JP2021091583A - Crystallized glass, crystalline glass, and production method of crystallized glass - Google Patents

Abstract

To provide crystallized glass having metallic gloss without being coated with a metal film and excellent designability.SOLUTION: Crystallized glass contains a first transition metal oxide excluding the group IV of over 1-10% in external mass% and has a crystallinity index of 70% or higher. The crystallized glass has a glass body and a metallic gloss layer formed on the surface of the glass body. Preferably, the metallic gloss layer has a surface resistivity different from that of the glass body. Preferably, the metallic gloss layer has a surface resistivity lower than that of the glass body. Further, the metallic gloss layer has a surface resistivity lower than that of the glass body preferably by 0.5 Ω cm or more, more preferably by 1 Ω cm or more, and still more preferably by 1.5 Ω cm or more. The larger the difference between the surface resistivity of the metallic gloss layer and that of the glass body is, the higher the performance of the glass used as a film resistor is.SELECTED DRAWING: Figure 1

Description

The present invention relates to crystallized glass, particularly crystallized glass having a metallic luster on its surface.

Conventionally, as a method for obtaining a glass article having a design property such as metallic luster, for example, as described in Patent Documents 1 and 2, a method of coating glass with a metal film by using sputtering is known.

However, when a large-area glass plate is coated with a metal film by a sputtering method, unevenness and film peeling are likely to occur. Further, there is a problem that a large-scale device for sputtering is required and the manufacturing cost tends to be high.

Japanese Unexamined Patent Publication No. 2019-026508 Japanese Patent No. 3057785

An object of the present invention is to provide a crystallized glass having a metallic luster and excellent designability without coating with a metal film.

As a result of diligent studies, the present inventor has made it possible to develop a metallic luster on the surface of the crystallized glass by containing a predetermined amount of the first transition metal oxide in the crystallized glass and further restricting the degree of crystallinity. We found out what we could do and came to propose the present invention.

The mechanism found by the present inventor is as follows. When crystalline glass containing a predetermined amount of the first transition metal oxide is crystallized to a certain degree of crystallinity or higher, the first transition metal ions that are difficult to dissolve in the crystals in the crystallinized glass are present in the crystallized glass. It is believed to be concentrated in the glass matrix. Then, it is considered that the concentrated first transition metal ion is transferred to the surface of the crystallized glass together with the glass matrix, and as a result, a metal-rich surface layer is formed and metallic luster is developed on the surface of the crystallized glass.

In general, the transition metal element is a general term for the elements existing between the 3rd to 11th group elements in the periodic table, and the transition metal element existing in the 4th period is referred to as the first transition metal element. Further, among the transition metal elements, the Group 4 element is difficult to contribute to the metallic luster of the surface because it dissolves in the crystal. Therefore, in the present invention, as the transition metal element, an element excluding these elements (specifically, Ti, Zr, Hf, Rf) is targeted.

That is, the crystallized glass of the present invention is characterized in that it contains more than 1 to 10% of the first transition metal oxide excluding Group 4 and has a crystallinity of 70% or more in mass% of the outer cover. To do.

Further, the crystallized glass of the present invention is preferably aluminosilicate glass.

Further, the crystallized glass of the present invention is preferably SiO ₂ 50 to 80%, Al ₂ O ₃ 10 to 25%, Li ₂ O 0.1 to 20%, MgO + CaO + SrO + BaO + ZnO 0 to 10% in mass%. ..

Further, the crystallized glass of the present invention preferably contains _{TiO 2} 0.1 to 5% and ZrO _{2 0.1 to 5% in mass%.}

Further, in the crystallized glass of the present invention, it is preferable that the first transition metal oxide _{is one or more selected from Fe 2} O ₃ , CoO, NiO and CuO.

In this way, it becomes easy to obtain crystallized glass having a metallic luster.

Further, in the crystallized glass of the present invention, it is preferable that the main crystal is β-quartz.

In this way, the crystallized glass body can be imparted with translucency. As a result, it becomes possible to obtain a highly designed glass article having a metallic luster and the translucency of glass.

