JP7339667B2 - Crystallized glass and its manufacturing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to crystallized glass and a method for producing the same.

Since blue LEDs (light-emitting diodes), which are high-power, mercury-free, and long-life, have been developed, lighting devices such as fluorescent lamps are being replaced with white LEDs. In recent years, from the viewpoint of output and energy efficiency, development of devices in which phosphors are mounted on blue LEDs and blue LDs has been actively carried out.

Here, many phosphors that can be excited by visible light have been developed so far, and various phosphors that emit light in various wavelength regions have been reported. Among them, phosphor materials that are excited by visible light and emit light in the deep red wavelength region (approximately 630 nm to 700 nm) are used as a light source for bioimaging in the medical field, and as a light source for plant cultivation and pest control in the agricultural field. Applications and effects are expected in various fields such as hair growth, hair thickening, and light sources for stain removal.

For example, Mn ⁴⁺ :K ₂ SiF ₆ can be excited by visible light and has been put to practical use in LED devices and the like as a phosphor material that exhibits sharp emission in the red wavelength region (Patent Document 1, Non-Patent Reference 1). However, this Mn ⁴⁺ :K ₂ SiF ₆ has very poor weather resistance, and since the life as a phosphor depends on the weather resistance of the organic resin and the like, it is difficult to use for a long period of time. In addition, since Mn ⁴⁺ :K ₂ SiF ₆ has a slightly short emission wavelength, it does not emit deep red light in the first place.

On the other hand, ruby is known as a phosphor material that emits light in a deep red wavelength region. Ruby is a substance in which a small amount of Cr ³⁺ is solid-solved with Al ₂ O ₃ as a base. Ruby is excited by visible light and exhibits very sharp luminescence around 694 nm (Non-Patent Document 2).

JP 2014-514388 A

H. F. Sijbom et al., ECS J. Solid State Sci. Technol. 5(1), R3040-R3048 (2016) T.H. Maiman, Nature, 187, 493-4 (1960)

However, since ruby is a crystalline material, it has poor workability and a low degree of freedom in shape, making it extremely difficult to increase the size. Furthermore, when ruby is used in the form of powder, it requires processes such as crystal synthesis, pulverization, and washing, resulting in high cost. In view of the above, there is a demand for the development of a material that can replace ruby as a phosphor material that emits light in the deep red wavelength region when excited by visible light.

As a technique for increasing fluorescence intensity, a method is known in which a transparent phosphor is produced and excitation light is confined inside a sphere. In view of this, it is desirable that the phosphor material described above can also be used as a transparent material.

SUMMARY OF THE INVENTION An object of the present invention is to advantageously solve the above problems, and to provide a transparent material containing a phosphor material that emits sharp light in the deep red wavelength region when excited by visible light. Another object of the present invention is to provide a method for manufacturing the material described above.

In order to achieve the above object, the inventors have made extensive studies. As a result, it was first found that Mn ⁴⁺ -doped Li ₂ Ge ₄ O ₉ crystals or LiNaGe ₄ O ₉ crystals exhibit sharp luminescence in the deep red wavelength region when excited by visible light. Next, the present inventor came up with the idea of precipitating such crystals in glass, and conducted further extensive studies. Then, it was found that Li ₂ Ge ₄ O ₉ crystals or LiNaGe ₄ O ₉ crystals doped with Mn ⁴⁺ can be precipitated in the glass by heat-treating a germanate glass having a predetermined composition to which Mn is added. Found it.

Furthermore, the present inventors have found that by further optimizing the glass components and optimizing the heating conditions, it is possible to obtain glass in which the above-described crystals are precipitated (crystallized glass) while maintaining transparency. The present invention has been achieved.

That is, the crystallized glass of the present invention is, in terms of oxide,
Li ₂ O: 7.5 to 13.0 mol%,
Na ₂ O: 2.0 to 5.0 mol%,
K ₂ O: 0 to 3.5 mol%,
(However, Li ₂ O + Na ₂ O + K ₂ O: 9.5 to 15.0 mol%)
ZnO: 12.0 to 14.0 mol%,
MgO: 0.5 to 2.5 mol%,
CaO: 0 to 2.5 mol%,
(However, ZnO + MgO + CaO: 12.5 to 15.0 mol%)
GeO ₂ : 53.5 to 65.0 mol%,
SiO ₂ : 5.0 to 14.5 mol%,
Al ₂ O ₃ : 0.5 to 10.0 mol%,
ZrO ₂ : 0 to 2.5 mol%,
P ₂ O ₅ : 0 to 0.3 mol %, and Ga ₂ O ₃ : 0 to 7.0 mol %,
(However, GeO ₂ +SiO ₂ +Al ₂ O ₃ +ZrO ₂ +P ₂ O ₅ +Ga ₂ O ₃ : 70.0 to 78.0 mol %)
(However, composition not considering manganese)
a molar ratio (X) represented by (SiO ₂ +Al ₂ O ₃ )/(GeO ₂ +SiO ₂ +Al ₂ O ₃ +ZrO ₂ +P ₂ O ₅ +Ga ₂ O ₃ ) is 0.075 or more and 0.310 or less;
Containing a component group in which the molar ratio (Y) represented by MgO/(ZnO+MgO+CaO) is 0.034 or more and 0.170 or less,
A crystallized glass containing 0.0189 to 1.27 parts by mass of manganese (however, the valence number is not limited) per 100 parts by mass in total of the above component group in terms of oxides,
having Mn ⁴⁺ -doped Li ₂ Ge ₄ O ₉ crystals and/or LiNaGe ₄ O ₉ crystals, and
It is characterized in that the transmittance of light having a wavelength of 700 nm at a thickness of 10 mm is 60% or more. Such crystallized glass has crystals formed therein that exhibit sharp luminescence in the deep red wavelength region when excited by visible light while maintaining transparency.

The crystallized glass of the present invention preferably has a peak half width of 25 nm or less in the range of 630 nm to 700 nm in the emission spectrum when irradiated with light of 430 nm.

The crystallized glass of the present invention has an electromotive force at the glass transition temperature (Tg) in a DTA curve (horizontal axis: temperature (°C), vertical axis: electromotive force (μV)) obtained by differential thermal analysis (DTA). Vg (μV), the electromotive force at the first crystallization peak temperature in the temperature range equal to or higher than the glass transition temperature (Tg) is Vc1 (μV), and the second crystal in the temperature range equal to or higher than the first crystallization peak temperature When the electromotive force at the peak temperature of quenching is Vc2 (μV), the following formula:
R = (Vc1-Vg)/(Vc2-Vg)
The peak intensity ratio R represented by is preferably less than 1.0.

