JP2010270003A - Patterned crystallized glass article and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a patterned crystallized glass article having sufficient strength, and free from pinhole defects of the surface. <P>SOLUTION: The patterned crystallized glass article includes a crystallized glass layer A formed by mutually fusing and bonding a plurality of crystallizable small glass bodies and crystallizing them, and a crystallized glass layer B placed on at least one face of the crystallized glass layer A in the state of fusion bonding, where a crystallizable glass plate B is subjected to crystallization to the central part thereof. The crystallized glass layer A includes at least one crystal selected from β-wollastonite and diopside as a main crystal. The crystallized glass layer B includes at least one crystal selected from β-wollastonite and diopside as a main crystal and has a thickness of ≤6 mm. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a crystallized glass article with a pattern used for exterior materials for buildings, top materials for interior materials and furniture, top plate materials for office tables, and the like, and a method for producing the same.

  Various crystallized glass articles are required as exterior materials for buildings, top plate materials for furniture and furniture, and top plate materials for office tables.

Crystallized glass used for this purpose is known to contain β-wollastonite (CaO · SiO 2) or diopside (CaO · MgO · 2SiO ₂ ) as the main crystal.
Moreover, as a manufacturing method of the crystallized glass article containing the crystal | crystallization mentioned above, (1) The manufacturing method (for example, refer patent document 1) which precipitates and grows a crystal | crystallization from the surface to the inside by heat-processing plate-like glass, (2) Manufacturing method called “accumulation method”; that is, molten glass is made into a crystalline glass body by a rapid cooling process such as water cooling, and this crystalline glass body is accumulated in a mold made of refractory bricks, etc. A manufacturing method (for example, refer to Patent Documents 2 to 8) is known in which the crystalline glass bodies are fused and integrated with each other to be crystallized by heat treatment.
Crystallized glass articles manufactured using these manufacturing methods have patterns such as natural marble patterns.

Japanese Patent Publication No.51-23966 Japanese Patent Publication No.53-39884 Japanese Patent Publication No.55-29018 JP 63-201037 A Japanese Patent Laid-Open No. 3-164446 JP-A-3-205323 Japanese Patent Laid-Open No. 5-163033 JP-A-6-24768

However, when a crystallized glass article is produced by heat-treating the plate-like glass shown in (1) above, since the nucleating agent is not contained in the plate-like glass, from the front and back surfaces and end surfaces of the plate-like glass. Crystals precipitate and grow inside. For this reason, for example, in the case of a plate-like crystallized glass article having a thickness of about 10 mm, a glass matrix having a thickness of about 4 mm that has not been crystallized remains as it is in the central portion thereof. Cracks have occurred.
This state will be described in more detail with reference to the drawings. FIG. 3 is a schematic cross-sectional view showing an example of a cross-sectional structure of a crystallized glass article obtained by heat-treating a plate-like glass as described above, in which 100 is a crystallized glass article, and 110 is a crystallizer. A glass matrix, 120 is a non-crystallized glass matrix, and 130 is a crack. As shown in FIG. 3, there is a non-crystallized glass matrix in a region surrounded by a crystallized glass matrix that has grown and crystallized from the front and back surfaces and from the end surface to the inside (the center of the sheet glass article). In the glass matrix 120, a crack 130 is generated.
For this reason, although the crystallized glass article obtained by the manufacturing method shown in said (1) does not show the crack observed in appearance, since the crack exists inside, the strength is insufficient.

On the other hand, when producing a crystallized glass article using the accumulation method shown in (2) above, air is confined in the gaps between the crystalline glass bodies when the crystalline glass bodies are accumulated in a mold. become. For this reason, bubbles are likely to be generated inside the produced crystallized glass article. In addition, when the surface of the crystallized glass article is polished for finishing, the bubbles generate semicircular pinhole defects on the surface.
When a crystallized glass article with a pattern having a pinhole defect on such a surface is used, for example, as a flooring material, the pinhole portion becomes black with time and the aesthetic appearance of the floor surface is impaired. In particular, when the color of the crystallized glass article with a pattern is white or a light color, the aesthetic appearance of the floor surface is significantly impaired.

  An object of the present invention is to solve the above problems. That is, an object of the present invention is to provide a patterned crystallized glass article having a sufficient strength and having no pinhole defects on the surface, and a method for producing the same.

The above-mentioned subject is achieved by the following present invention. That is, the present invention
<1> A crystallized glass layer A obtained by fusing and crystallizing a plurality of crystalline glass bodies,
A crystallized glass layer B provided in a state of being fused to at least one surface of the crystallized glass layer A and crystallizing the crystalline glass plate B to the center thereof, and
The crystallized glass layer A includes at least one crystal selected from β-wollastonite and diopside as a main crystal,
The crystallized glass layer B includes at least one crystal selected from β-wollastonite and diopside as a main crystal and has a thickness of 6 mm or less. It is an article.

<2> The patterned crystallized glass article according to <1>, wherein the crystallized glass layer B is provided in a state of being fused to both surfaces of the crystallized glass layer A.

<3> The absolute value of the difference between the thermal expansion coefficient at 30 to 380 degrees of the crystallized glass layer A and the thermal expansion coefficient at 30 to 380 degrees of the crystallized glass layer B is 0 to 10 ×. The crystallized glass article with a pattern according to <1> or <2>, wherein the crystallized glass article is within a range of 10 ⁻⁷ / ° C.

<4> 1) Laminate having a crystalline glass body layer in which a plurality of crystalline glass bodies are accumulated in a layered manner, and a crystalline glass plate B disposed on the surface of the crystalline glass body layer. ,
2) a laminate having a crystalline glass plate B and a crystalline glass body layer in which a plurality of crystalline glass bodies are layered on the surface of the crystalline glass plate B; and
3) a first crystalline glass plate B, a crystalline glass body layer in which a plurality of crystalline glass bodies are layered on the surface of the first crystalline glass plate B, and the crystalline glass body A laminate having a second crystalline glass plate B disposed on the surface of the layer,
Including at least a heat treatment step of heat-treating at least one laminate selected from the group consisting of:
In the heat treatment step, the crystalline glass bodies and the crystalline glass body layer and the crystalline glass plate B are fused together, and the crystalline glass body and the crystalline glass plate B are crystallized. By making
At least one crystal selected from β-wollastonite and diopside is precipitated as a main crystal in the crystalline glass body layer, and β as a main crystal in the crystalline glass plate B A method for producing a patterned crystallized glass article, wherein at least one crystal selected from wollastonite and diopside is precipitated to the center of the crystalline glass plate B.

  As described above, according to the present invention, it is possible to provide a crystallized glass article with a pattern having sufficient strength and having no pinhole defects on the surface, and a method for producing the same.

-Crystallized glass article-
The patterned crystallized glass article of the present invention (hereinafter sometimes abbreviated as “crystallized glass article”) includes a crystallized glass layer A in which a plurality of crystalline glass bodies are fused and crystallized. A crystallized glass layer B which is provided in a fused state on at least one surface of the crystallized glass layer A and crystallizes the crystalline glass plate B to the center thereof, and the crystallized glass layer A is Including at least one crystal selected from β-wollastonite and diopside as a main crystal, and the crystallized glass layer B is at least selected from β-wollastonite and diopside as a main crystal. It contains one type of crystal and has a thickness of 6 mm or less.

In the crystallized glass article of the present invention, the crystallized glass layer A is obtained by fusing and crystallizing a plurality of crystalline glass bodies to each other. Similar to the glass article, the crystallized glass layer A has a pattern such as a natural marble pattern.
In addition to this, the crystallized glass layer B having a thickness of 6 mm or less is fixed to at least one surface of the crystallized glass layer A in a fused state. The crystallized glass layer B is obtained by crystallizing the crystalline glass plate B up to the center, but is not opaque but translucent because the thickness is 6 mm or less. For this reason, when the crystallized glass article is viewed from the surface on the side where the crystallized glass layer B is provided, the pattern resulting from the crystallized glass layer A can be confirmed.

Further, since the surface on which the crystallized glass layer B is provided is a surface formed using the crystalline glass plate B, there is no pinhole defect.
For this reason, the crystallized glass article of the present invention is formed using the crystalline glass plate B when used for applications such as exterior materials and interior materials for buildings, or top plate materials for furniture and office tables. If the surface is used so that it is on the eye-catching side, there will be no problem that the aesthetic appearance is lost due to the pinhole portion becoming black over time.
Note that the crystallized glass layer B may be provided in a state of being fused to both surfaces of the crystallized glass layer A. In this case, a crystallized glass article free from pinhole defects on both sides can be obtained.

  Furthermore, since the crystallized glass article of the present invention is composed of the crystallized glass layer A and the crystallized glass layer B, it has sufficient strength. In addition, the crystallized glass layer B is obtained by crystallizing the crystalline glass plate B, and in the case of crystallization, β-wollastonite having a characteristic of crystal growth from the surface to the inside of the crystalline glass member and Since it contains at least one crystal selected from diopside, as illustrated in FIG. 3, a glass matrix having cracks remains in the center of the crystallized glass layer B, and the strength is insufficient. It is also a concern. However, since the crystallized glass layer B is crystallized up to the center thereof, there is no crack in the inside, and sufficient strength can be obtained.

Here, the thickness of the crystallized glass layer B needs to be 6 mm or less, preferably 5 mm or less, and more preferably 4 mm or less. When the thickness of the crystallized glass layer B exceeds 6 mm, the tendency to become translucent to opaque becomes strong, and when the crystallized glass article is viewed from the side on which the crystallized glass layer B is provided, the crystallized glass layer A It may be difficult to confirm the pattern resulting from the aesthetic properties of the crystallized glass article. And the glass matrix which was not crystallized tends to remain.
On the other hand, the lower limit of the thickness of the crystallized glass layer B is not particularly limited, but is preferably 1 mm or more, and more preferably 2 mm or more. If the thickness is less than 1 mm, it may be difficult to form the crystalline glass plate B.

