JP2010202434A - Colored crystallized glass article and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored crystallized glass article suitable for building materials which is made by using one kind of crystalline glass material, does not have white spot patterns of crystallized particles and achieves a uniform color tone deeper than that of usual articles by using the same amount of a coloring agent as usual, and a method for manufacturing the same. <P>SOLUTION: The colored crystallized glass article 10 is composed of a plurality of glass small regions S fused mutually in which acicular crystals N deposit from the interface K between glass small regions toward the inside and 0.01-3 mass% of a coloring agent consisting of a colored metal oxide from the interface K toward the inside is contained, and has a visible light average transmittance in thickness of 1 mm of 15% or more. The manufacturing method is that crystalline glass small bodies having an average transmittance in thickness of 1 mm of 35% or more after carrying out fusion unification and crystal deposition are mixed with 0.01-3 mass% of a coloring agent of the metal oxide and accumulated in a refractory container, and then heat-treated at a temperature higher than the softening point. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a colored crystallized glass article suitable as a building interior material and a decoration material, and a method for producing the same.

  In recent years, as a trend of glass building materials, in addition to the color based on white, a wide variety of dark building materials have attracted attention. As a conventional coloring method for crystallized glass articles, a dough body coloring method in which a metal oxide is added during glass melting has been mainly implemented. On the other hand, in order to cope with a small variety of products, a method is used in which a material glass that becomes white after crystallization is pulverized to a small particle size and mixed with an inorganic pigment and sintered. For example, Patent Document 1 discloses a patterned crystallized glass in which each portion has a different transmittance depending on a difference in crystal state, and a pattern appears based on the transmittance difference. When this patterned crystallized glass is produced, the patterned crystallized glass is colored by adding a colored oxide to the raw material of the glass body or by attaching an inorganic pigment powder to the surface of the glass body. Is disclosed.

  Further, Patent Document 2 discloses a conventional crystalline glass body having a high degree of crystallinity and low translucency, and a crushed product of translucent crystallized glass having an average transmittance of 35% or more at a thickness of 1 mm. A method for producing patterned crystallized glass in which a crystallized glass with a natural stone pattern having a translucent part is obtained by mixing a plurality of each of the above and accumulating them in a refractory mold and heat-treating them. Is disclosed. Further, it is disclosed that the patterned crystallized glass is colored with a colored oxide or an inorganic pigment powder.

  Furthermore, in Patent Document 3, a plurality of crystallized glass bodies that become translucent crystallized glass having an average transmittance of 35% or more at a thickness of 1 mm after heat treatment and a plurality of crushed crystallized glass are mixed. Then, a method for producing a crystallized glass with a pattern from which a crystallized glass with a natural stone pattern having a translucent part is obtained by being accumulated in a refractory mold and heat-treated is disclosed. Further, it is disclosed that the patterned crystallized glass is colored with a colored oxide or an inorganic pigment powder.

  Patent Document 4 discloses a method for manufacturing an artificial stone material that sinters a colored frit formed by heating and melting a raw material composition composed of a devitrifying substance, a colorant, and glass. Further, in Patent Document 5, an inorganic pigment is attached to and accumulated on the surfaces of a plurality of glass bodies on which acicular crystals are precipitated from the surface toward the inside by heat treatment at a temperature higher than the softening point. In addition, a method for producing colored crystallized glass is disclosed in which heat treatment is performed at a high temperature so that glass bodies are fused and integrated with each other and acicular crystals are precipitated from the surface toward the inside.

JP-A-5-163042 JP-A-5-163035 Japanese Patent Laid-Open No. 5-163033 JP-A-62-158134 JP-A-1-157432

  However, in the conventional crystallized glass articles described in Patent Documents 1 to 3, since two or more kinds of glass materials are used or a glass material having high crystallinity is used, the crystal shown in the photograph of FIG. A white spot 1b of crystallized particles always exists on the design surface 1a of the vitrified glass article 1 and does not have a uniform single color tone. Further, when the design surface 1a of the crystallized glass article 1 is polished, the color becomes light like the design surface 2a of the crystallized glass article 2 shown in the photograph of FIG. That is, there are problems such as an unfavorable color tone in appearance such as an increase in L * value of lightness in L * a * b * color system chromaticity. In addition, in the conventional method for producing a crystallized glass article, from the profit side, a large amount of material glass must be produced at a time. is there.

