JP4877646B2 - Crystallized glass article and method for producing the same - Google Patents

Description

  The present invention relates to a crystallized glass article that can be used for a building exterior material, interior material, and decorative material, and a method for producing the same.

  Crystallized glass products have excellent characteristics such as chemical durability and mechanical strength, and pursue a design that has a new and unique appearance that is different from stones, artificial stones, ceramic plates, tiles, colored glass, etc. Various proposals have been made.

  In recent years, building materials having various appearances have been developed with the diversification of buildings, and not only building materials made of crystallized glass but also buildings using various light-emitting substances shown in Patent Documents 1 to 5 below. Glass articles have also been developed.

For example, Patent Document 1 discloses a crystallized glass article to which Eu ₂ O ₃ and Sm ₂ O ₃ having a fluorescent action are added. Patent Document 2 discloses a crystallized glass article for dental material obtained by crystallizing fluorescent calcium phosphate glass that emits fluorescence, and a method for producing the same.

Further, Patent Document 3 discloses an antibacterial product having a titanium oxide-based photocatalyst layer and a phosphorescent material layer made of crystallized glass, and Patent Document 4 discloses a waste glass particle and a phosphorescent material made of acicular crystals. There is a disclosure relating to a porous glass molded body integrated by covering with precipitated crystallized glass and a method for producing the same, and Patent Document 5 laminates a large decorative plate made of crystallized glass and a transparent glass plate, and provides an intermediate adhesive layer. A decorative panel using phosphorescent pigments and glazes and a method for producing the same are disclosed.
JP-A-1-52633 Japanese Patent Laid-Open No. 4-16525 Japanese Patent Laid-Open No. 11-12114 JP 2004-175603 A JP 2004-292220 A

  However, there is a demand for a material that maintains mechanical strength, chemical durability, and thermal durability and exhibits a new appearance design that has never been seen before.

  Patent Documents 1 and 2 have a problem in that since the fluorescent material is exposed on the surface, light is not emitted due to oxidation or contamination of the fluorescent material at the light emitting site.

  In Patent Document 3, the thickness of the titanium oxide photocatalyst layer that achieves antifouling performance is as thin as less than 1 μm, the appearance itself is the same as the appearance of the phosphorescent material layer, and there is no sense of depth. Have no at all.

  Patent Document 4 uses a light-emitting material, but uses opaque powder particles such as metal, and waste glass cullet, and its appearance is poorly transparent. Instead of paving stones such as pavement interlocking blocks Can be used, but there is a problem in that it is not suitable as a decorative material such as a wall material. Moreover, in patent document 5, since the decorative panel which formed the roasting pattern in the intermediate | middle adhesive layer of large-sized decorative boards, such as a see-through | pervious glass plate and crystallized glass, has a feeling of depth by transparent glass, but is because of an adhesion structure. There are problems in terms of breakage due to differences in expansion coefficients and man-hours during production.

  The present invention pays attention to the above circumstances, maintains a characteristic necessary for building materials, and uses a light-emitting substance having a higher-grade appearance than a conventional crystallized glass article, and a novel crystallized glass article and its manufacture It is an object to provide a method.

  A crystallized glass article according to the present invention is a crystallized crystal having a light emitting layer made of crystallized glass on which a light emitting material is disposed, and fused to at least one surface of the light emitting layer, and the amount of precipitated crystals is 5 to 50% by mass. It has a translucent layer made of glass and having an average visible light transmittance of 5 to 30%, and the translucent layer is arranged on the design surface side.

In the crystallized glass article of the present invention, as the light-emitting layer made of crystallized glass, for example, one in which needle-like crystals precipitate from the surface toward the inside while being softened and deformed is suitable. ℃ even at a firing temperature in excess of a usable unless lose luminescent, Eu ²⁺ to SrAl ₂ O _4, and phosphorescent material doped with Dy ^3+, Cu ⁺ in ZnS, fluorescent material or the like doped with Al ³⁺ Is suitable. In order to suppress foaming and maintain surface smoothness and strength properties, the amount of precipitated crystals in the crystallized glass of the light emitting layer is more preferably 10 to 40% by mass.

