit of the content of Dy is preferably 0.01 mol% or more, more preferably 0.03 mol% or more, 0.05 mol% or more, 0.1 mol% or more, 0.2 mol% or more, 0.3 mol% or more, 0.4 mol% or more, 0.5 mol% or more, 0.7 mol% or more, 1 mol% or more, 2 mol% or more, 3 mol% or more, particularly preferably 5 mol% or more. ２ O ３ If the content of Dy is too high, the glass is likely to devitrify and lose its translucency due to crystallization. In addition, the intensity of light emitted by fluorescence becomes very low due to concentration quenching. ２ O ３ The upper limit of the content is preferably 10 mol% or less, more preferably 9.5 mol% or less, 9 mol% or less, 8.5 mol% or less, 8 mol% or less, 7.5 mol% or less, 7.0 mol% or less, 6.5 mol% or less, particularly preferably 6.0 mol% or less.

[0062] Ho ２ O ３ is a component that emits light in the vicinity of 2050 nm to 2150 nm by fluorescence. ２ O ３ If the content of Ho is too low, the intensity of the light emitted by fluorescence in the range of 2050 nm to 2150 nm will be low. ２ O ３ The lower limit of the content of Ho is preferably 0.01 mol% or more, more preferably 0.03 mol% or more, 0.05 mol% or more, 0.1 mol% or more, 0.2 mol% or more, 0.3 mol% or more, 0.4 mol% or more, 0.5 mol% or more, 0.7 mol% or more, 1 mol% or more, 2 mol% or more, 3 mol% or more, particularly preferably 5 mol% or more. ２ O ３If the content of Ho is too high, the glass is likely to devitrify and lose its translucency due to crystallization. In addition, the intensity of light emitted by fluorescence becomes very low due to concentration quenching. ２ O ３ The upper limit of the content is preferably 10 mol% or less, more preferably 9.5 mol% or less, 9 mol% or less, 8.5 mol% or less, 8 mol% or less, 7.5 mol% or less, 7.0 mol% or less, 6.5 mol% or less, particularly preferably 6.0 mol% or less.

[0063] Tm ２ O ３ is a component that emits light around 1950 nm to 2050 nm by fluorescence. ２ O ３ If the content is too low, the intensity of the light emitted by fluorescence in the range of 1950 nm to 2050 nm will be low. ２ O ３ The lower limit of the content of Tm is preferably 0.01 mol% or more, more preferably 0.03 mol% or more, 0.05 mol% or more, 0.1 mol% or more, 0.2 mol% or more, 0.3 mol% or more, 0.4 mol% or more, 0.5 mol% or more, 0.7 mol% or more, 1 mol% or more, 2 mol% or more, 3 mol% or more, particularly preferably 5 mol% or more. ２ O ３ If the content of Tm is too high, the glass is likely to devitrify and lose its translucency due to crystallization. In addition, the intensity of light emitted by fluorescence becomes very low due to concentration quenching. ２ O ３ The upper limit of the content is preferably 10 mol% or less, more preferably 9.5 mol% or less, 9 mol% or less, 8.5 mol% or less, 8 mol% or less, 7.5 mol% or less, 7.0 mol% or less, 6.5 mol% or less, particularly preferably 6.0 mol% or less.

[0064] The crystallized glass of the present invention may contain the following components in addition to the above components in its glass composition.

[0065] ZnO is a material in which the precipitated crystals are Li ２ O-Al ２ O ３ -SiO ２ In the case of Li-based crystals, ２O-Al ２ O ３ -SiO ２ It is a component that dissolves in the system crystal and has a significant effect on crystallinity. It is also a component that adjusts the thermal expansion coefficient and refractive index of the crystallized glass. If the content of ZnO is too high, the crystallinity becomes too strong, which makes the crystallized glass prone to devitrification and breakage. Therefore, the upper limit of the content of ZnO is preferably 10 mol% or less, and more preferably 9 mol% or less, 8 mol% or less, 7 mol% or less, 6 mol% or less, 5 mol% or less, 4 mol% or less, 3 mol% or less, 2 mol% or less, 1 mol% or less, 0.5 mol% or less, 0.1 mol% or less, 0.01 mol% or less, particularly 0.001 mol% or less. On the other hand, since ZnO is easily mixed as an impurity, if ZnO is to be completely removed, the raw material batch becomes expensive and the manufacturing cost tends to increase. Therefore, in order to suppress an increase in production costs, the lower limit of the ZnO content is preferably 0.00001 mol % or more, more preferably 0.00003 mol % or more, and particularly preferably 0.00005 mol % or more.

[0066] ZnO and MgO function as fluxes during the formation of molten glass, and also dissolve in the β-quartz solid solution that can become the primary crystal, changing the thermal expansion coefficient of the crystallized glass. Thus, ZnO and MgO are expected to have similar effects, but ZnO tends to be more expensive as a raw material compared to MgO. Therefore, the upper limit of the ZnO / (ZnO + MgO) molar ratio is preferably 0.9 or less, 0.8 or less, and particularly preferably 0.7 or less. Furthermore, the upper limit of the ZnO / MgO molar ratio is preferably 0.1 or less, 0.01 or less, and particularly preferably 0.001 or less.

[0067] B ２ O ３ is a component that reduces the viscosity of the glass and improves the meltability and formability of the glass. It can also be involved in the ease with which phase separation occurs during crystal nucleation. ２ O ３ If the content of B is too high, the glass is likely to devitrify and the crystallized glass is likely to break. ２ O ３ The amount of evaporation increases, and the environmental load increases. ２O ３ The upper limit of the content of is preferably 10 mol% or less, more preferably 9 mol% or less, 8 mol% or less, 7 mol% or less, 6 mol% or less, 5 mol% or less, 4 mol% or less, 3 mol% or less, 2 mol% or less, 1 mol% or less, 0.5 mol% or less, 0.1 mol% or less, 0.01 mol% or less, particularly preferably 0.001 mol% or less. ２ O ３ is easily mixed in as an impurity, ２ O ３ If we try to completely remove B, the raw material batch will become expensive and the manufacturing cost will tend to increase. ２ O ３ The lower limit of the content is preferably 0.00001 mol % or more, more preferably 0.00003 mol % or more, and particularly preferably 0.00005 mol % or more.