  Moreover, in the conventional crystallized glass article described in Patent Document 4, there is a problem of uneven color because the devitrifying substance precipitates colloidal crystals of fluoride. Moreover, in the conventional crystallized glass article described in Patent Document 5, white spots are generated and there is a problem in appearance.

  In view of the above problems, the subject of the present invention is to use a crystalline glass material of one kind of material, eliminate the spotted pattern of white crystallized particles, and with the same colorant amount as the conventional product, it is darker than the conventional product. Colored crystallization that can achieve a uniform monochromatic color tone, and has less increase in lightness L * value than that of the conventional product and less variation in lightness L * value than the conventional product after polishing. It is to provide a glass article and a method for manufacturing the same.

  The colored crystallized glass article according to the present invention is composed of crystallized glass in which a plurality of small glass regions are fused together, and needle-like crystals are precipitated inward from the interface between the small glass regions. It is characterized by containing 0.01 to 3% by mass of a colorant made of a metal oxide and having an average visible light transmittance of 15% or more at a thickness of 1 mm.

  When the average transmittance in the range of 400 to 700 nm, which is a visible light wavelength at a thickness of 1 mm, of the colored crystallized glass article is less than 15%, the colorant composed of a metal oxide that exists in the vicinity of the interface of the small glass region. Color development does not sufficiently appear on the design surface, and only the colorant near the surface contributes to the appearance, resulting in a light color development. As the colored crystallized glass constituting the colored crystallized glass article of the present invention, the average transmittance in the wavelength range of 400 to 700 nm at a thickness of 1 mm is 15% or more near the interface of the small glass region. This is important for better coloring of the many colorants present. Further, in order to realize a more vivid appearance by deepening the color development, it is preferable that the average visible light transmittance at a thickness of 1 mm is 20% or more.

  Moreover, in the crystallized glass article for building of the present invention, as the crystallized glass in which needle-like crystals are precipitated from the interface between the small glass regions toward the inside, it has the strength required as a building material, and A crystallized glass on which β-wollastonite is precipitated is preferable in that it has a marble-like appearance. Moreover, as the crystallized glass in the present invention, if the visible light average transmittance of the architectural crystallized glass article is 15% or more, one type of crystallized glass material that can easily suppress the manufacturing cost is used. Not limited to this, two or more kinds of translucent crystallized glass materials may be used.

  In the present invention, if the size of the small glass region constituting the colored crystallized glass article is less than 0.1 mm, there is a high probability of foreign matter being mixed during glass crushing, and the color tends to become dirty. On the other hand, when the size of the small glass region exceeds 3.0 mm, color unevenness tends to occur on the surface after crystallization. Further, if the design surface is an unpolished surface, the surface roughness tends to exceed 0.7 μm and the surface is not smooth. As a dimension of the glass small area | region which comprises the colored crystallized glass article of this invention, it is preferable that it is 0.1-3.0 mm.

In addition, in the colored crystallized glass article of the present invention, the inclusion of 0.01 to 3% by mass of a colorant made of a metal oxide at the interface between small glass regions means Co ₂ O _{3 that} functions as a colorant. , NiO, Fe ₂ O ₃ , MnO, SnO ₂ , ZrO _2, etc. It means that 0.01 to 3% by mass is contained with respect to the mass of the colored crystallized glass article toward the glass part. If the colorant is less than 0.01% by mass, sufficient color development cannot be obtained. On the other hand, if it exceeds 3% by mass, the coloring cost increases, and the color development is not good for the cost, which is uneconomical. In the colored crystallized glass article of the present invention, it is important to contain 0.01 to 3% by mass of a colorant made of a metal oxide from the interface between the small glass regions toward the inside of the small region.

