JP7052956B1 - Li2O-Al2O3-SiO2-based crystallized glass and Li2O-Al2O3-SiO2-based crystalline glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a Li2O-Al2O3-SiO2 system crystallized glass which is excellent in impact strength and thermal impact strength and has few residual bubbles even if the amount of a raw material containing lithium is reduced. SOLUTION: Li2O-Al2O3-SiO2-based crystallized glass and Li2O-Al2O3-SiO2-based crystalline glass have a mass percentage of SiO260.0 to 70.0%, Al2O315.0 to 25.0%, Li2O 1. 0 to 6.0%, TiO 21.0 to 4.0%, ZrO 20.5 to 3.0%, MnO 20.1 to 3.0%, Na2O 0.1 to 2.0%, K2O 0.1 to 2 It contains 0.0%, P2O 50.1 to 2.0%, MgO 0.1 to 1.5%, ZnO 0.1 to 3.0% and BaO 0.1 to 2.5%, and As2O3 is 0.1. Less than%. [Selection diagram] None

Description

The present disclosure relates to Li ₂ O-Al ₂ O ₃ -SiO ₂ crystallized glass and Li ₂ O-Al ₂ O ₃ -SiO ₂ crystallized glass.

Front windows for oil stoves, wood stoves and other stoves, substrates for electronic products such as color filters and image sensors, setters for firing electronic parts, shelf boards for microwave ovens, top plates for electromagnetic cookers, windowpanes for fire doors, etc. As a material, low-expansion crystallized glass of the Li ₂ O-Al ₂ O ₃ -SiO ₂ system is used. For example, Japanese Patent Application Laid-Open No. 39-21049, Japanese Patent Application Laid-Open No. 40-20182, JP-A-1-308845, JP-A-6-329439, JP-A-9-188538, JP-A-2001-48582, Japanese Unexamined Patent Publication No. 2001-48583 discloses Li ₂ O—Al ₂ O ₃ −SiO ₂ system crystallized glass obtained by precipitating a β-quartz solid solution or a β-spodium solid solution as a main crystal.

The Li ₂ O-Al ₂ O ₃ -SiO ₂ -based crystallized glass obtained by precipitating a β-quartz solid solution or a β-spodium solid solution has a low coefficient of thermal expansion, high mechanical strength, and excellent thermal properties. ing. Further, in the Li ₂ O—Al ₂ O ₃ −SiO ₂ system crystallized glass, the precipitated crystal can be changed by changing the heat treatment conditions in the crystallization step, so that the raw glass having the same composition (that is, crystalline). It is possible to produce both transparent crystallized glass and opaque crystallized glass from glass), and it is possible to make them according to the purpose.

Special Publication No. 39-21049 Special Publication No. 40-20182 Japanese Unexamined Patent Publication No. 1-308845 Japanese Unexamined Patent Publication No. 6-329439 Japanese Unexamined Patent Publication No. 9-188538 Japanese Unexamined Patent Publication No. 2001-48582 Japanese Unexamined Patent Publication No. 2001-48583

(1) In recent years, the electrification of automobiles has accelerated, and the demand for lithium-ion secondary batteries has rapidly expanded. Along with this, the prices of lithium carbonate, which is a raw material for the positive electrode of lithium-ion secondary batteries, and minerals containing lithium, which is a raw material for lithium carbonate (for example, lithia pyrophyllite, petalite, lepidolite, etc.), are steadily increasing. There is.
On the other hand, when producing Li ₂ O-Al ₂ O ₃ -SiO ₂ system crystallized glass, in order to obtain the components constituting the crystal, spodumene (LiAlSi ₂ O ₆ ) and petalite (LiAlSi ₄ O ₁₀ ) are used. ), Lithium-containing minerals such as lepidolite (K (Li, Al) ₃ (AlSi ₃ O ₁₀ ) (OH, F) ₂ ), or a large amount of lithium carbonate is used. In order to reduce the production cost of Li ₂ O-Al ₂ O ₃ -SiO ₂ -based crystallized glass, it is preferable to reduce the amount of the raw material containing lithium. However, if the amount of the raw material containing lithium is reduced, the crystal components of the Li ₂ O—Al ₂ O ₃ −SiO ₂ system crystallized glass are reduced, which makes it difficult to form crystals and the same crystals as before. The amount of crystallized glass treated by the heating curve of the chemical heat treatment becomes relatively small. Crystallized glass generally has lower impact strength and thermal shock strength as the amount of crystals decreases.