  In addition, as the light-transmitting layer in the present invention, for example, a kind of glass body made of crystalline glass is subjected to a heat treatment at a temperature higher than the softening point, so that the needle-like shape from the surface toward the inside while being softened and deformed. Crystals are precipitated and the amount of precipitated crystals is 5 to 50% by mass. If the amount of precipitated crystals is less than 5% by mass, the vitreous material is large, so that the viscosity at the time of firing becomes too low and not only a lot of foam is generated on the surface but also the mechanical strength is extremely lowered. On the other hand, if the amount of precipitated crystals exceeds 50% by mass, the vitreous properties are reduced, the viscosity during firing becomes too high, the surface smoothness becomes difficult to obtain, and the desired reaction layer is not formed, and amorphous glass is not formed. Adhesiveness with the layer becomes insufficient. On the other hand, if the amount of precipitated crystals exceeds 50% by mass, the vitreous properties are reduced and the viscosity becomes too high, so that the processing temperature for bending is too high.

  Furthermore, as the translucency of the translucent layer, when the visible light transmittance is less than 5%, the light from the light emitting layer cannot be sufficiently propagated to the design surface, and when the transmittance exceeds 30%, Therefore, the difference in design with the glass building material with transparent glass on the front is reduced, and the assertion of individuality as a stone-like building material becomes weak. Therefore, the surface of the light-emitting layer observed through the translucent light-transmitting layer, that is, the internal design surface that is the interface between the light-emitting layer and the light-transmitting layer, and the design that shines while scattering light emitted from the light-emitting layer in the dark As a surface, in order to obtain a crystallized glass article that gives a high-class feeling due to a unique depth expression, it is important that the transmittance of visible light of the light-transmitting layer is 5 to 30%.

  Further, in the crystallized glass article of the present invention, when the thickness of the light-transmitting layer is less than 50% with respect to the thickness of the light-emitting layer, the glass of the light-emitting layer is mixed with the glass of the light-transmitting layer and becomes unsightly in design. When the thickness of the light transmitting layer exceeds 200%, it becomes difficult to sufficiently propagate the light from the light emitting layer to the design surface. In the crystallized glass article of the present invention, the surface of the light emitting layer observed through the translucent light transmitting layer, that is, the internal design surface that is the interface between the light emitting layer and the light transmitting layer and the light emitted from the light emitting layer in the darkness. In order to realize a crystallized glass article that creates a high-class feeling with a unique depth expression as a design surface that shines while being scattered, the thickness of the light-transmitting layer is 50 to 200% with respect to the thickness of the light-emitting layer. preferable.

  Further, in the crystallized glass article of the present invention, it is preferable that the light emitting material includes a phosphorescent material in terms of light without using a light source, the degree of freedom of light production, and light emission efficiency.

  Further, in the crystallized glass article of the present invention, it is preferable that the light emitting material contains a fluorescent material in terms of emitting fluorescence with a slight amount of light, freedom of light production, and light emission efficiency.

In the crystallized glass article of the present invention, the crystallized glass may be diopsite (CaO · MgO · 2SiO ₂ ) based on crystal precipitation characteristics, but SiO ₂ 45 to 75 in terms of mass percentage. %, Al ₂ O ₃ 1-25%, CaO 2-25%, ZnO 0-18%, BaO 0-20%, MgO 0-1.5%, SrO 0-1.5%, Na ₂ O 1- 25%, K ₂ O 0-7%, Li ₂ O 0-5%, B ₂ O ₃ 0-1.5%, CeO ₂ 0-0.5%, SO ₃ 0-0.5%, As ₂ It has a composition of 0 to 1% of O _3, 0 to 1% of Sb ₂ O _{3 and} 0 to ₃ % of a colored oxide, and the amount of precipitated crystals is obtained by precipitating β-wollastonite as a main crystal. 5 to 50% by mass can suppress foaming, maintain the smoothness of the surface, and maintain the strength characteristics, and has a visible light transmittance of 5 to 30%. It is easy preferable to form a transparent layer. It is also possible to add an inorganic colorant of less than 3% as a colored oxide to a crystalline glass body having the same composition.