Further, the colored crystallized glass article of the present invention, crystallized glass, _SiO 2 57 to _62% by _{mass%, Al 2 O 3 6~7%} , CaO 9~11%, ZnO 6~8%, BaO 10 _{~12%, K 2 O 2~3%} , Na 2 O 2~4% B 2 O 3 0.2~0.4%, those containing a composition of _Sb 2 O 3 _0.2~0.5% It is characterized by being.

If SiO ₂ is higher than 62%, the melting temperature of the glass increases, and the viscosity increases, so that the fluidity during heat treatment tends to deteriorate. On the other hand, if it is less than 57%, the devitrification property at the time of molding tends to be strong. The content of SiO ₂ is preferably 57 to 62%.

When the Al ₂ O ₃ content is more than 7%, the solubility of the glass is deteriorated and different crystals (for example, anorthite) are precipitated, and the fluidity during heat treatment tends to be deteriorated. On the other hand, Al ₂ O ₃ is less devitrification property becomes stronger than 6% chemical durability tends to decrease. The content of Al ₂ O ₃ is preferably 6 to 7%.

  If the CaO content is more than 11%, the devitrification tends to be strong and the molding tends to be difficult, and the amount of β-wollastonite crystals deposited becomes too large, making it difficult to obtain the desired surface smoothness. On the other hand, if the CaO content is less than 9%, the precipitation amount of β-wollastonite becomes too small and the mechanical strength tends to decrease. The CaO content is preferably 9 to 11%.

  ZnO is a component added to promote the fluidity of the glass during crystallization. When ZnO in the crystallized glass is more than 8%, β-wollastonite crystals tend to be difficult to precipitate. The ZnO content is preferably 6-8%.

  BaO is also a component showing the effect of promoting the fluidity of glass similar to ZnO. When the BaO of the crystallized glass is less than 10%, the fluidity is deteriorated and the surface smoothness tends not to be obtained. On the other hand, when BaO is more than 12%, the precipitation amount of β-wollastonite crystal tends to decrease. The BaO content is preferably 10 to 12%.

When Na ₂ O is more than 4%, the scientific durability is deteriorated and the expansion coefficient tends to be high, which is not preferable. If it is less than 2%, the viscosity of the glass increases and the solubility and fluidity tend to deteriorate. The content of Na ₂ O is preferably 2 to 4%.

When K ₂ O is more than 3%, the chemical durability tends to decrease. The K ₂ O content is preferably 2-3%.

When B ₂ O ₃ is less than 0.2%, the fluidity of the glass is deteriorated, and the surface smoothness tends not to be obtained. On the other hand, if the amount of B ₂ O ₃ is more than 0.4%, different types of crystals are precipitated and the desired characteristics tend not to be obtained. The content of B ₂ O ₃ is preferably 0.2 to 0.4%.

Sb ₂ O ₃ is a refining agent, and if its content is less than 0.2%, the solubility of the glass tends to decrease and the quality of the glass tends to deteriorate. The content of Sb ₂ O ₃ is preferably 0.2 to 0.5%.

In the colored crystallized glass article of the present invention, the colorant is made of an inorganic pigment containing any one of transition metal oxides Co ₂ O ₃ , NiO, Fe ₂ O ₃ , MnO, SnO ₂ , and ZrO _2. It is characterized by.

In the present invention, it is possible that the colorant is made of an inorganic pigment containing any one of transition metal oxides Co ₂ O ₃ , NiO, Fe ₂ O ₃ , MnO, SnO ₂ , and ZrO ₂ to inhibit glass fluidity. It is preferable in that it does not. When this colorant is Co ₂ O ₃ , it exhibits a blue color, NiO exhibits an ocher color, Fe ₂ O ₃ exhibits a reddish brown color, MoO ₃ exhibits a milky white color, and SnO ₂ It exhibits a pink color, and in the case of ZrO ₂ , it exhibits a white color. Moreover, the crystallized glass articles which exhibit various colors can be obtained by combining these colorants. Furthermore, when used in combination with other oxide colorants, many colors are possible.

