HK1126750B

HK1126750B - Crystallized glass article having patterns and method of producing the same

Info

Publication number: HK1126750B
Application number: HK09105878.7A
Authority: HK
Inventors: 许国铨
Original assignee: 建权玻璃开发股份有限公司; 许国铨
Priority date: 2007-07-18
Filing date: 2009-06-30
Publication date: 2011-12-30

Description

Crystallized glass product with pattern and its making process

Cross Reference to Related Applications

This application is based on and claims priority from japanese patent application No. 2007-187654, filed on 18/7/2007, the entire contents of which are incorporated herein by reference.

Technical Field

The present invention relates to a crystallized glass product having a pattern, a method for producing the same, and use thereof in a building exterior material, interior material, furniture surface plate material, office table surface plate material, and the like.

Background

In recent years, with the transition of times, there has been a demand for various crystallized glass products as, for example, exterior materials, interior materials, furniture top sheets, and office table top sheets for buildings.

As crystallized glass used for these applications, crystallized glass is known which includes: beta-wollastonite (beta-wolfilastonite, beta-CaO. SiO)₂) Crystallized glass formed by main crystal precipitation, or diopside (CaO. MgO. 2 SiO)₂) Crystallized glass in which main crystals are precipitated.

Further, a method for producing a crystallized glass product containing the above crystal is known to include: (1) a production method in which a plate-shaped crystallized glass is subjected to heat treatment to precipitate and grow crystals from the surface to the inside (patent document 1); and (2) a production method called an "integration method", in which molten glass is rapidly cooled by water cooling or the like to form small crystalline glass bodies, the small crystalline glass bodies are integrated in a refractory mold, and the small crystalline glass bodies are sintered and integrated with each other by heat treatment to be crystallized (patent documents 2 to 8).

The crystallized glass product produced by these production methods has a pattern such as a natural marble pattern.

[ patent document 1] Japanese examined patent publication No. 51-23966

[ patent document 2] Japanese examined patent publication No. 53-39884

[ patent document 3] Japanese Kokoku publication No. 55-29018

[ patent document 4] Japanese patent application laid-open No. Sho 63-201037

[ patent document 5] Japanese patent application laid-open No. 3-164446

[ patent document 6] Japanese patent application laid-open No. 3-205323

[ patent document 7] Japanese patent application laid-open No. 5-163033

[ patent document 8] Japanese patent application laid-open No. 6-24768

However, when a crystallized glass product is produced by heat-treating a plate glass by the method disclosed in the above (1), since the plate glass does not contain a nucleating agent, crystals precipitate and grow from the surface, back surface and end surfaces of the plate glass to the inside. Therefore, for example, in the case of a plate-shaped crystallized glass product having a thickness of about 10mm, the central portion thereof is not crystallized, and a glass matrix having a thickness of about 4mm remains, and cracks may occur in these glass matrix portions.

Hereinafter, this state will be further described with reference to the drawings, and fig. 3 is a cross-sectional view showing a crystallized glass product obtained by heat-treating the above plate-like glass. In fig. 3, reference numeral 100 denotes a crystallized glass product, 110 denotes a crystallized glass body, 120 denotes an uncrystallized crystalline glass matrix, and 130 denotes a crack. As shown in fig. 3, crystals grow from the front surface, the back surface, and the end surfaces of the plate-shaped glass to the inside, and an uncrystallized crystallized glass matrix 120 exists in the region surrounded by the crystallized glass body 110 (the central portion of the plate-shaped glass product), and a crack 130 is generated in the crystallized glass matrix 120.

Therefore, the crystallized glass product 100 obtained by the manufacturing method disclosed in the above (1) has insufficient strength because the crack 130 is surely present inside although the crack 130 is not observed from the appearance.

On the other hand, when the crystallized glass product is produced by the integration method disclosed in (2) above and the crystallized small glass bodies are integrated into the refractory mold, air is trapped in the gaps between the crystallized small glass bodies. Therefore, bubbles are likely to be generated in the crystallized glass product to be produced. When the surface of the crystallized glass product is polished for fine processing, the bubbles tend to cause semicircular pore defects on the surface.

When the crystallized glass product having a pattern with the pinhole defect on the surface is used as a floor, for example, the pinhole part is gradually blackened with the lapse of time, which affects the appearance of the floor. Especially, when the crystallized glass product with patterns is white or light, the aesthetic property of the floor is more obviously affected.

Disclosure of Invention

In order to solve the above problems, the present invention provides a crystallized glass product having a pattern with sufficient strength and no surface pore defects, and a method for manufacturing the same.

In accordance with one embodiment of the present invention, there is provided a crystallized glass article having a pattern, comprising: a crystallized glass layer A which is patterned by sintering and simultaneously crystallizing a plurality of small crystallized glass bodies; a crystallized glass layer B which is formed in a translucent state by disposing a crystallized glass plate B on at least one surface of the crystallized glass layer A when the surface is in a sintered state, and crystallizing the crystallized glass plate B from the surface toward the inside to the center; and a crystallized glass layer C sintered to an end face portion of the crystallized glass layer A or end face portions of the crystallized glass layer A and the crystallized glass layer B, the crystallized glass layer C being formed by crystallizing a crystallized glass plate C from a surface to a center portion thereof and containing at least one crystal of beta-wollastonite and diopside as a main crystal, wherein the crystallized glass layer C has a thickness of 6mm or less, and the main crystal of the crystallized glass layer A is beta-wollastonite (beta-wollastonite, beta-CaO SiO. SiO)₂) And diopside (CaO. MgO. multidot.2SiO)₂) And the main crystal of the crystallized glass layer B is at least one of β -wollastonite and diopside, and the crystallized glass layer B has a thickness of about 0.1mm to about 6 mm.

In one embodiment, the crystallized glass layer B may be sintered on both upper and lower surfaces of the crystallized glass layer a. The absolute value of the difference between the thermal expansion coefficients of the crystallized glass layer A and the crystallized glass layer B at 30-380 ℃ is 0-10 x 10^-7In the range/° c.

In accordance with another embodiment of the present invention, there is provided a method for manufacturing a crystallized glass article having a pattern, which includes a heat treatment step of heat-treating at least one of the following laminated bodies: (1) a laminate comprising a plurality of layered crystallized glass gob layers composed of a plurality of crystallized small glass bodies, a crystallized glass plate B laminated and disposed on the surface of the crystallized small glass body layers, and a crystallized glass plate C disposed on the end face portion of the crystallized small glass body layers or the crystallized small glass layer and the end face portion of the crystallized glass plate B, (2) a laminate comprising a plurality of layered crystallized small glass bodies composed of a crystallized glass plate B, a plurality of crystallized small glass bodies positioned on the surface of the crystallized glass plate B, and a crystallized glass plate C disposed on the end face portion of the crystallized small glass layer or the crystallized small glass layer and the end face portion of the crystallized glass plate B, and (3) a layered crystallized small glass body layer composed of a first crystallized glass plate B, a plurality of crystallized small glass bodies positioned on the surface of the first crystallized glass plate B, A laminate comprising a second crystallized glass plate B disposed on the surface of the crystallized glass subbulk layer and a crystallized glass plate C disposed on the end face portion of the crystallized glass subbulk layer or the crystallized glass subbulk layer and the end face portion of the first or second crystallized glass plate B, the heat treatment steps comprising: sintering the plurality of crystallized glass bodies in the crystallized glass body layer to each other; and mutually sintering a crystallized glass frit layer and a crystallized glass plate B, the crystallized glass plate C, or the first and the second crystallized glass plates B, and simultaneously crystallizing a plurality of crystallized glass frits and a crystallized glass plate B, the crystallized glass plate C, or the first and the second crystallized glass plates B, and forming the crystallized glass frit layer A into the crystallized glass plate B, forming the crystallized glass plate B into a crystallized glass layer B, forming the first crystallized glass plate B and the second crystallized glass plate B into a first and a second crystallized glass layer B, and forming the crystallized glass plate C into a crystallized glass layer C into the crystallized glass plate C, wherein the crystallized glass layer A is patterned, and the crystallized glass layer B and the first and the second crystallized glass layers B assume a translucent state, wherein the crystallized glass plate B has a thickness of about 0.1mm to about 6mm, the first crystallized glass plate B and the second crystallized glass plate B each have a thickness of about 0.1mm to about 6mm, and the crystallized glass layer C has a thickness of 6mm or less, and the crystallized glass layer C contains at least one crystal of β -wollastonite and diopside as a main crystal. At least one crystal of β -wollastonite and diopside is precipitated as a main crystal in the crystalline vitreous microlayer, and at least one crystal of β -wollastonite and diopside is precipitated as a main crystal in the crystalline vitreous plate from the surface of the crystalline vitreous plate toward the inside to the center.

As described above, according to the present invention, a crystallized glass product having a pattern with sufficient strength and no surface pinhole defect and a method for manufacturing the same can be provided.

Drawings

FIGS. 1A to 1C are schematic cross-sectional views illustrating an example of a method for manufacturing a crystallized glass product according to the present invention;

FIG. 2 is a schematic cross-sectional view showing another example of the method for producing a crystallized glass article according to the present invention; and

FIG. 3 is a cross-sectional view of a crystallized glass product obtained by heat-treating the plate-like glass.