Further, the method for producing crystallized glass of the present invention is the above-described method for producing crystallized glass,
The raw material is heated and melted, converted to oxide,
Li ₂ O: 7.5 to 13.0 mol%,
Na ₂ O: 2.0 to 5.0 mol%,
K ₂ O: 0 to 3.5 mol%,
(However, Li ₂ O + Na ₂ O + K ₂ O: 9.5 to 15.0 mol%)
ZnO: 12.0 to 14.0 mol%,
MgO: 0.5 to 2.5 mol%,
CaO: 0 to 2.5 mol%,
(However, ZnO + MgO + CaO: 12.5 to 15.0 mol%)
GeO ₂ : 53.5 to 65.0 mol%,
SiO ₂ : 5.0 to 14.5 mol%,
Al ₂ O ₃ : 0.5 to 10.0 mol%,
ZrO ₂ : 0 to 2.5 mol%,
P ₂ O ₅ : 0 to 0.3 mol %, and Ga ₂ O ₃ : 0 to 7.0 mol %,
(However, GeO ₂ +SiO ₂ +Al ₂ O ₃ +ZrO ₂ +P ₂ O ₅ +Ga ₂ O ₃ : 70.0 to 78.0 mol %)
(however, the composition does not consider Mn),
a molar ratio (X) represented by (SiO ₂ +Al ₂ O ₃ )/(GeO ₂ +SiO ₂ +Al ₂ O ₃ +ZrO ₂ +P ₂ O ₅ +Ga ₂ O ₃ ) is 0.075 or more and 0.310 or less;
Containing a component group in which the molar ratio (Y) represented by MgO/(ZnO+MgO+CaO) is 0.034 or more and 0.170 or less,
a vitrification step of producing a glass containing 0.0189 to 1.27 parts by mass of manganese (however, the valence is not limited) with respect to the total 100 parts by mass of oxides of the above component group;
a heat treatment step of heat-treating the glass to precipitate Mn ⁴⁺ -doped Li ₂ Ge ₄ O ₉ crystals and/or LiNaGe ₄ O ₉ crystals therein to obtain crystallized glass;
with
The heating temperature (Z) when melting the raw material in the vitrification step is set to 1200° C. or more and 1350° C. or less,
The heat treatment temperature (W) in the heat treatment step is set to 520 to 540°C. According to this manufacturing method, it is possible to manufacture a crystallized glass in which crystals are formed that emit sharp light in the deep red wavelength range when excited by visible light while maintaining transparency.

ADVANTAGE OF THE INVENTION According to this invention, the crystallized glass in which the crystal|crystallization which shows sharp luminescence in a deep red wavelength range by visible light excitation while maintaining transparency is formed inside can be provided. Further, according to the present invention, it is possible to provide a crystallized glass manufacturing method capable of manufacturing the crystallized glass described above.

FIG. 4 is a diagram schematically showing transmission spectra of glass before heat treatment and glass after heat treatment in one example. FIG. 5 is a diagram schematically showing transmission spectra of glass before heat treatment and glass after heat treatment in a comparative example. FIG. 4 is a diagram schematically showing transmission spectra of glass before heat treatment and glass after heat treatment in one example and one comparative example. FIG. 2 is a diagram schematically showing an emission spectrum of glass (crystallized glass) after heat treatment in one example. FIG. 4 is a diagram schematically showing an emission spectrum of glass (crystallized glass) after heat treatment in a comparative example. It is a figure which shows typically the X-ray-diffraction pattern of the glass in one Example. It is a figure which shows typically the X-ray-diffraction pattern of the glass in one comparative example. FIG. 3 is a diagram schematically showing DTA curves of glass (crystallized glass) after heat treatment in one example and one comparative example.

(crystallized glass)
The crystallized glass of one embodiment of the present invention (hereinafter sometimes referred to as "the crystallized glass of the present embodiment") is
In terms of oxide,
Li ₂ O: 7.5 to 13.0 mol%,
Na ₂ O: 2.0 to 5.0 mol%,
K ₂ O: 0 to 3.5 mol%,
(However, Li ₂ O + Na ₂ O + K ₂ O: 9.5 to 15.0 mol%)
ZnO: 12.0 to 14.0 mol%,
MgO: 0.5 to 2.5 mol%,
CaO: 0 to 2.5 mol%,
(However, ZnO + MgO + CaO: 12.5 to 15.0 mol%)
GeO ₂ : 53.5 to 65.0 mol%,
SiO ₂ : 5.0 to 14.5 mol%,
Al ₂ O ₃ : 0.5 to 10.0 mol%,
ZrO ₂ : 0 to 2.5 mol%,
P ₂ O ₅ : 0 to 0.3 mol %, and Ga ₂ O ₃ : 0 to 7.0 mol %,
(However, GeO ₂ +SiO ₂ +Al ₂ O ₃ +ZrO ₂ +P ₂ O ₅ +Ga ₂ O ₃ : 70.0 to 78.0 mol %)
(However, the composition does not consider manganese (Mn)),
a molar ratio (X) represented by (SiO ₂ +Al ₂ O ₃ )/(GeO ₂ +SiO ₂ +Al ₂ O ₃ +ZrO ₂ +P ₂ O ₅ +Ga ₂ O ₃ ) is 0.075 or more and 0.310 or less;
Containing a component group in which the molar ratio (Y) represented by MgO/(ZnO+MgO+CaO) is 0.034 or more and 0.170 or less,
A crystallized glass containing 0.0189 to 1.27 parts by mass of manganese (however, the valence number is not limited) per 100 parts by mass in total of the above component group in terms of oxides,
having Mn ⁴⁺ -doped Li ₂ Ge ₄ O ₉ crystals and/or LiNaGe ₄ O ₉ crystals, and
It is characterized in that the transmittance of light having a wavelength of 700 nm at a thickness of 10 mm is 60% or more.
The crystallized glass of the present embodiment has an optimized composition and can be manufactured by a predetermined manufacturing method described later. Therefore, the crystallized glass of the present embodiment can have a desired crystal (phosphor material) inside while maintaining transparency, and therefore, can emit sharp light in a deep red wavelength region when excited by visible light. can be shown. Such crystallized glass is expected to have a wide range of applications in various fields, and new effects can be expected.

The term "crystallized glass" refers to a composite of glass and crystals, and can be produced, for example, by precipitating crystals inside glass. "Ceramic glass" is also called "glass-ceramics" in the art.

First, in the crystallized glass of the present embodiment, the reason for limiting the ratio of each component to the above ranges will be described. In describing the components of the crystallized glass of the present embodiment, manganese (Mn) is treated separately for the sake of convenience. That is, the value of "mol%" or "molar ratio" regarding the group of components other than manganese, which will be described later, is calculated based on the total being 100 mol% without considering manganese (Mn).

_<Li2O>
In this embodiment, Li ₂ O is an important component that contributes to the precipitation of Li ₂ Ge ₄ O ₉ crystals and LiNaGe ₄ O ₉ crystals. However, when the proportion of Li ₂ O exceeds 13.0 mol %, crystal growth is excessively promoted during heat treatment, resulting in loss of transparency. On the other hand, when the proportion of Li ₂ O is less than 7.5 mol%, the temperature for melting the raw materials increases, and Mn ⁴⁺ is reduced to Mn ²⁺ , resulting in light emission derived from Mn ⁴⁺ after heat treatment. cease to exist. Therefore, the proportion of Li ₂ O was set to 7.5 to 13.0 mol %. From the same point of view, the proportion of Li ₂ O is preferably 7.5 mol % or more, more preferably 9.5 mol % or more.