On the other hand, the thickness of the crystallized glass layer A is not particularly limited, and can be appropriately selected according to the thickness of the crystallized glass layer B and the crystallized glass article, but is 0.1 mm or more and 30 mm or less. Is preferably 1 mm or more and 15 mm or less.
Further, the thickness of the crystallized glass article is not particularly limited, but can be appropriately selected according to the use and purpose of the crystallized glass article. However, from a practical viewpoint such as securing of strength, manufacturability and cost, it is preferably in the range of 8 mm or more and 30 mm or less, and more preferably in the range of 15 mm or more and 25 mm or less.

The crystallized glass layer A needs to contain at least one crystal selected from β-wollastonite and diopside as a main crystal.
This is because β-wollastonite and diopside have a property of precipitating from the surface of the crystalline glass body toward the inside when it is precipitated in the crystalline glass body by crystallization. This is because a natural marble pattern or the like can be formed on the surface of the crystallized glass layer A due to special characteristics.
Furthermore, the crystallized glass layer B needs to contain at least one crystal selected from β-wollastonite and diopside as a main crystal. Thereby, since the difference in thermal expansion coefficient between the crystallized glass layer A and the crystallized glass layer B can be reduced, the crystallized glass article is prevented from being damaged when the crystallized glass article is produced by the method described later. Can do.

The absolute value of the difference between the thermal expansion coefficient of the crystallized glass layer A at 30 to 380 degrees and the thermal expansion coefficient of the crystallized glass layer B at 30 to 380 degrees (hereinafter referred to as “thermal expansion coefficient difference”). may be abbreviated as) is preferably in the range of 0~10 × 10 ^-7 / ℃, and more preferably in the range of 0~3 × 10 ^-7 / ℃.
When the difference in thermal expansion coefficient exceeds 10 × 10 ⁻⁷ / ° C., crystallization is performed by heat treatment and fused to each other at the stage of gradual cooling when producing a crystallized glass article by the production method described later. The difference in thermal shrinkage between the glass layer A and the crystallized glass layer B is increased, and the crystallized glass article may be damaged. Further, when the crystallized glass article of the present invention is used as a wall material or the like in a place where it is temporarily exposed to high temperatures such as a kitchen where a gas stove is installed, the crystallized glass article may be damaged. is there.

The thermal expansion coefficient was measured under the following conditions using a thermomechanical analyzer (TMA, manufactured by PERKIN ELMER, model number: TMA7).
-Reference: None-Temperature rising rate: 20 ° C / min
・ Static force: 10mN
・ Sample length: 10mm
・ Heating atmosphere: N ₂

In the crystallized glass article of the present invention, a member (crystallized glass layer C) having the same function as that of the crystallized glass layer B is fused to the end face part from the viewpoint of diversification of patterns and prevention of pinhole defects. Can be provided. In this case, the crystallized glass layer C may be provided in a state where it is fused only to the end face portion of the crystallized glass layer A, or to both the end face portions of the crystallized glass layer A and the crystallized glass layer B. It may be provided in a fused state.
The crystallized glass layer C is obtained by crystallizing the crystalline glass plate C to the center thereof, and includes at least one crystal selected from β-wollastonite and diopside as a main crystal. And if the thickness is 6 mm or less, it will not specifically limit. The glass composition of the crystalline glass plate C used for forming the crystallized glass layer C may be the same as or different from that of the crystalline glass plate B.

-Method for producing crystallized glass article-
Next, the manufacturing method of the crystallized glass article of this invention is demonstrated.
The crystallized glass article of the present invention is prepared by preparing a crystalline glass plate produced using a crystalline glass body capable of becoming a crystallized glass layer A and a crystalline glass plate capable of becoming a crystallized glass layer B, respectively. It is possible to manufacture the two types of crystalline glass plates by fusing them with each other by heating them in a superposed state, but from the standpoint of practicality and cost, the manufacturing method described below is used. It is preferable to make use.

  That is, when the crystallized glass article of the present invention is manufactured, first, (1) a crystalline glass body layer in which a plurality of crystalline glass bodies are accumulated in a layer form, and the surface of the crystalline glass body layer are overlapped. (2) Crystalline glass plate B, and a small crystalline glass plate in which a plurality of crystalline glass bodies are accumulated in layers on the surface of the crystalline glass plate B A laminated body having a body layer, and (3) a crystalline glass in which a first crystalline glass plate B and a plurality of crystalline glass bodies are accumulated on the surface of the first crystalline glass plate B in layers. At least one laminated body selected from the group consisting of a laminated body having a small body layer and a second crystalline glass plate B disposed on the surface of the crystalline glass small body layer is prepared.

Subsequently, the crystallized glass article of the present invention can be manufactured through at least a heat treatment step of heat-treating at least one of the laminates shown in the above (1) to (3).
The heat treatment step is usually carried out by placing the laminate in a refractory mold having an inner wall coated with a release agent as shown in FIG.

FIG. 1 is a schematic cross-sectional view for explaining an example of the method for producing a crystallized glass article of the present invention, and specifically shows a state in which a laminate is arranged in a refractory mold. In FIG. 1, 10 is a refractory mold, 12 is a crystalline glass body layer, 14, 14A, and 14B are crystalline glass plates B, 20A, 20B, and 20C are laminates.
Here, as shown in FIG. 1A, the laminate shown in the above (1) has a plurality of crystalline glass bodies in a refractory mold 10 in which a release agent (not shown) is applied to a wall surface. After the crystalline glass body layer 12 is formed by stacking in layers, a crystalline glass plate B14 is disposed thereon (laminated body 20A in the figure). Moreover, the laminated body shown in the above (2) is, after placing the crystalline glass plate 14 in the refractory mold 10 in which a release agent (not shown) is applied to the wall surface as shown in FIG. 1B. It is obtained by forming a crystalline glass body layer 12 by accumulating a plurality of crystalline glass bodies in a layered form thereon (laminate 20B in the figure). Moreover, as shown to FIG. 1C, the laminated body shown to said (3) has arrange | positioned 1st crystalline glass plate B14A in the refractory formwork 10 by which the mold release agent (not shown) was apply | coated to the wall surface. After disposing, a plurality of crystalline glass bodies are accumulated in layers to form a crystalline glass body layer 12, and a second crystalline glass plate B14B is further disposed thereon. Obtained (in the figure, laminate 20C).

When the crystallized glass layer C is also provided on the end face of the crystallized glass article of the present invention, for example, the crystalline glass body, the crystalline glass plate B, the crystalline glass is placed in the refractory mold by the following procedure. A plate C can be placed.
First, when forming a laminated body in a refractory mold, using a crystalline glass plate B that is slightly smaller than the bottom shape of the refractory mold, the side wall surface of the refractory mold and several mm to several tens of mm It arrange | positions so that a gap | interval of a grade may be formed and a laminated body may be formed. Next, the crystalline glass plate C is disposed in the gap between the end face of the laminate and the side wall of the refractory mold so as to be sandwiched between the end face of the laminate and the side of the side of the refractory mold. And if a heat treatment process is implemented in this state, the crystallized glass article by which the crystallized glass layer C was melt | fused by the end surface can be obtained.
Moreover, as a method other than the above, after arranging the crystalline glass plate C in advance on the side wall surface of the refractory mold, a laminated body may be formed, and then a heat treatment step may be performed.

FIG. 2 is a schematic cross-sectional view for explaining another example of the method for producing a crystallized glass article of the present invention. Specifically, the crystallized glass article in which the crystallized glass layer C is fused to the end face. In order to fabricate, a state in which the crystalline glass plate C and the laminated body are arranged in the refractory mold is shown. Here, in the figure, 16 represents a crystalline glass plate C, 20 represents a laminate, and the other symbols represent the same members as those shown in FIG.
In the example shown in FIG. 2, the laminated body 20 and the crystalline glass plate C are disposed in the refractory mold 10 so as to be sandwiched between the laminated body 20 and the side wall surface of the refractory mold 10. Has been. The layer structure of the stacked body 20 may be any of the stacked bodies 20A to 20C illustrated in FIGS. 1A to 1C.

  Further, in the heat treatment step, the heat treatment of the laminate is performed by fusing the crystalline glass bodies and the crystalline glass body layer and the crystalline glass plate B to each other, as well as the crystalline glass body and the crystalline glass plate B. To crystallize at least one crystal selected from β-wollastonite and diopside as a main crystal in the crystalline glass body layer, and in the crystalline glass plate B This is carried out under the condition that at least one crystal selected from β-wollastonite and diopside as the main crystal is precipitated to the center of the crystalline 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 crystalline glass body and the crystalline glass plate B.
The specific heat treatment temperature and heat treatment time are appropriately selected according to the softening point of the crystalline glass body or the crystalline glass plate B, the thickness of the crystalline glass body layer or the crystalline glass plate B, and the like. .
However, in general, after the temperature is increased from room temperature at a temperature increase rate of 60 ° C./hr to 600 ° C./hr, preferably within a range of 1030 ° C. to 1130 ° C., more preferably within a range of 1050 ° C. to 1100 ° C. After the heat treatment at a temperature of preferably 0.5 to 5 hours, it is preferable to cool slowly.
Further, the thickness of the crystalline glass plate B is preferably 6 mm or less, more preferably 5 mm or less, and still more preferably 4 mm or less. When the thickness of the crystalline glass plate B exceeds 6 mm, it is not possible to crystallize to the center of the crystalline glass plate B when heat treatment is performed, and a glass matrix having cracks remains in the center of the crystallized glass layer B. May end up.

  For crystallized glass articles obtained through the heat treatment process described above, a polishing process for polishing the surface for the purpose of adjusting the thickness of the crystallized glass article or surface finishing, if necessary, or a predetermined size. The cutting process etc. which cut | disconnect a crystallized glass article so that it may become a shape can be implemented.

  The “crystalline glass body” used in the manufacture of crystallized glass articles means particulate glass, and the shape is not particularly limited, such as spherical or rod-like, and the size is not particularly limited. However, it is preferable that the average particle size is about 1 mm or more and 7 mm or less. There is no particular limitation on the method for producing the crystalline glass body, and it can be produced by combining known methods. For example, a method of rapidly cooling a glass melt by water cooling or the like, and a known method for bulk glass are known mechanically. A method of pulverizing by a pulverization method can be used.