Description of the reference symbols:

10 refractory material mould

12 crystallized glass capsule layer

14 crystallized glass plate B

14A crystallized glass plate B

14B crystallized glass plate B

16 crystallized glass plate C

20 laminated body

20A laminate

20B laminate

20C laminate

100 crystallized glass product

110 crystallized glass body

120-type amorphous glass body

130 cracking

Detailed Description

(crystallized glass product)

In one embodiment of the present invention, a crystallized glass article having a pattern (hereinafter simply referred to as "crystallized glass article") of the present invention comprises: a crystallized glass layer A formed by sintering a plurality of small crystallized glass bodies and crystallizing the small crystallized glass bodies simultaneously; and a crystallized glass layer B sintered with at least one surface of the crystallized glass layer A. The crystallized glass layer B is formed by crystallizing the crystallized glass plate B from the surface to the center thereof. The crystallized glass layer A contains at least beta-wollastonite (beta-wollastonite, beta-CaO. SiO)₂) And diopside (CaO. MgO. multidot.2SiO)₂) One of the crystals is used as a main crystal. The crystallized glass layer B contains at least one crystal selected from the group consisting of β -wollastonite and diopside as a main crystal, and has a thickness of 6mm or less.

In the crystallized glass product of the present invention, since the crystallized glass layer a is formed by sintering a plurality of small crystallized glass bodies to each other and crystallizing them at the same time, the crystallized glass layer a can have a pattern such as a natural marble pattern, as in the case of a crystallized glass product conventionally manufactured by an integration method.

In addition, at least one surface of the crystallized glass layer A is sintered and fixed to a crystallized glass layer B having a thickness of 6mm or less. The crystallized glass layer B is formed by crystallization from the surface of the crystallized glass plate B to the center thereof, however, is not opaque but translucent because the thickness is less than 6 mm. Therefore, when the crystallized glass product is viewed from the side where the crystallized glass layer B is provided, the pattern formed by the crystallized glass layer a can be confirmed.

Since the crystallized glass layer B formed of the crystallized glass plate B is used as the surface of the crystallized glass product, no pores are present.

Therefore, when the crystallized glass product of the present invention is used for applications such as exterior and interior materials of buildings, and surface plates of furniture and desks, the crystallized glass product of the present invention is used to place the surface formed by the crystallized glass plate B on a side that is easy to see by a user, and even if time passes, the problem that the pores are blackened and the appearance is impaired does not occur.

In another embodiment of the present invention, the crystallized glass layer B may be sintered and fixed to both upper and lower surfaces of the crystallized glass layer a. In this case, a crystallized glass product having no pore defects on both sides can be obtained.

Further, the crystallized glass product of the present invention is composed of the crystallized glass layer a and the crystallized glass layer B, and therefore has sufficient strength. The crystallized glass layer B is formed by crystallizing the crystallized glass plate B, and when the crystallized glass plate B is crystallized, one of the crystals of beta-wollastonite and diopside is precipitated as a main crystal. Both of these crystals have a characteristic of growing from the surface of the crystalline glass material toward the inside. As shown in fig. 3, the crystallized glass matrix having cracks in the central portion of the crystallized glass layer B may be insufficient in strength. In order to solve the above problem, the crystallized glass layer B is crystallized from the surface to the center and has the crystallized glass layer a at the same time, so that sufficient strength can be obtained.

Here, the thickness of the crystallized glass layer B is required to be 6mm or less, preferably 5mm or less, and the thickness of the crystallized glass layer B is preferably 4mm or less. When the thickness of the crystallized glass layer B exceeds 6mm, the crystallized glass layer B changes from translucent to opaque, so that when the crystallized glass product is viewed from the side where the crystallized glass layer B is provided, it becomes difficult to confirm the pattern generated by the crystallized glass layer a, and the crystallized glass product is poor in aesthetic property. In addition, the crystallized glass layer B tends to leave a crystallized glass matrix.

On the other hand, the lower limit of the thickness of the crystallized glass layer B is preferably 0.1mm or more, more preferably 1mm or more, and most preferably 2mm or more. Accordingly, crystallized glass layer B may have a thickness ranging from about 0.1mm to about 6 mm.

On the other hand, the thickness of the crystallized glass layer a is not particularly limited, and may be appropriately selected depending on the thickness of the crystallized glass product, but may have the following thickness range: preferably 0.1mm to 30mm, more preferably 1mm to 15 mm.

The thickness of the crystallized glass product is not particularly limited, and may be appropriately selected depending on the use or purpose of the crystallized glass product. However, from the practical viewpoint of strength, manufacturability, cost, and the like, the thickness is preferably in the range of 8mm to 30mm, and more preferably in the range of 15mm to 25 mm.

The crystallized glass layer a must contain at least one crystal of β -wollastonite and diopside as a main crystal.

This is because β -wollastonite or diopside has a property of precipitating from the surface of the crystalline vitreous body toward the inside when it precipitates from the crystalline vitreous body during crystallization, and the surface of the crystallized glass layer a can be patterned into a natural marble pattern or the like due to this property.

The crystallized glass layer B also needs to contain at least one crystal of β -wollastonite and diopside as a main crystal. Since the crystallized glass layer a and the crystallized glass layer B can have a small difference in coefficient of thermal expansion by this arrangement, when a crystallized glass product is produced by a method described later, the crystallized glass product can be prevented from being broken.

The absolute value of the difference between the thermal expansion coefficients of the crystallized glass layer A and the crystallized glass layer B at 30 to 380 ℃ (hereinafter referred to simply as "thermal expansion coefficient difference") is 0 to 10 x 10^-7Preferably in the range of 0 to 3 x 10 DEG C^-7More preferably in the range/° c.

If the difference in thermal expansion coefficient exceeds 10X 10^-7When the crystallized glass product is produced by the production method described later, the crystallized glass layer a and the crystallized glass layer B are integrally sintered to each other while being crystallized by the heat treatment, and at this time, the difference in thermal shrinkage between the crystallized glass layer a and the crystallized glass layer B becomes large, and the crystallized glass product may be broken. Further, when the crystallized glass product is used for a wall material near a place where a high temperature is instantaneously generated, such as a gas furnace, breakage may occur.

The thermal expansion coefficient was measured under the following conditions using a thermomechanical analyzer (TMA, model TMA 7 manufactured by PERKIN ELMER).

Reference materials: is free of

Temperature rise rate: 20 ℃/min

Static force: 10mN

Sample length: 10mm

Heating ambient gas: n is a radical of₂

In the crystallized glass product of the present invention, the end face portion may be considered from the viewpoint of diversification of the pattern, prevention of the void defect, and the like, and therefore, a material having the same function as the crystallized glass layer B (crystallized glass layer C) may be sintered. In this case, the crystallized glass layer C may be sintered only to the end face portion of the crystallized glass layer a, or may be sintered to both end face portions of the crystallized glass layer a and the crystallized glass layer B.

The crystallized glass layer C is formed by crystallizing a crystallized glass plate C from the surface to the center thereof, and contains at least one crystal selected from β -wollastonite and diopside as a main crystal, and has a thickness of 6mm or less. In addition, the glass composition of the crystallized glass plate C used to form the crystallized glass layer C may or may not be the same as that of the crystallized glass plate B. (method for producing crystallized glass product)

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

A crystallized glass plate is prepared from a small volume of a crystallized glass material which can be a crystallized glass layer A, and a crystallized glass plate which can be a crystallized glass layer B is prepared. The two crystallized glass plates are placed in an overlapped state and heated to sinter the two crystallized glass plates to each other. By this method, the crystallized glass product of the present invention can be produced. However, from the viewpoint of practical use and cost, it is preferable to produce the crystallized glass product of the present invention by the production method described below.

That is, in the production of the crystallized glass product of the present invention, first, (1) a laminate comprising a layer-like crystallized glass small body layer in which a plurality of crystallized small glass bodies are integrated and a crystallized glass plate B laminated and arranged on the surface of the crystallized small glass body layer, (2) a laminate comprising a crystallized glass plate B and a layer-like crystallized small glass body layer in which a plurality of crystallized small glass bodies are integrated on the surface of the crystallized glass plate B, and (3) a laminate comprising a first crystallized glass plate B, a layer-like crystallized small glass body layer in which a plurality of crystallized small glass bodies are integrated on the surface of the first crystallized glass plate B, and a second crystallized glass plate B laminated and arranged on the surface of the crystallized small glass body layer are laminated. At least one kind of laminate selected from these groups is prepared.

Then, the crystallized glass product of the present invention can be produced by a heat treatment step of applying a heat treatment to at least one of the laminates (1) to (3).

Also, the heat treatment process is usually carried out in a refractory mold as shown in FIGS. 1A to 1C, which is coated with a mold release agent on its inner wall and is used to house the laminated body.

FIGS. 1A to 1C are schematic cross-sectional views illustrating an example of the method for producing a crystallized glass product of the present invention, and specifically show the arrangement state of a laminated body in a refractory mold. In fig. 1A to 1C, 10 denotes a refractory mold, 12 denotes a crystallized glass small body layer, 14A, and 14B denote crystallized glass plates B, and 20A, 20B, and 20C denote a laminate.

Here, the laminate of the above (1) is: as shown in fig. 1A, a crystallized glass gob layer 12 is formed by integrating a plurality of crystallized glass gobs into a layer in a refractory mold 10 having a mold release agent applied to the wall surface and the bottom surface (not shown), and then a crystallized glass plate B14 is disposed on the crystallized glass gob layer 12, and the layers 12 and 14 are combined (laminate 20A in the figure). The laminate of the above (2) is: as shown in fig. 1B, a crystallized glass plate B14 is disposed in a refractory mold 10 having a mold release agent applied to wall surfaces and a bottom surface (not shown), and then a crystallized glass platelet layer 12 is formed by integrating a plurality of crystallized glass platelets in a layer form on the upper surface of the crystallized glass plate B14, and the layers 14 and 12 are combined (laminate 20B in the figure). Further, the laminate of the above (3) is: as shown in fig. 1C, a first crystallized glass plate B14A is disposed in a refractory mold 10 having a mold release agent applied to wall surfaces and a bottom surface (not shown), a crystallized glass gob layer 12 is formed by integrating a plurality of crystallized glass gobs into a layer on the upper surface of the crystallized glass plate B14A, and a second crystallized glass plate B14B is disposed on the upper surface of the crystallized glass gob layer 12, and the first crystallized glass plate B, the second crystallized glass plate B, and the second crystallized glass plate B14B are combined to form a laminate 20C (shown in the figure).