  In the method for producing a colored crystallized glass article of the present invention, a plurality of crystalline glass bodies that precipitate needle-like crystals from the surface toward the inside by heat treatment at a temperature higher than the softening point are accumulated in a refractory container. By maintaining the temperature higher than the softening point by heat treatment, the crystalline crystallized glass article that precipitates acicular crystals from the surface toward the inside while fusing and integrating the crystalline glass bodies with each other. A method for manufacturing, wherein the crystalline glass body has a mean visible light transmittance of 35% or more at a thickness of 1 mm after being fused and integrated to form a crystal, and the crystalline glass body In addition, 0.01 to 3% by mass of a metal oxide colorant is mixed and accumulated in the refractory container.

  When the visible light average transmittance at a thickness of 1 mm after the crystalline glass bodies are fused and integrated to form a crystal is less than 35%, the visible light average transmittance at a thickness of 1 mm of the colored crystallized glass article is Less than 15%, the coloring of the colorant located in the vicinity of the back side interface of the small glass region on the design surface of the colored crystallized glass article is obstructed by the small glass region made of crystallized glass with low translucency. The small glass area becomes white and the lightness L * value becomes an undesirably large value. In the method for producing a colored crystallized glass article of the present invention, it is colored that the visible light average transmittance at a thickness of 1 mm after the crystalline glass body is fused and integrated to form a crystal is 35% or more. This is important for reducing the increase in the lightness L * value of the crystallized glass article and reducing the variation in the lightness L * value.

  Moreover, the manufacturing method of the colored crystallized glass article of the present invention is characterized by using a crystalline glass body having a particle size of 0.1 to 3.0 mm.

  When the particle size of the crystalline glass particles for forming the colored crystallized glass article is less than 0.1 mm, there is a high probability that foreign matter is mixed during the glass crushing, and the color tends to become dirty. On the other hand, when the particle size of the crystalline glass body exceeds 3.0 mm, color unevenness tends to occur on the design surface after crystallization. Further, if the design surface is an unpolished surface, the surface roughness tends to exceed 0.7 μm and the surface is not smooth. The crystalline glass body for forming the colored crystallized glass article of the present invention preferably has a particle size of 0.1 to 3.0 mm, more preferably for improving the uniformity of color development. 0.3 to 2.0 mm.

  The colored crystallized glass article of the present invention is composed of crystallized glass in which a plurality of small glass regions are fused to each other and needle-like crystals are precipitated inward from the interface between the small glass regions. 1% crystalline glass containing a coloring agent composed of a metal oxide and having an average visible light transmittance of 15% or more at a thickness of 1 mm, which can suppress production costs. By using only the material, the spotted pattern of white crystallized particles can be eliminated, and the same amount of colorant as in the conventional method can be used to produce a darker color and a uniform color tone than the conventional product.

  Further, according to the present invention, in the colored crystallized glass article after being polished, the increase in the L * value of the brightness is less than that in the conventional method, and the variation in the brightness L * value is made smaller than that in the conventional product. Can do.

  Furthermore, since the colored crystallized glass article of the present invention has a glass small region size of 0.1 to 3.0 mm, the design surface after the heat treatment can be uniformly colored with no color unevenness. Become. Further, even if the design surface is an unpolished surface, the surface roughness Ra value is 0.7 μm or less.

The crystallized glass constituting the colored crystallized glass article of the present invention is composed of 57 to 62% SiO ₂ , 6 to 7% Al ₂ O ₃ , 9 to 11% CaO, 6 to 8% ZnO, and BaO by mass%. _{10~12%, K 2 O 2~3%} , Na 2 O 2~4% B 2 O 3 0.2~0.4, those containing a composition of Sb ₂ O 3 0.2~0.5% Therefore, even when 0.01 to 3% by mass of a colorant made of a metal oxide is contained, the average visible light transmittance at a thickness of 1 mm is 15% or more, and needle-like crystals are directed from the interface toward the inside. It is possible to easily realize a colored crystallized glass article having excellent color developability, in which a plurality of small glass regions where the selenium is deposited are fused to each other.