Moreover, if the thickness of the crystallized glass layer B is 6 mm or less, it is not limited to what was produced using the one crystalline glass plate B. FIG.
For example, the crystallized glass layer B may be formed by performing a heat treatment process in a state where two or more crystalline glass plates B are laminated, and may be two or more rod-shaped crystalline glass plates B. May be formed by passing through a heat treatment step in a state where they are arranged on the surface of the crystalline glass body layer without any gap.
Similarly, the crystalline glass layer C can also be formed by using two or more crystalline glass plates C or using two or more rod-like crystalline glass plates C and undergoing a heat treatment step.

-Glass composition of crystalline glass body, crystalline glass plate B and crystalline glass plate C-
As the crystalline glass body, the crystalline glass plate B, and the crystalline glass plate C used for the production of the crystallized glass article of the present invention, when heat-treated at a temperature higher than the softening point, β-wollast as a main crystal A material made of a glass material having a surface crystallization type glass composition in which knight or diopside is precipitated from the surface to the inside is used.
As the glass composition satisfying the above conditions, the glass compositions shown in the following (1) to (12) are particularly preferable.

(1) By mass percentage, SiO ₂ is 50 to 65%, Al ₂ O ₃ is ₃ to 13%, CaO is 15 to 25%, ZnO is 2 to 10%, and the total amount of the coloring oxide is 0 to 5%. Glass composition contained in the ratio of each.
The glass material comprising the present glass composition can precipitate β-wollastonite as a main crystal by heat treatment at a temperature equal to or higher than the softening point.
The above coloring oxides, coloring colorless transparent glass material _{V 2 O 5, Cr 2 O} 3, MnO 2, Fe 2 O 3, CoO, NiO, by being contained in the glass, such as CuO It means at least one kind selected from known metal oxides (hereinafter, the same applies to the following description of the glass composition (2)).

(2) in mass percentage, SiO ₂ is 45 to 75% Al ₂ O ₃ is 1-13%, CaO is _{6~14.5%, Na 2 O + K} 2 O is 1-13%, the BaO 0 to 20 %, ZnO from 0 to 18%, BaO + ZnO from 4 to 24%, and the total amount of coloring oxides contained in a proportion of 0 to 10%, respectively.
The glass material comprising the present glass composition can precipitate β-wollastonite as a main crystal by heat treatment at a temperature equal to or higher than the softening point.

(3) by mass percentage, SiO ₂ is 45 to 75% Al ₂ O ₃ is 1 to 15% CaO is _{8~20%, Na 2 O + K} 2 O is 1 to 15% BaO is 0 to 18%, ZnO 0-18%, BaO + ZnO 4-25%, Fe ₂ O ₃ 2-8%, TiO ₂ 0.1-7%, MnO ₂ 0.1-5%, CoO 0-2% , B ₂ O ₃ is 0 to 3% as ₂ O ₃ 0 to 1%, the glass composition Sb ₂ O ₃ is contained respectively in a proportion of 0 to 1%.
The glass material comprising the present glass composition can precipitate β-wollastonite as a main crystal by heat treatment at a temperature equal to or higher than the softening point.

(4) by mass percentage, SiO ₂ is 48~68%, Al ₂ O ₃ is 0.5 to 17%, CaO is _{6~22%, Na 2 O + K} 2 O is 5 to 22%, MgO 0.2 ~ 8%, BaO is 0 to 8%, ZnO is 0 to 9%, the total amount of BaO and ZnO is 0% or more and less than 15%, B ₂ O ₃ is 0 to 6%, and the total amount of coloring oxide is 0 Glass composition contained at a ratio of 10% to 10%.
The glass material comprising the present glass composition can precipitate β-wollastonite as a main crystal by heat treatment at a temperature equal to or higher than the softening point.

(5) by mass percentage, SiO ₂ is 40~75%, Al ₂ O ₃ is 2 to 15%, CaO is 3 to 15%, ZnO is 0 to 15%, BaO is 0~20%, B ₂ O ₃ Is 0 to 10%, the total amount of Na ₂ O, K ₂ O and Li ₂ O is 2 to 20%, the total amount of the coloring oxide is 0 to 10%, As ₂ O ₃ is 0 to 1%, Sb ₂ Glass compositions each containing O _{3 at} a ratio of 0 to 1%.
The glass material comprising the present glass composition can precipitate β-wollastonite as a main crystal by heat treatment at a temperature equal to or higher than the softening point.

(6) by mass percentage, SiO ₂ is 45 to 75% Al ₂ O ₃ is 1 to 25% CaO is from 1 to 12.5% MgO 0.5 to 12%, and the total amount of CaO and MgO 1.5-13%, BaO is 0 to 18%, ZnO is 0~18%, Na ₂ O is 1~15%, K ₂ O is 0~7%, Li ₂ O is 0 to 5%, B ₂ O ₃ is 0 to 10%, P ₂ O ₅ is 0 to 10%, the total amount of coloring oxides is 0 to 10%, As ₂ O ₃ is 0 to 1%, and Sb ₂ O ₃ is 0 to 1%. Glass compositions included in proportions.
The glass material comprising the present glass composition can precipitate diopside as a main crystal by heat treatment at a temperature equal to or higher than the softening point.

(7) by mass percentage, SiO ₂ is 40~75%, Al ₂ O ₃ is 2 to 15%, CaO is 3 to 20%, ZnO is 0 to 15%, BaO is 0~20%, B ₂ O ₃ Is 0 to 10%, the total amount of Na ₂ O, K ₂ O and Li ₂ O is 2 to 20%, the total amount of the coloring oxide is 0 to 10%, As ₂ O ₃ is 0 to 1%, Sb ₂ Glass compositions each containing O _{3 at} a ratio of 0 to 1%.
The glass material comprising the present glass composition can precipitate β-wollastonite as a main crystal by heat treatment at a temperature equal to or higher than the softening point.

(8) in mass percentage, SiO ₂ is 45 to 75% Al ₂ O ₃ is 1 to 25% CaO is 1 to 20% MgO is 0.5 to 17% BaO is 0 to 18%, is ZnO 0~18%, Na ₂ O is 1~15%, K ₂ O is 0~7%, Li ₂ O is 0~5%, B ₂ O ₃ is 0~10%, P ₂ O ₅ 0-10 %, The total amount of the coloring oxide is 0 to 10%, As ₂ O ₃ is 0 to 1%, and Sb ₂ O ₃ is contained at a ratio of 0 to 1%.
The glass material comprising the present glass composition can precipitate diopside as a main crystal by heat treatment at a temperature equal to or higher than the softening point.

(9) by mass percentage, SiO ₂ is 45 to 70% Al ₂ O ₃ is 1 to 13% CaO is 6-25%, the total amount of Na ₂ O and K ₂ O and Li ₂ O 0.1 A glass composition containing -20%, BaO 0-20%, ZnO 0-18%, the total amount of BaO and ZnO 4-24%, and the total amount of coloring oxides 0-10%.
The glass material comprising the present glass composition can precipitate β-wollastonite as a main crystal by heat treatment at a temperature equal to or higher than the softening point.

(10) by mass percentage, SiO ₂ is 45 to 75% Al ₂ O ₃ from 1 to 15% CaO 6 to 20% total amount of 1% to 15% of Na ₂ O and K ₂ O, is BaO Glass compositions containing 0-18%, 0-18% ZnO, 4-25% total amount of BaO and ZnO, 0.05-5% NiO, and 0.01-5% CoO.
The glass material comprising the present glass composition can precipitate β-wollastonite as a main crystal by heat treatment at a temperature equal to or higher than the softening point.

(11) By mass percentage, SiO ₂ is 50 to 75%, Al ₂ O ₃ is 1 to 15%, CaO is 6 to 16.5%, Li ₂ O is 0.1 to 5%, and B ₂ O ₃ is 0 to 1.5%, the total amount of CaO, Li ₂ O and B ₂ O ₃ is 10 to 17.5%, ZnO is 2.5 to 12%, BaO is 0 to 12%, Na ₂ O and K ₂ The total amount with O is 0.1 to 15%, As ₂ O ₃ is 0 to 1%, Sb ₂ O ₃ is 0 to 1%, MgO is 0 to 1.5%, SrO is 0 to 1.5%, TiO ₂ is 0 to 1%, ZrO ₂ 0 to 1% P ₂ O ₅ 0 to 1%, the glass composition the total amount of coloring oxides are contained respectively in a proportion of 0%.
The glass material comprising the present glass composition can precipitate β-wollastonite as a main crystal by heat treatment at a temperature equal to or higher than the softening point.

(12) By mass percentage, SiO ₂ is 45 to 77%, Al ₂ O ₃ is 1 to 25%, CaO is 2 to 25%, ZnO is 0 to 18%, BaO is 0 to 20%, MgO is 0 to 0%. 17%, Na ₂ O 1-15%, K ₂ O 0-7%, Li ₂ O 0-5%, B ₂ O ₃ 0-1.5%, total amount of coloring oxide 0 10%, As ₂ O ₃ is 0 to 1%, Sb ₂ O ₃ is 0 to 1%, SrO is 0 to 1.5%, TiO ₂ is 0 to 1%, ZrO ₂ is 0 to 1%, P Glass compositions each containing ₂ O _{5 in} a proportion of 0 to 1%.
A glass material comprising the present glass composition can precipitate β-wollastonite and / or diopside as a main crystal by heat treatment at a temperature equal to or higher than the softening point.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

Example 1
First, by mass%, SiO ₂ 65.1%, Al ₂ O ₃ 6.6%, CaO 12.0%, Na ₂ O 3.3%, K ₂ O 2.3%, BaO 4.1%, ZnO 6 A glass material prepared to have a composition of 6% was melted at 1500 ° C. for 16 hours. Next, this molten glass was rapidly cooled in water, crushed, dried and classified to obtain crystalline glass bodies having a particle diameter of 1 to 3 mm. This crystalline glass body is a crystalline glass that precipitates β-wollastonite as a main crystal upon heat treatment and becomes a white crystallized glass having a thermal expansion coefficient of 65 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. is there.

