TW200904769A - Crystallized glass article having patterns and method of producing the same - Google Patents

Abstract

This invention provides a crystallized glass article having patterns, which includes a crystallized glass layer A formed by fusing a plurality of crystalline glass particles to connect each other and simultaneously crystallizing the fused glass particles, and a crystallized glass layer B formed by disposing a crystalline glass plate B onto at least one surface of the crystallized glass layer A in a fused state and inwardly crystallizing the crystalline glass plate B from the surface to the center thereof, wherein a main crystal of the crystallized glass layer A is at least one of β -wollastonite and diopside, and a main crystal of the crystallized glass layer B is at least one of β -wollastonite and diopside. In addition, this invention also provides a method of producing the crystallized glass article having patterns.

Description

200904769 IX. Inventive Note: [Reciprocal Reference of Related Application] This application is based on and claims the priority of Japanese Patent Application No. 2007-187654, which is filed on Jul. 18, 2007, its entire contents. This is incorporated herein by reference. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystallized glass article having a pattern and a method of manufacturing the same, which is applied to a building exterior material, an interior material or a furniture surface board, and a desk top board. [Prior Art] In recent years, with the change of the times, various crystallization glass articles such as building exterior materials, interior materials or furniture facing sheets, and office board sheets have been continually demanded. As a crystallized glass used for these purposes, it is well-known crystallization, and the glass contains · 召 石 石 灰 ( ( 万 万 石 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 / / / / / / / / / / / 为主 为主 为主 为主 为主 为主The crystallized glass is obtained, or a crystallized glass obtained by depositing diopside (di〇pside, Ca〇. Mg〇·2Si〇2) as a main crystal. In addition, a method for producing a crystallized glass article containing the above-mentioned crystals is known, and (1) a method for producing crystals from the surface to the inside by heat-treating the plate-shaped crystallized glass (Patent Document) And (2) the so-called "accumulation method", the production method, that is, the molten glass is subjected to rapid cooling treatment such as water cooling to form a crystalline glass t body, and the crystallized glass body is accumulated in a fire resistance model by heat treatment. The crystallized glass bodies are integrated with each other and the crystallization system and the method are simultaneously performed (Patent Documents 2 to 8). The crystallized glass articles produced by the method of the present invention have the Jiuran marble _ like the temple. [Patent Document 1] Japanese Patent Publication No. 51_23966 Publication No. 200504769

[Patent Document 3] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 7] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The surface, the back surface, and the end surface of the plate glass face the inside. For example, a plate-like crystallized glass article having a thickness of about _ is not crystallized at the center portion thereof, and a portion of the body portion having a residual thickness of about 4 mm is cracked. situation. ^1, 00. Test (4) can be explained by the pattern of the step-by-step, Figure 3 is a cross-sectional view showing the crystallization of the glass article obtained by heat treatment. In Fig. 3 m : 〇〇 * non-crystallized glass article, 110 denotes a crystallized glass body, 12 Å shows a crystalline glass precursor which is yttrium, and 130 represents a crack. As shown in Fig. 3, the crystal grows from the surface, the back surface, and the end surface of the plate-like layer, and there is uncrystallized in the region surrounded by the crystallized glass body 110 (the central portion of the sheet glass article). The knot and surface are 12G, and cracks (10) occur in this 120. - For the crystallization of the glass obtained by the production method disclosed in the above (1), 'the crack is not observed from the appearance (10) 130, so it will lead to insufficient strength. When the crystallization of the crystallized glass is produced by the accumulation method disclosed in the above (2), when the 纟σ 日 日 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Therefore, the produced crystallized glass 1 has a semi-fine pore defect in the surface of the bubble-bearing surface in order to perform fine treatment on the surface of the crystallized glass article. 200904769 Image=A crystallized glass article with a pattern of pore defects on the surface. For example, when /field is used as a floor, the pore portion will gradually become black over time and affect the visibility of the floor. When the color of the crystallized glass article having the color is white or light, the aesthetics of the floor are more significantly affected. SUMMARY OF THE INVENTION In order to solve the above problems, the present invention provides a crystallized glass article having a pattern having sufficient strength and having no rolling defects on its surface, and a method of manufacturing the same. According to one embodiment of the present invention, there is provided a crystallized glass article having a pattern comprising: a crystallized glass layer A formed by fusing a plurality of crystalline glass bodies and simultaneously crystallizing; The crystallized glass layer B is disposed on at least one surface of the crystallized glass sheet B when the at least one surface of the crystallized glass layer A is in a molten state, and the crystalline glass sheet b is brought from the surface toward the inside. The central portion is formed by crystallization, wherein the main crystal of the crystallized glass layer A is 々-wol lastonite (/9-CaO. Si〇2) and diopside (di〇pside, Ca〇·MgO) 2Si〇2) at least one of them, and the main crystal of the crystallized glass layer B is at least one of 召 矽 矽 ash and diopside, and the crystallized glass layer B has a thickness of about 6 mm. In one embodiment, the crystallized glass layer B can be fused to the upper and lower surfaces of the crystallized glass layer a. The absolute value of the difference in thermal expansion coefficient between the crystallized glass layer A and the crystallized glass layer b is from 3 〇 to 38 (TC is in the range of 〇 〇 1 〇 X 1 〇 _7 / 〇 c. According to another aspect of the present invention The invention provides a method for manufacturing a crystallized glass article having a pattern, comprising a heat treatment step for heat-treating at least one of the following laminates: (1) accumulating a plurality of crystalline glass bodies into a layered layer ^ a layered body composed of a crystallized glass body layer and a layered glass plate B laminated on the surface of the crystallized glass body layer, (2) a surface of the crystallized glass plate b and the surface of the glass plate B a laminate comprising a plurality of crystalline glass bodies in a layered crystalline glass body layer, and (3) a plurality of crystals on the surface of the first crystalline glass plate B from the first crystalline glass plate The glass body is deposited into a layer of 200,904,769, a crystalline body layer, and a layered body composed of the crystallized glass plate β, and these heat treatment steps I;., β-glass Multiple crystals in the body layer The glass bodies are fused to each other so that the crystallized glass is cut, the body layer and the crystalline glass plate are mutually sinuous, and at least one of the crystals of the crystallization, the phosgene and the diopside are crystallized, as the 曰φ0' raw glass plate, from the crystallization The surface of the glass plate faces inward i to ΐ