_<Na2O>
In this embodiment, Na ₂ O is an important component that contributes to the precipitation of LiNaGe ₄ O ₉ crystals and enhances the stability of the glass melt. However, if the proportion of Na ₂ O exceeds 5.0 mol %, crystals other than the desired crystals precipitate during the heat treatment, resulting in loss of transparency. On the other hand, if the proportion of Na ₂ O is less than 2.0 mol %, the stability of the glass melt deteriorates, and crystal growth is excessively promoted during heat treatment, resulting in loss of transparency. Therefore, the ratio of Na ₂ O was set to 2.0 to 5.0 mol %. From the same viewpoint, the proportion of Na ₂ O is preferably 2.2 mol% or more, more preferably 2.8 mol% or more, and preferably 4.8 mol% or less. , 4.0 mol % or less.

_<K2O>
In this embodiment, K ₂ O is a component that enhances the stability of the glass melt. However, if the proportion of K ₂ O exceeds 3.5 mol %, crystals other than the desired crystals precipitate during the heat treatment, resulting in loss of transparency. Therefore, the proportion of K ₂ O was set to 0 to 3.5 mol %. From the same viewpoint, the proportion of K ₂ O is preferably 2.0 mol% or less, more preferably 1.5% or less, and from the viewpoint of further enhancing the stability of the glass melt, It is preferably 0.1 mol % or more, more preferably 0.4 mol % or more.

< _Li2O + _Na2O + _K2O >
In the present embodiment, when the total ratio of Li ₂ O, Na ₂ O and K ₂ O is less than 9.5 mol%, the temperature for melting the raw materials increases, and Mn ⁴⁺ becomes Mn ²⁺ . It is reduced, resulting in no Mn ⁴⁺ -derived luminescence after heat treatment. On the other hand, if the total ratio of Li ₂ O, Na ₂ O and K ₂ O exceeds 15.0 mol %, crystals other than the desired crystals precipitate during heat treatment, resulting in loss of transparency. Therefore, the total ratio of Li ₂ O, Na ₂ O and K ₂ O was set to 9.5 to 15.0 mol %. From the same point of view, the total proportion of Li ₂ O, Na ₂ O and K ₂ O is preferably 10.0 mol % or more, and preferably 13.0 mol % or less.

<ZnO>
In the present embodiment, ZnO is an important component capable of improving the stability of the glass melt and controlling the precipitation and growth of crystals. However, if the proportion of ZnO exceeds 14.0 mol %, crystals other than the desired crystals precipitate during the heat treatment, resulting in loss of transparency. On the other hand, if the proportion of ZnO is less than 12.0 mol %, crystal growth is excessively promoted during heat treatment, resulting in loss of transparency. Therefore, the proportion of ZnO was set to 12.0 to 14.0 mol %. From the same point of view, the proportion of ZnO is preferably 12.7% or more, more preferably 13.1% or more, and preferably 13.8 mol% or less. % or less.

<MgO>
In the present embodiment, MgO is an important component capable of improving the stability of the glass melt and controlling crystal growth. However, if the proportion of MgO exceeds 2.5 mol%, the stability of the glass melt is rather deteriorated, and the temperature for melting the raw material is increased, so that Mn ⁴⁺ is reduced to Mn ²⁺ , resulting in As a result, no Mn ⁴⁺ -derived luminescence occurs after the heat treatment. On the other hand, when the proportion of MgO is less than 0.5 mol %, crystal growth is excessively promoted during heat treatment, resulting in loss of transparency. Therefore, the proportion of MgO was set to 0.5 to 2.5 mol %. From the same viewpoint, the proportion of MgO is preferably 0.7 mol % or more, more preferably 0.9 mol % or more, and preferably 2.0% or less. It is more preferably 8% or less.

<CaO>
In this embodiment, CaO is a component that enhances the stability of the glass melt. However, if the proportion of CaO exceeds 2.5 mol %, the stability of the glass melt may deteriorate, and glass may not be formed after cooling. Therefore, the proportion of CaO was set to 0 to 2.5 mol %. From the same point of view, the proportion of CaO is preferably 2.0 mol % or less, more preferably 1.6 mol % or less. It is preferably 2 mol % or more, more preferably 0.4 mol % or more.

<ZnO + MgO + CaO>
In the present embodiment, if the total proportion of ZnO, MgO and CaO is less than 12.5 mol %, crystal growth is excessively promoted during heat treatment, resulting in loss of transparency. On the other hand, when the total ratio of ZnO, MgO and CaO exceeds 15.0 mol %, crystals other than desired crystals precipitate during heat treatment, resulting in loss of transparency. Therefore, the total ratio of ZnO, MgO and CaO was set to 12.5 to 15.0 mol%. From the same point of view, the total ratio of ZnO, MgO and CaO is preferably 13.5 mol % or more, and preferably 14.5 mol % or less.

_<GeO2>
In this embodiment, GeO ₂ is an important component that enhances the stability of the glass melt and contributes to the precipitation of Li ₂ Ge ₄ O ₉ crystals and LiNaGe ₄ O ₉ crystals. However, if the proportion of GeO ₂ exceeds 65.0 mol %, crystal growth is excessively promoted during heat treatment, resulting in loss of transparency. On the other hand, if the proportion of GeO ₂ is less than 53.5 mol %, the stability of the glass melt cannot be sufficiently enhanced, and there is a risk that glass will not be formed after cooling. Therefore, the ratio of GeO ₂ was set to 53.5 to 65.0 mol %. From the same point of view, the proportion of GeO ₂ is preferably 55.5 mol or more, more preferably 57.0 mol % or more, and preferably 64.5 mol % or less. 0 mol % or less is more preferable.

_<SiO2>
In this embodiment, SiO ₂ is an important component that can enhance the stability of the glass melt and regulate crystal growth. However, if the proportion of SiO ₂ exceeds 14.5 mol %, there is a possibility that crystals cannot be precipitated even by heat treatment. On the other hand, if the proportion of SiO ₂ is less than 5.0 mol %, crystal growth is excessively promoted during heat treatment, resulting in loss of transparency. Therefore, the ratio of SiO ₂ was set to 5.0 to 14.5 mol %. From the same point of view, the proportion of _SiO2 is preferably 6.5 mol% or more, more preferably 7.5 mol% or more, and preferably 11.0 mol% or less, It is more preferably 10.0 mol % or less.

_{<Al2O3> _}
In the present embodiment, Al ₂ O ₃ is an important component that enhances the stability of the glass melt and controls crystal growth. However, when the proportion of Al ₂ O ₃ exceeds 10.0 mol%, the temperature for melting the raw materials increases, and Mn ⁴⁺ is reduced to Mn ²⁺ , and as a result, luminescence derived from Mn ⁴⁺ is emitted after the heat treatment. cease to exist. On the other hand, when the proportion of Al ₂ O ₃ is less than 0.5 mol %, crystal growth is excessively promoted during heat treatment, resulting in loss of transparency. Therefore, the proportion of Al ₂ O ₃ is set to 0.5 to 10.0 mol %. From the same point of view, the proportion of Al ₂ O ₃ is preferably 0.6 mol% or more, more preferably 0.8 mol% or more, and preferably 8.0% or less. , 5.0% or less.