The content of SiO ₂ is 45 to 75%, preferably 50 to 70%. If SiO ₂ is higher than 75%, the melting temperature of the glass increases and the viscosity increases, resulting in poor fluidity during heat treatment. On the other hand, if it is less than 45%, devitrification at the time of molding becomes strong.

The content of Al ₂ O ₃ is 1 to 25%, preferably 3 to 15%. If Al ₂ O ₃ is more than 25%, the solubility of the glass deteriorates and different crystals (anocite) precipitate, resulting in poor fluidity during heat treatment. If it is less than 1%, devitrification becomes strong and chemical durability. The nature is also reduced.

  The content of CaO is 2 to 25%, preferably 8 to 18%. If the CaO content is more than 25%, devitrification becomes strong and molding becomes difficult, and the precipitation amount of β-wollastonite crystal becomes too large, making it difficult to obtain desired surface smoothness. On the other hand, if it is less than 2%, the precipitation amount of β-wollastonite becomes too small, the mechanical strength is lowered, and it cannot be practically used as a building material.

  ZnO is a component added to promote the fluidity of the glass during crystallization, and its content is 0 to 18%, preferably 2 to 15%. If ZnO is more than 18%, β-wollastonite crystals are difficult to precipitate.

  BaO is also a component that exhibits the same effect as ZnO, and its content is 0 to 20%, preferably 1 to 10%. When BaO is also more than 20%, the amount of β-wollastonite crystals precipitated decreases.

  MgO and SrO are components that promote the solubility and fluidity of the glass. However, if it exceeds 1.5%, different crystals are precipitated, which is not preferable in terms of thermal characteristics, optical characteristics, and appearance.

The content of Na ₂ O is 1 to 15%, preferably 3 to 10%. When Na ₂ O is more than 15%, the scientific durability is deteriorated and the expansion coefficient is increased, which is not preferable as a building material. If it is less than 1%, the viscosity of the glass increases and the solubility and fluidity deteriorate.

The content of K ₂ O is 0 to 7%, preferably 0 to 5%. When K ₂ O is more than 7%, chemical durability is lowered.

Li ₂ O has the effect of increasing the crystallization rate and the effect of promoting fluidity, and its content is 0 to 5%, preferably 0.1 to 3%. When Li ₂ O is more than 5%, not only the chemical durability is lowered, but also the viscosity is lowered too much, so that foaming easily occurs.

The content of B ₂ O ₃ is 0 to 1.5%, preferably 0 to 1%. When B ₂ O ₃ is more than 1.5%, different crystals are precipitated, and desired characteristics cannot be obtained.

CeO ₂ is environmentally unfavorable for the addition of As ₂ O ₃ or Sb ₂ O ₃ as a clarifier, and therefore when the content thereof is 0.1% or less, the whiteness of the crystallized product decreases rapidly. , A component that suppresses the decrease in whiteness. The content of CeO ₂ for suppressing the decrease in whiteness is 0.01 to 0.5%, preferably 0.05 to 0.3%. The effect is to suppress the coloration of Fe ²⁺ by Fe ₂ O ₃ contained as an impurity in a glass melting environment under a reducing atmosphere, and is particularly effective by coexisting with SO ₃ (sodium nitrate). Appears prominently. When CeO ₂ is more than 0.5%, the brown coloration due to Ce ⁴⁺ becomes strong, and when it is less than 0.01%, it is difficult to obtain the above effect.

The content of SO ₃ is 0.01 to 0.5%, preferably 0.02 to 0.4%. When SO ₃ is more than 0.5%, different types of crystals are precipitated, and when it is less than 0.01%, the solubility of glass when the clarifying agents As ₂ O ₃ and Sb ₂ O ₃ are 0.1% or less. Decreases and the quality of the glass deteriorates.