In the broad section, at least one of the crystals of the smectite and the diopside is precipitated as the U. As described above, according to the present invention, the crystallized glass article having the pattern without void defects and its manufacture = surface can be provided. 】 (Crystalized glass article) 施 ϋ ϋ ϋ ' ' ' ' ' ' ' ' ' ' ' ' ' 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶A plurality of crystallized glass bodies are mutually fused, and at the same time, the glass layer B is fused to at least one surface of the crystallized glass layer A. f 曰曰 曰曰 = glass layer / is carried out from the surface of the crystalline glass plate B to the center portion thereof. b 曰 幵 成 y into. The above crystallized glass layer a contains at least a crystal of the smear-like stone (called [wollastonite, yS-CaO · Si〇2) and diopside (diOpside, CaO. MgO · ji〇2) as Main crystal. The above crystallized glass layer B contains at least one of cold-apatite and diopside as a main crystal, and has a thickness of 6 mm or less. In the crystallized glass article of the present invention, since the crystallized glass layer A is formed by fusing a plurality of crystallized glass bodies to each other and crystallizing them at the same time, as in the conventional method using the accumulation method, Crystallized Glass Article Generally, the crystallized glass layer A may have a pattern of a natural marble pattern or the like. In addition to the above, at least one surface of the crystallized glass layer A has a thickness of 6 and is fused with a crystallized glass layer B. Such a crystallized glass layer β is formed by crystallizing from the surface of the glass plate B to the center portion thereof. However, since the degree of dryness is less than 6 mm, it is transparent (four) translucent. Therefore, when the glass riding article is viewed from the side where the crystallized glass layer B is provided, the pattern produced by the glass layer A can be confirmed. Further, since the crystallized glass _B formed of the crystalline glass (4) is used as the surface of the crystallized glass article, there is no pore. 〆#_ When the exterior of the building is connected to the panel of the interior material, the furniture or the desk, the crystallized glass article of the present invention is used, and the surface formed by the crystalline glass plate β is placed on the side which is easy for the user to see. Even if time passes, there will be no problem that the pores become black and the appearance is affected. In addition, in the examples, the crystallized glass layer may be entangled on the upper and lower surfaces of the σθ-dayized glass layer A. In this case, we can obtain crystallized glass articles with no porosity defects on both sides. a The crystal glaze L of the present invention is composed of the correction glass layer _B, and therefore has sufficient strength. Further, the crystal/b = layer B is formed by crystallizing (four) crystallization of the crystalline slab B, and the fluorite and diopside are precipitated, and the crack is formed in the center portion of the crystallized glass layer β. 2 1 can occur when the strength is not ^. In order to improve the above problem, the glass is crystallized from the surface to the center, and at the same time has the layer A, so that sufficient strength can be obtained. . The thickness of β-glass layer β (4) in 6mm, 5m_ lower than 曰化#crystallized glass sugar (4) thicker than 6mm, ^ 曰曰 glass layer Β will change from translucent to opaque, so from the Crystallization],:: ί^^ίϊΒθθΐ^^σ〇σ0ί, the same, making the crystallized glass items lack of aesthetics. Further, in the surname glass layer, the crystalline glass precursor is easily left. ...曰化200904769 On the other hand, the thickness of the crystallized glass layer B is more preferably 1 or more, and more preferably 2 mm or more. Since it is more than m, it has a thickness range of from about 0.1 to about 6 mm. Therefore, the bismuth glass layer β may be preferably 0.1 mm or more and 30 mnm, more preferably 1 mm or more and 15 coffee or less. Moreover, the thickness of the w 1 crystallized glass article is not specifically defined, but it can be satisfactorily ^ ^ l5mm ^ 25fflm α^; ί 中 - must contain ❹ - money such as rumoxene at least because of the crystallization process Wei Shi or, when precipitated, has a surface orientation from a crystalline glass body; ^ =