_<ZrO2>
In this embodiment, ZrO ₂ is a component that enhances the stability of the glass melt. However, when the proportion of ZrO ₂ exceeds 2.5 mol%, the temperature for melting the raw materials increases, and Mn ⁴⁺ is reduced to Mn ²⁺ , and as a result, no light emission derived from Mn ⁴⁺ occurs after heat treatment. . Therefore, the proportion of ZrO ₂ was set to 0 to 2.5 mol %. From the same point of view, the proportion of ZrO ₂ is preferably 2.0 mol % or less, more preferably 1.0 mol % or less. It is preferably 0.2 mol % or more, more preferably 0.5 mol % or more.

_{<P2O5> _}
In this embodiment, P ₂ O ₅ is a component that lowers the temperature for melting the raw material. However, if the proportion of P ₂ O ₅ exceeds 0.3 mol %, the stability of the glass melt may deteriorate and glass may not be formed after cooling. Therefore, the proportion of P ₂ O ₅ was set to 0 to 0.3 mol %. From the same viewpoint, the proportion of P ₂ O ₅ is preferably 0.25 mol % or less, and from the viewpoint of effectively lowering the temperature for melting the raw materials, it is 0.1 mol % or more. It is preferably 0.15 mol % or more, more preferably 0.15 mol % or more.

_{<Ga2O3> _}
In this embodiment, Ga ₂ O ₃ is a component that enhances the stability of the glass melt. However, if the ratio of Ga ₂ O ₃ exceeds 7.0 mol %, crystals other than the desired crystals precipitate during the heat treatment, resulting in loss of transparency. Therefore, the ratio of Ga ₂ O ₃ was set to 0 to 7.0 mol %. From the same viewpoint, the proportion of Ga ₂ O ₃ is preferably 5.0 mol% or less, more preferably 2.0 mol% or less, and from the viewpoint of further increasing the stability of the glass melt. Therefore, it is preferably 0.2 mol % or more, more preferably 0.5 mol % or more.

_{< GeO2 + SiO2 + Al2O3} + _ZrO2 + _P2O5 + _Ga2O3 >
In the present embodiment, when the total proportion of GeO ₂ , SiO ₂ , Al ₂ O ₃ , ZrO ₂ , P ₂ O ₅ and Ga ₂ O ₃ is less than 70.0 mol%, the stability of the glass melt is There is a risk that it will not be high enough and no glass will form after cooling. On the other hand, when the total ratio of GeO ₂ , SiO ₂ , Al ₂ O ₃ , ZrO ₂ , P ₂ O ₅ and Ga ₂ O ₃ exceeds 78.0 mol %, crystal growth is excessively promoted during heat treatment, resulting in a transparent film. sex is lost. Therefore, the total ratio of GeO ₂ , SiO ₂ , Al ₂ O ₃ , ZrO ₂ , P ₂ O ₅ and Ga ₂ O ₃ was set to 70.0-78.0 mol %. From the same point of view, the total ratio of GeO ₂ , SiO ₂ , Al ₂ O ₃ , ZrO ₂ , P ₂ O ₅ and Ga ₂ O ₃ is preferably 71.0 mol % or more. It is preferably 0 mol % or less.

<Molar ratio (X)>
In the crystallized glass of the present embodiment, the molar ratio (X) represented by (SiO ₂ +Al ₂ O ₃ )/(GeO ₂ +SiO ₂ +Al ₂ O ₃ +ZrO ₂ +P ₂ O ₅ +Ga ₂ O ₃ ) is 0.075 or more and 0.310 or less. This is because if the molar ratio (X) is less than 0.075, crystals other than the desired crystals precipitate during the heat treatment, resulting in loss of transparency. In addition, when the molar ratio (X) exceeds 0.310, the temperature for melting the raw materials is increased, so that Mn ⁴⁺ is reduced to Mn ²⁺ , and as a result, no light emission derived from Mn ⁴⁺ occurs after the heat treatment. It is from.

<Molar ratio (Y)>
In the crystallized glass of this embodiment, the molar ratio (Y) represented by MgO/(ZnO+MgO+CaO) is set to 0.034 or more and 0.170 or less. This is because if the molar ratio (Y) is less than 0.034, crystals other than the desired crystals precipitate during the heat treatment, resulting in loss of transparency. In addition, when the molar ratio (Y) exceeds 0.170, the temperature for melting the raw materials is increased, so that Mn ⁴⁺ is reduced to Mn ²⁺ , and as a result, no light emission derived from Mn ⁴⁺ occurs after the heat treatment. It is from.

<Other ingredients>
The crystallized glass of the present embodiment may contain other components other than the components described above, for example, Fe ₂ O ₃ , Cr ₂ O ₃ , NiO, TiO ₂ , Nb ₂ O ₅ in terms of oxides, as long as the purpose is not deviated. , SnO ₂ , Bi ₂ O ₃ , Ta ₂ O ₅ , WO ₃ , RE ₂ O ₃ (RE is a rare earth element, that is, Sc (scandium), Y (yttrium), La (lanthanum) to Lu (lutetium) ( However, Pm (excluding promethium)) and the like can be appropriately contained. However, from the viewpoint of obtaining the desired effects more reliably, the ratio of the above-described other components in the crystallized glass of the present embodiment is preferably 10 mol % or less, more preferably 5 mol % or less. , is more preferably 3 mol % or less, even more preferably 1 mol % or less, and particularly preferably substantially 0 mol %.

On the other hand, the crystallized glass of the present embodiment substantially contains Co ₃ O ₄ , CuO, MoO ₃ , V ₂ O ₅ and HfO ₂ in terms of oxide notation from the viewpoint of obtaining the desired effect more reliably. preferably not.
In the present specification, the term "substantially does not contain" includes the case where the component is inevitably mixed as an impurity, specifically, the component is contained at a rate of 0.2 mol% or less. shall be

<Manganese>
The crystallized glass of the present embodiment contains manganese (Mn) in addition to the component group described above. In the crystallized glass of the present embodiment, manganese is, for example, divalent (MnO in oxide notation), trivalent (Mn ₂ O ₃ in oxide notation), tetravalent (MnO ₂ in oxide notation), or the like. can exist in The crystallized glass of the present embodiment is required to contain at least tetravalent manganese (Mn ⁴⁺ ). Tetravalent manganese (Mn ⁴⁺ ) is an important cation that serves as a luminescence center for exhibiting sharp luminescence in the deep red wavelength region when excited by visible light.