[0068] Fe ２ O ３ is a component that enhances the coloring of glass, especially TiO ２ and SnO ２ It is also a component that significantly intensifies coloring through interaction with Fe. ２ O ３ The upper limit of the content is preferably 0.10 mol% or less, and is preferably 0.08 mol% or less, 0.06 mol% or less, 0.05 mol% or less, 0.04 mol% or less, 0.035 mol% or less, 0.03 mol% or less, 0.02 mol% or less, 0.015 mol% or less, 0.013 mol% or less, 0.012 mol% or less, 0.011 mol% or less, 0.01 mol% or less, 0.009 mol% or less, 0.008 mol% or less, 0.007 mol% or less, 0.006 mol% or less, 0.005 mol% or less, 0.004 mol% or less, 0.003 mol% or less, particularly preferably 0.002 mol% or less. ２ O ３ is easily mixed in as an impurity, so Fe ２ O ３ If we try to completely remove Fe, the raw material batch will become expensive and the manufacturing cost will tend to increase. ２ O ３The lower limit of the content is preferably 0.0001 mol % or more, more preferably 0.0002 mol % or more, 0.0003 mol % or more, or 0.0005 mol % or more, and particularly preferably 0.001 mol % or more.

[0069] When titanium and iron coexist, ilmenite (FeTiO ３ )-like coloring may occur. ２ O-Al ２ O ３ -SiO ２ In TiO based crystallized glass, titanium and iron components that have not precipitated as crystal nuclei or main crystals after crystallization remain in the remaining glass, which can promote the development of the above-mentioned coloring. ２ / (TiO ２ +Fe ２ O ３ The upper limit of the molar ratio of TiO is preferably 0.09 or less, more preferably 0.08 or less, 0.07 or less, 0.06 or less, 0.05 or less, 0.045 or less, 0.04 or less, 0.035 or less, and particularly preferably 0.03 or less. On the other hand, although the amount of these components may be reduced in design, TiO ２ and Fe ２ O ３ Since TiO is easily mixed in as an impurity, if it is attempted to completely remove it, the raw material batch becomes expensive and the manufacturing cost tends to increase. ２ and Fe ２ O ３ In order to reduce the production cost, both components may be contained within the range in which coloring is acceptable. ２ / (TiO ２ +Fe ２ O ３ The lower limit of the molar ratio of ) is preferably 0.001 or more, more preferably 0.002 or more, 0.003 or more, 0.005 or more, 0.007 or more, 0.009 or more, and particularly preferably 0.01 or more.

[0070] Pt is a component that can be mixed into glass in the form of ions, colloids, metal, etc., and causes a yellow to brown coloration. This tendency becomes more pronounced after crystallization. Furthermore, extensive research has revealed that the inclusion of Pt can affect the nucleation and crystallization behavior of crystallized glass, making it more likely to become cloudy. Therefore, the upper limit of the Pt content is preferably 6000 mol ppm or less, more preferably 5700 mol ppm or less, 5500 mol ppm or less, 5300 mol ppm or less, 5100 mol ppm or less, 4900 mol ppm or less, 4700 mol ppm or less, 4500 mol ppm or less, 4300 mol ppm or less, 4100 mol ppm or less, 3900 mol ppm or less, 3700 mol ppm or less, 3500 mol ppm or less, 3300 mol ppm or less, 3100 mol ppm or less, 2900 mol ppm or less, 2700 mol ppm or less, 2500 mol ppm or less, particularly preferably 2000 mol ppm or less.Although Pt contamination should be avoided as much as possible, when using general melting equipment, it may be necessary to use Pt components to obtain homogeneous glass. Therefore, if Pt is completely removed, the manufacturing cost tends to increase. When coloring is permitted, in order to suppress an increase in manufacturing cost, the lower limit of the Pt content is preferably 0.0001 mol ppm or more, more preferably 0.001 mol ppm or more, 0.005 mol ppm or more, 0.01 mol ppm or more, 0.02 mol ppm or more, 0.03 mol ppm or more, 0.04 mol ppm or more, 0.05 mol ppm or more, 0.06 mol ppm or more, 0.07 mol ppm or more, 0.1 mol ppm or more, 1 mol ppm or more, 5 mol ppm or more, particularly preferably 10 mol ppm or more. Furthermore, when coloring is not adversely affected, Pt can be added to ZrO ２ and TiO ２ Similarly, Pt may be used as a nucleating agent to promote the precipitation of the main crystals. In this case, Pt may be used alone as a nucleating agent, or may be used in combination with other components as a nucleating agent. When Pt is used as a nucleating agent, the form of Pt is not particularly limited, such as colloid, metal crystal, etc.

[0071] Rh is a component that can be mixed into glass in the form of ions, colloids, metal, etc., and, like Pt, tends to cause a yellow to brown coloration and make the crystallized glass opaque. Therefore, the upper limit of the Rh content is preferably 5000 mol ppm or less, and more preferably 4800 mol ppm or less, 4600 mol ppm or less, 4400 mol ppm or less, 4200 mol ppm or less, 4000 mol ppm or less, 3800 mol ppm or less, 3600 mol ppm or less, 3400 mol ppm or less, 3200 mol ppm or less, 3000 mol ppm or less, 2800 mol ppm or less, 3000 mol ppm or less, 4 ... Preferably, the Rh content is 0 mol ppm or less, 2600 mol ppm or less, 2400 mol ppm or less, 2200 mol ppm or less, 2000 mol ppm or less, 1700 mol ppm or less, 1500 mol ppm or less, 1300 mol ppm or less, 1100 mol ppm or less, 900 mol ppm or less, 700 mol ppm or less, 500 mol ppm or less, and particularly 300 mol ppm or less. Although Rh contamination should be avoided as much as possible, when using a general melting equipment, it may be necessary to use Rh components to obtain a homogeneous glass. Therefore, if Rh is to be completely removed, the production cost tends to increase. In cases where coloring is acceptable, in order to suppress an increase in production costs, the lower limit of the Rh content is preferably 0.0001 mol ppm or more, more preferably 0.001 mol ppm or more, 0.005 mol ppm or more, 0.01 mol ppm or more, 0.02 mol ppm or more, 0.03 mol ppm or more, 0.04 mol ppm or more, 0.05 mol ppm or more, 0.06 mol ppm or more, 0.07 mol ppm or more, 0.1 mol ppm or more, 1 mol ppm or more, 3 mol ppm or more, 5 mol ppm or more, 10 mol ppm or more, particularly preferably 50 mol ppm or more. ２ and TiO ２ In this case, Rh may be used as a nucleating agent alone, or may be used in combination with other components. When Rh is used as a nucleating agent that promotes the precipitation of primary crystals, the form of Rh is not particularly limited, and may be a colloid, a metal crystal, or the like.