In the colored crystallized glass article of the present invention, the colorant is composed of an inorganic pigment containing any one of transition metal oxides Co ₂ O ₃ , NiO, Fe ₂ O ₃ , MnO, SnO ₂ , and ZrO ₂ . Unlike pigments made of ceramics, etc., it is excellent in melting to the amorphous glass part constituting the crystallized glass, and can realize a vivid colored colored crystallized glass article while maintaining appropriate translucency it can.

  In the method for producing a colored crystallized glass article of the present invention, a plurality of crystalline glass bodies that precipitate needle-like crystals from the surface toward the inside by heat treatment at a temperature higher than the softening point are accumulated in a refractory container. By maintaining the temperature higher than the softening point by heat treatment, the crystalline crystallized glass article that precipitates acicular crystals from the surface toward the inside while fusing and integrating the crystalline glass bodies with each other. A method for manufacturing, wherein the crystalline glass body has a mean visible light transmittance of 35% or more at a thickness of 1 mm after being fused and integrated to form a crystal, and the crystalline glass body In addition, 0.01 to 3% by mass of a colorant made of a metal oxide is mixed and accumulated in the refractory container, so that the colored crystallized glass article of the present invention is efficiently manufactured while maintaining high quality. be able to.

  Moreover, since the manufacturing method of the colored crystallized glass article of the present invention uses a crystalline glass body having a particle size of 0.1 to 3.0 mm, the average visible light transmittance at a thickness of 1 mm is 15% or more, The colored crystallization of the present invention, which is excellent in both strength and color developability formed by fusing together a plurality of small glass regions having a size of 0.1 to 3.0 mm in which needle-like crystals are deposited from the interface toward the inside. Glass articles can be easily manufactured.

It is explanatory drawing of the colored crystallized glass article of this invention, (a) is a photograph of the design surface of an unpolished product, (b) is a photograph of the design surface of an abrasive product, (c) is a small glass fused to each other. Explanatory drawing of an area | region. The graph which shows the transmittance | permeability of the visible region of the colored crystallized glass article of this invention and the conventional colored crystallized glass article. It is explanatory drawing of the conventional colored crystallized glass article, Comprising: (a) is a photograph of the design surface of an unpolished product, (b) is a photograph of the design surface of an abrasive product.

  The colored crystallized glass article of the present invention and the production method thereof will be described below with reference to examples.

The colored crystallized glass article 10 for building materials shown in the photograph of FIG. 1A of Example 1 has dimensions of 900 mm in length × 600 mm in width × 15 mm in thickness, and the photograph in FIG. An abrasive sample 12 obtained by polishing the surface of a vitrified glass article 10 is shown. As shown in the schematic diagram in which the design surface 12a of the abrasive article 12 is enlarged in FIG. 1 (c), the colored crystallized glass article 10 and the abrasive article sample 12 are composed of needle-like crystals from the interface K toward the inside as main crystals. It is made of crystallized glass on which β-wollastonite N is deposited, and is made of an aggregate in which a large number of small glass regions S having a dimension D of 0.5 to 1.8 mm are fused together. The colored crystallized glass article 10 and the abrasive sample 12 are heat-treated at a temperature higher than the softening point (about 800 ° C.), so that the degree of crystallinity is about 15%, and the interface K between the small glass regions S. To 1% by mass of an inorganic pigment mainly composed of Co ₂ O ₃ , ZnO, and Al ₂ O ₃ that develops a blue color.

  Next, the manufacturing method of the colored crystallized glass article 10 will be described.