(2) Conventionally, polyvalent ion oxides such as As ₂ O ₃ and Sb ₂ O ₃ have been used as a clarifying agent for Li ₂ O-Al ₂ O ₃ -SiO ₂ system crystallized glass. These clarifying agents are generally used in combination with NaNO ₃ or KNO ₃ . Clarifying agents such as As ₂ O ₃ and Sb ₂ O ₃ once capture the oxygen that NaNO ₃ or KNO ₃ decomposes at a relatively low temperature and releases it, and then releases the captured oxygen to a high temperature, thereby generating oxygen. The gas works effectively on the clarification of glass. In addition, some of the clarifying agents such as As ₂ O ₃ and Sb ₂ O ₃ are vaporized at high temperatures, so that they effectively act on the clarification of glass. However, if NaNO ₃ and KNO ₃ are not used, the effects of clarifying agents such as As ₂ O ₃ and Sb ₂ O ₃ are low.
By the mechanism described above, clarifying agents such as As ₂ O ₃ and Sb ₂ O ₃ act as effective clarifying agents when used in glass raw materials with NaNO ₃ or KNO ₃ . However, As ₂ O ₃ and Sb ₂ O ₃ pollute the environment by vaporization. When the heat treatment temperature is relatively low to suppress the vaporization of As ₂ O ₃ and Sb ₂ O ₃ in order to suppress environmental pollution, the glass in which As ₂ O ₃ or Sb ₂ O ₃ remains is REACH of the European Union (REACH). Registration, Evaluation, Authorization and Restriction of Chemicals) is not compliant and cannot be sold within the European Union. In addition, NaNO ₃ and KNO ₃ chemically react with each other and remain on the glass as Na ₂ O and K ₂ O, respectively. The higher the content of Na ₂ O and K ₂ O, the weaker the impact strength of the crystallized glass, and the larger the coefficient of thermal expansion, the weaker the thermal shock strength.

The embodiments of the present disclosure have been made under the circumstances of (1) and (2) above.
The present disclosure is to provide Li ₂ O—Al ₂ O ₃ −SiO ₂ system crystallized glass which is excellent in impact strength and thermal impact strength and has few residual bubbles even if the amount of lithium-containing raw material used is reduced. ..

As a result of various experiments conducted by the present inventor, the inclusion of MnO ₂ increases the mechanical strength of the Li ₂ O-Al ₂ O ₃ -SiO ₂ -based crystallized glass, and is excellent in impact strength and thermal shock strength. I found that. Furthermore, it was surprisingly found that even if the amount of As ₂ O ₃ and Sb ₂ O ₃ used is reduced, the residual bubbles in the Li ₂ O-Al ₂ O ₃ -SiO ₂ system crystallized glass can be suppressed. ..

The Li _{2 O-Al 2 O 3-SiO 2 system crystallized glass and the Li 2 O-Al 2 O 3 -SiO 2 system crystalline glass of} the present disclosure have a mass percentage of SiO ₂ 60.0 to 70.0%. , Al ₂ O ₃ 15.0 to 25.0%, Li ₂ O 1.0 to 6.0%, TiO ₂ 1.0 to 4.0%, ZrO ₂ 0.5 to 3.0%, MnO ₂ 0.1-3.0%, Na ₂ O 0.1-2.0%, K ₂ O 0.1-2.0%, P ₂ O ₅ 0.1-2.0%, MgO 0.1 It contains ~ 1.5%, ZnO 0.1 ~ 3.0% and BaO 0.1 ~ 2.5%, and As ₂ O ₃ is less than 0.1%.