J MaBa A and the 'crystallized glass layer B' must also contain $, and the limestone and diopside are at least in the middle of the crystal, as the main crystal. Because of this arrangement, it is possible to make the junction (f) bismuth glass layer A and the crystallized glass layer B have a small difference in thermal expansion coefficient, and when manufacturing the crystallized glass article by the method described later, we can prevent the day-to-day glass from being formed. The item has been damaged. Further, in the crystallized glass layer A and the crystallized glass layer 8, the absolute value of the difference in thermal expansion coefficient between 3 〇 and 38 〇 t: 2 (hereinafter referred to as "the difference in thermal expansion coefficient is preferably in the range of 〇 ΗΓ A 7 A: 'In the range of 〇~3 X 1G-7/t, it is more preferable. If the difference in thermal expansion coefficient exceeds 10 X 10-VC, crystallizing glass articles are produced by heat treatment, and crystallization is performed by heat treatment. The glass layer A and the crystallized glass @ B are fused together, and the difference in heat shrinkage between the crystallized glass layer A and the crystallized glass layer B becomes large, and the crystallized glass article may be damaged. In other cases, when such a crystallized glass product is used in a gas field such as gas 10 200904769, the high temperature field may be damaged. The thermal % expansion coefficient is based on thermal mechanical analysis equipment (TMA, pERKIN elmer). Manufacture, model: ΤΜΑ 7) Measurement was carried out under the following conditions: Reference material: no heating rate: 20 ° C / min Static force: 10 mN Sample length: l 〇 mm Heating ambient gas: N2. Further, in the crystallized glass of the present invention In the item, the variety Or considering the prevention of pore defects, etc., it is possible to melt the crystallized glass layer B with the same function (crystallized glass layer 〇. In this case, 'crystallized glass _ C can be melted only in crystallization. The end face portion of the glass layer A, g is simultaneously fused to the end faces of both the crystallized glass layer A and the crystallized layer B, and the crystallized glass layer c is such that the crystallized glass plate c is crystallized from the surface to the center portion thereof. a product formed containing Wei Shi and diopside, wherein the crystal is 'as the main crystal, and the thickness thereof is 6 mm or less. In addition, the glass composition of the crystalline sheet G for forming the crystallized glass layer c The same as the crystalline glass plate B. 〃 (Method for producing crystallized glass article) Next, a method for producing the crystallized glass article of the present invention will be described. A crystalline glass body which can be a crystallized glass layer is used. The raw material is made into a crystalline glass plate, and a crystalline glass plate which can be a crystallized glass layer β is prepared. The two crystalline glass plates are placed in an overlapping state and heated to form two kinds of crystallized glass. The plates are fused to each other. By this method, the crystallized glass article of the present invention can be produced. However, when it is considered from the viewpoint of practicability or cost, it is preferred to produce the crystallization of the present invention by the following production method. That is, in the production of the crystallized glass article of the present invention, first, (1) a crystalline glass body layer formed by laminating a plurality of 11 200904769 glaze bodies, and a surface of a laminated glass body layer The laminated layer composed of the crystalline glass plate β, the glass plate β, and the plurality of crystalline glass bodies are stacked on the crystallographic table to form a layered crystalline glass body layer. The first crystalline glass plate β and the plurality of crystalline glass bodies are stacked on the surface of the glass plate to form a layered crystalline glass body layer, and the second crystallized glass on the surface of the crystallized glass body layer A layered body composed of the plate β. From these groupings, choose at least the towel-layered body and prepare. • The secret crystal glass article of the present invention can be produced by heat treatment of the above (1) to (3) at least the towel-layer body. The heat treatment project is usually carried out in a refractory model as shown in the figure. The model is coated with a release agent on its inner wall to accommodate the laminate. The graphs jA to 1C illustrate the cross-section of an example of the method for producing a crystallized glass article of the present invention, and specifically show the arrangement state of the laminate in the refractory mold model. In Figs. 1A to 1C, 1〇 indicates a refractory material model, 12 indicates a crystalline glass body layer, and 14, 14A, and 14B indicate a crystalline glass plate B, and 2〇A, 2〇B, and 2〇c indicate a laminate. In the above-mentioned (1) laminated body, as shown in FIG. 1A, a plurality of crystalline glass bodies are accumulated in a refractory material model 10 coated with a release agent on a wall surface and a bottom surface (not shown). After the crystalline glass body layer 12 is formed in a layered form, the crystalline glass plate β η is placed on the upper surface of the crystallized glass body layer 12, and 12 and 14 are combined (the layered body 20Α in the drawing). Further, in the laminated body of the above (2), as shown in FIG. 1A, in the vapour model 10 in which the release agent is applied to the wall surface and the bottom surface (not shown), the crystallized glass plate 14 is disposed, and then crystallized. On the upper surface of the glass plate Β 14, a plurality of crystal-glass bodies are stacked to form a layer of the crystalline glass body layer 12, and 14 and 12 are combined (the layered body 20 in the figure). Further, in the layered body of the above (3), as shown in Fig. 1C, in the refractory material model in which the release agent is coated on the wall surface and the bottom surface (not shown), the crystal is crystallized and then crystallized. On the upper surface of the glass plate β 14Α, a plurality of crystalline glass bodies are layered to form a crystalline glass small 12 200904769 body layer 12 'and then 'the second crystalline glass plate β 14 is placed on the upper surface of the crystalline glass body layer 12 'Combined from 14Α, 12 and 14Β (layered body 20C in the figure). In addition, when it is desired to arrange the crystallized glass layer C on the end surface of the crystallized glass article of the present invention, for example, a crystal glass body or a crystallized glass plate 3 may be disposed in the refractory material model in the order of the following steps. Glass plate C.