First, in terms of mass%, SiO ₂ 60%, Al ₂ O ₃ 6.5%, B ₂ O ₃ 0.5%, CaO 10%, ZnO 6.5%, BaO 11%, Na ₂ O 3%, K ₂ A glass raw material mixture prepared to have a composition of O 2% and Sb ₂ O ₃ 0.5% is melted at 1400 to 1500 ° C. for 16 hours. Next, the molten glass is dropped into water and crushed, and then the obtained crushed material is dried and classified to produce crystalline glass coarse particles having a diameter of 1 to 5 mm. When the crystalline glass coarse particles are heat-treated at a temperature higher than the softening point (about 800 ° C.), acicular β-wollastonite is precipitated as a main crystal from the surface while being softened and deformed, and the crystallinity is about 15%. Thus, the average transmittance at a thickness of 1 mm is 55.50%. (See the uncolored sample in Table 1 and FIG. 2).

  Next, the crystalline glass coarse particles are finely pulverized and classified with an alumina roll crusher to produce a crystalline glass body having a diameter of 0.5 mm to 1.8 mm.

Next, the crystalline glass body is weighed so as to have a thickness of 15 mm after firing, and an inorganic pigment that develops blue color as an inorganic pigment, is mainly composed of Co ₂ O ₃ , ZnO, and Al ₂ O _3. After the pigment was mixed uniformly by 1% by mass and accumulated in a mold made of mullite coated with alumina powder, it was heat-treated at 1090 ° C. for 2 hours. A colored crystallized glass article 10 having a smooth design surface 10a having a surface roughness Ra value of 0.7 μm or less was obtained.

  The sintered colored crystallized glass article 10 was polished by a flat polishing machine to obtain a polished 12 of colored crystallized glass article having a gloss.

Further, as the coloring crystallized glass article of the present embodiment 2, the amorphous glass portion inside from the interface between the glass small regions, an inorganic pigment composed mainly of SnO ₂ which develops a brown containing 1 wt% A colored crystallized glass article was produced.

  As a comparative example with respect to these Examples 1 and 2, the conventional colored crystallized glass article shown in FIG. 3 using a crystalline glass body of the same particle size made of a crystalline glass that becomes a crystallized glass with low translucency. 1 was produced.

  For each of the samples of Examples 1 and 2 and the comparative example having a thickness of 1 mm, FIG. 2 shows a graph of the transmittance in the wavelength range of 300 to 800 nm, and the measured value of the average transmittance in the wavelength range of 400 to 700 nm. Table 1 shows. Further, the lightness L * value by the four-point colorimetric average and the variation R of the lightness L * value of the colored crystallized glass articles 10 and 12 of Example 1 and the fired and polished products of the conventional colored crystallized glass articles Are shown in Table 1.

  As shown in Table 1, the uncolored crystallized glass article using only the crystalline glass body has a 1 mm-thick visible light average transmittance of 55.5%, and the crystalline glass body is colored. The colored crystallized glass article 10 of Example 1 in which the design surface 10a of FIG. 1 (a) mixed with an agent and colored in blue is an unpolished fired surface has an average visible light transmittance of 21 at a thickness of 1 mm. As a colored product, it had a high translucency (see FIG. 2) that was not in the past. This colored crystallized glass article 10 has a smooth design surface 10a having a lightness L * of 28.4, a lightness L * variation R of 0.7, and a surface roughness Ra value of 0.7 μm or less. Met. Further, the sample of the polished product 12 having the design surface 12a shown in FIG. 1B as the polished surface has the same pigment concentration as the conventional product, the lightness L * is 30.9 and the color is dark, and the lightness L * value varies. R was 1.1, which was smaller than the conventional product. In addition, the polished product sample 12 is a dark colored crystallized glass article that has no white spots on the design surface 12a, exhibits a uniform blue color, and is close to the cloth body coloring method.

  The colored crystallized glass article of Example 2 has an average visible light transmittance of 20.57% at a thickness of 1 mm, excellent translucency (see FIG. 2), and is dark at the same pigment concentration as the conventional product. It was bright and had a uniform brown color.