An example of the embodiment of the Li _{2 O-Al 2 O 3-SiO 2 system crystallized glass and the Li 2 O-Al 2 O 3 -SiO 2 system crystalline glass of} the present disclosure is SiO ₂ 60.0 by mass percentage. ~ 70.0%, Al ₂ O ₃ 15.0 ~ 25.0%, Li ₂ O 1.0 ~ 6.0%, TiO ₂ 1.0 ~ 4.0%, ZrO ₂ 0.5 ~ 3. 0%, MnO ₂ 0.1-3.0%, Na ₂ O 0.1-2.0%, K ₂ O 0.1-2.0%, P ₂ O ₅ 0.1-2.0% , MgO 0.1-1.5%, ZnO 0.1-3.0% and BaO 0.1-2.5%, As ₂ O ₃ is less than 0.1%, Sb ₂ O ₃ Is less than 0.1%.

An example of the embodiment of the Li _{2 O-Al 2 O 3-SiO 2 system crystallized glass and the Li 2 O-Al 2 O 3 -SiO 2 system crystallized glass} of the present disclosure is As 2 O ₃ and As ₂ O 3 by mass percentage. Sb ₂ O ₃ is less than 0.2% in total.

An example of the embodiment of the Li ₂ O-Al ₂ O ₃ -SiO ₂ crystallized glass and the Li ₂ O-Al ₂ O ₃ -SiO ₂ crystallized glass of the present disclosure is F 0.1 to 1.0%. Including further.

Examples of the embodiments of the Li _{2 O-Al 2 O 3-SiO 2 system crystallized glass and the Li 2 O-Al 2 O 3 -SiO 2 system crystallized glass} of the present disclosure are V ₂ O ₅ , CoO, Cr ₂ . It further comprises at least one colorant selected from the group consisting of O ₃ , Fe ₂ O ₃ and NiO.

The Li ₂ O-Al ₂ O ₃ -SiO ₂ system crystallized glass of the present disclosure preferably has a β-quartz solid solution or a β-spodium solid solution as a main crystal.

According to the present disclosure, Li ₂ O—Al ₂ O ₃ −SiO ₂ system crystallized glass having excellent impact strength and thermal impact strength and having few residual bubbles even if the amount of lithium-containing raw material used is reduced is provided. ..

Hereinafter, embodiments of the present disclosure will be described. These explanations and examples are examples of embodiments and do not limit the scope of the embodiments.

The numerical range indicated by using "-" in the present disclosure indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.

The reasons for specifying the composition range of the Li ₂ O-Al ₂ O ₃ -SiO ₂ crystallized glass and the Li ₂ O-Al ₂ O ₃ -SiO ₂ crystallized glass of the present disclosure will be described below.

SiO ₂ is a network former of glass and a component constituting a crystal. If it is less than 60.0%, the coefficient of thermal expansion of glass becomes high and the mechanical strength becomes low, and if it is more than 70.0%. It may be difficult to melt the glass and defects such as bubbles and devitrified substances may occur.

Al ₂ O ₃ is a component constituting the crystal. If it is less than 15.0%, the devitrification of the glass becomes stronger and the chemical durability is lowered, and if it is more than 25.0%, the viscosity at the time of melting is high. It becomes too much and it becomes difficult to obtain uniform glass.

Li ₂ O is a component constituting crystals, but if it is less than 1.0%, it becomes difficult for desired crystals to precipitate and the meltability of glass decreases. On the other hand, if it is more than 6.0%, the devitrification of the glass becomes strong and molding becomes difficult.