Further, the crystallized glass of the present invention preferably has a metallic luster.

Further, the crystallized glass of the present invention preferably has a surface resistivity of 8 Ω · cm or less.

In this way, it can be used as a membrane resistor.

In the crystallized glass of the present invention, it is preferable that the crystallized glass has a glass body and a metallic luster layer formed on the surface thereof, and the surface resistivity of the metallic luster layer is different from the surface resistivity of the glass body. In the present invention, the glass body refers to glass from which at least the metallic luster layer has been completely removed, and more specifically, a layer having a thickness of 500 μm (0.5 mm) or more has been removed from the surface by polishing or the like. Refers to glass.

In the crystallized glass of the present invention, the surface resistivity of the metallic luster layer is preferably 0.5 Ω · cm or more lower than the surface resistivity of the glass body.

The crystalline glass of the present invention is a precursor of the crystallized glass, and preferably contains 1 to 10% of the first transition metal oxide excluding Group 4 in mass% of the outer cover.

The method for producing crystallized glass of the present invention is characterized in that the crystalline glass is crystallized by subjecting it to a heat treatment at 700 to 1000 ° C.

According to the present invention, it is possible to obtain a crystallized glass having a metallic luster and excellent designability without coating a metal film by a sputtering method or the like. Moreover, since the sputtering method is not used, unevenness and film peeling are unlikely to occur. Further, since a large-scale device is not required for sputtering, manufacturing cost and labor can be reduced.

Sample No. in Examples. It is an appearance photograph of the crystallized glass of 4. Sample No. in Examples. It is a photograph of the appearance of the crystalline glass before crystallization of No. 4.

The crystallized glass of the present invention contains a first transition metal oxide excluding Group 4. In the present invention, the content of the group 4 element, that is, the first transition metal oxide (hereinafter referred to as the first transition metal oxide) excluding _{TiO 2 is 1 by mass% of the outer cover with respect to the base glass.} Super-10%, 1.2-9%, 1.4-8.5%, 1.6-8%, 1.8-7.5%, 1.9-7%, 2-6% , Especially preferably 2.2 to 5%. If the content of the first transition metal oxide is too small, it becomes difficult to develop metallic luster on the surface of the crystallized glass. On the other hand, if the content of the first transition metal oxide is too large, the crystalline glass, which is a precursor of the crystallized glass, may become inhomogeneous or vitrification may become difficult, resulting in a decrease in productivity. There is.

By the way, in the crystallized glass of the present invention, since the second to fourth transition metal elements do not easily affect the metallic luster of the surface, the second to fourth transition metal oxides excluding Group 4 (hereinafter, the second to fourth transition metals). The content of (referred to as oxide) is not limited. However, since the transition metal element is a component that easily colors the glass, the content of the second to fourth transition metal oxides may be regulated from the viewpoint of reducing the coloring of the glass. In that case, the content of the second to fourth transition metal oxides is, preferably 0 to 10%, preferably 0.1 to 8%, more preferably 0.1 to 8% by mass of the outer glass with respect to the base glass. It is 0.5 to 5%.

Further, the first transition metal oxide according to the present invention _{is preferably one or more selected from V 2} O ₅ , Cr ₂ O ₃ , MnO, Fe ₂ O ₃ , CoO, NiO, and CuO. In this case, the _{total content of V 2} O ₅ , Cr ₂ O ₃ , MnO, Fe ₂ O ₃ , CoO, NiO, and CuO is preferably more than 1 to 10%, and 1.2 to 9%. , 1.4 to 8.5%, 1.6 to 8%, 1.8 to 7.5%, 1.9 to 7%, 2 to 6%, particularly 2.2% to 5%. By doing so, it is easier to obtain the effect of the present invention.

Further, the first transition metal oxide according to the present invention is more preferably one or more selected from _{Fe 2} O _{3, CoO, NiO, and CuO.} When these are used as the first transition metal oxide, the effect of the present invention can be easily obtained. In this case, the _{total content of Fe 2} O ₃ , CoO, NiO, and CuO is preferably more than 1 to 10%, 1.2 to 9%, 1.4 to 8.5%, and 1. 6 to 8%, 1.8 to 7.5%, 1.9 to 7%, 2 to 6%, particularly 2.2 to 5% are preferable. In this way, the effect of the present invention is particularly easy to obtain.