  On the other hand, the conventional colored crystallized glass article 1 in which the design surface 1a colored in blue shown in the photograph of FIG. 3 (a) of the comparative example is an unpolished fired surface has a visible light average transmittance at a thickness of 1 mm. Was 9.42%, which was poor in translucency (see FIG. 2), and color development inside the article was difficult to appear on the surface. This colored crystallized glass article 1 had a lightness L * of 42.7 and a lightness variation R = 1.7, and had a pattern of white spots 1b of white crystallized particles. Further, the sample of the polished product 2 of the conventional colored crystallized glass article in which the design surface 2a shown in the photograph of FIG. 3B is a polished surface has a lightness L * of 47.0 and a lightness L * variation R of 7. 0.0 and color unevenness were very large.

  The size of the small glass region of the colored crystallized glass article of the present invention was measured with a tool microscope equipped with a slide table with a micrometer head. Moreover, the measurement of the visible light average transmittance | permeability of the colored crystallized glass article of this invention sliced a colored crystallized glass article, produced the sample of 20x20x1mm optically polished, and manufactured by Shimadzu Corporation Using a photometer UV2500PC, the transmittance was measured, and the average value in the range of 400 to 700 nm of the visible light wavelength was calculated. Moreover, the amount of crystal precipitation was determined by the X-ray diffraction intensity by three-time integration measurement using a thin film X-ray diffractometer manufactured by Rigaku Corporation. Furthermore, the lightness L * value in the L * a * b * color system chromaticity of the colored crystallized glass article is measured using a colorimetric color difference meter X-RITE manufactured by Nippon Denshoku Industries Co., Ltd. The brightness L * value by the color average and the variation R of the L * value were measured. The particle size of the crystalline glass bodies was classified with a standard sieve.

  Although the present invention is directed to colored crystallized glass articles, the technical idea is applicable to transparent glass, translucent ceramics, transparent plastics, and the like.

1, 10 Colored crystallized glass article (unpolished fired product)
1a, 10a, 2a, 12a Design surface 1b White spots 2, 12 Polished product sample of colored crystallized glass article D Size of small glass region K Interface between small glass regions N β-wollastonite (needle crystals)
S glass small area

Claims (6)

  A plurality of small glass regions are fused together, and are composed of crystallized glass in which needle-like crystals are precipitated from the interface between the small glass regions toward the inside. A colored crystallized glass article containing 0.01 to 3% by mass and having an average visible light transmittance of 15% or more at a thickness of 1 mm.   The colored crystallized glass article according to claim 1, wherein the size of the small glass region is 0.1 to 3.0 mm. Crystallized glass, _SiO 2 57 to _62% by _{mass%, Al 2 O 3 6~7%} , CaO 9~11%, ZnO 6~8%, BaO 10~12%, K 2 O 2~3%, _{Na 2 O 2~4% B 2 O} 3 0.2~0.4%, according to claim 1 or claims, characterized in that those containing the composition of _Sb 2 O 3 _0.2~0.5% Item 3. A colored crystallized glass article according to Item 2. _{Colorant, Co} 2 _O 3, NiO of transition metal _oxides, Fe 2 O _{3, MnO,} claim 1, characterized in that an inorganic pigment comprising any of SnO 2, ZrO ₂ of claim 3 The colored crystallized glass article according to any one of the above. In a refractory container, a plurality of crystalline glass bodies that precipitate needle-like crystals from the surface toward the inside by heat treatment at a temperature higher than the softening point are accumulated and heat-treated to maintain the temperature higher than the softening point. A method for producing a colored crystallized glass article in which acicular crystals are precipitated from the surface toward the inside while fusing and integrating the crystalline glass bodies together,
The crystalline glass body has an average visible light transmittance of 35% or more at a thickness of 1 mm after being fused and integrated to form a crystal, and the crystalline glass body is made of metal oxide. A method for producing a colored crystallized glass article, wherein 0.01 to 3% by mass of a colorant is mixed and accumulated in the refractory container.   The method for producing a colored crystallized glass article according to claim 5, wherein a crystalline glass body having a particle size of 0.1 to 3.0 mm is used.