The total amount of SiO ₂ , Al ₂ O ₃ , and Li ₂ O, which are the components constituting the crystal, is preferably 90% or less, more preferably 88% or less, from the viewpoint of reducing the amount of the raw material containing lithium. 86% or less is further preferable, and from the viewpoint that the crystallized glass is excellent in impact strength and thermal shock strength, 80% or more is preferable, 82% or more is more preferable, and 84% or more is further preferable.

When TiO ₂ acts as a nucleating agent, if it is less than 1.0%, the effect of promoting crystallization cannot be obtained, it becomes difficult to obtain a desired crystal, and if it is more than 4.0%, the liquidus temperature becomes high. , Molding work becomes difficult. On the other hand, if it is more than 4.0%, when the transparent crystallized glass is produced, the glass is colored dark brown and the transparency is impaired.

When ZrO ₂ acts as a nucleating agent, if it is less than 0.5%, the effect of promoting crystallization cannot be obtained and it becomes difficult to obtain a desired crystal, and if it is more than 3.0%, the unmelted product of ZrO ₂ is not obtained. Is generated, and devitrification is generated in the glass.

MnO ₂ has an effect of promoting crystallization, but if it is less than 0.1%, the effect of promoting crystallization cannot be obtained, and it becomes difficult to obtain a desired crystal. The effect of increasing is not obtained. In addition, in the Li ₂ O-Al ₂ O ₃ -SiO ₂ system crystallized glass of the present disclosure, the effect of reducing residual bubbles was recognized in MnO ₂ . The content of MnO ₂ is preferably 0.5% or more, more preferably 0.8% or more, still more preferably 1.0% or more, still more preferably 1.5% or more. Further, since MnO ₂ acts as a colorant, the amount of expensive _{V2O 5 and} CoO used can be reduced by using MnO ₂ . On the other hand, if MnO ₂ is more than 3.0%, the devitrification of the glass becomes strong and molding becomes difficult.

Na ₂ O has the effect of improving the meltability of the glass, but if it is less than 0.1%, the effect cannot be obtained, and if it is more than 2.0%, the coefficient of thermal expansion and the dielectric loss of the glass become large. If it is more than 2.0%, the impact strength and chemical durability will decrease.

K ₂ O has the effect of improving the meltability of the glass, but if it is less than 0.1%, the effect cannot be obtained, and if it is more than 2.0%, the coefficient of thermal expansion and the dielectric loss of the glass become large. If it is more than 2.0%, the impact strength and chemical durability will decrease.

P ₂ O ₅ has the effect of improving the poor meltability of ZrO ₂ , but if it is less than 0.1%, the effect cannot be obtained, and if it is more than 2.0%, the glass tends to be phase-separated and is uniform. I can't get glass. Further, if it is more than 2.0%, the amount of crystals increases and it becomes difficult to obtain transparent crystallized glass.

MgO is a component that improves the meltability of glass and prevents the generation of bubble defects, but if it is less than 0.1%, the effect cannot be obtained and bubbles are likely to be generated. On the other hand, if it is more than 1.5%, the coefficient of thermal expansion of the glass becomes large and the thermal characteristics are inferior. Further, in the case of producing transparent crystallized glass, the glass may be colored yellow due to the presence of TiO ₂ , but if the amount of MgO is more than 1.5%, the coloring becomes deep and the transparency is impaired.

ZnO is a component that improves the meltability of glass and prevents the generation of bubble defects, but if it is less than 0.1%, the effect cannot be obtained and bubbles are likely to be generated. On the other hand, if it is more than 3.0%, the dielectric loss of the glass becomes large and hot spots may occur when used in a microwave oven. Further, in the case of producing transparent crystallized glass, the glass may be colored yellow due to the presence of TiO ₂ , but if ZnO is more than 3.0%, the coloring becomes deeper and the transparency is impaired.