The content of each of V ₂ O ₅ , Cr ₂ O ₃ , MnO, Fe ₂ O ₃ , CoO, NiO, and CuO is preferably 0 to 10%, and is more than 0 to 10%, 0.1 to 0. 9.6%, over 0.1 to 9.4%, 0.2 to 9%, 0.5 to 8.6%, 0.8 to 8.4%, 1 to 7.8%, 1.2 ~ 7.5%, 1.4-7%, 1.7-6.5%, 1.8-6%, 1.9-5.5%, particularly 2-5%. The above-mentioned first transition metal oxides may be used alone or mixed at an arbitrary ratio. From the viewpoint of environmental load and toxicity, the CoO content is preferably 0.04% or less, 0.035% or less, 0.03% or less, 0.02% or less, 0.01% or less. , Especially preferably not contained.

Further, as described above, the transition metal oxide is generally a component that enhances coloring in crystallized glass, but Nd ₂ O ₃ has an effect of reducing the transparency of the glass while reducing the coloring. It is also an ingredient. Therefore, _{the content of Nd 2} O ₃ is preferably 0 to 0.2%, more preferably 0 to 0.1%, and particularly preferably not substantially (specifically, 100 ppm or less). When less coloring is prioritized over high transparency, for example, about 500 ppm of _{Nd 2} O _{3 may be added.}

Further, the transition metal element according to the present invention refers to the transition metal element of the 3rd and 5th to 11th groups excluding the 4th group as described above, but the transition metal element is preferably the 5th to 5th. Group 11, more preferably groups 6 to 11, still more preferably groups 7 to 11, and particularly preferably groups 8 to 11. In this way, the transition metal element is easily ionized, so that it is possible to easily obtain a crystallized glass having a metallic luster.

The crystallinity of the present invention has a crystallinity of 70% or more, more preferably 72% or more, still more preferably 73% or more, 75% or more, 77% or more, and particularly preferably 79% or more. If the degree of crystallinity is too low, transition metal ions are less likely to be concentrated in the glass matrix in the crystallized glass, and thus it is difficult to develop metallic luster on the surface of the crystallized glass. On the other hand, the upper limit of the crystallinity is not particularly limited and may be 100%, but in reality, 99% or less, 95% or less, 90% or less, particularly 89% or less is preferable.

The crystallized glass of the present invention may have any glass composition as long as it contains a predetermined amount of the first transition metal oxide and has a crystallinity of 70% or more. As the glass composition of the crystallized glass, for example, aluminosilicate glass is preferable, and lithium aluminosilicate glass is particularly preferable.

The crystallized glass of the present invention preferably contains one or more kinds selected from β-quartz and β-spodium as crystals, and it is particularly preferable that the main crystal is β-quartz. In particular, crystallized glass containing a solid solution whose main crystal is β-quartz has translucency. Therefore, when a predetermined amount of the first transition metal oxide is contained in the crystalline glass whose main crystal contains a solid solution of β-quartz, a highly designed glass article having metallic luster and translucency of the glass can be obtained. Can be done.

The crystallized glass of the present invention has a surface resistivity (logρ) of preferably 8 Ω · cm or less, more preferably 7.5 Ω · cm or less, and further preferably 7 Ω · cm or less. In this way, the charge transfer rate can be increased, and the conductivity can be easily improved.

Further, it is preferable that the crystallized glass of the present invention has a glass body and a metallic luster layer formed on the surface thereof, and the surface resistivity of the metallic luster layer is different from the surface resistivity of the glass body. Further, it is preferable that the surface resistivity of the metallic luster layer is lower than the surface resistivity of the glass body. Further, the surface resistivity of the metallic luster layer is preferably 0.5 Ω · cm or more lower, more preferably 1 Ω · cm or more lower, and further preferably 1.5 Ω · cm or more lower than the surface resistivity of the glass body. Is preferable. The larger the difference between the surface resistivity of the metallic luster layer and the surface resistivity of the glass body, the higher the performance when used as a film resistor.