First, when a layered body is formed in a refractory material model, it is disposed using a crystallized glass sheet which is smaller than the shape of the bottom surface of the refractory material model, so that the side wall surface of the layered body and the refractory material model is formed in a few planes to a dozen or so. Gap. Next, the crystallized glass plate C is placed in a gap portion between the end face of the laminated body and the side wall surface of the refractory material model, so that the crystallizable glass plate C appears to be sandwiched between the end face of the laminated body and the side wall surface of the refractory material model. Then, by performing the heat treatment in this state, we can obtain a crystallized glass article in which the crystallized glass layer C is fused to the end faces. In addition to the above methods, the crystallized glass plate c may be placed on the side wall surface of the refractory material model to form a layered body, and the heat treatment process may be performed. Fig. 2 is a schematic cross-sectional view showing another example of a method for producing a crystallized glass article of the present invention. Specifically, in order to produce a crystallized glass article containing a crystallized glass layer C fused with an end surface, the pattern is The state after the arrangement of the crystalline plate c and the laminated body in the refractory material model is shown. In Fig. 2, 16 denotes a crystalline glass plate c, 20 denotes a laminated body 'the elements denoted by other symbols are the same as those of the elements of Figs. 1A to 0. In the embodiment shown in Fig. 2, in the refractory model 1〇 Inside, the crystalline glass plate C is seen to be sandwiched between the laminated body 2G and the side wall surface of the refractory material model 1 (). ^, t layer Γ - - layer structure can be the laminate bodies 20A to 2〇c shown in Figs. 1A to 1C. Further, regarding the heat treatment engineering, the heat of the laminate body is: = small, between the "melt, and Make the crystalline glass body layer === at least one of the crystals, as the main junction, 曰5 f2:^2, to make the crystalline glass body and the crystalline glass plate β: in the gentleman's glass body layer' It is precipitated as Lu-Shishi limestone and diopside stone. Moreover, in the crystalline glass plate β 13 200904769, it precipitates at least one of the crystals of /3 ash and diopside as the main knot. It is carried out under the condition that the crystal is deposited on the central portion of the crystallizable glass sheet B. The heat treatment is carried out at a temperature higher than the softening point of both the crystallizable glass body and the crystalline glass plate B in order to satisfy the above conditions. Further, we can select a specific heat treatment temperature or heat treatment time depending on the softening point of the crystalline glass body and the crystalline glass plate B, the thickness of the crystallized glass body layer or the crystalline glass plate B, etc. From normal temperature to 6 ° ° C / hr ~ 600 ° C / hr After the temperature is raised at a heating rate, it is preferred to maintain the temperature at 1 〇 3 (rc~113 (in the range of rc, more preferably in the range of 1050. 〇11 〇〇. ,, and then after about 〇 5 hours). When the temperature is 5 ^, the temperature is kept cold. In addition, the thickness of the solar glass sheet B is preferably below, preferably below, preferably below. When the thickness of the crystalline glass sheet B exceeds 6 mm, heat treatment is performed. Since the center portion of the crystallized glass sheet B is not crystallized, the crystallized glass precursor in which the crack remains in the center portion of the crystallized glass sound is obtained. The purpose of the thickness of the crystallized glass article or the need for the surface to be reinforced may be carried out by the grinding process of the surface = grinding, or the cutting process of cutting the crystallized glass article may be performed in accordance with the requirements of the size or the job.