BaO is a component that improves the meltability of glass and prevents the generation of foam defects, but if it is less than 0.1%, the effect cannot be obtained and bubbles are likely to be generated. On the other hand, if it is less than 0.1%, the liquidus temperature becomes high and the molding operation becomes difficult. On the other hand, if it is more than 2.5%, the coefficient of thermal expansion of the glass becomes large and the thermal characteristics are inferior. Further, if it is more than 2.5%, the dielectric loss of the glass becomes large.

The smaller the content of As ₂ O ₃ is, the more preferable it is from the viewpoint of environmental load. The content of As ₂ O ₃ is less than 0.1%, and 0% is particularly preferable.
As ₂ O ₃ has conventionally been used as a clarifying agent for crystallized glass, but in the Li ₂ O-Al ₂ O ₃ -SiO ₂ system crystallized glass of the present disclosure, surprisingly, As ₂ O ₃ is used. There was almost no residual air bubbles even when the amount used was small or not used. By having a small amount of residual bubbles, the yield rate of the crystallized glass is improved, and the impact strength and the thermal shock strength of the crystallized glass are increased.
When As ₂ O ₃ is used as a clarifying agent for crystallized glass, the clarifying effect is low unless the heat treatment temperature is relatively high, but if As ₂ O ₃ is not used as a clarifying agent for crystallized glass, the heat treatment temperature is relatively low. It is also advantageous in that it does not need to be heated to a high temperature and the manufacturing cost is reduced.

The smaller the content of Sb ₂ O ₃ is, the more preferable it is from the viewpoint of environmental load. The content of Sb ₂ O ₃ is preferably less than 0.1%, particularly preferably 0%.
Sb ₂ O ₃ has conventionally been used as a clarifying agent for crystallized glass, but surprisingly, in the Li ₂ O-Al ₂ O ₃ -SiO ₂ system crystallized glass of the present disclosure, Sb ₂ O ₃ is used. There was almost no residual air bubbles even when the amount used was small or not used. By having a small amount of residual bubbles, the yield rate of the crystallized glass is improved, and the impact strength and the thermal shock strength of the crystallized glass are increased.
When Sb ₂ O ₃ is used as a clarifying agent for crystallized glass, the clarifying effect is low unless the heat treatment temperature is relatively high, but if Sb ₂ O ₃ is not used as a clarifying agent for crystallized glass, the heat treatment temperature is relatively low. It is also advantageous in that it does not need to be heated to a high temperature and the manufacturing cost is reduced.

The total amount of As ₂ O ₃ and Sb ₂ O ₃ is preferably less than 0.2%, more preferably less than 0.1%, and particularly preferably 0%.

F has the effect of improving the meltability of the glass. When the crystallized glass and the crystallized glass of the present disclosure contain F, 0.1 to 1.0% is preferable. When it is 0.1% or more, the effect is obtained, and when it is 1.0% or less, erosion to the melting furnace can be suppressed.

V ₂ O ₅ , CoO, Cr ₂ O ₃ , Fe ₂ O ₃ and NiO act as colorants. When these are used, the total amount is preferably 0.1 to 3.0%. When the total amount is 0.1% or more, the coloring effect is easily obtained, and when the total amount is 3.0% or less, the cost can be suppressed.

The Li ₂ O-Al ₂ O ₃ -SiO ₂ system crystalline glass of the present disclosure can be produced by blending a glass raw material, melting the glass raw material to obtain molten glass, and molding the molten glass.
The Li ₂ O-Al ₂ O ₃ -SiO ₂ system crystallized glass of the present disclosure can be produced by crystallizing and heat-treating the Li ₂ O-Al ₂ O ₃ -SiO ₂ system crystalline glass of the present disclosure. The temperature rise rate, holding temperature and holding time of the crystallization heat treatment are not particularly limited, and conditions under which desired crystals (preferably β-quartz solid solution or β-spodium solid solution) are sufficiently precipitated and grown can be selected. ..