When the crystallized glass layer C is desirably disposed on the end face of the crystallized glass product of the present invention, for example, the crystallized glass gob, the crystallized glass plate B, and the crystallized glass plate C may be disposed in the refractory mold in the following order.

First, when the laminate is formed in the refractory mold, the crystallized glass plate B, which is smaller than the bottom surface of the refractory mold by one turn, is arranged so that a gap of about several mm to ten and several mm is formed between the laminate and the side wall surface of the refractory mold. Then, the crystallized glass plate C is arranged in a gap portion between the end face of the laminated body and the side wall face of the refractory mold so that the crystallized glass plate C seems to be sandwiched between the end face of the laminated body and the side wall face of the refractory mold. Then, the heat treatment step is performed in this state, and a crystallized glass product in which the crystallized glass layer C is sintered to the end face can be obtained.

In addition to the above method, the crystallized glass plate C may be disposed on the sidewall surface of the refractory mold, and then the heat treatment step may be performed after the laminated body is formed.

FIG. 2 is a schematic cross-sectional view showing another example of the method for producing a crystallized glass product of the present invention, and specifically, shows a state in which a crystallized glass plate C and a laminate are arranged in a refractory mold in order to produce a crystallized glass product having a crystallized glass layer C sintered to an end face. In fig. 2, 16 denotes a crystallized glass plate C, 20 denotes a laminated body, and the elements denoted by other symbols are the same as those in fig. 1A to 1C.

In the example shown in fig. 2, the crystallized glass sheet C is apparently held between the laminated body 20 and the side wall surface of the refractory mold 10 in the refractory mold 10. Also, the layer structure of the laminate 20 may be any of the laminates 20A to 20C shown in fig. 1A to 1C.

In the heat treatment step, the heat treatment of the laminate is: the crystallization of the crystallized small glass bodies and the crystallized glass plate B is carried out under the condition that the crystallized small glass bodies are sintered to each other, and the crystallized small glass body layer and the crystallized glass plate B are sintered to each other, so that at least one of the crystals of the β -wollastonite and the diopside is precipitated in the crystallized small glass body layer as a main crystal, and at least one of the crystals of the β -wollastonite and the diopside is precipitated in the crystallized glass plate B as a main crystal, and the crystals are precipitated in the central portion of the crystallized glass plate B.

In order to satisfy the above conditions, the heat treatment is performed at a temperature higher than the softening point of both the crystallized small glass body and the crystallized glass plate B.

The specific heat treatment temperature and heat treatment time may be appropriately selected depending on the softening points of the crystallized glass particles and the crystallized glass plate B, the thickness of the crystallized glass particle layer or the crystallized glass plate B, and the like.

After the temperature is raised at a rate of 60 to 600 ℃/hr from the normal temperature, the temperature is preferably maintained at 1030 to 1130 ℃, more preferably 1050 to 1100 ℃, and then the temperature is maintained for about 0.5 to 5 hours, followed by slow cooling.

The thickness of the crystallized glass plate B is preferably 6mm or less, more preferably 5mm or less, and still more preferably 4mm or less. When the thickness of the crystallized glass sheet B exceeds 6mm, the crystallized glass sheet B after the heat treatment cannot be crystallized at the center portion thereof, and therefore a cracked crystallized glass matrix remains at the center portion of the crystallized glass layer B.

The crystallized glass product obtained through the above heat treatment step may be subjected to a polishing step of surface polishing for the purpose of adjusting the thickness of the crystallized glass product or the need for surface processing, or may be subjected to a cutting step of cutting the crystallized glass product for the purpose of forming a predetermined size or shape.

The crystallized small glass body used for the production of the crystallized glass product is a granular glass, and the shape thereof is not limited to a sphere, a rod, and the like, and the size thereof is not particularly limited, but it preferably has an average particle diameter of about 1mm to 7 mm. The method for producing the crystalline glass bodies is not particularly limited, and the crystalline glass bodies may be produced by combining methods known in the art, for example, a method of rapidly cooling a molten glass by water cooling or the like, or a method of pulverizing a bulk glass by mechanical pulverization or the like known in the art.

When the thickness of the crystallized glass layer B is 6mm or less, the use of an article made of a single crystallized glass plate B is not limited.

For example, the crystallized glass layer B may be formed by stacking 2 or more crystallized glass plates B and then performing a heat treatment process; the glass plate may be formed by arranging 2 or more rod-shaped crystallized glass plates B on the surface of the crystallized glass layer in a close and seamless manner and then performing a heat treatment process.

Similarly, the crystallized glass layer C may be formed by using 2 or more crystallized glass plates C or 2 or more rod-shaped crystallized glass plates C through a heat treatment step.

(glass Components of the crystallized Small glass, the crystallized glass plate B and the crystallized glass plate C)

The crystallized glass bodies, crystallized glass plates B and crystallized glass plates C used for producing the crystallized glass product of the present invention have the following properties: when these crystalline glasses are heat-treated at a temperature higher than the softening point, β -wollastonite and diopside, which are main crystals, precipitate from the surface of these crystalline glasses toward the inside, that is, these crystalline glasses are glass components of surface crystal type.

The glass component satisfying the above conditions preferably has glass components shown in the following (1) to (12).

(1) The mass percentage is SiO₂：50～65％、A1₂O₃: 3-13% of CaO: 15-25%, and ZnO: 2E &10% and a glass component having a total amount of coloring oxides of 0 to 5%.

The glass material formed from the present glass composition can precipitate β -wollastonite as a main crystal by heat treatment at a temperature higher than the softening point.

Further, the coloring oxide is at least one metal oxide selected from the group consisting of: v₂O₅、Cr₂O₃、MnO₂、Fe₂O₃CoO, NiO, CuO, etc., and the addition of such a coloring oxide to glass can color a colorless transparent glass material.

(2) The mass percentage is SiO₂：45～75％、Al₂O₃：1～13％、CaO：6～14.5％、Na₂O+K₂O: 1-13%, BaO: 0-20%, ZnO: 0 to 18%, and BaO + ZnO: 4 to 24% by weight, and 0 to 10% by weight of a total amount of coloring oxides. The coloring oxide composition herein is the same as that of the glass component (1).

(3) The mass percentage is SiO₂：45～75％、Al₂O₃：1～15％、CaO：8～20％、Na₂O+K₂O：1～15％、BaO：0～18％、ZnO：0～18％、BaO+ZnO：4～25％、Fe₂O₃：2～8％、TiO₂：0.1～7％、MnO₂：0.1～5％、CoO：0～2％、B₂O₃：0～3％、As₂O₃: 0 to 1%, and Sb₂O₃: 0 to 1% of a glass component.

(4) The mass percentage is SiO₂：48～68％、Al₂O₃：0.5～17％、CaO：6～22％、Na₂O+K₂O: 5-22%, MgO: 0.2-8%, BaO: 0-8%, ZnO: 0-9%, BaO + ZnO: 0 to 15%, and B₂O₃: 0 to 6% and 0 to 10% of a total amount of coloring oxides.

(5) The mass percentage is SiO₂：40～75％、Al₂O₃：2～15％、CaO：3～15％、ZnO：0～15％、BaO：0～20％、B₂O₃：0～10％、Na₂O+K₂O+Li₂O：2～20％、As₂O₃: 0 to 1%, and Sb₂O₃: 0 to 1% and 0 to 10% of total amount of coloring oxide.

(6) The mass percentage is SiO₂：45～75％、Al₂O₃：1～25％、CaO：1～12.5％、MgO：0.5～12％、CaO+MgO：1.5～13％、BaO：0～18％、ZnO：0～18％、Na₂O：1～15％、K₂O：0～7％、Li₂O：0～5％、B₂O₃：0～10％、P₂O₅：0～10％、As₂O₃: 0 to 1%, and Sb₂O₃: 0 to 1% and 0 to 10% of total amount of coloring oxide.

The glass material formed from the present glass composition can precipitate diopside as a main crystal by heat treatment at a temperature higher than the softening point.

(7) The mass percentage is SiO₂：40～75％、Al₂O₃：2～15％、CaO：3～20％、ZnO：0～15％、BaO：0～20％、B₂O₃：0～10％、Na₂O+K₂O+Li₂O：2～20％、As₂O₃: 0 to 1%, and Sb₂O₃: 0 to 1% and 0 to 10% of total amount of coloring oxide.

(8) The mass percentage is SiO₂：45～75％、Al₂O₃：1～25％、CaO：1～20％、MgO：0.5～17％、BaO：0～18％、ZnO：0～18％、Na₂O：1～15％、K₂O：0～7％、Li₂O：0～5％、B₂O₃：0～10％、P₂O₅：0～10％、As₂O₃: 0 to 1%, and Sb₂O₃: 0 to 1% and 0 to 10% of total amount of coloring oxide.

(9) The mass percentage is SiO₂：45～70％、Al₂O₃：1～13％、CaO：6～25％、Na₂O+K₂O+Li₂O: 0.1-20%, BaO: 0-20%, ZnO: 0 to 18%, and BaO + ZnO: 4 to 24% by weight, and 0 to 10% by weight of a total amount of coloring oxides.