[0072] The upper limit of Pt+Rh is preferably 10,000 mol ppm or less, and is preferably 9,000 mol ppm or less, 8,500 mol ppm or less, 8,000 mol ppm or less, 7,500 mol ppm or less, 7,300 mol ppm or less, 7,100 mol ppm or less, 6,900 mol ppm or less, 6,700 mol ppm or less, 6,500 mol ppm or less, 6,300 mol ppm or less, 6,100 mol ppm or less, 5,900 mol ppm or less, 5,700 mol ppm or less, 5,500 mol ppm or less, 5,300 mol ppm or less, 5,100 mol ppm or less, Preferably, the content of Pt and Rh is 4900 mol ppm or less, 4700 mol ppm or less, 4500 mol ppm or less, 4300 mol ppm or less, 4100 mol ppm or less, 3900 mol ppm or less, 3700 mol ppm or less, 3500 mol ppm or less, 3300 mol ppm or less, 3100 mol ppm or less, 2900 mol ppm or less, 2700 mol ppm or less, 2500 mol ppm or less, 2300 mol ppm or less, 2100 mol ppm or less, 1900 mol ppm or less, 1700 mol ppm or less, particularly 1500 mol ppm or less. Note that, although the inclusion of Pt and Rh should be avoided as much as possible, when using general melting equipment, it may be necessary to use Pt and Rh components to obtain homogeneous glass. Therefore, if Pt and Rh are to be completely removed, production costs tend to increase. When coloration is tolerable, in order to suppress an increase in production costs, the lower limit of Pt+Rh is preferably 0.0001 mol ppm or more, and is preferably 0.001 mol ppm or more, 0.005 mol ppm or more, 0.01 mol ppm or more, 0.02 mol ppm or more, 0.03 mol ppm or more, 0.04 mol ppm or more, 0.05 mol ppm or more, 0.06 mol ppm or more, 0.07 mol ppm or more, 1.0 mol ppm or more, 10 mol ppm or more, 50 mol ppm or more, 90 mol ppm or more, and particularly preferably 1000 mol ppm or more.

[0073] In developing glass materials, it is common to produce glasses of various compositions using various crucibles. Therefore, platinum and rhodium often evaporate from the crucible and are present inside the electric furnace used for melting. It has been confirmed that Pt and Rh present inside the electric furnace are mixed into the glass. To control the amount of Pt and Rh mixed in, it is possible to control the Pt and Rh content in the glass by selecting the raw materials and crucible materials used, attaching a quartz lid to the crucible, lowering the melting temperature, shortening the melting time, etc.

[0074] Lm ２ O ３ (Lm is at least one element selected from La, Y, and Lu) does not itself exhibit fluorescence in the glass, but has the effect of suppressing aggregation of other rare earth metal elements that act as fluorescence centers in the glass. ２ O ３ If the content of Lm is too high, the glass is likely to devitrify and lose its translucency due to crystallization. ２ O ３ The upper limit of the content of Lm is preferably 10 mol% or less, more preferably 9.5 mol% or less, 9 mol% or less, 8.5 mol% or less, 8 mol% or less, 7.5 mol% or less, 7.0 mol% or less, 6.5 mol% or less, particularly preferably 6.0 mol% or less. ２ O ３ The lower limit of the content is preferably 0.1 mol% or more, more preferably 0.2 mol% or more, 0.3 mol% or more, 0.4 mol% or more, 0.5 mol% or more, 0.7 mol% or more, 1 mol% or more, 2 mol% or more, 3 mol% or more, particularly preferably 5 mol% or more.

[0075] La ２ O ３ In the glass of the present invention, La is a component that has the effect of suppressing aggregation of other rare earth metal elements that serve as fluorescence centers in the glass, and prevents concentration quenching of fluorescence. ２ O ３ If the content of Lm is too high, the glass is likely to devitrify and lose its translucency due to crystallization. ２ O ３The upper limit of the content of Lm is preferably 10 mol% or less, more preferably 9.5 mol% or less, 9 mol% or less, 8.5 mol% or less, 8 mol% or less, 7.5 mol% or less, 7.0 mol% or less, 6.5 mol% or less, particularly preferably 6.0 mol% or less. ２ O ３ The lower limit of the content is preferably 0.1 mol% or more, more preferably 0.2 mol% or more, 0.3 mol% or more, 0.4 mol% or more, 0.5 mol% or more, 0.7 mol% or more, 1 mol% or more, 2 mol% or more, 3 mol% or more, particularly preferably 5 mol% or more.

[0076] Y ２ O ３ In the glass of the present invention, Y is a component that has the effect of suppressing aggregation of other rare earth metal elements that serve as fluorescence centers in the glass, and prevents concentration quenching of fluorescence. ２ O ３ If the content of Y is too high, the glass is likely to devitrify and lose its translucency due to crystallization. ２ O ３ The upper limit of the content of Y is preferably 10 mol% or less, more preferably 9.5 mol% or less, 9 mol% or less, 8.5 mol% or less, 8 mol% or less, 7.5 mol% or less, 7.0 mol% or less, 6.5 mol% or less, and particularly preferably 6.0 mol% or less. ２ O ３ The lower limit of the content is preferably 0.1 mol% or more, more preferably 0.2 mol% or more, 0.3 mol% or more, 0.4 mol% or more, 0.5 mol% or more, 0.7 mol% or more, 1 mol% or more, 2 mol% or more, 3 mol% or more, particularly preferably 5 mol% or more.

[0077] Lu ２ O ３ In the glass of the present invention, Lu is a component that has the effect of suppressing aggregation of other rare earth metal elements that serve as fluorescence centers in the glass, and prevents concentration quenching of fluorescence. ２ O ３ If the content of Lu is too high, the glass is likely to devitrify and lose its translucency due to crystallization. ２ O ３The upper limit of the content of Lu is preferably 10 mol% or less, more preferably 9.5 mol% or less, 9 mol% or less, 8.5 mol% or less, 8 mol% or less, 7.5 mol% or less, 7.0 mol% or less, 6.5 mol% or less, particularly preferably 6.0 mol% or less. ２ O ３ The lower limit of the content is preferably 0.1 mol% or more, more preferably 0.2 mol% or more, 0.3 mol% or more, 0.4 mol% or more, 0.5 mol% or more, 0.7 mol% or more, 1 mol% or more, 2 mol% or more, 3 mol% or more, particularly preferably 5 mol% or more.

[0078] As ２ O ３ and Sb ２ O ３ are highly toxic and may pollute the environment during the glass manufacturing process, disposal of waste glass, etc. Therefore, it is preferable that the crystallized glass of the present invention is substantially free of these components (specifically, less than 1 mol ppm).

[0079] The crystallized glass of the present invention may contain, in addition to the above components, e.g., H ２ , CO ２ , CO, H ２ O, He, Ne, Ar, N ２ The glass may contain trace components such as Ag, Au, Pd, Ir, V, Cr, Sc, Pm, Gd, Ac, Th, Pa, U, etc., up to 0.1 mol% each. Furthermore, intentionally adding Ag, Au, Pd, Ir, V, Cr, Sc, Pm, Gd, Ac, Th, Pa, U, etc. to the glass tends to increase raw material costs and manufacturing costs. On the other hand, when glass containing Ag, Au, etc. is irradiated with light or heat treated, aggregates of these components are formed, which can serve as the starting point for promoting crystallization. Furthermore, Pd and other elements have various catalytic properties, and by incorporating them, it is possible to impart unique functions to the glass or crystallized glass. In light of these circumstances, when the purpose is to promote crystallization or to impart other functions, the above components may be contained in amounts of 1 mol% or less, 0.5 mol% or less, 0.3 mol% or less, or 0.1 mol% or less, respectively. Otherwise, it is preferable to contain 500 ppm or less, 300 ppm or less, 100 ppm or less, and particularly 10 ppm or less.