Further, SiO ₂ 65.1% by _{mass%, Al 2 O 3 6.6%} , CaO 12.0%, Na 2 O 3.3%, K 2 O 2.3%, BaO 4.1%, ZnO The glass raw material prepared to have a composition of 6.6% was melted at 1500 ° C. for 16 hours. Next, this molten glass was formed into a plate shape by a roll-out method to obtain a crystalline glass plate having a thickness of 5 mm. This crystalline glass plate is a crystalline glass that precipitates β-wollastonite as a main crystal upon heat treatment and becomes a white crystallized glass having a thermal expansion coefficient of 65 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. .

Next, the produced crystalline glass bodies were accumulated in a refractory mold coated with a release agent so as to be layered. The thickness of the accumulated crystalline glass bodies was about 12 mm. A crystalline glass plate prepared so as to flatten the surface of the layer made of the accumulated crystalline glass bodies and completely cover the surface of the layer made of the crystalline glass bodies was disposed.
Thereafter, the temperature is raised at a rate of 240 ° C. per hour, held at 1100 ° C. for 1 hour, and then cooled to room temperature over about 5 hours, whereby a plurality of crystalline glass bodies are fused while the crystals are fused. A crystallized glass article was obtained in which a crystallized glass layer B formed by precipitating crystals while the crystalline glass plate B was fused on the crystallized glass layer A thus formed was obtained.

  The crystallized glass article thus obtained had a thickness of about 16 mm. Next, after lightly polishing the surface of the crystallized glass article, the crystallized glass article was observed from the surface on the side where the crystallized glass layer B was provided, and the crystallized glass layer B having a thickness of 5 mm was half A transparent pattern was formed, and the natural marble pattern appearing on the surface of the crystallized glass layer A was confirmed in a slightly stagnant state through the translucent crystallized glass layer B. Moreover, since the translucent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer A can be visually recognized at the same time, a natural marble-like appearance in which a subtle three-dimensional effect is expressed can be confirmed.

The reason why the crystallized glass layer B has a semi-transparent pattern is that crystals grow from the surface of the crystalline glass plate B to the inner side when heat-treated. Further, when the natural marble pattern of the crystallized glass layer A was compared with the natural marble pattern of the crystallized glass article produced by the integration method under substantially the same heat treatment conditions using only the crystalline glass particles, almost all It was the same pattern. In addition to this, as a result of separately measuring the crystallized glass layer A and the crystallized glass layer B by X-ray diffraction, the crystallized glass layer A and the crystallized glass layer B have β-wollastonite as a main crystal. Was deposited.
Furthermore, when the cross section of the crystallized glass layer B was observed with the naked eye, no crack was generated. Furthermore, when the cross section was observed with a scanning electron microscope with respect to the thickness direction of the crystallized glass layer B, it was confirmed that crystals were precipitated in all thickness directions, and the crystallized glass layer B was crystallized to the center. I found out.

(Example 2)
First, by mass%, SiO ₂ 65.1%, Al ₂ O ₃ 6.6%, CaO 12.0%, Na ₂ O 3.3%, K ₂ O 2.3%, BaO 4.1%, ZnO 6 A glass material prepared to have a composition of 6% was melted at 1500 ° C. for 16 hours. Next, this molten glass was rapidly cooled in water, crushed, dried and classified to obtain crystalline glass bodies having a particle diameter of 1 to 3 mm. This crystalline glass body is a crystalline glass that precipitates β-wollastonite as a main crystal upon heat treatment and becomes a white crystallized glass having a thermal expansion coefficient of 65 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. is there.

Further, in terms of mass%, SiO ₂ 65.1%, Al ₂ O ₃ 6.6%, CaO 12.0%, Na ₂ O ₃ 3.3%, K ₂ O 2.3%, BaO 4.1%, A glass raw material prepared to have a composition of ZnO 6.6% was melted at 1500 ° C. for 16 hours. Next, this molten glass was formed into a plate shape by a roll-out method to obtain a crystalline glass plate having a thickness of 5 mm. This crystalline glass plate is a crystalline glass that precipitates β-wollastonite as a main crystal upon heat treatment and becomes a white crystallized glass having a thermal expansion coefficient of 65 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. .

Next, after laying the produced crystalline glass plate in a refractory mold coated with a release agent, the crystalline glass body produced so as to completely cover the surface of the crystalline glass plate is layered. And the surface of the layer was flattened. The thickness of the layer made of crystalline glass bodies was about 12 mm.
Thereafter, the temperature is raised at a rate of 240 ° C. per hour, held at 1100 ° C. for 1 hour, and then cooled to room temperature over about 5 hours to precipitate crystals while the crystalline glass plate is fused. A crystallized glass article was obtained in which a crystallized glass layer A formed by depositing crystals on the crystallized glass layer B while a plurality of crystalline glass bodies were fused together was obtained.

  The crystallized glass article thus obtained had a thickness of about 16 mm. Next, after lightly polishing both surfaces of the crystallized glass article, the crystallized glass article was observed from the side on which the crystallized glass layer B was provided, and the crystallized glass layer B having a thickness of 5 mm was half A transparent pattern was formed, and the natural marble pattern appearing on the surface of the crystallized glass layer A was confirmed in a slightly stagnant state through the translucent crystallized glass layer B. Moreover, since the translucent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer A can be visually recognized at the same time, a natural marble-like appearance in which a subtle three-dimensional effect is expressed can be confirmed.

The reason why the crystallized glass layer B has a semi-transparent pattern is that crystals grow from the surface of the crystalline glass plate B to the inner side when heat-treated. Further, when the natural marble pattern of the crystallized glass layer A was compared with the natural marble pattern of the crystallized glass article produced by the integration method under substantially the same heat treatment conditions using only the crystalline glass particles, almost all It was the same pattern. In addition to this, as a result of separately measuring the crystallized glass layer A and the crystallized glass layer B by X-ray diffraction, the crystallized glass layer A and the crystallized glass layer B have β-wollastonite as a main crystal. Was deposited.
Furthermore, when the cross section of the crystallized glass layer B was observed with the naked eye, no crack was generated. Furthermore, when the cross section was observed with a scanning electron microscope with respect to the thickness direction of the crystallized glass layer B, it was confirmed that crystals were precipitated in all thickness directions, and the crystallized glass layer B was crystallized to the center. I found out.

(Example 3)
First, by mass% SiO ₂ 62.2%, Al ₂ O ₃ 5.9%, CaO 13.0%, Na ₂ O 4.5%, K ₂ O 2.1%, Li ₂ O 1.0%, A glass raw material prepared to have a composition of BaO 6.0%, ZnO 5.2%, NiO 0.1% was melted at 1450 ° C. for 16 hours, and then the molten glass was rapidly cooled in water to be crushed and dried. Then, classification was performed to obtain a crystalline glass body having a particle size of 3 to 7 mm. This crystalline glass body precipitates β-wollastonite as a main crystal upon heat treatment, and becomes a beige crystallized glass having a thermal expansion coefficient of 69 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. It is glass.

Further, SiO ₂ 62.2% by _{mass%, Al 2 O 3 5.9%} , CaO 13.0%, Na 2 O 4.5%, K 2 O 2.1%, Li 2 O 1.0% , BaO 6.0%, ZnO 5.2%, NiO 0.1% composition was melted at 1450 ° C. for 16 hours, and then the molten glass was formed into a plate shape by a roll-out method. A crystalline glass plate having a thickness of 3 mm was obtained. This crystalline glass plate precipitates β-wollastonite as a main crystal upon heat treatment, and becomes a crystalline glass of beige color having a thermal expansion coefficient of 69 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. It is.

Next, the produced crystalline glass bodies were accumulated in a refractory mold coated with a release agent so as to be layered. The thickness of the accumulated crystalline glass bodies was about 14 mm. A crystalline glass plate prepared so as to flatten the surface of the layer made of the accumulated crystalline glass bodies and completely cover the surface of the layer made of the crystalline glass bodies was disposed.
Thereafter, the temperature is raised at a rate of 120 ° C. for 1 hour, held at 1050 ° C. for 2 hours, and then cooled to room temperature over about 5 hours, whereby a plurality of crystalline glass bodies are fused while the crystals are fused. A crystallized glass article was obtained in which a crystallized glass layer B formed by precipitating crystals while the crystalline glass plate B was fused on the crystallized glass layer A thus formed was obtained.

  The crystallized glass article thus obtained had a thickness of about 16 mm. Next, after lightly polishing the surface of the crystallized glass article, the crystallized glass article was observed from the surface on the side where the crystallized glass layer B was provided, and the crystallized glass layer B having a thickness of 3 mm was half A transparent pattern was formed, and the natural marble pattern appearing on the surface of the crystallized glass layer A was confirmed in a slightly stagnant state through the translucent crystallized glass layer B. Moreover, since the translucent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer A can be visually recognized at the same time, a natural marble-like appearance in which a subtle three-dimensional effect is expressed can be confirmed.

The reason why the crystallized glass layer B has a semi-transparent pattern is that crystals grow from the surface of the crystalline glass plate B to the inner side when heat-treated. Further, when the natural marble pattern of the crystallized glass layer A was compared with the natural marble pattern of the crystallized glass article produced by the integration method under substantially the same heat treatment conditions using only the crystalline glass particles, almost all It was the same pattern. In addition to this, as a result of separately measuring the crystallized glass layer A and the crystallized glass layer B by X-ray diffraction, the crystallized glass layer A and the crystallized glass layer B have β-wollastonite as a main crystal. Was deposited.
Furthermore, when the cross section of the crystallized glass layer B was observed with the naked eye, no crack was generated. Furthermore, when the cross section was observed with a scanning electron microscope with respect to the thickness direction of the crystallized glass layer B, it was confirmed that crystals were precipitated in all thickness directions, and the crystallized glass layer B was crystallized to the center. I found out.