(10) The mass percentage is SiO₂：45～75％、Al₂O₃：1～15％、CaO：6～20％、Na₂O+K₂O：1～15％、BaO：0～18％、ZnO：0-18%, BaO + ZnO: 4-25%, NiO: 0.05 to 5%, and CoO: 0.01 to 5% of a glass component.

(11) The mass percentage is SiO₂：50～75％、Al₂O₃：1～15％、CaO：6～16.5％、Li₂O：0.1～5％、B₂O₃：0～1.5％、CaO+Li₂O+B₂O₃：10～17.5％、ZnO：2.5～12％、BaO：0～12％、Na₂O+K₂O：0.1～15％、As₂O₃：0～1％、Sb₂O₃：0～1％、MgO：0～1.5％、SrO：0～1.5％、TiO₂：0～1％、ZrO₂: 0 to 1%, and P₂O₅: 0 to 1% and 0 to 10% of total amount of coloring oxide.

(12) The mass percentage is SiO₂：45～77％、Al₂O₃：1～25％、CaO：2～25％、ZnO：0～18％、BaO：0～20％、MgO：0～17％、Na₂O：1～15％、K₂O：0～7％、Li₂O：0～5％、B₂O₃：0～1.5％、As₂O₃：0～1％、Sb₂O₃：0～1％、SrO：0～1.5％、TiO₂：0～1％、ZrO₂: 0 to 1%, and P₂O₅: 0 to 1% and 0 to 10% of total amount of coloring oxide.

The glass material formed from the present glass composition can precipitate β -wollastonite and/or diopside as main crystals by heat treatment at a temperature higher than the softening point.

[ examples ]

Hereinafter, examples will be presented to explain the present invention in more detail, however, the present invention is not limited to the following examples.

(example 1)

Firstly, to SiO in mass percent₂：65.1％、Al₂O₃：6.6％、CaO：12.0％、Na₂O：3.3％、K₂O: 2.3%, BaO: 4.1%, and ZnO: a glass raw material having a composition of 6.6% is subjected to a melting treatment at 1500 ℃ for 16 hours, and then the molten glass is quenched in water to form cullets, and the cullets are dried and classified, whereby crystalline glass bodies having a particle size of 1 to 3mm can be obtained. The crystalline glass bodies can become main crystals by using beta-wollastonite after heat treatment, and have a thermal expansion coefficient of 65 x 10 within a temperature range of 30 to 380 DEG C^-7White crystallized glass at/° c.

Second, to mass percent is SiO₂：65.1％、Al₂O₃：6.6％、CaO：12.0％、Na₂O：3.3％、K₂O: 2.3%, BaO: 4.1%, and ZnO: a glass raw material having a composition of 6.6% was subjected to a melting treatment at 1500 ℃. The crystallized glass plate can become a main crystal by using beta-wollastonite after heat treatment, and has a thermal expansion coefficient of 65 x 10 within a temperature range of 30 to 380 DEG C^-7White crystallized glass at/° c.

And secondly, integrating the prepared crystallized small glass bodies into a refractory material mold coated with a release agent in a layered mode. The thickness of the integrated crystallized glass corpuscle is about 12mm, the surface of the integrated crystallized glass corpuscle layer is flattened, and at the same time, a crystallized glass plate is placed on the surface of the crystallized glass corpuscle layer in a manner of completely covering the crystallized glass corpuscle layer.

Then, the temperature was raised at a rate of 240 ℃ per hour, and after the temperature was maintained at 1100 ℃ for 1 hour, the mixture was cooled to room temperature for about 5 hours. Through this heat treatment, the plurality of small crystallized glass bodies are sintered with each other while precipitating crystals to form the crystallized glass layer a, and the crystallized glass plate B can be softened while precipitating crystals to form the crystallized glass layer B while being sintered with the small crystallized glass bodies, whereby a crystallized glass product formed of the crystallized glass layer a and the crystallized glass layer B can be obtained.

Thus, the thickness of the crystallized glass product obtained was about 16 mm. Then, by polishing the surface of the crystallized glass product and observing the crystallized glass product from the surface on which the crystallized glass layer B is laid, a translucent pattern can be formed in the crystallized glass layer B having a thickness of 5mm, and a natural marble pattern on the surface of the crystallized glass layer A can be observed by the crystallized glass layer B which is translucent and has a slightly blurred state. Further, since the translucent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer a can be viewed at the same time, the natural marble pattern showing a subtle stereoscopic impression can be viewed.

The reason why the crystallized glass layer B has a translucent pattern is that crystals grow from the surface of the crystallized glass plate B to the inside during the heat treatment. In addition, the crystallized glass layer a has almost the same natural marble pattern as that of the above-described crystallized glass product produced by the integration method using only small crystallized glass bodies under almost the same heat treatment conditions. Further, the crystallized glass layer a and the crystallized glass layer B were measured by X-ray diffraction (XRD), respectively, and as a result, it was found that the crystallized glass layer a and the crystallized glass layer B precipitated with β -wollastonite as a main crystal.

Further, when the cross section of the crystallized glass layer B was observed with the naked eye, no cracks were found. Further, as a result of observing the cross section of the crystallized glass layer B in the thickness direction by a Scanning Electron Microscope (SEM), it was found that crystals were precipitated in the entire thickness direction, and it was confirmed that the degree of crystallization of the crystallized glass layer B reached the center portion of the cross section.

(example 2)

Secondly, the prepared crystallized glass plate is placed in a refractory material mold coated with a release agent. The crystallized small glass bodies are integrated on the surface of the crystallized glass plate in a layered manner, the surface of the crystallized glass plate is completely covered, and then the surface of the crystallized small glass bodies is leveled, and the thickness of the crystallized small glass bodies is about 12 mm.

Then, the temperature was raised at a rate of 240 ℃ per hour, and after the temperature was maintained at 1100 ℃ for 1 hour, the mixture was cooled to room temperature for about 5 hours. Through this heat treatment, the crystallized glass plate can be softened while precipitating crystals to form the crystallized glass layer B while being sintered with the small crystallized glass bodies, and the plurality of small crystallized glass bodies can be sintered while precipitating crystals to form the crystallized glass layer a on the crystallized glass layer B, and therefore, a crystallized glass product formed of the crystallized glass layer a and the crystallized glass layer B can be obtained.

Thus, the thickness of the crystallized glass product obtained was about 16 mm. Next, after both surfaces of the crystallized glass product were polished, the crystallized glass product was observed from the surface on the side where the crystallized glass layer B was laid, and the crystallized glass layer B having a thickness of 5mm formed a translucent pattern, and the crystallized glass layer B appeared translucent and slightly blurred, thereby allowing the natural marble pattern on the surface of the crystallized glass layer a to be observed. Since the translucent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer a can be viewed at the same time, the natural marble pattern showing a subtle stereoscopic impression can be viewed.

The reason why the crystallized glass layer B has a translucent pattern is that crystals grow from the surface of the crystallized glass plate B to the inside during the heat treatment. In addition, the crystallized glass layer a has almost the same natural marble pattern as that of the above-described crystallized glass product produced by the integration method using only small crystallized glass bodies under almost the same heat treatment conditions. Further, the X-ray diffraction measurements were carried out on the crystallized glass layer A and the crystallized glass layer B, respectively, and it was found that the crystallized glass layer A and the crystallized glass layer B were precipitated with β -wollastonite as a main crystal.

In addition, when the cross section of the crystallized glass layer B was observed with the naked eye, no cracks were found. When the cross section of the crystallized glass layer B was observed in the thickness direction by a scanning electron microscope, it was found that crystals were precipitated in the entire thickness direction, and it was confirmed that the degree of crystallization of the crystallized glass layer B reached the center of the cross section.

(example 3)

Firstly, to SiO in mass percent₂：62.2％、Al₂O₃：5.9％、CaO：13.0％、Na₂O：4.5％、K₂O：2.1％、Li₂O: 1.0%, BaO: 6.0%, ZnO: 5.2%, and NiO: after melting treatment at 1450 ℃ for 16 hours is performed on a glass raw material having a composition of 0.1%, the molten glass is quenched in water to form cullets, and the cullets are dried and classified, whereby crystalline glass bodies having a particle size of 3 to 7mm can be obtained. The crystalline glass bodies can become main crystals by using beta-wollastonite after heat treatment, and have a thermal expansion coefficient of 69 x 10 within a temperature range of 30 to 380 DEG C^-7Beige crystallized glass at/° c.

Second, to mass percent is SiO₂：62.2％、Al₂O₃：5.9％、CaO：13.0％、Na₂O：4.5％、K₂O：2.1％、Li₂O: 1.0%, BaO: 6.0%, ZnO: 5.2%, and NiO: a glass raw material having a composition of 0.1% was subjected to melting treatment at 1450℃ for 16 hours, and then formed into a plate shape by a roll pressing method, whereby a crystallized glass plate having a thickness of 3mm was obtained. The crystallized glass plate can become a main crystal by using beta-wollastonite after heat treatment, and has a thermal expansion coefficient of 69 x 10 within a temperature range of 30-380 DEG C^-7Beige crystallized glass at/° c.

And secondly, integrating the prepared crystallized small glass bodies into a refractory material mold coated with a release agent in a layered mode. The thickness of the integrated crystallized glass body is about 14 mm. The surface of the crystallized glass subbulk layer after the integration is flattened, and at the same time, a crystallized glass plate is placed on the surface of the crystallized glass subbulk layer in such a manner as to completely cover the crystallized glass subbulk layer.