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

In the method for producing a crystallized glass article according to the present invention, a mixture obtained by mixing a crystalline glass body and a light emitting material is accumulated in a refractory container to form a first accumulation layer, and the first accumulation layer is fired. A glass body having a deposited crystal amount of 5 to 50% by mass is accumulated to form a laminated body as a second integrated layer, and the laminated body is heated to a temperature at which the viscosity of the glass is 10 ⁴ to 10 ⁵ poise. By calcination in the region, the light-emitting layer is made of crystallized glass on which a light-emitting material is arranged, and is made of crystallized glass that is fused to the light-emitting layer and has an average visible light transmittance of 5 to 30%. A light-transmitting layer is formed.

  In the production method of the present invention, as a crystalline glass body that accumulates in a refractory container, for example, when it is heat-treated at a temperature higher than the softening point, acicular crystals from the surface to the inside while being softened and deformed Is made of crystalline glass having a precipitated crystal amount of 5 to 50% by mass, which is suitable for suppressing foaming, maintaining the smoothness of the surface, and further maintaining the strength characteristics. Moreover, as a crystalline glass body which forms the translucent translucent layer used as the design surface side, it is preferable that it is easy to form a layer with a visible light transmittance of 5 to 30%. In the present invention, the crystalline glass body means a crystalline glass body having a crystallized crystal quantity after firing of 5 to 50% by mass, preferably 5 to 40% by mass, which has not yet sufficiently crystallized. And a crystallized glass body in which crystals having a crystal amount of 5 to 50% by mass, preferably 5 to 40% by mass are precipitated. In this crystallized glass body, if the amount of precipitated crystals is in the above-mentioned range, the cutting waste is similarly produced regardless of whether it is a plate shape, a tubular shape or a lump shape generated in the manufacturing process of a conventional crystallized glass article. It can also be used after pulverization.

  Further, in the production method of the present invention, as a means for mixing the crystalline glass body and the luminescent material into a mixture, a mixer that does not contain rust and metal powder, which are impurities that affect coloring and properties, and the like Any mixing means can be used. In addition, the refractory container is preferably made of a material that does not soften and deform at a temperature of 1100 ° C. or lower, and a refractory container such as mullite, cordierite, or alumina ceramic is preferable. In addition, when using a refractory ceramic sheet, it can be used without any limitation as long as it acts as a release material between the crystallized glass article and the refractory container, but fiber sheets such as silica, mullite, alumina, etc. are particularly preferred, You may use individually or in combination. In addition, the method of applying the refractory ceramic sheet in the refractory container includes a method of making the sheet into a box shape, a method of dividing the sheet and installing it on the inner wall of the container, but a fine powder such as alumina on the inner wall of the container in advance. The coating by air spray coating, brush coating, dip coating or the like is suitable for preventing fusion.

  When carrying out the method for producing a crystallized glass article according to the present invention, first, the amount of crystallized crystals after firing is 5 to 50% by mass, preferably 5 to 40% by mass, or the crystal content is 5 to 5% by mass. A crystallized glass body of 50% by weight, preferably 5 to 40% by weight, is obtained.

Next, a mixture obtained by mixing the obtained crystalline glass body and the light emitting material such as the fluorescent material or the phosphorescent material is accumulated in a refractory frame made of mullite cordierite or the like to form a first accumulation layer. Further, a crystalline glass body or a crystallized glass body capable of ensuring translucency after firing is laminated on the first integrated layer by 30 to 70% with respect to the total mass, By doing so, a laminated body is formed in the refractory frame. Thereafter, the laminated body together with the refractory frame is baked in a temperature range in which the viscosity of the glass portion of the crystalline glass or crystallized glass exhibits 10 ⁴ to 10 ⁵ poise, thereby softening and deforming each crystalline glass body. The crystalline glass bodies are fused and integrated together, and the sintered body is formed by depositing the above-mentioned amount of acicular crystals in the crystalline glass.