[0080] Furthermore, as long as there is no adverse effect on coloration, the crystallized glass of the present invention can be ３ , MnO, Cl ２ , MoO ３ , W.O. ３ , HfO ２ , Ta ２ O ５ , Nb ２ O ５ , RfO ２ However, since the raw material batches of the above components are expensive and tend to increase the manufacturing cost, they may not be added unless there are special circumstances. ２ The raw material cost is high, ２ O ５ Since these components may become conflict minerals, the total amount of these components is preferably 5 mol% or less, and more preferably 4 mol% or less, 3 mol% or less, 2 mol% or less, 1 mol% or less, 0.5 mol% or less, 0.4 mol% or less, 0.3 mol% or less, 0.2 mol% or less, 0.1 mol% or less, 0.05 mol% or less, less than 0.05 mol%, 0.049 mol% or less, 0.048 mol% or less, 0.047 mol% or less, 0.046 mol% or less, and particularly preferably 0.045 mol% or less.

[0081] That is, in implementing the crystallized glass of the present invention, it is preferable to use SiO ２ 65 to 75 mol%, Al ２ O ３ 13 to 16 mol %, Li ２ O 3 to 10 mol%, SnO ２ 0 to 1.5 mol %, ZrO ２ 0-3 mol%, MgO 0-5 mol%, CaO 0-5 mol%, SrO 0-5 mol%, BaO 0-5 mol%, Na ２ O 0 to 5 mol%, K ２ O 0 to 5 mol%, P ２ O ５ 0 to 5 mol %, TiO ２ 0 to 4 mol%, Ln ２ O ３ (Ln is at least one selected from Ce, Nd, Yb, Er, Pr, Sm, Eu, Tb, Dy, Ho, and Tm) 0.01 to 10 mol % in a molar ratio of Li ２O / (MgO+CaO+SrO+BaO+Na ２ O+K ２ O) is 8 or less, (Li ２ O + Na ２ O+K ２ O) / ZrO ２ 0-9.0, TiO ２ / (TiO ２ +Fe ２ O ３ ) is 0.09 or less. More preferably, SiO ２ 65 to 75 mol%, Al ２ O ３ 13 to 16 mol %, Li ２ O 3 to 10 mol%, SnO ２ 0 to 1.5 mol %, ZrO ２ 0-3 mol%, MgO 0-5 mol%, CaO 0-5 mol%, SrO 0-5 mol%, BaO 0-5 mol%, Na ２ O 0 to 5 mol%, K ２ O 0 to 5 mol%, P ２ O ５ 0 to 5 mol %, TiO ２ 0 to 4 mol%, Ln ２ O ３ (Ln is at least one selected from Ce, Nd, Yb, Er, Pr, Sm, Eu, Tb, Dy, Ho, and Tm) 0.01 to 10 mol%, Fe ２ O ３ Contains 0 to 0.1 mol % of Li, in molar ratio ２ O / (MgO+CaO+SrO+BaO+Na ２ O+K ２ O) is 8 or less, (Li ２ O + Na ２ O+K ２ O) / ZrO ２ 0-8.5, TiO ２ / (TiO ２ +Fe ２ O ３ ) is 0.09 or less. More preferably, SiO ２ 65 to 75 mol%, Al ２ O ３ 13 to 16 mol %, Li ２ O 3 to 10 mol%, SnO ２ 0 to 1.5 mol %, ZrO２ 0-3 mol%, MgO 0-5 mol%, CaO 0-5 mol%, SrO 0-5 mol%, BaO 0-5 mol%, Na ２ O 0 to 5 mol%, K ２ O 0 to 5 mol%, P ２ O ５ 0 to 5 mol %, TiO ２ 0 to 4 mol%, Ln ２ O ３ (Ln is at least one selected from Ce, Nd, Yb, Er, Pr, Sm, Eu, Tb, Dy, Ho, and Tm) 0.01 to 10 mol%, Fe ２ O ３ 0 to 0.1 mol %, Pt + Rh 0 to 8000 mol ppm, in molar ratio, Li ２ O / (MgO+CaO+SrO+BaO+Na ２ O+K ２ O) is 8 or less, (Li ２ O + Na ２ O+K ２ O) / ZrO ２ 0 to 5.6, TiO ２ / (TiO ２ +Fe ２ O ３ ) is 0.09 or less. More preferably, SiO ２ 65 to 75 mol%, Al ２ O ３ 13 to 16 mol%, B ２ O ３ 0 to 3 mol %, Li ２ O 3 to 10 mol%, SnO ２ 0 to 1.5 mol %, ZrO ２ 0-3 mol%, MgO 0-5 mol%, CaO 0-5 mol%, SrO 0-5 mol%, BaO 0-5 mol%, Na ２ O 0 to 5 mol%, K ２ O 0 to 5 mol%, P ２ O ５ 0 to 5 mol %, TiO ２ 0 to 4 mol%, Ln ２ O ３ (Ln is at least one selected from Ce, Nd, Yb, Er, Pr, Sm, Eu, Tb, Dy, Ho, and Tm) 0.01 to 10 mol%, Fe ２ O３ 0 to 0.1 mol %, Pt + Rh 0 to 8000 mol ppm, in molar ratio, Li ２ O / (MgO+CaO+SrO+BaO+Na ２ O+K ２ O) is 8 or less, (Li ２ O + Na ２ O+K ２ O) / ZrO ２ 0 to 5.6, TiO ２ / (TiO ２ +Fe ２ O ３ ) is 0.09 or less. Particularly preferably, SiO ２ 65 to 75 mol%, Al ２ O ３ 13 to 16 mol%, B ２ O ３ 0 to 3 mol %, Li ２ O 3 to 10 mol%, SnO ２ 0 to 1.5 mol %, ZrO ２ 0-3 mol%, MgO 0-5 mol%, CaO 0-2.5 mol%, SrO 0-5 mol%, BaO 0-5 mol%, Na ２ O 0 to 5 mol%, K ２ O 0 to 5 mol%, P ２ O ５ 0 to 5 mol %, TiO ２ 0 to 4 mol%, Ln ２ O ３ (Ln is at least one selected from Ce, Nd, Yb, Er, Pr, Sm, Eu, Tb, Dy, Ho, and Tm) 0.1 to 10 mol%, Fe ２ O ３ 0 to 0.1 mol%, Pt+Rh 0 to 8000 mol ppm, HfO ２ +Ta ２ O ５ Contains 0 to less than 0.05 mol %, in molar ratio, Li ２ O / (MgO+CaO+SrO+BaO+Na ２ O+K ２ O) is 8 or less, (Li ２ O + Na ２ O+K ２ O) / ZrO ２ 0 to 5.4, TiO ２ / (TiO２ +Fe ２ O ３ ) is 0.09 or less.