Then, the temperature was raised at a rate of 120 ℃ per hour, and after the temperature was maintained at 1050 ℃ for 2 hours, the mixture was cooled to room temperature for about 5 hours. Through this heat treatment, the plurality of small crystallized glass bodies are sintered with each other while precipitating crystals to form the crystallized glass layer a, and the crystallized glass plate B can be softened while precipitating crystals to form the crystallized glass layer B while being sintered with the small crystallized glass bodies, whereby a crystallized glass product formed of the crystallized glass layer a and the crystallized glass layer B can be obtained.

Thus, the thickness of the crystallized glass product obtained was about 16 mm. Next, after the surface of the crystallized glass product was polished, the crystallized glass product was observed from the surface on the side where the crystallized glass layer B was laid, and the crystallized glass layer B having a thickness of 3mm formed a translucent pattern, and the crystallized glass layer B appeared translucent and slightly blurred, thereby allowing the natural marble pattern on the surface of the crystallized glass layer a to be observed. Since the translucent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer a can be viewed at the same time, the natural marble pattern showing a subtle stereoscopic impression can be viewed.

The reason why the crystallized glass layer B has a translucent pattern is that crystals grow from the surface of the crystallized glass plate B to the inside during the heat treatment. In addition, the crystallized glass layer a has a natural marble pattern almost identical to that of the above-described crystallized glass product produced by the integration method using only small crystallized glass bodies under almost identical heat treatment conditions. Further, the X-ray diffraction measurements were carried out on the crystallized glass layer A and the crystallized glass layer B, respectively, and it was found that the crystallized glass layer A and the crystallized glass layer B were precipitated with β -wollastonite as a main crystal.

Further, when the cross section of the crystallized glass layer B was observed with the naked eye, no cracks were found. When the cross section of the crystallized glass layer B was observed in the thickness direction by a scanning electron microscope, it was found that crystals were precipitated in the entire thickness direction, and it was confirmed that the degree of crystallization of the crystallized glass layer B reached the center portion of the cross section.

(example 4)

Firstly, to SiO in mass percent₂：62.0％、Al₂O₃：9.0％、CaO：9.0％、MgO：4.5％、BaO：4.6％、Na₂O：5.0％、K₂O：3.0％、B₂O₃：0.5％、P₂O₅：2.0％、Sb₂O₃: 0.4%, and CoO: after a glass raw material having a composition of 0.05% is subjected to a melting treatment at 1500 ℃ for 16 hours, the molten glass is quenched in water to form cullets, and the cullets are dried and classified, whereby crystalline glass bodies having a particle size of 1 to 3mm can be obtained. These crystalline glass bodies can be converted into diopside as a main crystal after heat treatment, and have a thermal expansion coefficient of 71 x 10 in a temperature range of 30 to 380 DEG C^-7Grey crystallized glass at/° c.

Second, to mass percent is SiO₂：62.0％、Al₂O₃：9.0％、CaO：9.0％、MgO：4.5％、BaO：4.6％、Na₂O：5.0％、K₂O：3.0％、B₂O₃：0.5％、P₂O₅：2.0％、Sb₂O₃: 0.4%, and CoO: a glass raw material having a composition of 0.05% was subjected to a melting treatment at 1500 ℃. The crystallized glass plate can become diopside as main crystal after heat treatment, and has a thermal expansion coefficient of 71 x 10 within a temperature range of 30-380 DEG C^-7Grey crystallized glass at/° c.

Next, the prepared crystallized glass plate is placed in a refractory mold coated with a release agent, and then the crystallized glass bodies are integrated in layers on the surface of the crystallized glass plate so as to completely cover the surface of the crystallized glass plate. The thickness of the integrated crystallized glass body is about 12 mm. And leveling the surface of the integrated crystallized glass small body layer, and simultaneously, placing a crystallized glass plate on the surface of the crystallized glass small body layer in a mode of completely covering the surface of the crystallized glass small body layer. Thus configured, the resulting crystallized glass packet layer can be sandwiched between 2 crystallized glass plates.

Then, the temperature was raised at a rate of 120 ℃ per hour, and after the temperature was maintained at 1100 ℃ for 2 hours, the mixture was cooled to room temperature for about 5 hours. Through this heat treatment, the crystallized glass plate may be softened while precipitating crystals to form the first crystallized glass layer B while being sintered with the crystallized glass bodies, a plurality of crystallized glass bodies may be sintered while precipitating crystals to form the crystallized glass layer a on the first crystallized glass layer B, and the crystallized glass plate may be softened while precipitating crystals to form the second crystallized glass layer B while being sintered with the crystallized glass bodies on the crystallized glass layer a. Therefore, a crystallized glass product including the first crystallized glass layer B, the crystallized glass layer a, and the second crystallized glass layer B can be obtained.

Thus, the thickness of the crystallized glass product obtained was about 17 mm. Then, by polishing both surfaces of the crystallized glass product and observing the crystallized glass product from the surface on which the crystallized glass layer B was laid, a translucent pattern was formed in the crystallized glass layer B having a thickness of 3mm, and a natural marble pattern on the surface of the crystallized glass layer A was observed by the crystallized glass layer B which was translucent and slightly hazy. Since the translucent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer a can be viewed at the same time, the natural marble pattern showing a subtle stereoscopic impression can be viewed. The same result was obtained when the crystallized glass product was observed from the surface on the side of the other crystallized glass layer B.

The reason why the crystallized glass layer B has a translucent pattern is that crystals grow from the surface of the crystallized glass plate B to the inside during the heat treatment. In addition, the crystallized glass layer a has a natural marble pattern almost identical to that of the above-described crystallized glass product produced by the integration method using only small crystallized glass bodies under almost identical heat treatment conditions. Further, the X-ray diffraction measurements were carried out on the crystallized glass layer a and the crystallized glass layer B, respectively, and it was found that the crystallized glass layer a and the crystallized glass layer B were precipitated with diopside as a main crystal.

Further, when the cross section of the two crystallized glass layers B was observed with the naked eye, it was found that no crack occurred in any of the layers. When the cross sections of the two crystallized glass layers B were observed along the thickness direction of the crystallized glass layers B by a scanning electron microscope, it was found that crystals were precipitated in the entire thickness direction, and therefore, it was confirmed that the degree of crystallization of both the crystallized glass layers B reached the center of the cross section.

(example 5)

Firstly, to SiO in mass percent₂：60.0％、A1₂O₃：6.0％、CaO：7.6％、MgO：3.8％、BaO：3.5％、ZnO：6.5％、Na₂O：3.8％、K₂O：2.5％、Li₂O：0.4％、B₂O₃：5.4％、As₂O₃: 0.3%, and NiO: a glass raw material having a composition of 0.2% is subjected to a melting treatment at 1500 ℃ for 16 hours, and then the molten glass is formed into a ribbon shape, and is crushed and classified to obtain a crystalline vitreous body having a particle size of 1 to 3 mm. These crystalline glass bodies can be converted into diopside as a main crystal after heat treatment, and have a thermal expansion coefficient of 73X 10 in a temperature range of 30 to 380 DEG C^-7Beige crystallized glass at/° c.

Second, to mass percent is SiO₂：60.0％、Al₂O₃：6.0％、CaO：7.6％、MgO：3.8％、BaO：3.5％、ZnO：6.5％、Na₂O：3.8％、K₂O：2.5％、Li₂O：0.4％、B₂O₃：5.4％、As₂O₃: 0.3%, and NiO: a glass raw material having a composition of 0.2% was subjected to a melting treatment at 1500 ℃. The crystallized glass plate can become diopside as main crystal after heat treatment, and has a thermal expansion coefficient of 73 × 10 at 30-380 deg.C^-7Beige crystallized glass at/° c.

And secondly, integrating the prepared crystallized small glass bodies into a refractory material mold coated with a release agent in a layered mode. The thickness of the integrated crystallized glass body is about 16 mm. Then, the surface of the crystallized glass bulk layer after the integration is flattened, and at the same time, a crystallized glass plate is placed on the surface of the crystallized glass bulk layer in a manner of completely covering the crystallized glass bulk layer.

The thickness of the crystallized glass product thus obtained was about 16 mm. Then, by polishing the surface of the crystallized glass product and observing the crystallized glass product from the side where the crystallized glass layer B is laid, the crystallized glass layer B having a thickness of 1mm can form a translucent pattern, and the crystallized glass layer B which is translucent and has a slightly blurred state can be observed to see the natural marble pattern on the surface of the crystallized glass layer A. Since the translucent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer a can be viewed at the same time, the natural marble pattern showing a subtle stereoscopic impression can be viewed.

Further, when the cross section of the crystallized glass layer B was observed with the naked eye, no crack was observed. When the cross section of the crystallized glass layer B was observed along the thickness direction of the crystallized glass layer B by a scanning electron microscope, it was found that crystals were precipitated in the entire thickness direction, and therefore, it was confirmed that the degree of crystallization of the crystallized glass layer B reached the center portion of the cross section.

(example 6)

Second, to mass percent is SiO₂：62.2％、Al₂O₃：5.9％、CaO：13.0％、Na₂O：4.6％、K₂O：2.1％、Li₂O: 1.0%, BaO: 6.0%, and ZnO: a glass raw material having a composition of 5.2% was subjected to melting treatment at 1450℃ for 16 hours, and then formed into a plate shape by a roll pressing method, whereby a crystallized glass plate having a thickness of 3mm could be obtained. The crystallized glass plate can become a main crystal by using beta-wollastonite after heat treatment, and has a thermal expansion coefficient of 69 x 10 within a temperature range of 30-380 DEG C^-7White crystallized glass at/° c.