Further, in the crystallized glass of the present invention, the thickness of the metallic luster layer is preferably 10 to 500 μm, 30 to 300 μm, and 50 to 100 μm. The thinner the metallic luster layer, the easier it is to manufacture precise parts. On the other hand, the thicker the metallic luster layer, the more stable the performance is when used as a film resistor.

The glass composition of the base glass of the crystallized glass of the present invention will be described in detail below. In the following description, "%" indicates mass% unless otherwise specified. Further, regarding the term "containing", it means that the component defined as "0 to" may be "0%", that is, may not be contained at all.

As described above, the crystallized glass of the present invention may have any glass composition, but for example, in terms of mass%, SiO ₂ 50 to 80%, Al ₂ O ₃ 10 to 25%, Li ₂ O 0.1 to 20%, etc. It is preferable to contain MgO + CaO + SrO + BaO + ZnO 0 to 10%. In this way, crystallized glass can be easily obtained. It is considered that the crystallized glass of the present invention develops metallic luster by concentrating transition metal ions in the glass matrix in the crystallized glass in the crystallization step. Therefore, it is important that the precursor crystalline glass can be easily made into crystallized glass.

SiO ₂ is a skeleton component of glass and is a component constituting crystals in crystallized glass. The content of SiO ₂ is preferably 50 to 80%, more preferably 55 to 73%, and even more preferably 63 to 70%. If _{the content of SiO 2} is too small, the amount of crystal precipitation is small, and it becomes difficult to obtain crystallized glass having a metallic luster. On the other hand, if the amount is too large, the meltability of the glass is lowered and molding becomes difficult.

Al ₂ O ₃ is a skeleton component of glass and is also a component constituting crystals in crystallized glass. The content of Al ₂ O ₃ is preferably 10 to 25%, more preferably 17 to 24%, and even more preferably 18 to 22.5%. If _{the content of Al 2} O ₃ is too small, the amount of crystal precipitation is small, and it becomes difficult to obtain crystallized glass having a metallic luster. On the other hand, if the amount is too large, the meltability of the glass is lowered and molding becomes difficult.

Li ₂ O has a great influence on the crystallinity of glass. Li ₂ O is a component that constitutes crystals of crystallized glass. The content of Li ₂ O is preferably 0.1 to 20%, more preferably 2 to 10%, still more preferably 3 to 5%. If _{the content of Li 2} O is too small, the amount of crystal precipitation will be small, and it will be difficult to obtain crystallized glass with metallic luster. On the other hand, if the amount is too large, the crystallinity becomes excessively strong, and it tends to be difficult to mold the glass.

MgO, CaO, SrO, BaO and ZnO is a component that dissolves in β quartz instead of Li ₂ O. It is also a component that reduces the viscosity of glass and improves meltability and moldability. The content of MgO + CaO + SrO + BaO + ZnO is preferably 0 to 10%, more preferably 0 to 5%, still more preferably 0.1 to 2%. If the content of MgO + CaO + SrO + BaO + ZnO is too large, the crystallinity tends to be excessively strong and the glass tends to be devitrified, which makes it difficult to mold the glass. In addition, the glass is easily broken. In addition, "MgO + CaO + SrO + BaO + ZnO" refers to the total amount of the contents of MgO, CaO, SrO, BaO and ZnO.

The content of each of MgO, CaO, SrO, BaO and ZnO is preferably 0 to 2%, more preferably 0 to 1.5%, and further preferably 0.1 to 1.2%. .. If the contents of each of MgO, CaO, SrO, BaO and ZnO are too large, the crystallinity tends to be excessively strong and the glass tends to be devitrified, which makes it difficult to mold the glass. In addition, the glass is easily broken.

In addition to the above components, TiO ₂ and ZrO ₂ can be contained as components of the base glass.