[0082] The crystallized glass of the present invention having the above composition tends to have a transparent appearance.

[0083] The crystallized glass of the present invention has a strain point (when the viscosity of the glass is about 10 １４．５ The lower limit of the strain point temperature (temperature corresponding to a viscosity of 1000 sq ft dPa s) is preferably 600° C. or higher, 605° C. or higher, 610° C. or higher, 615° C. or higher, 620° C. or higher, 630° C. or higher, 635° C. or higher, 640° C. or higher, 645° C. or higher, 650° C. or higher, particularly preferably 655° C. or higher. If the strain point temperature is too low, the glass before crystallization is likely to break when molded.

[0084] The crystallized glass of the present invention has a temperature of 1000°C (when the viscosity of the glass is about 10°C) in the glass state before crystallization. １３ The lower limit of the annealing point (temperature corresponding to viscosity in dPa s) is preferably 680° C. or higher, 685° C. or higher, 690° C. or higher, 695° C. or higher, 700° C. or higher, 705° C. or higher, 710° C. or higher, 715° C. or higher, 720° C. or higher, particularly preferably 725° C. or higher. If the annealing point is too low, the glass before crystallization is likely to break when molded.

[0085] The crystallized glass of the present invention is characterized in that the precipitated crystals are Li ２ O-Al ２ O ３ -SiO ２ In the case of a glass-ceramic crystal, it is preferable that a β-quartz solid solution is precipitated as the main crystal. If a β-quartz solid solution is precipitated as the main crystal, the crystal grain size tends to be 100 nm or less, and the transmittance in the ultraviolet to infrared range tends to be increased. In addition, the thermal expansion coefficient of the glass-ceramic is 30×10 ―７ / °C or less. In addition, even when the main crystal is a β-spodumene solid solution, the thermal expansion coefficient of the crystallized glass of the present invention can be reduced to 30×10 ―７ / °C or less.

[0086] In the crystallized glass of the present invention, the upper limit of the thermal expansion coefficient at 20 to 200°C is 30 × 10 －７ / °C or less, and －７ / ℃ or less, 20 x 10 －７ / ℃ or less, 15 × 10 －７ / °C or less, especially 10 x 10 －７ If the thermal expansion coefficient at 20 to 200°C is too high, the glass is more likely to be broken due to thermal expansion, making it difficult to use as a fluorescent material. On the other hand, the lower limit of the thermal expansion coefficient at 20 to 200°C is -20×10 －７ / °C or more, and -10 × 10 －７ / ℃ or more, -9 × 10 －７ / ℃ or more, -8 × 10 －７ / ℃ or more, -7 × 10 －７ / ℃ or more, -6 × 10 －７ / ℃ or more, -5 × 10 －７ / ℃ or more, -4 × 10 －７ / °C or more, especially -3 × 10 －７ / °C or more.

[0087] In the crystallized glass of the present invention, the upper limit of the thermal expansion coefficient at 20 to 380°C is 30 × 10 －７ / °C or less, and －７ / ℃ or less, 20 x 10 －７ / ℃ or less, 15 × 10 －７ / °C or less, especially 10 x 10 －７ If the thermal expansion coefficient at 20 to 380°C is too high, the glass is more likely to be broken due to thermal expansion, making it difficult to use as a fluorescent material. On the other hand, the lower limit of the thermal expansion coefficient at 20 to 380°C is -20 × 10 －７ / °C or more, and -10 × 10 －７ / ℃ or more, -9 × 10 －７ / ℃ or more, -8 × 10 －７ / ℃ or more, -7 × 10 －７ / ℃ or more, -6 × 10 －７ / ℃ or more, -5 × 10 －７ / ℃ or more, -4 × 10 －７ / °C or more, especially -3 × 10 －７ / °C or more.

[0088] In the crystallized glass of the present invention, the upper limit of the thermal expansion coefficient at 20 to 750°C is 30 × 10 －７ / °C or less, and－７ / ℃ or less, 20 x 10 －７ / ℃ or less, 15 × 10 －７ / °C or less, especially 11 x 10 －７ If the thermal expansion coefficient at 20 to 750°C is too high, the glass is more likely to be broken due to thermal expansion, making it difficult to use as a fluorescent material. On the other hand, the lower limit of the thermal expansion coefficient at 20 to 750°C is -20 × 10 －７ / °C or more, and -10 × 10 －７ / ℃ or more, -9 × 10 －７ / ℃ or more, -8 × 10 －７ / ℃ or more, -7 × 10 －７ / ℃ or more, -6 × 10 －７ / ℃ or more, -5 × 10 －７ / ℃ or more, -4 × 10 －７ / °C or more, especially -3 × 10 －７ / °C or more.

[0089] The crystallized glass of the present invention preferably has haze of 5% or less, more preferably 4% or less, 3% or less, 2% or less, 1% or less, 0.5% or less, 0.3% or less, 0.2% or less, 0.1% or less, 0.05% or less, 0.01% or less, 0.005%, particularly preferably 0.001% or less. Note that, haze can be measured according to JIS K7136 using a haze meter (NDH 8000SP manufactured by Nippon Denshoku Industries Co., Ltd.) or the like.

[0090] In the crystallized glass of the present invention, the lower limit of the density change rate before and after crystallization is preferably 0.5% or more, and is preferably 1.0% or more, 1.5% or more, 2.0% or more, 2.5% or more, 3.0% or more, 3.5% or more, and particularly preferably 4.0% or more. If the density change rate before and after crystallization is too small, the glass will not be sufficiently crystallized, making it difficult to obtain the desired thermal expansion coefficient. On the other hand, the upper limit of the density change rate before and after crystallization is preferably 10% or less, and is preferably 9% or less, 7% or less, and particularly preferably 5% or less. If the density change rate before and after crystallization is too large, the amount of volumetric shrinkage during crystallization will be large, making cracks more likely to occur. Here, the "density change rate before and after crystallization" means {(density after crystallization (g / cm ３ ) - density before crystallization (g / cm ３)) / density before crystallization (g / cm ３ )} × 100 (%). The sample of the crystallized glass of the present invention before crystallization is obtained by placing the crystallized sample in a rhodium-free strengthened platinum crucible, melting it at 1650 ° C for 1 hour, rolling it to a thickness of 5 mm, and then heat-treating it at 700 ° C for 30 minutes in an annealing furnace, and then cooling the annealing furnace to room temperature at a rate of 100 ° C / h. In addition, in order to accurately measure the density, it is preferable to measure the part where the volume of bubbles contained before and after crystallization is less than 0.01% of the total volume of the sample.