The crystallized glass of the present embodiment contains 0.0189 to 1.27 parts by mass of manganese (however, the valence number is not limited) per 100 parts by mass of the above component group in terms of oxides. If the content of manganese in the external fraction is less than 0.0189 parts by mass, the manganese valence cannot be well controlled during the production of crystallized glass, and finally the tetravalent (Mn ⁴⁺ ) becomes difficult to exist. On the other hand, if the content of manganese in the outer fraction exceeds 1.27 parts by mass, the stability of the glass melt may deteriorate and glass may not be formed after cooling. From the same point of view, the content of manganese in the external ratio is preferably 0.0631 parts by mass or more, more preferably 0.316 parts by mass or more, and 0.822 parts by mass or less. is preferred, and 0.569 parts by mass or less is more preferred.

From the viewpoint of obtaining the desired effects more reliably, the crystallized glass of the present embodiment has a composition (in terms of oxides, Li ₂ O, Na ₂ O, ZnO, MgO, GeO ₂ , SiO ₂ and Al ₂ O ₃ and manganese as essential components, and may contain only optional components selected from K ₂ O, CaO, ZrO ₂ , P ₂ O ₅ and Ga ₂ O ₃ ). It is preferable to have
In this specification, "consisting only of the above-mentioned components" means that impurity components other than the components are inevitably mixed, specifically, the case where the ratio of impurity components is 0.2 mol% or less. shall be included.

The crystallized glass of this embodiment has a transmittance of 60% or more for light with a wavelength of 700 nm at a thickness of 10 mm. Therefore, the crystallized glass of this embodiment has higher transparency than conventionally known materials having Li ₂ Ge ₄ O ₉ crystals.

The crystallized glass of this embodiment has Mn ⁴⁺ -doped Li ₂ Ge ₄ O ₉ crystals and/or LiNaGe ₄ O ₉ crystals. Such crystals can exhibit sharp luminescence in the deep red wavelength region when excited by visible light.
Whether or not the crystallized glass contains the crystals described above can be determined by X-ray diffraction.

In addition, the crystallized glass of the present embodiment preferably does not contain crystals other than the crystals described above (for example, Zn ₂ GeO ₄ crystals, etc.) in order to exhibit sharper light emission in the deep red wavelength region. .

The crystallized glass of the present embodiment preferably has a peak half width of 25 nm or less in the range of 630 nm to 700 nm in the emission spectrum when irradiated with light of 430 nm as excitation light. In this case, sharper emission can be exhibited in the deep red wavelength region due to the presence of more Mn ⁴⁺ .

The crystallized glass of the present embodiment has a glass transition temperature (Tg) (°C) in a DTA curve (horizontal axis: temperature (°C), vertical axis: electromotive force (μV)) obtained by differential thermal analysis (DTA). is the electromotive force of Vg (μV), and the electromotive force at the first crystallization peak temperature (Tc1, around 560° C.) in the temperature range above the glass transition temperature (Tg) is Vc1 (μV), and the first crystallization peak When the electromotive force at the second crystallization peak temperature (Tc2, around 600°C) in the temperature range above the temperature is Vc2 (μV), the following formula:
R = (Vc1-Vg)/(Vc2-Vg)
The peak intensity ratio R represented by is preferably less than 1.0. In other words, the crystallized glass of the present embodiment preferably has a lower intensity at the first crystallization peak temperature than at the second crystallization peak temperature in the DTA curve. In this case, since excessive crystal growth during heat treatment is suppressed, good transparency can be maintained. From the same point of view, the peak intensity ratio R is more preferably 0.9 or less, even more preferably 0.7 or less.

The crystallized glass of the present embodiment is suitable for applications requiring deep red light, such as bioimaging light sources in the medical field, plant cultivation or pest control devices in the agricultural field, or hair growth, hair thickening, and staining in the beauty field. It can be used as a light source for taking pictures.

(Method for producing crystallized glass)
A method for producing crystallized glass according to an embodiment of the present invention (hereinafter sometimes referred to as “a production method according to the present embodiment”) is a method for producing the above-described crystallized glass. And the manufacturing method of this embodiment is
The raw material is heated and melted, converted to oxide,
Li ₂ O: 7.5 to 13.0 mol%,
Na ₂ O: 2.0 to 5.0 mol%,
K ₂ O: 0 to 3.5 mol%,
(However, Li ₂ O + Na ₂ O + K ₂ O: 9.5 to 15.0 mol%)
ZnO: 12.0 to 14.0 mol%,
MgO: 0.5 to 2.5 mol%,
CaO: 0 to 2.5 mol%,
(However, ZnO + MgO + CaO: 12.5 to 15.0 mol%)
GeO ₂ : 53.5 to 65.0 mol%,
SiO ₂ : 5.0 to 14.5 mol%,
Al ₂ O ₃ : 0.5 to 10.0 mol%,
ZrO ₂ : 0 to 2.5 mol%,
P ₂ O ₅ : 0 to 0.3 mol %, and Ga ₂ O ₃ : 0 to 7.0 mol %,
(However, GeO ₂ +SiO ₂ +Al ₂ O ₃ +ZrO ₂ +P ₂ O ₅ +Ga ₂ O ₃ : 70.0 to 78.0 mol %)
(however, the composition does not consider Mn),
a molar ratio (X) represented by (SiO ₂ +Al ₂ O ₃ )/(GeO ₂ +SiO ₂ +Al ₂ O ₃ +ZrO ₂ +P ₂ O ₅ +Ga ₂ O ₃ ) is 0.075 or more and 0.310 or less;
Containing a component group in which the molar ratio (Y) represented by MgO/(ZnO+MgO+CaO) is 0.034 or more and 0.170 or less,
a vitrification step of producing a glass containing 0.0189 to 1.27 parts by mass of manganese (however, the valence is not limited) with respect to the total 100 parts by mass of oxides of the above component group;
a heat treatment step of heat-treating the glass to precipitate Mn ⁴⁺ -doped Li ₂ Ge ₄ O ₉ crystals and/or LiNaGe ₄ O ₉ crystals therein to obtain crystallized glass;
Prepare. And the manufacturing method of this embodiment is
The heating temperature (Z) when melting the raw material in the vitrification step is set to 1200° C. or more and 1350° C. or less,
One feature is that the heat treatment temperature (W) in the heat treatment step is 520 to 540.degree.
According to the manufacturing method of this embodiment, the above-described crystallized glass, that is, the glass in which the phosphor material exhibiting sharp luminescence in the deep red wavelength region when excited by visible light is formed while maintaining transparency. can be made.

In addition, the manufacturing method of this embodiment may include other steps such as a cooling step of cooling the glass produced in the vitrification step, in addition to the steps described above.

<Vitrification process>
As described above, in the vitrification process, all raw materials are heated and melted to produce glass (uncrystallized) having a predetermined composition. The suitable ratio of each component in the glass produced in the vitrification process is the same as the suitable ratio of each component already described for the above-described crystallized glass.

As raw materials, oxides, carbonates, nitrates, etc. corresponding to each of the component groups can be used. In particular, it is preferable to use MnO ₂ as a source of manganese. By using tetravalent manganese as a raw material, crystallized glass having desired luminous properties can be more easily produced.
Incidentally, the manganese ratio of 0.0189 to 1.27 parts by mass described above corresponds to approximately 0.03 to 2.0 parts by mass when converted to MnO ₂ .