Zhuang, V ί crystallized glass produced by f-crystallization of the article, the system refers to the shape of the glass, but the shape is not limited, the shape is not particularly limited, j, which is preferred It has an average particle diameter of about 1 coffee or more and 7 mm or less. The manufacturing method of the body is also not particularly limited, and we can also use the industry to find out == to manufacture 'for example, it is possible to use a system in which a glass melt is cooled by water, etc.' Further, when the thickness of the crystallized glass layer is 6 or less, the article made of a single crystallized glass plate is not limited. For example, the 'crystallized glass layer Β can be formed by using two or more crystalline glass sheets 14 200904769 m layer λ / by heat treatment; or (10) for more than 2 夕 4 glass, the anti-β is closely and seamlessly arranged in the crystallization. After the surface of the glass body layer, it is formed through a heat treatment process. In the case of the crystallized layer g, it is also possible to form two or more glass sheets C, or two or more rod-shaped crystalline glass sheets C, which are formed by heat treatment. The glass composition of the U-shaped glass body, the crystallized glass plate B, and the crystallized glass plate c) - the crystallized glass produced by the crystallized article of the invention is small, and the crystal glass plate β and crystal The glass plate C has the following properties: when these crucibles are heat-treated at a temperature lower than the softening point, the as the main crystal of the gamma-ray and the diopside will be from the surface of these solar cells. It is precipitated to the inside, that is, these crystallized glasses are a glass composition of a surface crystal type. The glass composition satisfying the above conditions preferably has the following glass compositions as shown in (1) to (12). (1) The mass percentages are Si〇2: 50 to 65%, Al2〇3: 3 to 13%, Ca0: 15 to 25%, and ZnO: 2 to 10%, and the total amount of colored oxides is 〇~5. % glass composition. The glass material formed of the present glass composition can be precipitated as a main crystal by the heat treatment at a temperature higher than the softening point. Further, the coloring oxide is selected from at least one of the following metal oxides: V2〇5, 〇2〇3, Mn〇2, Fe^, C〇0, NiO, CuO, etc., the coloring oxide Adding to the glass allows the colorless transparent glass material to be colored. (2) The mass percentage is Si〇2: 45~75%, Al2〇3:1~13%, CaO: 6~14. 5%, Na2〇+K2 〇: 1 to 13%, BaO: G~m, ZnO: G~18%, and BaO+ZnO: 4 to 24%, and the total color of the coloring oxide is 1 to 10% of the glass composition. Coloring oxidation: The composition of the composition is the same as that of the glass composition (1). The glass material formed by the composition of the present glass can be precipitated as a main crystal by heat treatment at a temperature higher than the softening point. 3) The percentage of Wuli is Si〇2: 45~75%, AI2O3: 1~15%, CaO: 8~20%, 15 200904769

Na2〇+K2〇 : 1 to 15%, BaO: (M8%, ZnO: 〇~18%, BaO+ZnO: 4~25%,

Fe2〇3 : 2 to 8%, Ti〇2 : 〇. 1 to 7%, Mn〇2 : 〇. 1 to 5%, CoO: 〇~2%, B2O3: 0 to 3%, 仏2〇3: 〇~1%, and Sb2〇3: 0~1% glass composition. The glass material formed of the present glass composition can be precipitated as a main crystal by heat treatment at a temperature higher than the softening point. (4) The mass percentage is Si〇2: 48~68%, Al2〇3:0. 5~17%, Ca0: 6~22%, %2〇+〖2〇: 5~22%, MgO: 0. 2 to 8%, BaO: 〇~8%, ZnO: 0 to 9%, BaO+ZnO: 〇~15%, and & 〇3: 〇~6%, and the total amount of colored oxides is 〇~ Glass-glass composition. r The glass material formed of the present glass composition can be precipitated as a main crystal by heat treatment at a temperature higher than the softening point. (5) Mass percentage Si〇2: 40~75%, Al2〇3: 2~15%, Ca0: 3~15%,

ZnO : 0 to 15%, BaO: 0 to 20%, B2O3: 0 to 1%, Na2〇+K2〇+Li2〇: 2 to 20%,

AszO3 : 〇~1%, and Sb2〇3 : (M%, and the glass composition of the total color of the colored oxide is 〇~1〇0/〇. The glass material formed by the glass composition is higher than the softening point The heat treatment is carried out at a temperature to precipitate the ruthenium-free as the main crystal. (6) The mass percentage is Si〇2: 45 to 75%, Al2〇3:1 to 25%, and CaO: 1 to 12.50/. ,

MgO : 〇. 5~12%, CaO+MgO: 1. 5~13%, BaO: 〇~m, ZnO: 0~18%, Na2〇: Bu 15%, Μ: 0~7%, Li2〇: 0~5%, B2〇3: 0~10%, p2〇5: 〇~1〇%,

Asz〇3 : 〇~1%, and Sb〇3: 〇~1%, and a glass composition in which the total amount of colored oxides is Q 〜1〇%.