[0091] The crystallized glass of the present invention may be subjected to chemical strengthening or the like. The conditions for the chemical strengthening treatment may be appropriately selected by taking into consideration the glass composition, the degree of crystallization, the type of molten salt, etc., such as the treatment time and temperature. For example, the Na content that may be contained in the remaining glass may be reduced to facilitate chemical strengthening after crystallization. ２ A glass composition containing a large amount of O may be selected, or the degree of crystallization may be intentionally reduced. The molten salt may contain an alkali metal such as Li, Na, or K, either singly or in combination. Furthermore, not only the usual single-stage strengthening but also multi-stage chemical strengthening may be selected. Furthermore, the crystallized glass of the present invention can be treated by chemical strengthening or the like before crystallization to reduce the Li content of the sample surface. ２ The O content can be reduced compared to the interior of the sample. When such glasses are crystallized, the crystallinity of the sample surface becomes lower than that of the interior of the sample, and the thermal expansion coefficient of the sample surface becomes relatively higher, allowing compressive stress due to the difference in thermal expansion to be applied to the sample surface. Furthermore, when the crystallinity of the sample surface is low, the glass phase increases on the surface, and depending on the glass composition selected, chemical resistance and gas barrier properties can be improved.

[0092] The fluorescent crystallized glass according to this embodiment can be suitably used as various optical elements. The optical element using the above crystallized glass can be used as a light-emitting element, a wavelength conversion member, etc. Furthermore, the optical element according to this embodiment can be suitably used as an optical device equipped with the same. An example of such a suitable embodiment is a wavelength conversion member for a light-emitting device.

[0093] Fig. 1 shows one embodiment of a light emitting device of the present invention. As shown in Fig. 1, the light emitting device 1 includes a wavelength conversion member 2 and a light source 3. The light source 3 irradiates the wavelength conversion member 2 with excitation light L1. The excitation light L1 incident on the wavelength conversion member 2 is converted into light L2 of a different wavelength, which is emitted from the opposite side of the light source 3. In this case, a composite light L3 may be emitted, which is a composite light of the wavelength-converted light L2 and the excitation light L1 that was transmitted without being wavelength-converted.

[0094] Figure 2 shows another embodiment of the light-emitting device of the present invention. As shown in Figure 2, the light-emitting device 11 includes a wavelength conversion member 12, a light source 13, and a light source 14. The light source 13 irradiates the wavelength conversion member 12 with excitation light L1. The light source 14 irradiates light L4 having a different wavelength from that of the light source 13. The excitation light L1 incident on the wavelength conversion member 12 is converted into light L2 having a different wavelength, and emitted from a direction different from that of the light source 13. In this case, a combined light L5 consisting of the wavelength-converted light L2, the excitation light L1 that was transmitted without wavelength conversion, and the light L4 from the light source 14 may be emitted. In this case, the wavelengths of the light L2 and the light L4 may be the same.

[0095] Another embodiment of the light-emitting device of the present invention is shown in Figure 3. As shown in Figure 3, the light-emitting device 21 includes a wavelength conversion member 22 and at least one light source 23. The light source 23 irradiates the wavelength conversion member 22 with excitation light L1. The excitation light L1 incident on the wavelength conversion member 22 is converted into light L2 of a different wavelength and emitted from a direction different from that of the light source 23. In this case, an optical filter 4 may be provided to extract only the wavelength-converted light L2.

[0096] Next, a method for producing the crystallized glass of the present invention will be described.

[0097] First, a raw material batch prepared to form glass of the above composition is placed in a glass melting furnace, melted at 1500 to 1750°C, and then formed. The glass may be melted by a flame melting method using a burner or an electric melting method using electrical heating. Melting by laser irradiation or plasma is also possible.

[0098] The resulting crystallizable glass (crystallizable glass) is then heat-treated to crystallize. Crystallization conditions include nucleation at 700-950°C (preferably 750-900°C) for 0.1-100 hours (preferably 1-60 hours), followed by crystal growth at 800-1050°C (preferably 800-1000°C) for 0.1-50 hours (preferably 0.2-10 hours). In this way, transparent crystallized glass in which β-quartz solid solution crystals are precipitated as the primary crystals can be obtained. Heat treatment may be performed at a specific temperature only, or may be performed stepwise by holding at two or more temperatures, or may be performed while applying a temperature gradient.

[0099] Crystallization may also be promoted by applying or irradiating sound waves or electromagnetic waves. Furthermore, the cooling rate of the crystallized glass at a high temperature may be performed at a specific temperature gradient, or may be performed at two or more levels of temperature gradient. If sufficient thermal shock resistance is desired, it is desirable to control the cooling rate to sufficiently relax the structure of the remaining glass phase. The average cooling rate from 800 ° C. to 25 ° C. is preferably 3000 ° C. / min, 1000 ° C. / min or less, 500 ° C. / min or less, 400 ° C. / min or less, 300 ° C. / min or less, 200 ° C. / min or less, 100 ° C. / min or less, 50 ° C. / min or less, 25 ° C. / min or less, 10 ° C. / min or less, particularly 5 ° C. / min or less, at the inner part of the thickness farthest from the surface of the crystallized glass. Furthermore, when long-term dimensional stability is desired, the cooling rate is preferably 2.5°C / min or less, 1°C / min or less, 0.5°C / min or less, 0.1°C / min or less, 0.05°C / min or less, 0.01°C / min or less, 0.005°C / min or less, 0.001°C / min or less, 0.0005°C / min or less, and particularly preferably 0.0001°C / min or less. Except when physical strengthening treatment is performed using air cooling, water cooling, or the like, it is desirable that the cooling rate of the crystallized glass be similar between the surface and the inner part of the thickness farthest from the surface. The value obtained by dividing the cooling rate at the inner part of the thickness farthest from the surface by the cooling rate at the surface is preferably 0.0001 to 1, 0.001 to 1, 0.01 to 1, 0.1 to 1, 0.5 to 1, 0.8 to 1, 0.9 to 1, and particularly preferably 1. By being close to 1, residual strain is less likely to occur at all positions in the crystallized glass sample, making it easier to achieve long-term dimensional stability. The surface cooling rate can be estimated using a contact thermometer or a radiation thermometer, and the internal temperature can be estimated by placing high-temperature crystallized glass in a cooling medium, measuring the heat quantity and rate of heat change of the cooling medium, and then using this numerical data and the specific heat and thermal conductivity of the crystallized glass and the cooling medium.