Then, the crystallized glass sheet obtained by the roll pressing method is used for forming the crystallized glass layer C in addition to the crystallized glass layer B, and therefore, two kinds of crystallized glass sheets having different shapes can be cut in accordance with the size of each layer.

And secondly, integrating the prepared crystallized small glass bodies into a refractory material mold coated with a release agent in a layered mode. The thickness of the integrated crystallized glass body is about 14 mm. Then, the surface of the crystallized glass bulk layer after the integration is flattened, and at the same time, a crystallized glass plate is placed on the surface of the crystallized glass bulk layer in a manner of completely covering the crystallized glass bulk layer. Further, the size of the crystallized glass plate is slightly smaller than that of the refractory mold. The four sides of the crystallized glass plate were each spaced 3mm from the side wall surface of the refractory mold and placed on the crystallized glass capsule layer.

Then, a crystallized glass plate having a thickness of 3mm was inserted between the laminated body formed by stacking the crystallized glass gob and the crystallized glass plate and the side wall surface of the refractory mold so that the plate thickness direction was parallel to the bottom surface of the refractory mold, and as shown in fig. 2, the crystallized glass plate was disposed between the end surface of the laminated body and the side wall surface of the refractory mold. The crystallized glass plate is disposed in close contact with the periphery of the end face of the laminate.

Then, the temperature was raised at a rate of 120 ℃ per hour, and after the temperature was maintained at 1050 ℃ for 1 hour, the mixture was cooled to room temperature for about 5 hours. Through this heat treatment, the plurality of crystallized glass bodies are sintered with each other while precipitating crystals to form the crystallized glass layer a, the crystallized glass plate B can be softened while precipitating crystals to form the crystallized glass layer B while being sintered with the crystallized glass bodies on the crystallized glass layer a, and at the same time, the crystallized glass plate C can be softened while precipitating crystals to form the crystallized glass layer C while being sintered with the laminate around the end face of the laminate formed by the crystallized glass layer a and the crystallized glass layer B. Therefore, a crystallized glass product including the crystallized glass layer a, the crystallized glass layer B, and the crystallized glass layer C can be obtained.

Thus, the thickness of the crystallized glass product obtained was about 16 mm. Then, by polishing the surface and end faces of the crystallized glass product and observing the crystallized glass product from the side where the crystallized glass layer B was laid, the crystallized glass layer B having a thickness of 3mm formed a translucent pattern, and the crystallized glass layer B appeared translucent and slightly blurred, thereby allowing the natural marble pattern on the surface of the crystallized glass layer A to be observed. Since the translucent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer a can be viewed at the same time, the natural marble pattern showing a subtle stereoscopic impression can be viewed.

Further, the results obtained by observing the crystallized glass product from the side where the crystallized glass layer C having a thickness of 3mm was laid were the same as those obtained by observing the crystallized glass product from the side where the crystallized glass layer B was laid.

The translucent patterns of the crystallized glass layer B and the crystallized glass layer C are caused by the crystal growth from the surface to the inside of the crystallized glass layer B and the crystallized glass layer C. In addition, the crystallized glass layer a has a natural marble pattern almost identical to that of the above-described crystallized glass product produced by the integration method using only small crystallized glass bodies under almost identical heat treatment conditions. Further, the X-ray diffraction measurements were carried out on each of the crystallized glass layer a, the crystallized glass layer B, and the crystallized glass layer C, and it was found that the crystallized glass layer a was precipitated with diopside as a main crystal, and the crystallized glass layer B and the crystallized glass layer C were precipitated with β -wollastonite as a main crystal.

Further, when the cross section of the crystallized glass layer B was visually observed, no cracks were found. When the cross section of the crystallized glass layer B was observed in the thickness direction by a scanning electron microscope, it was found that crystals were precipitated in the entire thickness direction, and it was confirmed that the degree of crystallization of the crystallized glass layer B reached the center portion of the cross section. The crystallized glass layer C also has this same result.

(example 7)

Firstly, to SiO in mass percent₂：62.2％、Al₂O₃：5.9％、CaO：13.0％、Na₂O：4.5％、K₂O：2.1％、Li₂O: 1.0%, BaO: 6.0%, ZnO: 5.2%, and NiO: after melting treatment at 1450 ℃ for 16 hours of a glass raw material having a composition of 0.1%, the molten glass is quenched in water to glass cullet, and the glass cullet is dried and classified to obtain a crystalline glass body having a particle size of 3 to 7 mm. The crystalline glass bodies can become main crystals by using beta-wollastonite after heat treatment, and have a thermal expansion coefficient of 69 x 10 within a temperature range of 30 to 380 DEG C^-7Beige crystallized glass at/° c.

Second, to mass percent is SiO₂：62.2％、Al₂O₃：5.9％、CaO：13.0％、Na₂O：4.5％、K₂O：2.1％、Li₂O: 1.0%, BaO: 6.0%, ZnO: 5.2%, and NiO: a glass raw material having a composition of 0.1% was subjected to a melting treatment at 1450 ℃ for 16 hours, and then formed into a plate shape by a roll pressing method, whereby a crystallized glass plate having a thickness of 2mm could be obtained. The crystallized glass plate can become a main crystal by using beta-wollastonite after heat treatment, and has a thermal expansion coefficient of 69 x 10 within a temperature range of 30-380 DEG C^-7Beige crystallized glass at/° c.

Next, the prepared crystallized glass plate is placed in a refractory mold coated with a release agent, and then the crystallized glass corpuscles are integrated on the surface of the crystallized glass plate in a layered manner so as to completely cover the surface of the crystallized glass plate. The thickness of the integrated crystallized glass body is about 14 mm. And leveling the surface of the integrated crystallized glass small body layer, and simultaneously, placing a crystallized glass plate on the surface of the crystallized glass small body layer in a mode of completely covering the surface of the crystallized glass small body layer. Thus configured, the resulting crystallized glass packet layer can be sandwiched between 2 crystallized glass plates.

Further, the size of the 2 crystallized glass plates is slightly smaller than that of the refractory mold. The four sides of the crystallized glass plate were spaced from the side wall surface of the refractory mold by 2mm, respectively, and placed on the upper and lower surfaces of the crystallized glass capsule layer.

Then, a 2 mm-thick crystallized glass plate was inserted between the laminated body of the crystallized glass small body layer and the crystallized glass plate and the side wall surface of the refractory mold so that the plate thickness direction was parallel to the bottom surface of the refractory mold. As shown in fig. 2, the crystallized glass plate is disposed between the end face of the laminate and the side wall face of the refractory mold. The crystallized glass plate is disposed in close contact with the periphery of the end face of the laminate.

Then, the temperature was raised at a rate of 180 ℃ per hour, and after the temperature was maintained at 1050 ℃ for 2 hours, the mixture was cooled to room temperature for about 5 hours. Through this heat treatment, the crystallized glass plate may be softened while precipitating crystals to form the first crystallized glass layer B while being sintered with the crystallized glass bodies, the plurality of crystallized glass bodies may be sintered with each other while precipitating crystals to form the crystallized glass layer a on the first crystallized glass layer B, and the crystallized glass plate may be softened while precipitating crystals to form the second crystallized glass layer B while being sintered with the crystallized glass bodies on the crystallized glass layer a. At the same time, the crystallized glass layer A and the first and second crystallized glass layers B arranged on both sides thereof form a laminate, and the crystallized glass plate C can be softened and crystallized around the end face of the laminate to form the crystallized glass layer C and simultaneously sintered with the laminate, so that a crystallized glass product formed of the crystallized glass layer A, the crystallized glass layer B and the crystallized glass layer C can be obtained.

Thus, the thickness of the crystallized glass product obtained was about 17 mm. Then, both surfaces and end faces of the crystallized glass product were polished, and the crystallized glass product was observed from the surface on the side where the crystallized glass layer B was laid, whereby the crystallized glass layer B having a thickness of 2mm formed a translucent pattern, and the crystallized glass layer B appeared translucent and slightly blurred, thereby allowing the natural marble pattern on the surface of the crystallized glass layer a to be observed. Since the translucent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer a can be viewed at the same time, the natural marble pattern showing a subtle stereoscopic impression can be viewed.

Further, the results obtained by observing the crystallized glass product from the side where the crystallized glass layer C having a thickness of 2mm was laid were the same as those obtained by observing the crystallized glass product from the side where the crystallized glass layer B was laid. Further, a line pattern after stretching the rib can be observed along the interface portion between the crystallized glass layer B and the crystallized glass layer C in the direction orthogonal to the interface.

The translucent patterns of the crystallized glass layer B and the crystallized glass layer C are caused by the crystal growth from the surface to the inside of the crystallized glass layer B and the crystallized glass layer C. In addition, the crystallized glass layer a has a natural marble pattern almost identical to that of the above-described crystallized glass product produced by the integration method using only small crystallized glass bodies under almost identical heat treatment conditions. Further, the X-ray diffraction measurements were carried out on each of the crystallized glass layer a, the crystallized glass layer B, and the crystallized glass layer C, and it was found that the crystallized glass layer a, the crystallized glass layer B, and the crystallized glass layer C precipitated with β -wollastonite as a main crystal.

(example 8)

Firstly, to SiO in mass percent₂：65.1％、Al₂O₃：6.6％、CaO：12.0％、Na₂O：3.3％、K₂O: 2.3%, BaO: 4.1%, and ZnO: after a glass raw material having a composition of 6.6% is subjected to a melting treatment at 1500 ℃ for 16 hours, the molten glass is quenched in water to form cullets, and the cullets are dried and classified, whereby crystalline glass bodies having a particle size of 1 to 3mm can be obtained. The crystalline glass bodies can become main crystals by using beta-wollastonite after heat treatment, and have a thermal expansion coefficient of 65 x 10 within a temperature range of 30 to 380 DEG C^-7White crystallized glass at/° c.