The melting can be carried out by sufficiently mixing the raw materials, putting the mixture into a melting container (for example, a precious metal crucible) that does not react with the raw materials, and using a furnace such as an electric furnace. After melting, it can be homogenized and clarified in a furnace before being poured into a mold preheated to a suitable temperature and optionally slow cooled in a furnace to remove distortions.

The heating temperature (Z) when melting the raw material in the vitrification step is required to be 1200° C. or higher and 1350° C. or lower. If the heating temperature (Z) is less than 1200° C., the glass may not be sufficiently melted and uniform glass may not be obtained. On the other hand, when the heating temperature (Z) exceeds 1350° C., manganese in the raw material is reduced to divalent (Mn ²⁺ ), and as a result, light emission derived from Mn ⁴⁺ does not occur after the heat treatment. From the same point of view, the heating temperature (Z) is preferably as low as possible (for example, 1325° C. or lower, particularly 1300° C. or lower).
In the vitrification step, it is important to appropriately adjust the type of raw material and the composition of the glass so that the raw material is reliably melted at a predetermined heating temperature (Z).

Here, when manganese with a valence of 3 or higher is used as a raw material and the heating temperature (Z) is set within the range of 1200° C. or higher and 1350° C. or lower, more of the manganese is trivalent (Mn ³⁺ ) (or avoid reduction to divalent). Such control is preferable from the viewpoint of obtaining sharp light emission in the deep red wavelength region, that is, from the viewpoint of finally allowing manganese to exist in a tetravalent state.

Moreover, from the viewpoint of effectively controlling manganese to be trivalent (Mn ³⁺ ), it is preferable to perform the vitrification step in an oxidizing atmosphere.

<Heat treatment process>
In the heat treatment step, the glass produced above is heat treated. It is believed that in this heat treatment, manganese controlled to be trivalent (Mn ³⁺ ) in the vitrification process changes to tetravalent due to some transfer of energy. By this heat treatment, Mn ⁴⁺ -doped Li ₂ Ge ₄ O ₉ crystals and/or LiNaGe ₄ O ₉ crystals are precipitated inside the glass to obtain crystallized glass.

The heat treatment temperature (W) in the heat treatment step should be 520 to 540.degree. By heat-treating at such a temperature, Mn ⁴⁺ -doped Li ₂ Ge ₄ O ₉ crystals and/or LiNaGe ₄ O ₉ crystals can be precipitated with sufficient certainty.

The heat treatment time is not particularly limited, but can be, for example, 30 minutes to 2 hours.

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

(vitrification)
As glass raw materials for each component, corresponding oxides, carbonates or nitrates are prepared, weighed and mixed so that the composition after vitrification is as shown in Tables 1 to 4, and mixed to obtain raw materials. Obtained. MnO ₂ was used as a raw material for manganese. This prepared raw material was placed in a platinum crucible, heated in an electric furnace to a temperature within the range of 1200 to 1350° C. in principle, melted for several hours, and stirred at appropriate times to achieve homogenization. Then, after being clarified, it was poured into a mold, strain-removed and cooled to obtain a glass. At this time, the heating temperature (Z) and stability during melting were evaluated according to the following procedure. The results are shown in Tables 1-4.
Also, the obtained glass block (glass before heat treatment) was processed into a size of 10 mm×10 mm×10 mm (length×width×thickness), and both surfaces were optically polished to obtain an evaluation sample. Such a sample was used for evaluation of transparency and deposited crystals together with a sample after heat treatment, which will be described later.

<Heating temperature (Z) during melting>
For the heating temperature (Z) during melting, the raw material was put into a platinum crucible placed in an electric furnace with a temperature setting, and after 1 hour, a uniform liquid surface (no crystals were deposited, It was defined as the temperature of the electric furnace when a state in which no film was formed) was observed.

<Stability>
The melt after melting was taken out of the furnace together with the platinum crucible, and the time from stirring until devitrification occurred was measured. Then, the stability was evaluated according to the following criteria.
Less than 1 minute (not vitrified) ... ×
1 minute or more and less than 2 minutes・・・△
2 minutes or more・・・〇

(Heat treatment)
The glass obtained as described above was heat-treated at approximately 530° C. for 1 hour. This caused some of the glass to crystallize in some instances. The obtained glass block (crystallized glass) was processed into a size of 10 mm×10 mm×10 mm (length×width×thickness), and both surfaces were optically polished to obtain an evaluation sample. Using such a sample, evaluations of transparency, luminescence properties, deposited crystals, and peak intensity ratio R of crystallization temperature were carried out according to the following procedures. Tables 1 to 4 show the evaluation results of transparency, luminous properties and deposited crystals.

<Transparency>
For the above samples (glass before heat treatment and glass after heat treatment), a transmission spectrum was obtained using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, UV-visible-near-infrared spectrophotometer, "U-4100"). Then, the transmittance of light having a wavelength of 700 nm (700 nm transmittance) was read from the obtained spectrum, and the transparency was evaluated according to the following criteria. In the table, "-" is shown for those that could not be evaluated due to the fact that no glass was formed.
700 nm transmittance of 60% or more for both samples before and after heat treatment ... ◯ At least the sample after heat treatment has a 700 nm transmittance of less than 60% ... x

For reference, FIG. 1 schematically shows the transmission spectra of the glass before heat treatment and the glass after heat treatment in Examples 1 and 10, and FIG. 3 schematically shows the transmission spectra of the glass before heat treatment and the glass after heat treatment in Example 16, and the transmission spectra of the glass before heat treatment and after heat treatment in Example 9, Comparative Example 29 and Comparative Example 30. typically shown.

<Luminous characteristics>
Emission characteristics were evaluated using an emission spectrum. More specifically, the emission spectrum obtained when the above sample (glass after heat treatment) was irradiated with light of 430 nm as excitation light was obtained using a fluorometer. Then, when a relatively sharp spectrum is observed in the 630 nm to 700 nm (deep red wavelength region) (when the half width of the peak is 25 nm or less), the presence of Mn ⁴⁺ is recognized, so "4+" When a relatively broad spectrum was observed in the vicinity of 560 nm to 700 nm (when the half width of the peak was greater than 25 nm), the presence of Mn ⁴⁺ was not observed and was evaluated as "2+". . In the table, "-" is shown for those that could not be evaluated due to the fact that no glass was formed.

For reference, FIG. 4 schematically shows the emission spectrum of the glass (crystallized glass) after heat treatment in Examples 7 and 22, and FIG. 24 and 28 schematically show the emission spectra of the glasses (crystallized glass) after the heat treatment of No. 24 and Comparative Example 28.