Example 4
First, by mass%, SiO ₂ 62.0%, Al ₂ O ₃ 9.0%, CaO 9.0%, MgO 4.5%, BaO 4.6%, Na ₂ O 5.0%, K ₂ O A glass raw material prepared to have a composition of 0%, B ₂ O ₃ 0.5%, P ₂ O ₅ 2.0%, Sb ₂ O ₃ 0.4%, and CoO 0.05% at 1500 ° C. for 16 Melted for hours. Next, this molten glass was rapidly cooled in water, crushed, dried and classified to obtain crystalline glass bodies having a particle diameter of 1 to 3 mm. This crystalline glass body is a crystalline glass that precipitates diopside as a main crystal upon heat treatment, and becomes a gray crystallized glass having a thermal expansion coefficient of 71 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. .

Further, SiO ₂ 62.0% by _{mass%, Al 2 O 3 9.0%} , CaO 9.0%, MgO 4.5%, BaO4.6%, Na 2 O 5.0%, K 2 O 3 A glass raw material prepared to have a composition of 0.0%, B ₂ O ₃ 0.5%, P ₂ O ₅ 2.0%, Sb ₂ O ₃ 0.4%, CoO 0.05% at 1500 ° C. Melted for 16 hours. Next, this molten glass was formed into a plate shape by a roll-out method to obtain a crystalline glass plate having a thickness of 3 mm. This crystalline glass plate is a crystalline glass that precipitates diopside as a main crystal upon heat treatment, and becomes a gray crystallized glass having a thermal expansion coefficient of 71 × 10 ⁻⁷ / ° C. at 30 to 380 ° C.

Next, after laying the produced crystalline glass plate in a refractory mold coated with a release agent, the crystalline glass body produced so as to completely cover the surface of the crystalline glass plate is layered. Accumulated. The thickness of the layer made of this crystalline glass body was about 12 mm. Further, a crystalline glass plate produced by flattening the surface of the layer made of crystalline glass bodies and completely covering the surface of the layer made of crystalline glass bodies was disposed. As a result, the layer composed of the crystalline glass bodies was sandwiched between the two crystalline glass plates.
Thereafter, the temperature is raised at a rate of 120 ° C. per hour, held at 1100 ° C. for 2 hours, and then cooled to room temperature over about 5 hours to precipitate crystals while the crystalline glass plate is fused. A crystallized glass layer A is formed on the first crystallized glass layer B by depositing crystals while fusing a plurality of crystalline glass bodies. A crystallized glass article was obtained in which a second crystallized glass layer B formed by precipitating crystals while the crystalline glass plate was fused.

  The crystallized glass article thus obtained had a thickness of about 17 mm. Next, after lightly polishing both surfaces of the crystallized glass article, the crystallized glass article was observed from the side on which one crystallized glass layer B was provided, and the crystallized glass layer B having a thickness of 3 mm was observed. In addition to forming a translucent pattern, the natural marble pattern appearing on the surface of the crystallized glass layer A could be confirmed in a state of being slightly stagnant through the translucent crystallized glass layer B. Moreover, since the translucent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer A can be visually recognized at the same time, a natural marble-like appearance in which a subtle three-dimensional effect is expressed can be confirmed. In addition, when the crystallized glass article was observed from the surface on the side where the other crystallized glass layer B was provided, the same pattern could be confirmed.

The reason why the crystallized glass layer B has a semi-transparent pattern is that crystals grow from the surface of the crystalline glass plate B to the inner side when heat-treated. Further, when the natural marble pattern of the crystallized glass layer A was compared with the natural marble pattern of the crystallized glass article produced by the integration method under substantially the same heat treatment conditions using only the crystalline glass particles, almost all It was the same pattern. In addition to this, the crystallized glass layer A and the crystallized glass layer B were separately measured by X-ray diffraction. As a result, diopside was precipitated as the main crystal in the crystallized glass layer A and the crystallized glass layer B. Was.
Furthermore, when the cross sections of the two crystallized glass layers B were observed with the naked eye, no cracks occurred in any of the layers. Furthermore, when each cross section of the two crystallized glass layers B was observed with a scanning electron microscope with respect to the thickness direction of the crystallized glass layer B, it was confirmed that crystals were precipitated in all the thickness directions. It was found that the crystallized glass layer B was crystallized up to the center.

(Example 5)
First, by mass%, SiO ₂ 60.0%, Al ₂ O ₃ 6.0%, CaO 7.6%, MgO 3.8%, BaO 3.5%, ZnO 6.5%, Na ₂ O 3.8% , K ₂ O 2.5%, Li ₂ O 0.4%, B ₂ O ₃ 5.4%, As ₂ O ₃ 0.3%, NiO 0.2% Was melted at 1500 ° C. for 16 hours. Next, this molten glass was formed into a film and then pulverized and classified to obtain a crystalline glass body having a particle size of 1 to 3 mm. This crystalline glass body is a crystalline glass that becomes a beige crystallized glass having a thermal expansion coefficient of 73 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. when diopside is precipitated as a main crystal upon heat treatment. is there.

Further, SiO ₂ 60.0% by _{mass%, Al 2 O 3 6.0%} , CaO 7.6%, 3.8% MgO, BaO3.5%, 6.5% ZnO, Na 2 O 3.8 %, K ₂ O 2.5%, Li ₂ O 0.4%, B ₂ O ₃ 5.4%, As ₂ O ₃ 0.3%, NiO 0.2% The raw material was melted at 1500 ° C. for 16 hours. Next, this molten glass was formed into a plate shape by a roll-out method to obtain a crystalline glass plate having a thickness of 1 mm. This crystalline glass plate is a crystalline glass that precipitates diopside as a main crystal upon heat treatment and becomes a beige crystallized glass having a thermal expansion coefficient of 73 × 10 ⁻⁷ / ° C. at 30 to 380 ° C.

Next, the produced crystalline glass bodies were accumulated in a refractory mold coated with a release agent so as to be layered. The thickness of the accumulated crystalline glass bodies was about 16 mm. A crystalline glass plate prepared so as to flatten the surface of the layer made of the accumulated crystalline glass bodies and completely cover the surface of the layer made of the crystalline glass bodies was disposed.
Thereafter, the temperature is raised at a rate of 120 ° C. for 1 hour, held at 1050 ° C. for 2 hours, and then cooled to room temperature over about 5 hours, whereby a plurality of crystalline glass bodies are fused while the crystals are fused. A crystallized glass article was obtained in which a crystallized glass layer B formed by precipitating crystals while the crystalline glass plate B was fused on the crystallized glass layer A thus formed was obtained.

  The crystallized glass article thus obtained had a thickness of about 16 mm. Next, after lightly polishing the surface of the crystallized glass article, the crystallized glass article was observed from the surface on the side where the crystallized glass layer B was provided, and the crystallized glass layer B having a thickness of 1 mm was half A transparent pattern was formed, and the natural marble pattern appearing on the surface of the crystallized glass layer A was confirmed in a slightly stagnant state through the translucent crystallized glass layer B. Moreover, since the translucent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer A can be visually recognized at the same time, a natural marble-like appearance in which a subtle three-dimensional effect is expressed can be confirmed.

The reason why the crystallized glass layer B has a semi-transparent pattern is that crystals grow from the surface of the crystalline glass plate B to the inner side when heat-treated. Further, when the natural marble pattern of the crystallized glass layer A was compared with the natural marble pattern of the crystallized glass article produced by the integration method under substantially the same heat treatment conditions using only the crystalline glass particles, almost all It was the same pattern. In addition to this, the crystallized glass layer A and the crystallized glass layer B were separately measured by X-ray diffraction. As a result, diopside was precipitated as the main crystal in the crystallized glass layer A and the crystallized glass layer B. Was.
Furthermore, when the cross section of the crystallized glass layer B was observed with the naked eye, no crack was generated. Furthermore, when the cross section was observed with a scanning electron microscope with respect to the thickness direction of the crystallized glass layer B, it was confirmed that crystals were precipitated in all thickness directions, and the crystallized glass layer B was crystallized to the center. I found out.

(Example 6)
First, by mass%, SiO ₂ 62.0%, Al ₂ O ₃ 9.0%, CaO 9.0%, MgO 4.5%, BaO 4.6%, Na ₂ O 5.0%, K ₂ O A glass raw material prepared to have a composition of 0%, B ₂ O ₃ 0.5%, P ₂ O ₅ 2.0%, Sb ₂ O ₃ 0.4%, and CoO 0.05% at 1500 ° C. for 16 Melted for hours. Next, the molten glass was rapidly cooled in water to be crushed, dried and classified to obtain a crystalline glass body having a particle size of 1 to 3 mm. This crystalline glass body is a crystalline glass that precipitates diopside as a main crystal upon heat treatment, and becomes a gray crystallized glass having a thermal expansion coefficient of 71 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. .

Further, SiO ₂ 62.2% by _{mass%, Al 2 O 3 5.9%} , CaO 13.0%, Na 2 O 4.6%, K 2 O 2.1%, Li 2 O 1.0% A glass raw material prepared to have a composition of BaO 6.0% and ZnO 5.2% was melted at 1450 ° C. for 16 hours. Next, this molten glass was formed into a plate shape by a roll-out method to obtain a crystalline glass plate having a thickness of 3 mm. This crystalline glass plate is a crystalline glass that precipitates β-wollastonite as a main crystal upon heat treatment and becomes a white crystallized glass having a thermal expansion coefficient of 69 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. .
In addition, since the crystalline glass plate obtained by the roll-out method is used for forming the crystallized glass layer C in addition to the formation of the crystallized glass layer B, it is cut according to the size of each layer, Two types of crystalline glass plates having different shapes were obtained.