  Further, in the method for producing a crystallized glass article of the present invention, if the luminescent material contains a phosphorescent material, the crystal is excellent in terms of light without a light source, freedom of directing light, and light emission efficiency. It becomes possible to produce a vitrified glass article. In addition, if the light-emitting material contains a fluorescent material, the crystallized glass article is excellent in that it emits fluorescence with a slight amount of light, can be rendered with a fluorescent color that gives a bright impression in pastel tone, and light emission efficiency. Can be manufactured.

  Further, in the present invention, the luminous material, particularly the phosphorescent material, reduces the light emitting ability when oxidized by the outside air during firing, and the light emitting ability is lowered even after firing due to oxidation with the outside air or contact with moisture. Therefore, in the method for producing a crystallized glass article of the present invention, when the laminate is fired, the second integrated layer made of crystalline glass covers the first integrated layer in which the mixture of the crystalline glass body and the light emitting material is integrated. Oxidation is suppressed, and the crystallized glass article after firing is sealed with a light-transmitting layer made of crystallized glass, so that it is isolated from the outside air to prevent oxidation, thereby enabling semi-permanent light emission. .

  In the method for producing a crystallized glass article of the present invention, if the thickness of the second integrated layer is less than 50% with respect to the thickness of the first integrated layer, the crystallized glass of the first integrated layer after firing is the first. When the thickness of the second integrated layer exceeds 200%, it becomes difficult to sufficiently propagate the light from the light emitting layer to the design surface. In the method for producing a crystallized glass article of the present invention, light is emitted from the light-emitting layer on the surface of the light-emitting layer observed through the translucent light-transmitting layer, that is, the internal design surface and the darkness that are the interface between the light-emitting layer and the light-transmitting layer. In order to realize the manufacture of a crystallized glass article that gives a sense of quality with a unique depth expression as a design surface that shines far while scattering light, the thickness of the light-transmitting layer relative to the thickness of the light-emitting layer is 50 to 200 %, It is preferable to form a laminated body in which the thickness of the second integrated layer is 50 to 200% with respect to the thickness of the first integrated layer in the refractory container.

  According to the crystallized glass article of the present invention, a light emitting layer made of crystallized glass on which a light emitting material is disposed, and fused to at least one surface of the light emitting layer, and the amount of precipitated crystals is 5 to 50% by mass It is made of crystallized glass and has a translucent layer with an average visible light transmittance of 5 to 30%. Since the translucent layer is arranged on the design surface side, the characteristics necessary for building materials are maintained. In addition, a novel crystallized glass article having a high-quality appearance as a light-emitting substance can be provided.

  In addition, since the crystallized glass article of the present invention has the above-mentioned two-layer structure, a high-quality appearance mainly composed of reflected light from the surface is obtained while it is bright. The light-emitting layer, which is lowered by the thickness of the light-transmitting layer, emits much light through the light-transmitting light-transmitting layer, making it a unique design surface and realizing a building material with a new duality in a light and dark environment be able to. Furthermore, when the light emitting layer includes a phosphorescent material, it is possible to produce light with a high degree of freedom by using a wall surface that efficiently shines without a light source or a structure using the crystallized glass article even in the dark.

Further, according to the method for producing a crystallized glass article of the present invention, a mixture obtained by mixing a crystalline glass body and a light emitting material is accumulated in a refractory container to form a first accumulation layer. On top of this, crystalline glass bodies having a deposited crystal amount after firing of 5 to 50% by mass are accumulated to form a laminate as a second accumulation layer, and the viscosity of the laminate is 10 ⁴ to 10 ^5. By firing in a temperature range showing a poise, a light emitting layer made of crystallized glass on which a light emitting material is disposed, and a crystal fused to the light emitting layer and having an average visible light transmittance of 5 to 30% As described above, it has a high-quality appearance mainly of reflected light while bright, and has a two-sidedness in a light and dark environment where the surface shines when dark. Crystallized glass articles with new and unique design surface and strength performance It can be manufactured efficiently.

  In the method for producing a crystallized glass article according to the present invention, the amount of the crystalline glass bodies of the second integrated layer integrated on the first integrated layer is 30 to 70% by mass of the total. A light-transmitting layer having an appropriate translucency with a transmittance of 5 to 30% can be formed, and the colored surface of the light-emitting layer colored with a fluorescent material or other coloring substance that develops a pastel tone, that is, the internal interface A crystallized glass article having a design surface that gives a sense of depth by the thickness of the translucent layer and whose surface shines through the translucent layer when it becomes dark can be produced.