<Precipitated crystal>
An X-ray diffraction pattern was obtained for the above samples (glass before heat treatment and glass after heat treatment) using an X-ray diffractometer (manufactured by Rigaku Corporation, sample horizontal X-ray diffractometer “Ultima IV”). Precipitated crystals were confirmed from the obtained X-ray diffraction pattern. In the glass after heat treatment, the case where only one of Li ₂ Ge ₄ O ₉ crystals and LiNaGe ₄ O ₉ crystals was confirmed was evaluated as “L”, and Li ₂ Ge ₄ O ₉ crystals and LiNaGe ₄ O ₉ crystals In addition to at least one of these, the case where crystals other than these were confirmed was evaluated as "M", and the case where crystals were not confirmed was evaluated as "N". In the table, "-" is shown for those that could not be evaluated due to the fact that no glass was formed.

6 schematically shows the X-ray diffraction patterns of the glasses of Examples 5, 18 and 25, and FIG. 7 shows the X-ray diffraction patterns of the glasses of Comparative Examples 30 and 31. Schematically shows a diffraction pattern.

<Peak intensity ratio R of crystallization temperature>
For the above sample (glass after heat treatment), a DTA curve (horizontal axis: temperature (° C.), vertical axis: electromotive force (μV) using a differential thermal analyzer (manufactured by Mac Science Co., Ltd., "TG-DTA2000S") ). Then, from the obtained DTA curve, the glass transition temperature (Tg), the first crystallization peak temperature (Tc1, around 560 ° C.) in the temperature range above Tg, and the second crystallization peak temperature in the temperature range above Tc1 (Tc2, around 600°C) was obtained. Then, when the electromotive forces at Tg, Tc1 and Tc2 are respectively Vg, Vc1 and Vc2 (all μV), the following formula:
R = (Vc1-Vg)/(Vc2-Vg)
A peak intensity ratio R represented by was obtained. As a result, it was confirmed that all of the heat-treated glasses (crystallized glasses) of Examples had R<1.0.

For reference, the DTA curves of Example 6, Example 23, Comparative Example 7, Comparative Example 30, and Comparative Example 31 are schematically shown in FIG.

From Tables 1 and 2, the heat-treated glass (crystallized glass) of the example has a transmittance of 60% or more for light with a wavelength of ⁷⁰⁰ nm. When irradiated, a relatively sharp spectrum was observed in the vicinity of 630 nm to 700 nm, and at least one of Li ₂ Ge ₄ O ₉ crystals and LiNaGe ₄ O ₉ crystals was confirmed. That is, the heat-treated glass (crystallized glass) of the examples has Mn ⁴⁺ -doped Li ₂ Ge ₄ O ₉ crystals and/or LiNaGe ₄ O ₉ crystals, and has good transparency. , it can be seen that it can exhibit sharp emission in the deep red wavelength region by visible light excitation.

On the other hand, the heat-treated glass of Comparative Example 1 was inferior in transparency. This is probably because the amount of Li ₂ O was too large and the crystal growth was excessively promoted during the heat treatment.
The glass of Comparative Example 2 did not exhibit sharp emission in the deep red wavelength region. This is probably because the amount of Li ₂ O was too small and the temperature for melting the raw material became high, resulting in the reduction of Mn ⁴⁺ to Mn ²⁺ .

The heat-treated glass of Comparative Example 3 was inferior in transparency. This is probably because the amount of Na ₂ O was too large and crystals other than the desired crystals precipitated during the heat treatment.
The heat-treated glass of Comparative Example 4 was inferior in transparency. This is probably because the amount of Na ₂ O was too small, deteriorating the stability of the glass melt, and excessively promoting crystal growth during the heat treatment.

The heat-treated glass of Comparative Example 5 was inferior in transparency. This is probably because the amount of K ₂ O was too large and crystals other than the desired crystals precipitated during the heat treatment.

The heat-treated glass of Comparative Example 6 was inferior in transparency. This is probably because the amount of ZnO was too large and crystals other than the desired crystals precipitated during the heat treatment.
The heat-treated glass of Comparative Example 7 was inferior in transparency. This is probably because the amount of ZnO was too small and the crystal growth was excessively promoted during the heat treatment.

The heat-treated glass of Comparative Example 8 did not exhibit sharp emission in the deep red wavelength region. This is because the amount of MgO is too large, the stability of the glass melt deteriorates, and the temperature for melting the raw materials rises, resulting in the reduction of Mn ⁴⁺ to Mn ²⁺ . it is conceivable that.
The heat-treated glass of Comparative Example 9 was inferior in transparency. It is considered that this is because the amount of MgO was too small and the crystal growth was excessively promoted during the heat treatment.

In Comparative Example 10, the glass melt had poor stability and did not form glass after cooling. This is considered to be due to the excessive amount of CaO.

The heat-treated glass of Comparative Example 11 was inferior in transparency. This is probably because the amount of GeO ₂ was too large and the crystal growth was excessively promoted during the heat treatment.
In Comparative Example 12, the glass melt had poor stability and did not form glass after cooling. This is believed to be due to the amount of GeO ₂ being too low.

Crystals were not precipitated in the heat-treated glass of Comparative Example 13. This is believed to be due to the excessive amount of _SiO2 .
The heat-treated glass of Comparative Example 14 was inferior in transparency. This is probably because the amount of SiO ₂ was too small and the crystal growth was excessively promoted during the heat treatment.

The heat-treated glass of Comparative Example 15 did not exhibit sharp emission in the deep red wavelength region. This is probably because the amount of Al ₂ O ₃ was too large and the temperature for melting the raw materials was increased, resulting in the reduction of Mn ⁴⁺ to Mn ²⁺ .
The heat-treated glass of Comparative Example 16 was inferior in transparency. This is probably because the amount of Al ₂ O ₃ was too small and the crystal growth was excessively promoted during the heat treatment.

The heat-treated glass of Comparative Example 17 did not exhibit sharp emission in the deep red wavelength region. This is probably because the amount of ZrO ₂ was too large and the temperature for melting the raw materials was increased, resulting in the reduction of Mn ⁴⁺ to Mn ²⁺ .

In Comparative Example 18, the glass melt had poor stability and did not form glass after cooling. This is probably due to the excessive amount of P ₂ O ₅ .

The heat-treated glass of Comparative Example 19 was inferior in transparency. This is probably because the amount of Ga ₂ O ₃ was too large and crystals other than the desired crystals precipitated during the heat treatment.

In Comparative Example 20, the glass melt had poor stability and did not form glass after cooling. This is considered to be due to the excessive amount of Mn.
The heat-treated glass of Comparative Example 21 did not exhibit sharp emission in the deep red wavelength region. This is probably because the amount of Mn was too small to retain tetravalent Mn after the heat treatment.

The heat-treated glass of Comparative Example 22 did not exhibit sharp emission in the deep red wavelength region. This is probably because the molar ratio (X) was too large and the temperature for melting the raw materials became high, resulting in reduction of Mn ⁴⁺ to Mn ²⁺ .
The heat-treated glass of Comparative Example 23 was inferior in transparency. This is probably because the molar ratio (X) was too small and crystals other than the desired crystals precipitated during the heat treatment.