TiO ₂ is a nucleation component for precipitating crystals in the crystallization step. The content of TiO ₂ is preferably 0.1 to 5%, more preferably 0.1 to 4%, 0.2 to 3.5%, 0.5 to 3%, 0.8 to 2. It is 8%, 1 to 2.6%, more than 1 to 2.5%, and particularly preferably 1.2 to 2.3%. If _{the content of TiO 2} is too high, the glass tends to be devitrified and easily broken. On the other hand, if the amount is too small, crystal nuclei may not be sufficiently formed, and coarse crystals may precipitate and be damaged.

Like TiO ₂ , ZrO ₂ is a component that constitutes a crystal nucleus for precipitating crystals in the crystallization step. The content of ZrO ₂ is preferably 0.1 to 5%, more preferably 0.1 to 4%, and even more preferably 0.5 to 3%. If _{the content of ZrO 2} is too large, the glass tends to be devitrified when it is melted, and it tends to be difficult to mold the glass. On the other hand, if the amount is too small, crystal nuclei may not be sufficiently formed, and coarse crystals may precipitate and be damaged.

Further, in addition to the above components, various components can be added as long as the required properties are not impaired.

P ₂ O ₅ is a component that promotes phase separation of glass and facilitates the formation of crystal nuclei. The content of P ₂ O ₅ is preferably 0 to 5%, more preferably 0 to 3%, still more preferably 0.1 to 2%. If _{the content of P 2} O ₅ is too large, the glass tends to be excessively phase-separated in the melting step, making it difficult to obtain a glass having a desired composition and making it opaque.

Na ₂ O and K ₂ O are components that reduce the viscosity of glass and improve the melting and moldability of glass. The content of Na ₂ O is preferably 0 to 3%, more preferably 0 to 2%, and even more preferably 0.3 to 0.7%. The K ₂ O content is preferably 0 to 3%, more preferably 0 to 2%, and even more preferably 0.3 to 0.7%. If _{the content of Na 2} O or K ₂ O is too high, the glass tends to be devitrified.

B ₂ O ₃ is a component having an effect of suppressing the precipitation of β-spodium. It also has the effect of promoting the _{melting of the SiO 2} raw material in the glass melting step. The content of B ₂ O ₃ is preferably 0.05 to 1.5%, more preferably 0.1 to 1%. If _{the content of B 2} O ₃ is too small, it becomes difficult to obtain the above-mentioned effects. On the other hand, _{if the content of B 2} O ₃ is too large, the glass tends to become cloudy, and it becomes difficult to obtain a glass having a high transparency. Further, B ₂ O ₃ is concentrated in the residual glass phase by crystallization, and the viscosity of the residual glass phase is reduced. Therefore, when the crystallized glass is used at a high temperature, it is easily softened and deformed.

SnO ₂ is an effective component for clarifying glass and obtaining a homogeneous glass. The SnO ₂ content is preferably 0.1 to 2%, more preferably 0.1 to 1%, and even more preferably 0.2 to 0.8%. If _{the content of SnO 2} is too small, it becomes difficult to obtain the effect as a fining agent. On the other hand, _{if the content of SnO 2} is too large, the crystallized glass tends to be yellowish. Further, although the details of the mechanism are unknown, since SnO ₂ has a function of increasing the devitrification rate of β-spodium, devitrification is likely to occur if the amount added is too large.

_{Further, SO 2} or Cl may be added alone or in combination as a fining agent, if necessary. The total amount of these components is preferably 0.5% or less. It should be noted that Sb ₂ O _{3 is} also a clarification component and can be contained, but it is preferable that it does not contain a large environmental load.

Further, in the present invention, it is preferable that arsenic oxide and lead oxide, which have a large environmental load, are not substantially contained. In the present invention, "substantially free" means that the glass is not intentionally added, and does not completely eliminate unavoidable impurities. More objectively, it means that the content including impurities is 0.01% or less.

Further, the crystalline glass of the present invention is preferably a precursor of the above-mentioned crystallized glass, that is, glass before crystallization. The glass composition and the like of the crystalline glass are the same as those of the crystallized glass described above, and the specific preferable range is omitted from the description.