The glass material formed of the present glass composition can be precipitated as a main crystal by heat treatment at a temperature higher than the softening point. X (7) Mass percentage Si〇2: 40~75%, Al2〇3: 2~15%, CaO: 3~20%, - Zn0: 0~15%, Ba0: 0~20%, B2〇3 : 〇~ let, Na2〇+K2〇+Li2〇: 2~20%,

As2〇3 : 〇~1%, and SbOa: (H%, and the glass composition of the total color of the colored oxide is 〇~. The glass material formed by the composition of the glass is at a temperature higher than the softening point 16 200904769 After heat treatment, /5-ashite can be precipitated as the main crystal. (8) Mass percentage is Si〇2: 45~75%, Al2〇3:1~25%, CaO: 1~20%,

Mg〇: 0. 5~17%, BaO: 0~18%, ZnO: 〇~18%, Na2〇: 1~15%, K2〇: 〇~7%, Li2〇: 0~5%, Β2〇 3 : 0 to 10%, ρ2 〇 5 : 〇 ~ dish, As2 〇 3 : 〇 κ, and Sb2 〇 3 : 0 to 1% ' and the total color of the colored oxide is 0 to 10% of the glass composition. The glass material formed of the present glass composition can be precipitated as a main crystal by heat treatment at a temperature higher than the softening point. (9) Mass percentage Si〇2: 45~70%, Al2〇3: 1~13%, Ca0: 6~25%, Na2〇+K2〇+Li2〇: 0.1~20%, BaO: 0~20 %, ZnO: (M8%, and BaO+ZnO: 4~24%' and the glass composition of the total amount of colored oxides is 〇~. The glass material formed by the composition of the glass is at a temperature higher than the softening point. By heat treatment, asbestos can be precipitated as the main crystal. (10) Mass percentages Si〇2: 45~75%, Al2〇3: 1~15%, CaO: 6~20〇/〇, Na2〇+K2〇 : 1 to 15%, BaO: (M8%, ZnO: (M8%, BaO+ZnO: 4 to 25%,

Ni〇 . 0. 05~5%, and C〇0: 0. 01~5% of the glass composition. The glass material formed of the present glass composition can be precipitated as a main crystal by heat treatment at a temperature higher than the softening point. (11) Mass percentage Si〇2: 50~75%, Al2〇3: 1~15%, CaO: 6~16·5%, Li2〇: 0.1~5%, B2〇3: (M· 5% , CaO+Li2〇+B2〇3: HM7. 5%, ZnO: 2. 5~12%, BaO: 0~12%, Na2〇+K2〇: 〇·1~15%, As2〇3: 0~ 1〇/〇, Sb2〇3 ··〇~1%, Mg〇: 〇~1. 5%, SrO: (M. 5%, Ti〇2: 0~1%, Zr〇2: 〇~1% And P2〇s : (H%, and a glass composition in which the total amount of colored oxides is 〇~. The glass material formed by the present glass composition can be precipitated by heat treatment at a temperature higher than the softening point. As the main crystal. (12) Mass percentage Si〇2: 45~77°/., Al2〇3:1~25%, CaO: 2~25%, ZnO: 〇~ irrigation, BaO: 0~ 20%, MgO: 0~17%, %2〇: Bu 15%, K2〇: 〇~7%, Li2〇: 〇~5%, Β203: 0~1. 5%, As2〇3: 0~l %, Sb2〇3: 0~l%, SrO: (Η· 5%,

Ti〇2: 0~1%, Zr〇2: 0~1%, and p2〇5: 〇~ι%, and the coloring oxide total 17 200904769 The amount of glass is 0~10%. The glass material formed of the present glass composition can be precipitated as a main crystal by -3 ash and/or diopside by heat treatment at a temperature higher than the softening point. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, however, the present invention is not limited to the following examples. (Example 1) First, the mass percentage is Si〇2: 65. 1%, Α1203: 6.6%, CaO: 12.0%, ΙΟ: 3.3%, Μ: 2·3%, BaO: 4.1% And ZnO: 6.6% glass raw material is subjected to 150 (TC X 16 hours of melting treatment, the molten glass is cooled in water, cooled into glass, and the glass is crushed, dried, and classified, and then we can obtain the particle size. 1~3mm crystallized glass bodies. These crystallized glass bodies can be made into Lu-Yttrium as the main crystal after heat treatment, and have a thermal expansion coefficient of 65 X 10 in the temperature range of 3〇~38〇〇c. Next, the mass percentage of Si〇2: 65.1%, Al2〇3: 6.6%, CaO: 12. 0%,