  Furthermore, in the method for producing a crystallized glass article of the present invention, even when a light-emitting material includes a light-storing material, and even when a light-storing material that has conventionally been considered impossible to efficiently shine under a firing condition of 1000 ° C. Since the phosphorescent material is protected by being sealed with amorphous glass during firing, it is possible to produce a crystallized glass article that shines efficiently without a light source even in the dark.

  Hereinafter, embodiments of the present invention will be described based on examples and comparative examples.

As Example 1, two types of crystalline glass pieces were prepared. One type is expressed in mass percentage, SiO ₂ 64%, Al ₂ O ₃ 5%, CaO 14%, ZnO 5%, BaO 5%, Na ₂ O 3%, K ₂ O 2%, Li ₂ O 0.4. %, B ₂ O ₃ 1%, Sb ₂ O ₃ 0.6% glass raw material was melted at 1500 ° C. for 12 hours, and the molten glass was poured into water and crushed to produce crystals. Glass piece A. In order to confirm the crystalline amount of the crystalline glass piece A, a part of the water-crushed glass piece was accumulated in a refractory container and then fired at 1100 ° C. for 2 hours to obtain crystallized glass. As a result of X-ray diffraction, the crystallized glass had a precipitated crystal amount of about 30% by mass, and it was confirmed that β-wollastonite was precipitated as the main crystal. Further, when the thermal expansion coefficient of the crystalline glass piece was measured by the DILATO method, it was 61 × 10 ⁻⁷ / K, and the viscosity was measured at a viscosity of 10 ⁴ and 10 ⁵ poise with a parallel plate viscometer, It was 1110 ° C. for 10 ⁴ poise and 1010 ° C. for 10 ⁵ poise. Another type is mass percentage display, SiO ₂ 65%, Al ₂ O ₃ 8%, CaO 7%, ZnO 7%, BaO 5%, Na ₂ O 4%, K ₂ O 2%, Li ₂ O 0. 4%, B ₂ O ₃ 1%, Sb ₂ O ₃ 0.6% glass raw material prepared so as to melt at 1500 ° C. for 12 hours, this molten glass is poured into water and water-crushed, A crystalline glass piece B was obtained. In order to confirm the crystalline amount of the crystalline glass piece B, a part of the water-crushed glass piece was accumulated in a refractory container and then fired at 1100 ° C. for 2 hours to obtain crystallized glass. As a result of X-ray diffraction, the crystallized glass had a precipitated crystal amount of about 30% by mass, and it was confirmed that β-wollastonite was precipitated as the main crystal. Further, when the thermal expansion coefficient of the crystalline glass piece was measured by the DILATO method, it was 61 × 10 ⁻⁷ / K, and the viscosity was measured at a viscosity of 10 ⁴ and 10 ⁵ poise with a parallel plate viscometer, It was 1110 ° C. for 10 ⁴ poise and 1010 ° C. for 10 ⁵ poise.

  Further, the water-crushed crystalline glass pieces A and B were classified into 1 mm to 5 mm with a sieve to obtain crystalline glass bodies A and B. The crystalline glass bodies A and B were used in Examples and Comparative Examples.

Next, a mold made of mullite cordierite having an inner size of 900 mm × 600 mm × depth of 30 mm was prepared, and 12 kg of the previously prepared crystalline glass body A and phosphorescent material powder (SrAl ₂ O ₄ with Eu ²⁺ 300 g of α-FLASH PB500 manufactured by LTI Co., Ltd., doped with Dy ^3+, having an average particle size of 500 μm) was mixed to obtain a mixture, and this was accumulated as a first accumulation layer. This mass is such that the thickness of the first integrated layer after the heat treatment is about 7.7 mm after firing. Next, an integrated layer made of 12 kg of crystalline glass bodies B was integrated on the first integrated layer as a second integrated layer. This mass is such that the thickness of the second integrated layer becomes about 7.7 mm after firing.