Next, the produced crystalline glass bodies were accumulated in a refractory mold coated with a release agent so as to be layered. The thickness of the accumulated crystalline glass bodies was about 14 mm. A crystalline glass plate prepared so as to flatten the surface of the layer made of the accumulated crystalline glass bodies and completely cover the surface of the layer made of the crystalline glass bodies was disposed. In addition, this crystalline glass plate has a size slightly smaller than the refractory mold, and the distance between each of the four sides of the crystalline glass plate and the side wall surface of the refractory mold is 3 mm. It placed on a layer consisting of crystalline glass bodies.
Subsequently, the thickness direction of the crystalline glass plate having a thickness of 3 mm is set between the laminated body formed by laminating the crystalline glass body layer and the crystalline glass plate and the side wall surface of the refractory mold. It pushed in so that it might become parallel with the bottom face of a formwork, and as shown in FIG. 2, the crystalline glass plate was arrange | positioned between the end surface of a laminated body, and the side wall surface of a refractory formwork. In addition, this crystalline glass plate was arrange | positioned so that it might closely_contact | adhere to the end surface perimeter of a laminated body.
Thereafter, the temperature is raised at a rate of 120 ° C. per hour, held at 1050 ° C. for 1 hour, and then cooled to room temperature over about 5 hours, whereby a plurality of crystalline glass bodies are fused while the crystals are fused. A crystallized glass layer B formed by depositing crystals while the crystalline glass plate B is fused on the crystallized glass layer A is formed, and the crystallized glass layer A and the crystallized glass layer B are formed. A crystallized glass article was obtained in which a crystallized glass layer C formed by precipitating crystals while the crystallized glass plate C was fused to the entire periphery of the end surface of the laminated body portion was formed.

The crystallized glass article thus obtained had a thickness of about 16 mm. Next, after lightly polishing the surface and end face of the crystallized glass article, the crystallized glass article was observed from the surface on the side where the crystallized glass layer B was provided, and the crystallized glass layer B having a thickness of 3 mm was observed. In addition to forming a translucent pattern, the natural marble pattern appearing on the surface of the crystallized glass layer A could be confirmed in a state of being slightly stagnant through the translucent crystallized glass layer B. Moreover, since the translucent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer A can be visually recognized at the same time, a natural marble-like appearance in which a subtle three-dimensional effect is expressed can be confirmed.
In addition, when the crystallized glass article is observed from the surface on the side where the crystallized glass layer C having a thickness of 3 mm is provided, it is the same as that observed from the surface on the side where the crystallized glass layer B is provided. The pattern was confirmed.

The reason why the crystallized glass layer B and the crystallized glass layer C have a translucent pattern is that crystals grow from the surface of the crystallized glass layer B and the crystallized glass layer C to the inside. . Further, when the natural marble pattern of the crystallized glass layer A was compared with the natural marble pattern of the crystallized glass article produced by the integration method under substantially the same heat treatment conditions using only the crystalline glass particles, almost all It was the same pattern. In addition to this, the crystallized glass layer A, the crystallized glass layer B, and the slightly crystallized glass layer C were separately measured by X-ray diffraction. As a result, diopside was precipitated as the main crystal in the crystallized glass layer A. In the crystallized glass layer B and the crystallized glass layer C, β-wollastonite was precipitated as the main crystal.
Furthermore, when the cross section of the crystallized glass layer B was observed with the naked eye, no crack was generated. Furthermore, when the cross section was observed with a scanning electron microscope with respect to the thickness direction of the crystallized glass layer B, it was confirmed that crystals were precipitated in all thickness directions, and the crystallized glass layer B was crystallized to the center. I found out. This result was the same for the crystallized glass layer C.

(Example 7)
First, by mass% SiO ₂ 62.2%, Al ₂ O ₃ 5.9%, CaO 13.0%, Na ₂ O 4.5%, K ₂ O 2.1%, Li ₂ O 1.0%, A glass raw material prepared to have a composition of BaO 6.0%, ZnO 5.2%, and NiO 0.1% was melted at 1450 ° C. for 16 hours. Next, the molten glass was rapidly cooled in water, crushed, dried, and classified to obtain a crystalline glass body having a particle size of 3 to 7 mm. This crystalline glass body precipitates β-wollastonite as a main crystal upon heat treatment, and becomes a beige crystallized glass having a thermal expansion coefficient of 69 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. It is glass.

The SiO ₂ 62.2% by _{mass%, Al 2 O 3 5.9%} , CaO 13.0%, Na 2 O 4.5%, K 2 O 2.1%, Li 2 O 1.0%, A glass raw material prepared to have a composition of BaO 6.0%, ZnO 5.2%, and NiO 0.1% was melted at 1450 ° C. for 16 hours, and then this molten glass was formed into a plate shape by a roll-out method. A crystalline glass plate having a thickness of 2 mm was obtained. This crystalline glass plate precipitates β-wollastonite as a main crystal upon heat treatment, and becomes a crystalline glass of beige color having a thermal expansion coefficient of 69 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. It is.
In addition, since the crystalline glass plate obtained by the roll-out method is used for forming the crystallized glass layer C in addition to the formation of the crystallized glass layer B, it is cut according to the size of each layer, Two types of crystalline glass plates having different shapes were obtained.

Next, after laying the produced crystalline glass plate in a refractory mold coated with a release agent, the crystalline glass body produced so as to completely cover the surface of the crystalline glass plate is layered. Accumulated. The thickness of the layer made of this crystalline glass body was about 14 mm. Further, a crystalline glass plate produced by flattening the surface of the layer made of crystalline glass bodies and completely covering the surface of the layer made of crystalline glass bodies was disposed. As a result, the layer composed of the crystalline glass bodies was sandwiched between the two crystalline glass plates.
The two crystalline glass plates have a size slightly smaller than the refractory mold, and the distance between each of the four sides of the crystalline glass plate and the side wall surface of the refractory mold is 2 mm. In this manner, the layers were arranged on the upper and lower surfaces of the crystalline glass bodies.
Subsequently, the thickness direction of the 2 mm thick crystalline glass plate is fireproof between the laminate formed by laminating the crystalline glass body layer and the crystalline glass plate and the side wall surface of the refractory mold. It pushed in so that it might become parallel with the bottom face of a formwork, and as shown in FIG. 2, the crystalline glass plate was arrange | positioned between the end surface of a laminated body, and the side wall surface of a refractory formwork. In addition, this crystalline glass plate was arrange | positioned so that it might closely_contact | adhere to the end surface perimeter of a laminated body.
Thereafter, the temperature is raised at a rate of 180 ° C. for 1 hour, held at 1050 ° C. for 2 hours, and then cooled to room temperature over about 5 hours to precipitate crystals while the crystalline glass plate is fused. A crystallized glass layer A is formed on the first crystallized glass layer B by depositing crystals while fusing a plurality of crystalline glass bodies, and the crystallinity is formed on the crystallized glass layer A. A second crystallized glass layer B is formed by precipitating crystals while the glass plate is fused, and the first and second crystallized glass layers B are provided on both sides of the crystallized glass layer A. Thus, a crystallized glass article was obtained in which a crystallized glass layer C formed by precipitating crystals while the crystallized glass plate C was fused to the entire periphery of the end face of the laminate portion was formed.

The crystallized glass article thus obtained had a thickness of about 17 mm. Next, after lightly polishing both surfaces and end surfaces of the crystallized glass article, the crystallized glass article was observed from the surface on the side where the crystallized glass layer B was provided. In addition to forming a translucent pattern, the natural marble pattern appearing on the surface of the crystallized glass layer A could be confirmed in a state of being slightly stagnant through the translucent crystallized glass layer B. Moreover, since the translucent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer A can be visually recognized at the same time, a natural marble-like appearance in which a subtle three-dimensional effect is expressed can be confirmed.
In addition, when the crystallized glass article is observed from the surface on the side where the crystallized glass layer C having a thickness of 2 mm is provided, it is the same as that observed from the surface on the side where the crystallized glass layer B is provided. The pattern was confirmed. In the portion along the interface between the crystallized glass layer B and the crystallized glass layer C, a stripe pattern having streaks extending in a direction perpendicular to the interface was observed.

The reason why the crystallized glass layer B and the crystallized glass layer C have a translucent pattern is that crystals grow from the surface of the crystallized glass layer B and the crystallized glass layer C to the inside. . Further, when the natural marble pattern of the crystallized glass layer A was compared with the natural marble pattern of the crystallized glass article produced by the integration method under substantially the same heat treatment conditions using only the crystalline glass particles, almost all It was the same pattern. In addition to this, the crystallized glass layer A, the crystallized glass layer B, and the crystallized glass layer C were separately measured by X-ray diffraction. As a result, the crystallized glass layer A, the crystallized glass layer B, and the crystallized glass layer were measured. In C, β-wollastonite was precipitated as a main crystal.
Furthermore, when the cross section of the crystallized glass layer B was observed with the naked eye, no crack was generated. Furthermore, when the cross section was observed with a scanning electron microscope with respect to the thickness direction of the crystallized glass layer B, it was confirmed that crystals were precipitated in all thickness directions, and the crystallized glass layer B was crystallized to the center. I found out. This result was the same for the crystallized glass layer C.

(Example 8)
First, it has a composition of SiO2 65.1%, Al2O3 6.6%, CaO 12.0%, Na2O 3.3%, K2O 2.3%, BaO 4.1%, ZnO 6.6% by mass. The glass raw material prepared in 1 was melted at 1500 ° C. for 16 hours. Next, this molten glass was rapidly cooled in water, crushed, dried and classified to obtain crystalline glass bodies having a particle diameter of 1 to 3 mm. This crystalline glass body is a crystalline glass that precipitates β-wollastonite as a main crystal upon heat treatment and becomes a white crystallized glass having a thermal expansion coefficient of 65 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. is there.

Further, SiO ₂ 65.1% by _{mass%, Al 2 O 3 6.6%} , CaO 12.0%, Na 2 O 3.3%, K 2 O 2.3%, BaO 4.1%, ZnO The glass raw material prepared to have a composition of 6.6% was melted at 1500 ° C. for 16 hours. Next, this molten glass was formed into a plate shape by a roll-out method to obtain a crystalline glass plate having a thickness of 2 mm. This crystalline glass plate is a crystalline glass that precipitates β-wollastonite as a main crystal upon heat treatment and becomes a white crystallized glass having a thermal expansion coefficient of 65 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. . The crystallized glass plate was cut into a rod shape by cutting so that the width was 10 mm.