Naf: 3.3%, L0: 2·3%, BaO: 4.1%, and ZnO: 6.6% of the glass frit material is 150 (TC X 16 hours of melting treatment, formed by roll pressing to ^ Then, we can get a crystal glass plate with a thickness of 5mm. This crystallized glass can be made into a crystallization of 10,000-millimeter, and the coefficient of thermal expansion is 温度 in the temperature range of 3〇~38〇C. Next, the white crystallized glass of X. Next, the prepared crystalline glass body is layered in a mold which is coated with the refractory material. The thickness of the crystallized glass body which is accumulated is about the accumulation element. The surface of the crystalline glass body layer is flattened, and at the same time, the crystallized glass plate is placed on the surface of the crystalline glass body layer in a manner of completely disc-crystalline glass body layer. After that, it is 240 per hour (: The temperature is raised, and after 1 hour of holding at 1100X, it is cooled to room temperature for about 5 hours. Through this heat treatment, a plurality of crystallized glass 18 200904769 bodies are mutually fused and simultaneously crystallized to form a crystallized glass layer A, Crystallinity above the crystallized glass layer A The glass plate b can be softened while precipitating crystals to form the crystallized glass layer B and simultaneously fused with the crystallized glass body. Therefore, the crystallization of the crystallized glass layer A and the crystallized glass layer b can be obtained. The thickness of the crystallized glass article obtained by the glass material is about 16 circles. Secondly, after the surface of the crystallized glass article is polished, the crystallized glass article is viewed from the side on which the crystallized glass layer B is laid. The crystallized glass layer b can form a translucent pattern, and at the same time, through the crystallized glass layer B which exhibits a translucent and slightly blurred state, we can see the natural marble pattern on the surface of the crystallized glass layer A. By observing the semi-transparent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer, a natural marble pattern exhibiting a subtle stereoscopic effect can be observed. Almost the same natural marble pattern. X-ray diffraction of the crystallized glass layer (XRD 5 X- 士, again, the crystallized ruthenium layer 8 presents a translucent pattern, Since the heat-treated dry crystals grow from the surface of the crystallized glass sheet B to the inside, in addition, the natural marble of the glass article is obtained by the same reduction conditions as the crystallized surface body. The crystallized glass layer has a measurement of the crystallized glass layer A x_ray diffraction, and the 1 ί glass layer A and the crystallized glass layer β are mainly composed of a point-stone ash stone, although When the cross section of the crystallized glass layer β is observed with the naked eye, the turtle will not be found.

Crystallization is now precipitated throughout the thickness direction, and the degree of crystallization reaches the center of the section. (Example 2) 丨 3: 6.6%, CaO: 12.0 〇 / 〇,

First, the mass percentage is Si〇2: 65.1%, A12Q 19 200904769 (four) quasi-two = 20 · 2.3%, Ba0: 4.1%, and Zn0: 6.6% composition of glass two 1 + 500 CX 16 hours of melting After the treatment, the molten glass is crushed in water and the glass is dried, classified, and then we can use ~3 mm of crystalline glass bodies. These crystallized glass bodies can be white crystallized glass having a thermal expansion number of ^1GVC in a temperature range of 30 to 3,801 after passing through the second. w η ., 〇t Negative 1% Si〇2: 65.1%, Al2〇3: 6.(10), Ca0:12. 〇%, 2, 2: 2.3%, Ba0: 4.1%, and Zn〇: 6 After 6% of the composition of the glass crucible c X for 16 hours, a crystallized glass plate having a thickness of 5 legs was obtained by a roll forming method according to #二二二ft. This crystallized glass can be used as a white crystallized glass having a rule of stone as a main crystal and having a heat-wearing coefficient of 65 X l〇-V °C in a range of 30, C/m^; (4): ίί 'Place the prepared crystalline _ plate on the crystal-resistant glass body coated with the release agent, which is layered on the surface of the surface of the crystalline glass plate, completely covered, and the crystallized glass The surface layer of the small body layer has a thickness of about 12 awake. The eclipse f ί is warmed up at a rate of 24 〇 t: per hour, held at 110 liters, and after 1 hour of temperature, 丨 room temperature. By such a reduction, the crystallized glass plate can be formed into a crystallized glass layer and simultaneously formed with the crystallized glass to form a crystallized glass layer A. Therefore, the glass can be obtained by the glass 3 A crystallized glass article formed by layer A and crystallized glass layer B.