The Li ₂ O-Al ₂ O ₃ -SiO ₂ system crystallized glass of the present disclosure has a β-quartz solid solution (Li ₂ O · Al ₂ O ₃ · nSiO ₂ , nSiO) as a main crystal from the viewpoint of lowering the coefficient of thermal expansion. It is preferable to have ≧ 2) or β-spodium solid solution (Li ₂ O · Al ₂ O ₃ · nSiO ₂ , n ≧ 4).

Hereinafter, the Li ₂ O-Al ₂ O ₃ -SiO ₂ crystallized glass and the Li ₂ O-Al ₂ O ₃ -SiO ₂ crystallized glass of the present disclosure will be described in more detail with reference to examples. The materials, amounts, ratios, treatment procedures, etc. shown in the following examples may be changed as long as they do not deviate from the gist of the present disclosure. Therefore, the range of the Li ₂ O-Al ₂ O ₃ -SiO ₂ crystallized glass and the Li ₂ O-Al ₂ O ₃ -SiO ₂ crystallized glass of the present disclosure is limitedly interpreted by the following specific examples. Should not be done.

Tables 1 and 2 show examples (samples No. 1 to 8) and comparative examples (samples No. 9 to 10) of the Li ₂ O-Al ₂ O ₃ -SiO ₂ system crystallized glass of the present disclosure. There is.

Each sample in Table 1 and Table 2 was prepared as follows.
The glass raw materials were prepared so as to have the compositions shown in Tables 1 and 2, mixed uniformly, and then melted at 1660 ° C. for 12 hours using a crucible. Next, the molten glass was poured onto a metal platen and molded into a 4 mm thick plate glass using a stainless roller. Next, each plate glass was crystallized under the heat treatment conditions as shown in Tables 1 and 2, and then cooled in a furnace to obtain a sample.

For each sample, the main crystal, appearance, color tone, residual bubbles, impact strength and thermal shock strength were observed.
The main crystal was identified by X-ray diffraction.
The appearance and color tone were observed with the naked eye.
As for the residual bubbles, the number of bubbles was counted by visually observing a glass plate having a size of 300 mm × 300 mm × 4 mm.
The impact strength was evaluated by the height of the steel ball when a 535 g steel ball was freely dropped to give an impact to the center point of a 300 mm × 300 mm × 4 mm glass plate and the glass plate was broken. First, the steel ball was freely dropped from a height of 10 cm, and if the glass plate did not break, the height of the steel ball was raised by 10 cm and repeated until the glass plate cracked.
The thermal shock strength is when a glass plate of 300 mm x 300 mm x 4 mm is placed in a high-temperature furnace for 30 minutes, then the glass plate is taken out from the furnace, and the glass plate is thrown into water (normal temperature) to break the glass. It was evaluated by the temperature inside the furnace. First, set the temperature inside the furnace to 800 ° C (temperature difference 500 ° C if the color tone of the glass plate is opaque) with water (normal temperature), and if the glass plate does not break, raise the temperature inside the furnace by 10 ° C to the glass plate. Repeated until it cracked. When the glass plate was broken due to a temperature difference of 800 ° C. (when the color tone of the glass plate was opaque, the temperature difference was 500 ° C.), the temperature in the furnace was lowered by 10 ° C. and repeated until the glass plate did not break.

As can be seen from Tables 1 and 2, transparent crystallized glass having a β-quartz solid solution as a main crystal and opaque crystallized glass having a β-spodium solid solution as a main crystal were obtained depending on the heat treatment conditions.

The results shown in Tables 1 and 2 show Li ₂ O-Al ₂ O ₃ -SiO ₂ system crystals containing 0.1% to 3.0% of MnO ₂ and less than 0.1% of As ₂ O ₃ . It is shown that the glass-ceramic is excellent in impact strength and thermal shock strength and has few residual bubbles even if the components constituting the crystal are relatively small.
The results shown in Tables 1 and 2 show that MnO ₂ is 0.1% to 3.0% and As ₂ O ₃ is 0.1 as Li ₂ O-Al ₂ O ₃ -SiO ₂ -based crystallized glass. It shows that the form which is less than% and Sb ₂ O ₃ is less than 1% is preferable.