The heat-treated glass of Comparative Example 24 did not exhibit sharp emission in the deep red wavelength region. This is probably because the molar ratio (Y) was too large and the temperature for melting the raw materials became high, resulting in reduction of Mn ⁴⁺ to Mn ²⁺ .
The heat-treated glass of Comparative Example 25 was inferior in transparency. This is probably because the molar ratio (Y) was too small and crystals other than the desired crystals precipitated during the heat treatment.

The heat-treated glass of Comparative Example 26 did not exhibit sharp emission in the deep red wavelength region. This is probably because the heating temperature (Z) during melting was too high and Mn ⁴⁺ was reduced to Mn ²⁺ .
In Comparative Example 27, uniform glass could not be obtained. This is probably because the heating temperature (Z) during melting was too low.

Comparative Examples 28 to 31 are examples imitating the composition described in a certain technical document.
Mn ⁴⁺ -doped Li ₂ Ge ₄ O ₉ crystals or LiNaGe ₄ O ₉ crystals were confirmed in all the glasses after the heat treatment of Comparative Examples 28 to 30, but they were inferior in transparency. This is probably because the crystal growth was excessively accelerated during the heat treatment because the composition was not optimized.
Li ₂ Ge ₄ O ₉ crystals were confirmed in the heat-treated glass of Comparative Example 31, but it was inferior in transparency and did not exhibit sharp light emission in the deep red wavelength region. This is because the Zn ₂ GeO ₄ crystals precipitated further caused the loss of transparency, and the Mn ²⁺ -doped Zn ₂ GeO ₄ crystals dominated the emission in the green wavelength region. it is conceivable that.

ADVANTAGE OF THE INVENTION According to this invention, the crystallized glass in which the crystal|crystallization which shows sharp luminescence in a deep red wavelength range by visible light excitation while maintaining transparency is formed inside can be provided. Further, according to the present invention, it is possible to provide a crystallized glass manufacturing method capable of manufacturing the crystallized glass described above.

Claims (4)

In terms of oxide,
Li ₂ O: 7.5 to 13.0 mol%,
Na ₂ O: 2.0 to 5.0 mol%,
K ₂ O: 0 to 3.5 mol%,
(However, Li ₂ O + Na ₂ O + K ₂ O: 9.5 to 15.0 mol%)
ZnO: 12.0 to 14.0 mol%,
MgO: 0.5 to 2.5 mol%,
CaO: 0 to 2.5 mol%,
(However, ZnO + MgO + CaO: 12.5 to 15.0 mol%)
GeO ₂ : 53.5 to 65.0 mol%,
SiO ₂ : 5.0 to 14.5 mol%,
Al ₂ O ₃ : 0.5 to 10.0 mol%,
ZrO ₂ : 0 to 2.5 mol%,
P ₂ O ₅ : 0 to 0.3 mol %, and Ga ₂ O ₃ : 0 to 7.0 mol %,
(However, GeO ₂ +SiO ₂ +Al ₂ O ₃ +ZrO ₂ +P ₂ O ₅ +Ga ₂ O ₃ : 70.0 to 78.0 mol %)
(However, composition not considering manganese)
a molar ratio (X) represented by (SiO ₂ +Al ₂ O ₃ )/(GeO ₂ +SiO ₂ +Al ₂ O ₃ +ZrO ₂ +P ₂ O ₅ +Ga ₂ O ₃ ) is 0.075 or more and 0.310 or less;
Containing a component group in which the molar ratio (Y) represented by MgO/(ZnO+MgO+CaO) is 0.034 or more and 0.170 or less,
A crystallized glass containing 0.0189 to 1.27 parts by mass of manganese (however, the valence number is not limited) per 100 parts by mass in total of the above component group in terms of oxides,
having Mn ⁴⁺ -doped Li ₂ Ge ₄ O ₉ crystals and/or LiNaGe ₄ O ₉ crystals, and
A crystallized glass having a transmittance of 60% or more for light having a wavelength of 700 nm at a thickness of 10 mm. 2. The crystallized glass according to claim 1, wherein the half width of the peak in the range of 630 nm to 700 nm in the emission spectrum when irradiated with light of 430 nm is 25 nm or less. In a DTA curve obtained by differential thermal analysis (DTA) (horizontal axis: temperature (° C.), vertical axis: electromotive force (μV)), the electromotive force at the glass transition temperature (Tg) is Vg (μV), and the glass Let Vc1 (μV) be the electromotive force at the first crystallization peak temperature in the temperature region equal to or higher than the transition temperature (Tg), and let Vc1 (μV) be the electromotive force at the second crystallization peak temperature in the temperature region equal to or higher than the first crystallization peak temperature. When Vc2 (μV), the following formula:
R = (Vc1-Vg)/(Vc2-Vg)
3. The crystallized glass according to claim 1, wherein the peak intensity ratio R represented by is less than 1.0. A method for producing crystallized glass according to any one of claims 1 to 3,
The raw material is heated and melted, converted to oxide,
Li ₂ O: 7.5 to 13.0 mol%,
Na ₂ O: 2.0 to 5.0 mol%,
K ₂ O: 0 to 3.5 mol%,
(However, Li ₂ O + Na ₂ O + K ₂ O: 9.5 to 15.0 mol%)
ZnO: 12.0 to 14.0 mol%,
MgO: 0.5 to 2.5 mol%,
CaO: 0 to 2.5 mol%,
(However, ZnO + MgO + CaO: 12.5 to 15.0 mol%)
GeO ₂ : 53.5 to 65.0 mol%,
SiO ₂ : 5.0 to 14.5 mol%,
Al ₂ O ₃ : 0.5 to 10.0 mol%,
ZrO ₂ : 0 to 2.5 mol%,
P ₂ O ₅ : 0 to 0.3 mol %, and Ga ₂ O ₃ : 0 to 7.0 mol %,
(However, GeO ₂ +SiO ₂ +Al ₂ O ₃ +ZrO ₂ +P ₂ O ₅ +Ga ₂ O ₃ : 70.0 to 78.0 mol %)
(however, the composition does not consider Mn),
a molar ratio (X) represented by (SiO ₂ +Al ₂ O ₃ )/(GeO ₂ +SiO ₂ +Al ₂ O ₃ +ZrO ₂ +P ₂ O ₅ +Ga ₂ O ₃ ) is 0.075 or more and 0.310 or less;
Containing a component group in which the molar ratio (Y) represented by MgO/(ZnO+MgO+CaO) is 0.034 or more and 0.170 or less,
a vitrification step of producing a glass containing 0.0189 to 1.27 parts by mass of manganese (however, the valence is not limited) with respect to the total 100 parts by mass of oxides of the above component group;
a heat treatment step of heat-treating the glass to precipitate Mn ⁴⁺ -doped Li ₂ Ge ₄ O ₉ crystals and/or LiNaGe ₄ O ₉ crystals therein to obtain crystallized glass;
with
The heating temperature (Z) when melting the raw material in the vitrification step is set to 1200° C. or more and 1350° C. or less,
A method for producing crystallized glass, wherein the heat treatment temperature (W) in the heat treatment step is 520 to 540°C.

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