[0100] The glass of the present invention can be formed into a hemispherical, spherical, fiber, powder, thin plate, tubular or bulb shape by a press method, spray method, roll method, film method, overflow (fusion) method, hand-blowing method or the like.

[0101] The present invention will be described below based on examples, but the present invention is not limited to the following examples. Tables 1 to 26 show the glass compositions of the examples (samples 1 to 118) of the present invention and the comparative example (sample 119). Tables 27 to 56 also show the heat treatment conditions for the examples (samples 1 to 118) and the comparative example (sample 119), as well as the measured values ​​of various physical properties before and after crystallization.

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[0158] First, each raw material was mixed in the form of oxide, hydroxide, carbonate, nitrate, etc. to obtain a glass batch having the composition shown in Tables 1 to 26. The obtained glass batch was placed in a rhodium-free tempered platinum crucible and melted at 1600°C for 4 to 100 hours, then heated to 1650 to 1680°C and melted for 0.5 to 20 hours, rolled to a thickness of 5 mm, and further heat-treated at 700°C for 30 minutes in an annealing furnace. The annealing furnace was cooled to room temperature at a rate of 100°C / h to obtain a crystallizable glass. The melting was performed using an electric melting method, which is widely used in the development of glass materials.

[0159] It was also confirmed that the glass composition of Sample No. 1 could be used to pour a molten glass onto a liquid having a higher specific gravity than Sample No. 1, and then solidify the glass composition into a plate by subsequent cooling. Incidentally, the glasses produced by either method could be crystallized under the conditions shown in Table 27.

[0160] The Pt and Rh content of the prepared samples was analyzed using an ICP-MS device (Agilent 8800 manufactured by AGILEINT TECHNOLOGY). First, the prepared glass sample was crushed and wetted with pure water, and then perchloric acid, nitric acid, sulfuric acid, hydrofluoric acid, etc. were added to melt the sample. Then, the Pt and Rh content of the sample was measured by ICP-MS. The Pt and Rh content of each measurement sample was determined based on a calibration curve created using a previously prepared Pt and Rh solution of known concentration. The measurement mode was Pt:He gas / HMI (low mode), Rh:HEHe gas / HMI (medium mode), and the mass numbers were Pt: 198 and Rh: 103. Note that the Li of the prepared sample ２ The O content was analyzed using an atomic absorption spectrometer (ContrAA600 manufactured by Analytik Jena). The melting process of the glass sample and the use of a calibration curve were basically the same as in the analysis of Pt and Rh. In addition, the other components, Pt, Rh, Li, etc. ２ As with O, measurements were made by ICP-MS or atomic absorption spectrometry, or a glass sample with a known concentration previously determined using an ICP-MS or atomic absorption spectrometry was used as a calibration curve sample, and a calibration curve was then created using an XRF analyzer (ZSX Primus 4 manufactured by RIGAKU).The actual content of each component was then determined from the XRF analysis value of the measurement sample based on the calibration curve. During the XRF analysis, the tube voltage, tube current, exposure time, etc. were adjusted as needed depending on the components being analyzed.

[0161] The prepared glasses were subjected to nucleation under the heat treatment conditions shown in Tables 27 to 56, followed by crystal growth and crystallization. The obtained crystallized glasses were evaluated for density, precipitated crystals, thermal expansion coefficient, cracking, transparency, transmittance, fluorescence, and luminescence intensity. In addition, the density, strain point, annealing point, and high-temperature viscosity of the glasses before crystallization were evaluated.

[0162] The precipitated crystals were evaluated using an X-ray diffractometer (Rigaku Smart Lab, fully automated multipurpose horizontal X-ray diffractometer). The scan mode was 2θ / θ measurement, the scan type was continuous scan, the scattering and divergence slit width was 1°, the receiving slit width was 0.2°, the measurement range was 10 to 60°, the measurement step was 0.1°, and the scan speed was 5° / min. The main crystals and crystal grain size were evaluated using the analysis software installed in the package of the same model.

[0163] The thermal expansion coefficient was evaluated by measuring the average linear thermal expansion coefficient of a crystallized glass sample processed to 20 mm × 3.8 mmφ in the temperature ranges of 20 to 200° C., 20 to 380° C., and 20 to 750° C. A Dilatometer manufactured by NETZSCH was used for the measurement.

[0164] The density was measured by the Archimedes method.

[0165] The strain point and annealing point were evaluated by the fiber elongation method. The crystallizable glass was prepared into fiber samples by hand drawing.

[0166] The high-temperature viscosity was evaluated using the platinum ball pulling method. For the evaluation, a block glass sample was crushed to an appropriate size and placed in an alumina crucible, taking care to minimize the inclusion of air bubbles. The alumina crucible was then heated to melt the sample, and the viscosity of the glass at multiple temperatures was measured. The constants of the Vogel-Fulcher equation were calculated to create a viscosity curve, and the temperature at each viscosity was calculated.

[0167] The cracks were evaluated as "good" when no cracks were visually observed in the crystallized glass, and "poor" when cracks were observed.

[0168] The transparency was evaluated by visual observation, with the crystallized glass being transparent being rated as "good" and the glass not being transparent being rated as "poor."

[0169] The haze was measured in accordance with JIS K7136 using a haze meter (NDH 8000SP manufactured by Nippon Denshoku Industries Co., Ltd.) or the like.

[0170] Fluorescence was evaluated by irradiating light of the excitation wavelength of the rare earth metal element contained in the glass of the example with the glass and determining whether or not fluorescence was observed. Those that exhibited fluorescence were evaluated as "Good", and those that did not exhibit fluorescence were evaluated as "Poor". The excitation light and emission were measured using a fluorescence spectrophotometer (SPEX Fluorolog 3-21 manufactured by HORIBA).

[0171] The emission intensity was evaluated for a 10 mm square x 3 mm thick (10 mm square, thickness: 3 mm) crystallized glass sample using a fluorescence spectrophotometer (HORIBA SPEX Fluorolog 3-21). The excitation light wavelength was 808 nm, the measurement wavelength range was 840 nm to 1400 nm, the excitation and emission slits were 3 nm, the step width was 1 nm, and the scan speed was 10 nm / sec. The signal intensity (cps) was measured.

[0172] The temperature dependence of the emission intensity was measured using a cryostat attached to the sample chamber of the above-mentioned fluorescence spectrophotometer. The measurement temperatures were 30°C, 75°C, and 100°C. The excitation light wavelength was 808 nm, the measurement wavelength range was 840 nm to 1400 nm, the excitation and emission slits were 3 nm, the step width was 1 nm, and the scan speed was 10 nm / sec. The signal intensity (cps) was measured.

[0173] As is clear from Table 27, in the crystallized glass of Sample No. 1, β-quartz solid solution was precipitated as the main crystal, and the thermal expansion coefficient was low. Furthermore, in the evaluation of fluorescence, no cracks were observed even when irradiated with excitation light, and the glass was transparent and showed fluorescence. The excitation light wavelength was 960 nm, and the fluorescence wavelength was 1120 nm.