  Then, the laminated body which consists of the crystalline glass bodies A and B integrated | stacked in the formwork was baked with roller hearth kiln. As firing conditions, the temperature was raised at a rate of 300 ° C. per hour and held at 1100 ° C. for 1 hour to obtain a fired body, whereby a crystallized glass plate was obtained.

A perspective view of the crystallized glass sheet for building materials thus obtained is shown in FIG. The crystallized glass plate 1 has a schematic dimension of 900 mm in length, about 600 mm in width, and about 15.4 mm in thickness. The light-emitting layer 2 is made of crystallized glass A and has a thickness of 7.7 mm. And a light-transmitting layer 3 having a thickness of 7.7 mm and made of a light-transmitting crystallized glass B. The visible light transmittance of the light transmissive layer 3 is 15%. Further, the difference in thermal expansion coefficient between the light emitting layer 2 made of crystallized glass and the light transmitting layer 3 is 1 × 10 ⁻⁷ / K or less and can be ignored.

  The appearance of the crystallized glass plate 1 thus obtained is such that the design surface 1a, which is fired and glossy in a bright environment, has an appropriate translucency with an average visible light transmittance of 15%. On the other hand, the surface of the light-emitting layer 2 that is observed through the translucent light-transmitting layer 3 without a light source for several hours in a dark environment, that is, the light-emitting layer 2 and the light-transmitting layer 3 is presented. As the design surface 1a that shines far while being scattered by the light-transmitting layer 3, the light emitted from the internal design surface, which is the interface with the surface, brings out a high-class feeling with a unique depth expression.

As Example 2, a crystalline glass piece obtained by water-pulverizing molten crystalline glasses A and B having the same composition as in Example 1 was pulverized for several hours using a ball mill using alumina balls, After classification with a sieve, crystalline glass bodies A and B of 2 mm or less were obtained. Next, the phosphorescent material powder (SrAl ₂ O ₄ was doped with Eu ²⁺ and Dy ³⁺ with respect to 8 kg (33% by mass of the whole) of this crystalline glass body A (33% by mass of the whole). 2.5% by mass of α-FLASH PB500 manufactured by LTI (average particle size: 500 μm), 1% by mass of an Al—Co—Zn spinel-based inorganic pigment powder, several drops of PVA, and a mixer And mixed to obtain a mixture. Further, 8 kg of the crystalline glass body B is accumulated in the mold to form another second accumulation layer, and 8.2 kg of the mixture of the crystalline glass bodies A is used as the first accumulation layer, and 8 kg of the crystalline glass body is obtained. B was integrated to form a three-layer laminate as the second integrated layer. The firing was performed in the same manner as in Example 1 to obtain a fired body, and the surface of the light-transmitting layer 3 that was on the lower side in the mold was polished. In this way, a pattern with a sense of depth is exhibited by the light-transmitting layers 3 and 3 in a bright environment, while the surface of the light-emitting layer 2 passes through the light-transmitting layers 3 and 3 even in the dark environment without a light source for several hours. A crystallized glass plate 10 as shown in FIG. 2 having a unique appearance in which the design surface 10a shines far was obtained.

In Example 3, the crystalline glass pieces obtained by water-pulverizing molten crystalline glasses A and B having the same composition as in Example 1 were pulverized for several hours using a ball mill using alumina balls. After classifying with a sieve, crystalline glass bodies A and B of 2 mm or less were obtained. Next, 200 g (0.8% by mass of the total) of fluorescent material (ZnS doped with Cu ⁺ and Al ³⁺ , manufactured by Nemoto Special Chemical Co., Ltd.) with respect to 8 kg (33% by mass of the total) of this crystalline glass body A No. GSS) was added in an amount of 2.5% by mass, and further 1% by mass of an Al—Co—Zn spinel inorganic pigment powder was added. A few drops of PVA were added and mixed using a mixer to obtain a mixture. Further, 8.2 kg of a mixture of crystalline glass bodies A was accumulated in the mold to form a first accumulation layer, and 8 kg of crystalline glass bodies B were accumulated to form a laminate as a second accumulation layer. . Then, firing is performed in the same manner as in Example 1, and as the fired body, a pattern having a sense of depth is exhibited by the light-transmitting layer 3 in a bright environment, while the light-emitting layer 2 without a light source is used for several hours in a dark environment. A crystallized glass plate having a two-layer structure similar to that shown in FIG. 1 having a unique appearance that the surface shines through the light-transmitting layer 3 was obtained.