The method for producing crystallized glass of the present invention can be produced by crystallizing the above-mentioned crystalline glass. For example, it is preferable to crystallize the above-mentioned crystalline glass by subjecting it to a heat treatment at 700 to 1000 ° C. If the lower limit of the heat treatment temperature is regulated as described above, it becomes easy to obtain crystallized glass having a crystallinity of 70% or more and a metallic luster. On the other hand, if the upper limit of the heat treatment temperature is regulated as described above, only β-quartz and / or β-spodium crystals can be precipitated.

As an example of the crystallization method, the formed crystalline glass is heat-treated at, for example, 600 to 800 ° C. for 1 to 5 hours to form crystal nuclei, and then further heat-treated at 700 to 1000 ° C. for several minutes to several hours. A method of precipitating β-quartz and / or β-spodium crystals as the main crystal can be mentioned.

In the crystallized glass of the present invention, the L * value indicated by the CIE standard L * a * b * is 4 mm thick, preferably 45 or more, 50 or more, 55 or more, and particularly 60 or more. It is preferable to have. In this way, the appearance becomes bright and crystallized glass with high design can be obtained. Further, in the crystallized glass of the present invention, the b * value indicated by L * a * b * of the CIE standard is 4 mm thick, preferably 4.5 or less, 4 or less, 3 or less, 2 or less, particularly 1.4. The following is preferable. In this way, yellow coloring is reduced and the design is excellent. Further, the transmittance at 430 nm is 4 mm thick, preferably 7% or more, 10% or more, 15% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more. It is preferably 80% or more, 82.5% or more, and particularly preferably 83% or more. In this way, since the crystallized glass has translucency, it is possible to obtain a crystallized glass having a high design.

Further, the crystallized glass of the present invention has a coefficient of thermal expansion in the temperature range of 30 to 380 ° C., preferably −2.5 × ^{10-7 to} 2.5 × ^10-7 / ° C., more preferably. -1.5 is × ^{10 -7} /℃~1.5×10 ^-7 / ℃. If the coefficient of thermal expansion becomes too small or too large, the risk of breakage tends to increase.

The crystallized glass of the present invention may be subjected to processing such as cutting, polishing, bending, and strengthening. However, it is preferable not to polish the portion requiring a metallic luster surface. Further, when there is a risk that the metallic luster is impaired, it is preferable not to perform strengthening treatment such as thermal strengthening or chemical strengthening.

Hereinafter, the present invention will be described in detail with reference to Examples, but it is clear that the present invention is not limited to these Examples.

Tables 1 and 2 show the base glass and Examples (No. 1 to 8) and Comparative Examples (No. 9 to 13) of the present invention.

Each sample was prepared as follows. First, a base glass batch was prepared so as to have the composition shown in Table 1. Further, each batch was prepared by adding the transition metal oxides shown in Table 2 to the base glass batch in the mass% of the outer cover so as to have the ratio shown in Table 2. Next, each batch was melted at 1550 to 1650 ° C. for 20 hours using a platinum crucible, two spacers with a thickness of 5 mm were placed on a carbon plate, and molten glass was poured between the spacers and uniformed with a roller. It was formed into a plate with the thickness of. Further, the plate-shaped sample was put into an electric furnace held at 650 to 750 ° C., held for 30 minutes, slowly cooled to 300 ° C. for about 6 hours, and then allowed to cool to room temperature to prepare crystalline glass.

Then, the obtained crystalline glass was cut into a plate having a size of about 30 × 30 mm and polished to obtain a mirror-polished surface.

Next, crystallized glass having a size of about 30 × 30 mm was heat-treated in an electric furnace according to the following STEP to obtain crystallized glass.
STEP1: Raise the temperature from room temperature to 660 to 700 ° C and hold for 20 minutes to 5 hours STEP2: Raise the temperature from 660 to 700 ° C to 870 to 910 ° C and hold for 10 minutes to 2 hours STEP3: From 870 to 910 ° C to room temperature It takes about 10 hours to cool down to room temperature

For each sample obtained as described above, the crystals in the crystallized glass were identified and the crystallinity was measured by appearance observation and XRD.