[0174] Furthermore, as is clear from Tables 27 to 56, β-quartz solid solution or β-spodumene solid solution precipitated in the crystallized glass of Samples 2 to 12 and 14 to 117, and the samples for which the thermal expansion coefficient could be measured had low thermal expansion coefficients. Furthermore, similar crystal precipitation was observed in samples for which the thermal expansion coefficient was not measured, and therefore the thermal expansion coefficient is considered to be low. Furthermore, in the evaluation of fluorescence, no cracks were observed even when irradiated with excitation light, and the samples were transparent and showed fluorescence.

[0175] As is clear from Table 30, the crystallized glass of sample No. 13 also had a β-quartz solid solution precipitated as the main crystal, and had a low thermal expansion coefficient. Furthermore, in the evaluation of the emission intensity, no cracks were observed even when irradiated with excitation light, and the glass was transparent and showed fluorescence. Figure 4 shows the emission wavelength and its intensity. As is clear from Figure 4, the fluorescence wavelength at that time was 1059 nm.

[0176] Figure 5 shows the thermal expansion coefficient versus temperature and the luminescence intensity at 1059 nm for sample No. 13. Figure 6 shows the thermal expansion coefficient versus temperature and the luminescence intensity at 1059 nm for sample No. 42. The smooth line represents the thermal expansion coefficient (ΔL / L) on the right axis. ０ ) and the marker indicates the luminescence intensity on the left axis. ΔL is the change in sample length, L ０ is the sample length at room temperature (25° C.). As is clear from Figures 5 and 6, negative expansion, or contraction, was observed in the temperature range from room temperature to 100° C., and fluorescent sensitization with temperature increase was also observed.

[0177] Although the mechanism is unclear, it is generally known that when a fluorescent material is heated, the probability of non-radiative transitions increases, causing thermal quenching. However, in the sample, the stress generated by the contraction of the crystalline phase and the expansion of the glassy phase upon heating caused a change in the local coordination structure around Nd, resulting in an increase in fluorescence intensity. The temporary decrease in emission intensity in Figure 6 is thought to be due to the thermal quenching process being dominant over the fluorescence sensitization process caused by the change in the coordination structure around Nd. The effect of this fluorescence sensitization cannot be interpreted as being limited to this mechanism of action.

[0178] As is clear from Tables 26 and 56, the crystallized glass of Sample No. 119 has a Ln ２ O ３ It did not contain any fluorescein and did not exhibit any fluorescence.

[0179] The crystallized glass of the present invention contains a rare earth metal element that exhibits fluorescence, has high transmittance in the ultraviolet to infrared range, and has low thermal expansion, and therefore can be suitably used as a fluorescent material.

[0180] 1, 11, 21: Light emitting device 2, 12, 22: Wavelength conversion member 3, 13, 23: Light source 14: Light source 4: Optical filter

Claims

1. SiO ２ 40 to 90 mol%, Al ２ O ３ 5 to 30 mol %, Li ２ O 1 to 15 mol%, SnO ２ 0 to 20 mol %, ZrO ２ 0-5 mol%, MgO 0-10 mol%, CaO 0-10 mol%, SrO 0-10 mol%, BaO 0-10 mol%, Na ２ O 0 to 10 mol%, K ２ O 0 to 10 mol%, P ２ O ５ 0 to 10 mol %, TiO ２ 0 to 4 mol%, Ln ２ O ３ (Ln is at least one selected from Ce, Nd, Yb, Er, Pr, Sm, Eu, Tb, Dy, Ho, and Tm) 0.01 to 10 mol % in a molar ratio of Li ２ O / (MgO+CaO+SrO+BaO+Na ２ O+K ２ 0) is 8 or less.

2. Ln ２ O ３ 2. The crystallized glass according to claim 1, containing 1 to 10 mol % of Ln, wherein Ln is at least one element selected from the group consisting of Ce, Nd, Yb, Er, Pr, Sm, Eu, Tb, Dy, Ho, and Tm.

3. Nd ２ O ３ 3. The crystallized glass according to claim 2, containing 1 to 10 mol % of Zn.

4. Furthermore, ZnO 0 to 10 mol %, B ２ O ３ 4. The crystallized glass according to claim 3, wherein the glass contains 0 to 10 mol % of Zn.

5. Furthermore, Fe ２ O ３ 5. The crystallized glass according to claim 1, wherein the glass contains 0.10 mol % or less of Zn.

6. MgO / (Li ２ 5. The crystallized glass according to claim 1, wherein the ratio of MgO to O is 0.08 or more.

7. MgO+CaO+SrO+BaO+Na ２ O+K ２ 5. The crystallized glass according to claim 1, which contains 1.3 mol % or more of O.

8. ZrO ２ + TiO ２ 5. The crystallized glass according to claim 1, wherein the glass contains 0.5 to 5.3 mol % of Zn.

9. In molar ratio, (SiO ２ +Al ２ O ３ +Li ２ O) / SiO ２ 5. The crystallized glass according to claim 1, wherein the value of the crystallization coefficient is less than 1.

41.

10. In molar ratio, (SiO ２ +Al ２ O ３ +Li ２ O) / Al ２ O ３ 5. The crystallized glass according to claim 1, wherein the value of the crystallization coefficient is 6.0 or more.

11. Molar ratio of ZrO ２ / Li ２ 5. The crystallized glass according to claim 1, wherein O is 0.01 or more.

12. SnO in mole ratio ２ / (SnO ２ + TiO ２ 5. The crystallized glass according to claim 1, wherein the value of (x, y) is 0.1 or more.

13. Crystallized glass according to any one of claims 1 to 4, characterized in that the molar ratio of ZnO / (ZnO+MgO) is 0.9 or less.

14. In mole ratio, Al ２ O ３ / (SnO ２ + ZrO ２ 5. The crystallized glass according to any one of claims 1 to 4, wherein σ is greater than 5.

5.

15. In molar ratio, (Li ２ O + Na ２ O+K ２ O) / ZrO ２ 5. The crystallized glass according to claim 1, wherein the value of the crystallized glass is 9.0 or less.

16. TiO in molar ratio ２ / (TiO ２ +Fe ２ O ３ 5. The crystallized glass according to claim 1, wherein the value of (a) is 0.09 or less.

17. Crystallized glass according to any one of claims 1 to 4, characterized in that it contains 6000 mol ppm or less of Pt.

18. Crystallized glass according to any one of claims 1 to 4, characterized in that it contains 5000 mol ppm or less of Rh.

19. An optical element comprising the crystallized glass according to any one of claims 1 to 4.

20. An optical device comprising the optical element according to claim 19.

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