Next, the produced crystalline glass bodies were accumulated in a refractory mold coated with a release agent so as to be layered. The thickness of the accumulated crystalline glass bodies was about 15 mm. The surface of the layer made of the collected crystalline glass bodies was flattened, and the rod-like crystalline glass plates were arranged without gaps so as to completely cover the surface of the layer made of the crystalline glass bodies.
Thereafter, the temperature is raised at a rate of 240 ° C. per hour, held at 1100 ° C. for 1 hour, and then cooled to room temperature over about 5 hours, whereby a plurality of crystalline glass bodies are fused while the crystals are fused. A crystallized glass article was obtained in which a crystallized glass layer B formed by depositing crystals while a plurality of rod-like crystallized glass plates B were fused on the crystallized glass layer A thus deposited was obtained.

  The crystallized glass article thus obtained had a thickness of about 16 mm. Next, after lightly polishing the surface of the crystallized glass article, the crystallized glass article was observed from the surface on the side where the crystallized glass layer B was provided, and the crystallized glass layer B having a thickness of 2 mm was striped. A translucent pattern sandwiched between the patterns was formed, and a natural marble pattern appearing on the surface of the crystallized glass layer A was confirmed in a slightly stagnant state through the translucent crystallized glass layer B. Moreover, since the striped pattern and translucent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer A can be visually recognized at the same time, a natural marble with a subtle three-dimensional appearance was confirmed.

The reason why the crystallized glass layer B has a semi-transparent pattern is that crystals grow from the surface of the rod-like crystalline glass plate B to the inner side when heat-treated. Further, when the natural marble pattern of the crystallized glass layer A was compared with the natural marble pattern of the crystallized glass article produced by the integration method under substantially the same heat treatment conditions using only the crystalline glass particles, almost all It was the same pattern. In addition to this, as a result of separately measuring the crystallized glass layer A and the crystallized glass layer B by X-ray diffraction, the crystallized glass layer A and the crystallized glass layer B have β-wollastonite as a main crystal. Was deposited.
Furthermore, when the cross section of the crystallized glass layer B was observed with the naked eye, no crack was generated. Furthermore, when the cross section was observed with a scanning electron microscope with respect to the thickness direction of the crystallized glass layer B, it was confirmed that crystals were precipitated in all thickness directions, and the crystallized glass layer B was crystallized to the center. I found out.

Example 9
First, by mass%, SiO ₂ 65.1%, Al ₂ O ₃ 6.6%, CaO 12.0%, Na ₂ O 3.3%, K ₂ O 2.3%, BaO 4.1%, ZnO 6 A glass material prepared to have a composition of 6% was melted at 1500 ° C. for 16 hours. Next, this molten glass was rapidly cooled in water, crushed, dried and classified to obtain crystalline glass bodies having a particle diameter of 1 to 3 mm. This crystalline glass body is a crystalline glass that precipitates β-wollastonite as a main crystal upon heat treatment and becomes a white crystallized glass having a thermal expansion coefficient of 65 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. is there.

Further, SiO ₂ 65.1% by _{mass%, Al 2 O 3 6.6%} , CaO 12.0%, Na 2 O 3.3%, K 2 O 2.3%, BaO 4.1%, ZnO The glass raw material prepared to have a composition of 6.6% was melted at 1500 ° C. for 16 hours. Next, this molten glass was formed into a plate shape by a roll-out method to obtain a crystalline glass plate having a thickness of 5 mm. This crystalline glass plate is a crystalline glass that precipitates β-wollastonite as a main crystal upon heat treatment and becomes a white crystallized glass having a thermal expansion coefficient of 65 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. .

Next, the produced crystalline glass bodies were accumulated in a refractory mold coated with a release agent so as to be layered. The thickness of the accumulated crystalline glass bodies was about 14 mm. The surface of the layer made of the collected crystalline glass bodies was flattened, and two crystalline glass plates were laminated so as to completely cover the surface of the layer made of the crystalline glass bodies.
Thereafter, the temperature is raised at a rate of 240 ° C. per hour, held at 1100 ° C. for 1 hour, and then cooled to room temperature over about 5 hours, whereby a plurality of crystalline glass bodies are fused while the crystals are fused. A crystallized glass article was obtained in which the crystallized glass layer B formed by depositing crystals while the two crystallized glass plates B laminated on the crystallized glass layer A deposited were fused. .

  The crystallized glass article thus obtained had a thickness of about 16 mm. Next, after lightly polishing the surface of the crystallized glass article, the crystallized glass article was observed from the surface on the side where the crystallized glass layer B was provided, and the crystallized glass layer B having a thickness of 3 mm was half A transparent pattern was formed, and the natural marble pattern appearing on the surface of the crystallized glass layer A was confirmed in a slightly stagnant state through the translucent crystallized glass layer B. Moreover, since the translucent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer A can be visually recognized at the same time, a natural marble-like appearance in which a subtle three-dimensional effect is expressed can be confirmed.

The reason why the crystallized glass layer B has a semi-transparent pattern is that crystals grow from the surface of the crystalline glass plate B to the inner side when heat-treated. Further, when the natural marble pattern of the crystallized glass layer A was compared with the natural marble pattern of the crystallized glass article produced by the integration method under substantially the same heat treatment conditions using only the crystalline glass particles, almost all It was the same pattern. In addition to this, as a result of separately measuring the crystallized glass layer A and the crystallized glass layer B by X-ray diffraction, the crystallized glass layer A and the crystallized glass layer B have β-wollastonite as a main crystal. Was deposited.
Furthermore, when the cross section of the crystallized glass layer B was observed with the naked eye, no crack was generated. Furthermore, when the cross section was observed with a scanning electron microscope with respect to the thickness direction of the crystallized glass layer B, it was confirmed that crystals were precipitated in all thickness directions, and the crystallized glass layer B was crystallized to the center. I found out.

(Comparative Example 1)
First, by mass%, SiO ₂ 65.1%, Al ₂ O ₃ 6.6%, CaO 12.0%, Na ₂ O 3.3%, K ₂ O 2.3%, BaO 4.1%, ZnO 6 A glass material prepared to have a composition of 6% was melted at 1500 ° C. for 16 hours. Next, this molten glass was rapidly cooled in water, crushed, dried and classified to obtain crystalline glass bodies having a particle diameter of 1 to 3 mm. This crystalline glass body is a crystalline glass that precipitates β-wollastonite as a main crystal upon heat treatment and becomes a white crystallized glass having a thermal expansion coefficient of 65 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. is there.

Further, SiO ₂ 51.0% by _{mass%, Al 2 O 3 19.0%} , MgO 4.7%, ZnO 4.1%, TiO 2 2.2%, ZrO 2 1.5%, B 2 O ₃ A glass material prepared to have a composition of 6.0%, Na ₂ O 8.5%, K ₂ O 2.8%, CaO 0.2% was melted at 1500 ° C. for 16 hours. Next, this molten glass was formed into a plate shape by a roll-out method to obtain a crystalline glass plate having a thickness of 3 mm. This crystalline glass plate precipitates forsterite (2MgO.SiO ₂ ) as a main crystal when heat-treated, and becomes a white crystallized glass having a thermal expansion coefficient of 67 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. It is glass.

Next, the produced crystalline glass bodies were accumulated in a refractory mold coated with a release agent so as to be layered. The thickness of the accumulated crystalline glass bodies was about 14 mm. A crystalline glass plate prepared so as to flatten the surface of the layer made of the accumulated crystalline glass bodies and completely cover the surface of the layer made of the crystalline glass bodies was disposed.
Thereafter, the temperature is raised at a rate of 120 ° C. for 1 hour, held at 1100 ° C. for 2 hours, and then cooled to room temperature over about 5 hours, whereby a plurality of crystalline glass bodies are fused while the crystals are fused. A crystallized glass article was obtained in which a crystallized glass layer B formed by precipitating crystals while the crystalline glass plate B was fused on the crystallized glass layer A thus formed was obtained.

The crystallized glass article thus obtained had a thickness of about 16 mm. Next, after lightly polishing the surface of the crystallized glass article, the crystallized glass article was observed from the surface on which the crystallized glass layer B was provided, and the crystallized glass layer B having a thickness of 3 mm was transparent. There was no feeling and it was white, and even the presence of the crystallized glass layer A through the crystallized glass layer B could not be confirmed.
The crystallized glass layer B is not transparent and has a white color because the crystal does not grow from the surface of the crystalline glass plate B to the inner side when heat-treated, but the crystalline glass plate B This is because crystals grow at the same time regardless of the position inside. Further, when a crystallized glass article produced by an accumulation method under substantially the same heat treatment condition using only the crystalline glass body was observed, a natural marble pattern appeared. From this, it is presumed that a natural marble pattern could be confirmed if the crystallized glass layer B was transparent or translucent.
The crystallized glass layer A and the crystallized glass layer B were separately measured by X-ray diffraction, and as a result, β-wollastonite was precipitated as the main crystal in the crystallized glass layer A. In the layer B, forsterite was precipitated as the main crystal.

(Comparative Example 2)
First, by mass%, SiO ₂ 65.1%, Al ₂ O ₃ 6.6%, CaO 12.0%, Na ₂ O 3.3%, K ₂ O 2.3%, BaO 4.1%, ZnO 6 A glass material prepared to have a composition of 6% was melted at 1500 ° C. for 16 hours. Next, this molten glass was rapidly cooled in water, crushed, dried and classified to obtain crystalline glass bodies having a particle diameter of 1 to 3 mm. This crystalline glass body is a crystalline glass that precipitates β-wollastonite as a main crystal upon heat treatment and becomes a white crystallized glass having a thermal expansion coefficient of 65 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. is there.