The presence or absence of the metallic luster layer was visually determined, and the constituent elements of the metallic luster layer were identified by EDX (S-3400N manufactured by Hitachi).

Further, the surface resistivity of the glass is a double ring method having an internal electrode diameter of 50 mm and an external electrode diameter of 57.2 mm according to JIS6911 (1995), an applied voltage of 1000 V, a resistance correction coefficient of 100, and a measurement temperature of 25 ° C. The measurement was performed in an air atmosphere with a measurement humidity of 35%. The measurement was performed 5 times, and the arithmetic mean value was adopted. After measuring the resistance of the metallic luster layer, the surface was polished by 500 to 1000 μm to completely remove the metallic luster layer to expose the crystallized glass body to the surface, and the surface resistivity of the surface of the glass body was measured. For the glass on which the metallic luster layer was not formed, the surface resistivity of the glass before polishing and the surface resistivity of the glass after polishing were measured, respectively.

In FIG. 1, the sample No. The external photograph of the crystallized glass of No. 4 is shown, and FIG. 2 shows the external photograph of the crystalline glass before crystallization. From FIG. 2, it can be seen that the crystalline glass before crystallization has translucency as a whole. Further, from FIG. 1, it can be seen that the surface of the crystallized glass after crystallization has a metallic luster layer. Further, when the crystallized glass body of FIG. 1 was confirmed by polishing and removing the metallic luster layer, the glass body had translucency.

Further, as is clear from Table 2, the sample No. which is an example. Nos. 1 to 8 had a metallic luster on the surface layer of the crystallized glass. Furthermore, the sample No. In No. 2, the surface resistivity of the metallic luster layer was lower than the surface resistivity of the crystallized glass body from which the metallic luster layer was removed.

The crystallized glass of the present invention can be used as a mirror for optical parts and a top plate for a cooker having excellent design. Further, since the surface resistance of the metal gloss layer of the crystallized glass of the present invention is lower than the surface resistance inside the crystallized glass from which the metal gloss layer has been removed, the crystallized glass of the present invention can also be used as a film resistor. It is available.

Claims (12)

A crystallized glass having a crystallinity of 70% or more, containing 1 to 10% of the first transition metal oxide excluding Group 4 in mass% of the outer shell. The crystallized glass according to claim 1, wherein the glass is an aluminosilicate glass. The invention according to claim 1 or 2, wherein the mass% is SiO ₂ 50 to 80%, Al ₂ O ₃ 10 to 25%, Li ₂ O 0.1 to 20%, MgO + CaO + SrO + BaO + ZnO 0 to 10%. Crystallized glass. The crystallized glass according to any one of claims 1 to 3, which contains TiO ₂ 0.1 to 5% and ZrO _{2 0.1 to 5% by mass.} The crystallized glass according to any one of claims 1 to 4, wherein the first transition metal oxide _{is one or more selected from Fe 2} O _{3, CoO, NiO, and CuO.} The crystallized glass according to any one of claims 1 to 5, wherein the main crystal is β-quartz. The crystallized glass according to any one of claims 1 to 6, which has a metallic luster. The crystallized glass according to any one of claims 1 to 7, wherein the surface resistivity is 8 Ω · cm or less. Any of claims 1 to 8, wherein the crystallized glass has a glass body and a metallic luster layer formed on the surface thereof, and the surface resistivity of the metallic luster layer is different from the surface resistivity of the glass body. Crystallized glass described in Crab. The crystallized glass according to any one of claims 1 to 9, wherein the surface resistivity of the metallic luster layer is 0.5 Ω · cm or more lower than the surface resistivity of the glass body. A crystalline glass that is a precursor of the crystallized glass according to any one of claims 1 to 10 and contains more than 1 to 10% of the first transition metal oxide excluding Group 4 in mass% of the outer cover. .. A method for producing a crystallized glass according to claim 11, wherein the crystalline glass is crystallized by subjecting it to a heat treatment at 700 to 1000 ° C.

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