Second, to mass percent is SiO₂：65.1％、Al₂O₃：6.6％、CaO：12.0％、Na₂O：3.3％、K₂O: 2.3%, BaO: 4.1%, and ZnO: a glass raw material having a composition of 6.6% was subjected to a melting treatment at 1500 ℃. The crystallized glass plate can become a main crystal by using beta-wollastonite after heat treatment, and has a thermal expansion coefficient of 65 x 10 within a temperature range of 30 to 380 DEG C^-7White crystallized glass at/° c. The crystallized glass plate was cut and processed into a rod having a width of 10 mm.

And secondly, integrating the prepared crystallized small glass bodies into a refractory material mold coated with a release agent in a layered mode. The thickness of the integrated crystallized glass body is about 15 mm. Then, the surface of the crystallized glass subbulk layer after the integration is flattened, and at the same time, a crystallized glass plate is placed on the surface of the crystallized glass subbulk layer in a manner of completely covering the crystallized glass subbulk layer.

Then, the temperature was raised at a rate of 240 ℃ per hour, and after the temperature was maintained at 1100 ℃ for 1 hour, the mixture was cooled to room temperature for about 5 hours. By this heat treatment, the plurality of small crystallized glass bodies are sintered to each other and simultaneously crystallized to form the crystallized glass layer a, and the plurality of rod-shaped crystallized glass plates B are sintered to each other and simultaneously crystallized to form the crystallized glass layer B and simultaneously sintered to the small crystallized glass bodies on the crystallized glass layer a, so that a crystallized glass product comprising the crystallized glass layer a and the crystallized glass layer B can be obtained.

Thus, the thickness of the crystallized glass product obtained was about 16 mm. Next, the surface of the crystallized glass product was polished, and the crystallized glass product was observed from the surface on the side where the crystallized glass layer B was laid, and the crystallized glass layer B having a thickness of 2mm formed a translucent pattern with lines interposed therebetween, and the natural marble pattern on the surface of the crystallized glass layer a was observed through the crystallized glass layer B which was translucent and slightly hazy. Since the translucent pattern of the lines of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer a can be viewed simultaneously, the natural marble pattern showing a subtle stereoscopic impression can be viewed.

The reason why the crystallized glass layer B has a translucent pattern is that crystals grow from the surface of the rod-like crystallized glass plate B to the inside during the heat treatment. In addition, the crystallized glass layer a has a natural marble pattern almost identical to that of the above-described crystallized glass product produced by the integration method using only small crystallized glass bodies under almost identical heat treatment conditions. Further, the X-ray diffraction measurements were carried out on the crystallized glass layer A and the crystallized glass layer B, respectively, and it was found that the crystallized glass layer A and the crystallized glass layer B were precipitated with β -wollastonite as a main crystal.

Further, when the cross section of the crystallized glass layer B was visually observed, no cracks were found. When the cross section of the crystallized glass layer B was observed in the thickness direction by a scanning electron microscope, it was found that crystals were precipitated in the entire thickness direction, and it was confirmed that the degree of crystallization of the crystallized glass layer B reached the center portion of the cross section.

(example 9)

And secondly, integrating the prepared crystallized small glass bodies into a refractory material mold coated with a release agent in a layered mode. The thickness of the integrated crystallized glass body is about 14 mm. Then, the surface of the integrated crystallized glass subbulk layer was flattened, and at the same time, 2 crystallized glass plates were placed on the surface of the crystallized glass subbulk layer in such a manner as to overlap and completely cover the crystallized glass subbulk layer.

Then, the temperature was raised at a rate of 240 ℃ per hour, and after the temperature was maintained at 1100 ℃ for 1 hour, the mixture was cooled to room temperature for about 5 hours. Through this heat treatment, the plurality of crystallized glass bodies are sintered to each other and simultaneously crystallized to form the crystallized glass layer a, and the 2 crystallized glass plates B on the crystallized glass layer a are sintered to each other and simultaneously crystallized to form the crystallized glass layer B and simultaneously sintered to the crystallized glass bodies, so that a crystallized glass product formed of the crystallized glass layer a and the crystallized glass layer B can be obtained.

Thus, the thickness of the crystallized glass product obtained was about 16 mm. Then, by polishing the surface of the crystallized glass product and observing the crystallized glass product from the side where the crystallized glass layer B was laid, the crystallized glass layer B having a thickness of 3mm formed a translucent pattern, and the crystallized glass layer B appeared translucent and slightly blurred, thereby allowing the natural marble pattern on the surface of the crystallized glass layer A to be observed. Since the translucent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer a can be viewed at the same time, the natural marble pattern showing a subtle stereoscopic impression can be viewed.

Comparative example 1

Firstly, to SiO in mass percent₂：65.1％、Al₂O₃：6.6％、CaO：12.0％、Na₂O：3.3％、K₂O：2.3%, BaO: 4.1%, and ZnO: a glass raw material having a composition of 6.6% is subjected to a melting treatment at 1500 ℃ for 16 hours, and then the molten glass is quenched in water to form cullets, and the cullets are dried and classified, whereby crystalline glass bodies having a particle size of 1 to 3mm can be obtained. The crystalline glass bodies can become main crystals by using beta-wollastonite after heat treatment, and have a thermal expansion coefficient of 65 x 10 within a temperature range of 30 to 380 DEG C^-7White crystallized glass at/° c.

Second, to mass percent is SiO₂：51.0％、Al₂O₃：19.0％、MgO：4.7％、ZnO：4.1％、TiO₂：2.2％、ZrO₂：1.5％、B₂O₃：6.0％、Na₂O：8.5％、K₂O: 2.8%, and CaO: a glass raw material having a composition of 0.2% was subjected to a melting treatment at 1500 ℃. The crystallized glass plate becomes forsterite (2 mgo. sio) after heat treatment₂) Is a main crystal and has a coefficient of thermal expansion of 67 x 10 within a temperature range of 30 to 380 DEG C^-7White crystallized glass at/° c.

And secondly, integrating the prepared crystallized small glass bodies into a refractory material mold coated with a release agent in a layered mode. The thickness of the integrated crystallized glass body is about 14 mm. Then, the surface of the crystallized glass subbulk layer after the integration is flattened, and at the same time, a crystallized glass plate is placed on the surface of the crystallized glass subbulk layer in a manner of completely covering the crystallized glass subbulk layer.

Then, the temperature was raised at a rate of 120 ℃ per hour, and after the temperature was maintained at 1100 ℃ for 2 hours, the mixture was cooled to room temperature for about 5 hours. Through this heat treatment, the plurality of small crystallized glass bodies are sintered with each other while precipitating crystals to form the crystallized glass layer a, and the crystallized glass plate B can be softened while precipitating crystals to form the crystallized glass layer B while being sintered with the small crystallized glass bodies, whereby a crystallized glass product formed of the crystallized glass layer a and the crystallized glass layer B can be obtained.

Thus, the thickness of the crystallized glass product obtained was about 16 mm. Then, when the surface of the crystallized glass product was polished and the crystallized glass product was observed from the surface on the side where the crystallized glass layer B was laid, the crystallized glass layer B having a thickness of 3mm exhibited a white color without a transparent feeling, and the crystallized glass layer a was not observed through the crystallized glass layer B.

The reason why the crystallized glass layer B has a white color without a transparent feeling is that: when the heat treatment is performed, the crystals do not grow from the surface of the crystallized glass plate B to the inside, but simultaneously grow from any position in the crystallized glass plate B. Further, when a crystallized glass product produced by an integration method using only the above small crystallized glass bodies under almost the same heat treatment conditions was observed, a natural marble pattern was exhibited. From this, it is considered that the natural marble pattern can be observed as long as the crystallized glass layer B is transparent or translucent.

Further, the X-ray diffraction measurements were carried out on the crystallized glass layer A and the crystallized glass layer B, respectively, and it was found that the crystallized glass layer A precipitated with β -wollastonite as a main crystal. The crystallized glass layer B is precipitated with forsterite as a main crystal.

Comparative example 2

Second, to mass percent is SiO₂：51.0％、Al₂O₃：19.0％、MgO：4.7％、ZnO：4.1％、TiO₂：2.2％、ZrO₂：1.5％、B₂O₃：6.0％、Na₂O：8.5％、K₂O: 2.8%, and CaO: a glass raw material having a composition of 0.2% was subjected to a melting treatment at 1500 ℃. The crystallized glass plate can become forsterite as main crystal after heat treatment, and has a thermal expansion coefficient of 67 x 10 within a temperature range of 30-380 DEG C^-7White crystallized glass at/° c.

Next, the prepared crystallized glass plate is placed in a refractory mold coated with a release agent, and then the crystallized glass bodies are integrated in layers on the surface of the crystallized glass plate so as to completely cover the surface of the crystallized glass plate. The thickness of the integrated crystallized glass body is about 14 mm. And leveling the surface of the integrated crystallized glass small body layer, and simultaneously, placing a crystallized glass plate on the surface of the crystallized glass small body layer in a mode that the surface of the crystallized glass small body layer is completely covered. Thus configured, the resulting crystallized glass packet layer can be sandwiched between 2 crystallized glass plates.