Further, SiO ₂ 51.0% by _{mass%, Al 2 O 3 19.0%} , MgO 4.7%, ZnO 4.1%, TiO 2 2.2%, ZrO 2 1.5%, B 2 O ₃ A glass material prepared to have a composition of 6.0%, Na ₂ O 8.5%, K ₂ O 2.8%, CaO 0.2% was melted at 1500 ° C. for 16 hours. Next, this molten glass was formed into a plate shape by a roll-out method to obtain a crystalline glass plate having a thickness of 2 mm. This crystalline glass plate precipitates forsterite (2MgO.SiO ₂ ) as a main crystal when heat-treated, and becomes a white crystallized glass having a thermal expansion coefficient of 67 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. It is glass.
In addition, since the crystalline glass plate obtained by the roll-out method is used for forming the crystallized glass layer C in addition to the formation of the crystallized glass layer B, it is cut according to the size of each layer, Two types of crystalline glass plates having different shapes were obtained.

Next, after laying the produced crystalline glass plate in a refractory mold coated with a release agent, the crystalline glass body produced so as to completely cover the surface of the crystalline glass plate is layered. Accumulated. The thickness of the layer made of this crystalline glass body was about 14 mm. Further, a crystalline glass plate produced by flattening the surface of the layer made of crystalline glass bodies and completely covering the surface of the layer made of crystalline glass bodies was disposed. As a result, the layer composed of the crystalline glass bodies was sandwiched between the two crystalline glass plates.
The two crystalline glass plates have a size slightly smaller than the refractory mold, and the distance between each of the four sides of the crystalline glass plate and the side wall surface of the refractory mold is 2 mm. In this manner, the layers were arranged on the upper and lower surfaces of the crystalline glass bodies.
Subsequently, the thickness direction of the 2 mm thick crystalline glass plate is fireproof between the laminate formed by laminating the crystalline glass body layer and the crystalline glass plate and the side wall surface of the refractory mold. It pushed in so that it might become parallel with the bottom face of a formwork, and as shown in FIG. 2, the crystalline glass plate was arrange | positioned between the end surface of a laminated body, and the side wall surface of a refractory formwork. In addition, this crystalline glass plate was arrange | positioned so that it might closely_contact | adhere to the end surface perimeter of a laminated body.
Thereafter, the temperature is raised at a rate of 120 ° C. for 1 hour, held at 1050 ° C. for 2 hours, and then cooled to room temperature over about 5 hours to precipitate crystals while the crystalline glass plate is fused. A crystallized glass layer A is formed on the first crystallized glass layer B by depositing crystals while fusing a plurality of crystalline glass bodies, and the crystallinity is formed on the crystallized glass layer A. A second crystallized glass layer B is formed by precipitating crystals while the glass plate is fused, and the first and second crystallized glass layers B are provided on both sides of the crystallized glass layer A. Thus, a crystallized glass article was obtained in which a crystallized glass layer C formed by precipitating crystals while the crystallized glass plate C was fused to the entire periphery of the end face of the laminate portion was formed.

The crystallized glass article thus obtained had a thickness of about 17 mm. Next, after lightly polishing both surfaces and end surfaces of the crystallized glass article, the crystallized glass article was observed from the side on which the crystallized glass layer B and the crystallized glass layer C were provided. The crystallized glass layer B and the crystallized glass layer C have a transparent white color, and the presence of the crystallized glass layer A can be confirmed through the crystallized glass layer B and the crystallized glass layer C. There wasn't.
The crystallized glass layer B and the crystallized glass layer C are not transparent and exhibit a white color because they are crystallized from the surface of the crystalline glass plate B or the crystalline glass plate C to the inner side when heat-treated. This is because the crystal grows at the same time regardless of the position in the crystalline glass plate B or the crystalline glass plate C. Further, when a crystallized glass article produced by an accumulation method under substantially the same heat treatment condition using only the crystalline glass body was observed, a natural marble pattern appeared. From this, if the crystallized glass layer B and the crystallized glass layer C are transparent or translucent, it is presumed that a natural marble pattern has been confirmed.
Further, the crystallized glass layer A, the crystallized glass layer B, and the crystallized glass layer C were separately measured by X-ray diffraction. As a result, β-wollastonite was precipitated as a main crystal in the crystallized glass layer A. In the crystallized glass layer B and the crystallized glass layer C, forsterite was precipitated as the main crystal.

(Comparative Example 3)
The crystalline glass bodies used in Example 3 were accumulated in a refractory mold coated with a release agent so as to form a layer. The thickness of the accumulated crystalline glass bodies was about 18 mm. The surface of the layer consisting of the accumulated crystalline glass bodies was flattened.
Thereafter, the temperature is raised at a rate of 120 ° C. for 1 hour, held at 1100 ° C. for 2 hours, and then cooled to room temperature over about 5 hours, whereby a plurality of crystalline glass bodies are fused while the crystals are fused. A crystallized glass article consisting only of a crystallized glass layer formed was obtained.

  The crystallized glass article thus obtained had a thickness of about 16 mm. Next, after the surface of the crystallized glass article was polished to a mirror surface, the surface of the crystallized glass article was observed, and a natural marble pattern appeared. However, when the surface of the crystallized glass article was observed, pinhole defects having a diameter of about 0.1 mm to 1 mm were observed.

(Comparative Example 4)
The glass raw material for producing the crystalline glass plate used in Example 1 was melted at 1500 ° C. for 16 hours. Next, this molten glass was formed into a plate shape by a roll-out method to obtain a crystalline glass plate having a thickness of 10 mm. This crystalline glass plate is a crystalline glass that precipitates β-wollastonite as a main crystal upon heat treatment and becomes a white crystallized glass having a thermal expansion coefficient of 65 × 10 ⁻⁷ / ° C. at 30 to 380 ° C. .

Next, after laying the produced crystalline glass plate in a refractory mold coated with a release agent, the temperature was raised at a rate of 180 ° C. in 1 hour, held at 1100 ° C. for 1 hour, and then about room temperature. By cooling for 5 hours, a crystallized glass article obtained by crystallizing a crystalline glass plate was obtained.
The crystallized glass article thus obtained had a thickness of about 10 mm. Next, after lightly polishing both surfaces of the crystallized glass article, the surface of the crystallized glass article was observed, and natural marble-like was confirmed. Moreover, as a result of measuring the crystallized glass article by X-ray diffraction, β-wollastonite was precipitated as the main crystal.

  However, when the cross section of the crystallized glass article was observed, a crack occurred in the central portion in the thickness direction. Further, when the cross section was observed with respect to the thickness direction, crystals were precipitated up to about 3 mm from both the upper and lower surfaces to the inner side, but no crystals were precipitated at the central portion of about 4 mm in the thickness direction. It turned out that it was not converted.

It is a schematic cross section for demonstrating an example of the manufacturing method of the crystallized glass article of this invention. It is a schematic cross section for demonstrating the other example of the manufacturing method of the crystallized glass article of this invention. It is a schematic cross section which shows an example of the cross-section of the crystallized glass article obtained by heat-processing plate glass.

DESCRIPTION OF SYMBOLS 10 Refractory mold 12 Crystalline glass body layers 14, 14A, 14B Crystalline glass plate B
16 Crystalline glass plate C
20, 20A, 20B, 20C Laminate 100 Crystallized glass article 110 Crystallized glass matrix 120 Non-crystallized glass matrix 130 Crack

Claims (8)

A plurality of crystalline glass bodies fused together and crystallized crystallized glass layer A;
A translucent crystallized glass layer B provided in a fused state on at least one side of the crystallized glass layer A and crystallizing the crystalline glass plate B to the center thereof,
The crystallized glass layer A includes at least one crystal selected from β-wollastonite and diopside as a main crystal,
The crystallized glass layer B is a patterned crystallized glass article including at least one crystal selected from β-wollastonite and diopside as a main crystal and having a thickness of 6 mm or less,
The crystallized glass layer A has a pattern on the surface, and the pattern can be confirmed when viewed from the surface of the crystallized glass article with the pattern where the crystallized glass layer B is provided. A patterned crystallized glass article characterized by the following:   The crystallized glass with a pattern according to claim 1, wherein the pattern is formed on the surface of the crystallized glass layer A by precipitation of crystals from the surface of the crystalline glass body toward the inside. Goods.   The patterned crystallized glass article according to claim 1 or 2, wherein the crystallized glass layer B has a thickness of 2 mm or less.   The crystallized glass article with a pattern according to any one of claims 1 to 3, wherein the crystallized glass layer B has no pinhole defect.   The patterned crystallized glass according to any one of claims 1 to 4, further comprising a crystallized glass layer B on the entire periphery of the end face of the laminate having the crystallized glass layer A and the crystallized glass layer B. Goods.   The patterned crystallized glass according to any one of claims 1 to 5, wherein the crystallized glass layer B is provided in a fused state on both surfaces of the crystallized glass layer A. Goods. The absolute value of the difference between the thermal expansion coefficient at 30 to 380 degrees of the crystallized glass layer A and the thermal expansion coefficient at 30 to 380 degrees of the crystallized glass layer B is 0 to 10 × 10 ^−7. The crystallized glass article with a pattern according to any one of claims 1 to 6, wherein the crystallized glass article is within a range of / ° C. 1) A laminated body having a crystalline glass body layer in which a plurality of crystalline glass bodies are accumulated in a layered manner, and a crystalline glass plate B disposed on the surface of the crystalline glass body layer,
2) a laminate having a crystalline glass plate B and a crystalline glass body layer in which a plurality of crystalline glass bodies are layered on the surface of the crystalline glass plate B; and
3) a first crystalline glass plate B, a crystalline glass body layer in which a plurality of crystalline glass bodies are layered on the surface of the first crystalline glass plate B, and the crystalline glass body A laminate having a second crystalline glass plate B disposed on the surface of the layer,
Including at least a heat treatment step of heat-treating at least one laminate selected from the group consisting of:
In the heat treatment step, the crystalline glass bodies and the crystalline glass body layer and the crystalline glass plate B are fused together, and the crystalline glass body and the crystalline glass plate B are crystallized. By making
At least one crystal selected from β-wollastonite and diopside is precipitated as a main crystal in the crystalline glass body layer, and β as a main crystal in the crystalline glass plate B The at least one crystal selected from wollastonite and diopside is precipitated up to the central part of the crystalline glass plate B, according to any one of claims 1 to 7, A method for producing a patterned crystallized glass article.

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