  As Comparative Example 1, first, 24 kg of crystalline glass A having the same composition as in the example was prepared, and then fired in the same manner in a refractory mold to obtain a fired body of crystallized glass. Although this crystallized glass had a preferable appearance that flowed sufficiently, it was not an appearance with a sense of depth. When crystallized crystals of this crystallized glass were confirmed by X-ray diffraction, about 30% of the same β-wollastonite crystals as in Examples were precipitated.

  As described above, Example 1, Example 2 and Example 3 had a desired depth, and showed a design surface that emits light when dark. Since Comparative Example 1 has a single layer structure of crystallized glass and does not have translucent glass, it naturally did not exhibit a sense of depth. Since Comparative Example 1 does not have a light-transmitting layer, these Examples 1 to 3 exhibit a design surface with a sense of depth due to an appropriate light-transmitting layer on the light-emitting layer 2 of crystallized glass. Of course, it was a natural marble-like appearance without a deep pattern as in the example.

The perspective view of the crystallized glass article of this invention. The perspective view of the other crystallized glass article of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 10 Crystallized glass article 1a, 10a Design surface 2 Light emitting layer 3 Translucent layer

Claims (8)

  A light-emitting layer made of crystallized glass on which a light-emitting material is disposed, and a crystallized glass fused to at least one surface of the light-emitting layer and having a precipitated crystal content of 5 to 50% by mass, and an average visible light transmittance A crystallized glass article, wherein the crystallized glass article has a translucent layer of 5 to 30%, and the translucent layer is disposed on the design surface side.   The crystallized glass article according to claim 1, wherein the light emitting material includes a phosphorescent material.   The crystallized glass article according to claim 1 or 2, wherein the light-emitting material contains a fluorescent material. Crystallized glass, SiO ₂ 45 to 75% by mass _{percentage, Al 2 O 3 1~25%,} CaO 2~25%, ZnO 0~18%, BaO 0~20%, MgO 0~1.5% _{, SrO 0~1.5%, Na 2 O} 1~25%, K 2 O 0~7%, Li 2 O 0~5%, B 2 O 3 0~1.5%, CeO 2 0~0. 5%, SO ₃ 0 to 0.5%, As ₂ O ₃ 0 to 1%, Sb ₂ O ₃ 0 to 1%, colored oxide 0 to 3%, β-wolast as main crystal 4. The crystallized glass article according to claim 1, wherein the crystallized glass article is formed by depositing knight. In a refractory container, a mixture obtained by mixing crystalline glass bodies and a light emitting material is integrated to form a first integrated layer, and the amount of precipitated crystals after firing becomes 5 to 50% by mass on the first integrated layer. The light emitting material is arranged by stacking the crystalline glass bodies to form a laminate as a second integration layer, and firing the laminate in a temperature range where the viscosity of the glass is 10 ⁴ to 10 ⁵ poise. A crystal comprising: a light-emitting layer made of crystallized glass; and a light-transmitting layer made of crystallized glass that is fused to the light-emitting layer and has an average visible light transmittance of 5 to 30%. A method for producing a vitrified glass article.   6. The method for producing a crystallized glass article according to claim 5, wherein the amount of the crystalline glass bodies of the second integrated layer integrated on the first integrated layer is 30 to 70% by mass of the whole.   The method for producing a crystallized glass article according to claim 5 or 6, wherein the luminescent material includes a phosphorescent material.   The method for producing a crystallized glass article according to any one of claims 5 to 7, wherein the luminescent material contains a fluorescent material.

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