The Li ₂ O-Al ₂ O ₃ -SiO ₂ system crystallized glass of the present disclosure is excellent in impact strength and thermal shock strength and has few residual bubbles. In addition, the Li ₂ O-Al ₂ O ₃ -SiO ₂ system crystallized glass of the present disclosure has stable physical and chemical properties by specifying its composition as described above. Therefore, it can be used as many industrial materials such as stove front windows, electronic product substrates, electronic component firing setters, microwave oven shelves, and electromagnetic cooker top plates.

Claims (9)

By mass percentage,
SiO ₂ 60.0-70.0%,
Al ₂ O ₃ 15.0-25.0%,
Li ₂ O 1.0-6.0%,
TIM ₂ 1.0-4.0%,
ZrO ₂ 0.5-3.0%,
MnO ₂ 1.5-3.0 %,
Na ₂ O 0.1-2.0%,
K ₂ O 0.1-2.0%,
P ₂ O ₅ 0.1-2.0%,
MgO 0.1-1.5%,
Containing ZnO 0.1-3.0% and BaO 0.1-2.5%
The total amount of SiO ₂ , Al ₂ O ₃ and Li ₂ O is 88% or less, and
As ₂ O ₃ is less than 0.1%,
Li ₂ O-Al ₂ O ₃ -SiO ₂ -based crystallized glass. The Li ₂ O—Al ₂ O ₃ −SiO ₂ system crystallized glass according to claim 1, wherein As ₂ O ₃ and Sb ₂ O ₃ are less than 0.2% in total by mass percentage. The Li ₂ O-Al ₂ O ₃ -SiO ₂ system crystallized glass according to claim 1 or 2, further comprising F 0.1 to 1.0%. The Li according to any one of claims 1 to 3, further comprising at least one colorant selected from the group consisting of V ₂ O ₅ , CoO, Cr ₂ O ₃ , Fe ₂ O ₃ and NiO. ₂ O-Al ₂ O ₃ -SiO ₂ system crystallized glass. The Li ₂ O-Al ₂ O ₃ -SiO ₂ system crystallized glass according to any one of claims 1 to 4, which has a β-quartz solid solution or a β-spodium solid solution as a main crystal. Li ₂ O-Al ₂ O ₃ - SiO ₂ system crystallized glass raw glass.
By mass percentage,
SiO ₂ 60.0-70.0%,
Al ₂ O ₃ 15.0-25.0%,
Li ₂ O 1.0-6.0%,
TIM ₂ 1.0-4.0%,
ZrO ₂ 0.5-3.0%,
MnO ₂ 1.5-3.0 %,
Na ₂ O 0.1-2.0%,
K ₂ O 0.1-2.0%,
P ₂ O ₅ 0.1-2.0%,
MgO 0.1-1.5%,
Containing ZnO 0.1-3.0% and BaO 0.1-2.5%
The total amount of SiO ₂ , Al ₂ O ₃ and Li ₂ O is 88% or less, and
As ₂ O ₃ is less than 0.1%,
Li ₂ O-Al ₂ O ₃ -SiO ₂ -based crystalline glass. The Li ₂ O—Al ₂ O ₃ −SiO ₂ system crystalline glass according to claim 6, wherein As ₂ O ₃ and Sb ₂ O ₃ total less than 0.2% by mass percentage. The Li ₂ O-Al ₂ O ₃ -SiO ₂ -based crystalline glass according to claim 6 or 7, further comprising 0.1 to 1.0% of F. The Li according to any one of claims 6 to 8, further comprising at least one colorant selected from the group consisting of V ₂ O ₅ , CoO, Cr ₂ O ₃ , Fe ₂ O ₃ and NiO. ₂ O-Al ₂ O ₃ -SiO ₂ -based crystalline glass.