Then, the temperature was raised at a rate of 120 ℃ per hour, and after the temperature was maintained at 1050 ℃ for 2 hours, the mixture was cooled to room temperature for about 5 hours. Through this heat treatment, the crystallized glass plate may be softened while precipitating crystals to form the first crystallized glass layer B while being sintered with the crystallized glass bodies, the plurality of crystallized glass bodies may be sintered with each other while precipitating crystals to form the crystallized glass layer a on the first crystallized glass layer B, and the crystallized glass plate may be softened while precipitating crystals to form the second crystallized glass layer B while being sintered with the crystallized glass bodies on the crystallized glass layer a. In other words, the first and second crystallized glass layers B are disposed on both sides of the crystallized glass layer a to form a laminate, and the crystallized glass plate C can be softened and crystallized around the end face of the laminate to form the crystallized glass layer C and sintered with each other, whereby a crystallized glass product formed of the crystallized glass layer a, the crystallized glass layer B, and the crystallized glass layer C can be obtained.

Thus, the thickness of the crystallized glass product obtained was about 17 mm. Then, both surfaces and end faces of the crystallized glass product were polished, and the crystallized glass product was observed from the surface on the side where the crystallized glass layer B or the crystallized glass layer C was laid, and the crystallized glass layer B and the crystallized glass layer C having a thickness of 2mm exhibited a white color without a transparent feeling, and the crystallized glass layer a was not observed through the crystallized glass layer B and the crystallized glass layer C.

The reason why the crystallized glass layer B and the crystallized glass layer C exhibit white color without a transparent feeling is that: in the heat treatment, the crystals do not grow from the surface to the inside of the crystallized glass plates B and C, but simultaneously grow from any position of the crystallized glass plates B and C. Further, it was observed that crystallized glass products produced by the integration method using only the above-mentioned small crystallized glass bodies under almost the same heat treatment conditions exhibited natural marble patterns. From this case, it is considered that the natural marble pattern can be observed as long as the crystallized glass layer B and the crystallized glass layer C are transparent or translucent.

Further, the X-ray diffraction measurements were carried out on each of the crystallized glass layer a, the crystallized glass layer B, and the crystallized glass layer C, and it was found that the crystallized glass layer a was precipitated with β -wollastonite as a main crystal, and the crystallized glass layer B and the crystallized glass layer C were precipitated with forsterite as a main crystal.

Comparative example 3

The crystalline glass bodies used in example 3 were integrated in layers in a refractory mold coated with a mold release agent. The thickness of the integrated crystallized glass corpuscle layer is about 18mm, and the surface of the integrated crystallized glass corpuscle layer is flattened.

Then, the temperature was raised at a rate of 120 ℃ per hour, and after the temperature was maintained at 1100 ℃ for 2 hours, the mixture was cooled to room temperature for about 5 hours. By this heat treatment, the plurality of small crystallized glass bodies are sintered to each other and simultaneously crystallized to form a crystallized glass layer, and thus a crystallized glass product formed of the crystallized glass layer can be obtained.

Thus, the thickness of the crystallized glass product obtained was about 16 mm. Next, the surface of the crystallized glass product was polished to a mirror surface, and then the surface of the crystallized glass product was observed, and as a result, it was found that the surface of the crystallized glass product exhibited a natural marble pattern. However, when the surface of the crystallized glass article was observed, pinhole defects having a diameter of about 0.1mm to 1.0mm were observed.

Comparative example 4

1500 glass raw materials used in example 1 for producing a crystallized glass plateAfter the melting treatment at 16 hours, the glass was shaped into a plate shape by a roll method, and a crystallized glass plate having a thickness of 10mm was obtained. The crystallized glass plate can become a main crystal by using beta-wollastonite after heat treatment, and has a thermal expansion coefficient of 65 x 10 within a temperature range of 30 to 380 DEG C^-7White crystallized glass at/° c.

Next, the prepared crystallized glass plate was placed in a refractory mold coated with a release agent, and then the temperature was raised at a rate of 180 ℃ per hour, held at 1100 ℃ for 1 hour, and then cooled to room temperature for about 5 hours, and through this heat treatment, a crystallized glass product crystallized from the crystallized glass plate was obtained.

Thus, the thickness of the crystallized glass product obtained was about 10 mm. Next, the surface of the crystallized glass article was observed after polishing both surfaces of the crystallized glass article, and as a result, it was found that a natural marble pattern was observed. Further, the X-ray diffraction measurement of the crystallized glass product revealed that the crystallized glass product precipitated with β -wollastonite as a main crystal.

However, when the cross section of the crystallized glass product is observed after the crystallized glass product is cut, it is found that a crack occurs in the central portion in the thickness direction. Further, as a result of observing the cross section of the crystallized glass product along the thickness direction, it was found that crystals were precipitated from the upper and lower surfaces of the crystallized glass product to the inside by about 3mm, and no crystals were precipitated in the portion having a thickness of about 4mm in the central portion in the thickness direction, and thus it was found that this portion was not crystallized.

Although the present invention has been described with reference to preferred embodiments, those skilled in the art will appreciate that various modifications, substitutions and changes can be made thereto without departing from the spirit and scope of the present invention. However, such modifications, substitutions and variations are intended to fall within the scope of the appended claims.

Claims

1. A crystallized glass article having a pattern, comprising:

a crystallized glass layer A in which a plurality of small crystallized glass bodies are sintered and crystallized simultaneously to form a pattern;

a crystallized glass layer (B) which is formed in a translucent state by disposing a crystallized glass plate (B) on at least one surface of the crystallized glass layer (A) while the surface is in a sintered state, and crystallizing the crystallized glass plate (B) from the surface toward the inside to the center;

and

a crystallized glass layer C sintered to the end face portion of the crystallized glass layer A or the end face portions of the crystallized glass layer A and the crystallized glass layer B, the crystallized glass layer C being formed by crystallizing a crystallized glass plate C from the surface to the center thereof and containing at least one crystal of β -wollastonite and diopside as a main crystal, wherein the thickness of the crystallized glass layer C is 6mm or less,

wherein the main crystal of the crystallized glass layer A is at least one of beta-wollastonite and diopside, the main crystal of the crystallized glass layer B is at least one of beta-wollastonite and diopside, and the crystallized glass layer B has a thickness of 0.1mm to 6 mm.

2. The patterned crystallized glass article of claim 1, wherein the crystallized glass layer a has a thickness of 0.1mm to 30 mm.

3. The patterned crystallized glass article of claim 1, wherein the crystallized glass article has a thickness of from 8mm to 30 mm.

4. The crystallized glass article having a pattern according to claim 1, wherein said crystallized glass layer B is provided on both upper and lower surfaces of said crystallized glass layer A, respectively, when both of said upper and lower surfaces are in a sintered state.

5. The crystallized glass article having pattern according to claim 1, wherein the absolute value of the difference between the thermal expansion coefficients of said crystallized glass layer A and said crystallized glass layer B in the range of 30 to 380 ℃ is 0 to 10X 10^-7In the range/° c.

6. A method for producing a crystallized glass article having a pattern, comprising a heat treatment step of heat-treating at least one of the following laminates:

(1) a laminate comprising a plurality of layered crystallized glass gob layers formed by integrating a plurality of crystallized glass gobs, a crystallized glass plate B disposed on the surface of the crystallized glass gob layers, and a crystallized glass plate C disposed on an end face portion of the crystallized glass gob layer or on both the crystallized glass gob layer and the end face portion of the crystallized glass plate B;

(2) a laminate comprising a crystallized glass plate B, a plurality of crystallized glass bodies on the surface of the crystallized glass plate B, wherein the crystallized glass bodies are layered and integrated into a layer, and a crystallized glass plate C disposed at an end face portion of the crystallized glass bodies or at both the crystallized glass bodies and the end face portion of the crystallized glass plate B; and

(3) a laminate comprising a first crystallized glass plate B, a layered crystallized glass gob layer comprising a plurality of crystallized glass gobs on the surface of the first crystallized glass plate B, a second crystallized glass plate B disposed on the surface of the crystallized glass gob layer, and a crystallized glass plate C disposed on the end face portion of the crystallized glass gob layer or the crystallized glass gob layer and the end face portion of the first or second crystallized glass plate B,

wherein the heat treatment step comprises:

sintering the plurality of crystallized glass bodies in the crystallized glass body layer to each other; and

mutually sintering the crystallized glass frit layer and the crystallized glass plate B, the crystallized glass plate C, or the first and the second crystallized glass plates B, and simultaneously crystallizing the plurality of crystallized glass frits and the crystallized glass plate B, the crystallized glass plate C, or the first and the second crystallized glass plates B, and forming the crystallized glass frit layer A into the crystallized glass frit layer B, forming the crystallized glass frit layer B into the first crystallized glass plate B and the second crystallized glass plate B into the first and the second crystallized glass layers B, and forming the crystallized glass frit layer C into the crystallized glass frit layer A, wherein the crystallized glass layer A is patterned, and the crystallized glass layer B and the first and the second crystallized glass layers B are in a translucent state,

wherein at least one kind of crystals selected from the group consisting of beta-wollastonite and diopside is precipitated as main crystals in the crystalline glass platelet layer, and at least one kind of crystals selected from the group consisting of beta-wollastonite and diopside is precipitated as main crystals in the crystalline glass sheet B or the first and second crystalline glass sheets B from the surface of the crystalline glass sheet B or the first and second crystalline glass sheets B toward the inside thereof to the center thereof,

wherein the crystallized glass plate B has a thickness of 0.1mm to 6mm, the first crystallized glass plate B and the second crystallized glass plate B have a thickness of 0.1mm to 6mm, respectively, and the crystallized glass layer C has a thickness of 6mm or less, the crystallized glass layer C containing at least one crystal of β -wollastonite and diopside as a main crystal.

7. The method for producing a crystallized glass article having a pattern according to claim 6, wherein the crystallized glass gob layer has a thickness of 0.1mm to 30 mm.