The thickness of the crystallized glass article obtained at 曰' is about 16%. Secondly, after grinding both sides of the glass article, from the paved crystallized glass layer B:=5 to observe the glass, the 5 brain thick crystallized glass layer B can form the second glass. A crystallized cord that is translucent and has a slightly blurred state is presented. Two-two to see the surface of the crystallized glass layer A, the natural marbled glass, the translucent pattern of the crystallized glass layer β and the natural marble pattern of the crystallized glass layer, so that we can see The natural marble pattern that shows the micro 20 200904769. Further, the reason why the crystallized glass layer B exhibits a translucent pattern is because the crystal grows from the surface φ of the crystallized glass sheet B to the surface during the heat treatment. Further, the crystallized glass layer A is almost the same natural Dali as the above-mentioned crystallized glass article produced by using the crystallized glass body by the accumulation method under almost the same heat treatment conditions; 5® case. In addition, the day-to-day solarized glass layer A and the crystallized glass layer B were subjected to X-ray side determination, and it was found that the crystallized glass layer A and the crystallized glass layer B were mainly composed of /3 test limestone. Precipitate.

In addition, the broken crack of the crystallized glass layer B was observed. When the crystallization of the crystallized glass layer B reaches the smashing of the smear, the crystallization degree of the crystallization glass layer B is reached (Example 3). First, the mass percentage is Si〇2: 62 2%, A1.

Na20 : 4· 5%, K2〇: 2.1%, (4): 1 shoulder, Μ): 6 ()% n〇aH and NiO: 〇. 1% of the glass raw material is 145〇' Ζη0. 5. %, later The quenched glass is quenched in water to become the classification of the broken glass, and then we can obtain _ 3~7mm of the dried line, and the crystallized glass body is broken after the heat treatment. These junctions 30 to 38 (the coefficient of thermal expansion in the temperature range of TC is biting. The main crystal of limestone is in the glass. / beige crystallization of bismuth. Next, the mass percentage is Si〇2: 6p 9<) / A1

Na2〇: 4. 5%, K2〇: 2.1%, Li2〇: i 〇%, β°, :3: and 1% of glass raw materials are carried out · 6.Q%, ZnQ: 5.2%, later, via roller The press method was formed into a plate shape, and after the autumn, five people X j 6 hours of molten glass plate. _, crystallized glass plate in "3 coffee thick crystallinity as the main crystal, in the temperature range of 30~38Gt 敎 becomes % ash stone beige crystallized glass. 'The expansion coefficient is 卯X 1 (rVt: ^ 21 200904769 (4) The crystallized glass bodies prepared by the method are layered and accumulated in the coated ί fire material mold. The surface of the crystalline glass body layer completed by the integrated crystalline glass body is leveled, and at the same time Plated glass, j, body layer, on the surface of the crystallized glass plate glass body layer. 罝在,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, 'In 1G5 (after rc is held for 2 hours, crystallization occurs during 以 to form crystallized glass layer A'. The crystallized glass plate B can be softened while crystallizing to form crystallized J layer B and simultaneously with crystallinity. The glass bodies are fused to each other. Therefore, we can obtain the glass material rtrf ° formed by the crystallized glass layer A and the crystallized glass _ β, and the obtained crystallized glass article has a thickness of about 16 ug. After grinding the surface of the Ϊ 化 Ϊ Ϊ Ϊ Ϊ , The crystallized glass article is observed on the side of the crystallization glass layer, and the crystallized glass layer β of 3 mm thick can form a semi-transparent crystallization which is translucent and slightly ambiguous, and the glass can be viewed by us. The natural marble pattern on the surface of the crystallized glass layer. Because of the half-gamma pattern and the crystallized marble pattern of the crystallized glass _ 可 can be viewed, we can see the natural marble pattern that exhibits a subtle three-dimensional effect. The reason why the crystallized glass layer B is rendered translucent is due to the heat treatment, and the σ crystal grows from the surface of the crystalline glass sheet B to the inside. Further, compared with the above, only the crystalline glass body is used. The natural cassava of the crystallized glass article produced by the accumulation method under almost the same heat treatment conditions, the crystallized glass layer has almost the same natural marble pattern as above, and the crystallized glass layer a and the crystallization are respectively When the B-line was set on the side of the X-ray, it was found that the crystallized glass layer A and the crystallized glass layer B were precipitated by the main crystal of /3 - ash stone. In addition, when the cross section of the crystallized glass layer β was observed by the naked eye, no crack was found. When the cross section of the crystallized glass layer was observed by the scanning electron microscope along the thickness side 22 200904769, it was found throughout the thickness. Crystallization is precipitated in the direction, and the degree of crystallization of the crystallized glass layer B reaches the center of the cross section. ^ (Example 4) First, the mass percentage is Si〇2: 62·〇%, Al2〇3: 9• (10)

MgO : 4. 5% ^ BaO : 4. 6% ^ Na2〇: 5. 0%. K2〇: 3. 〇% . β2〇3: 〇5, Ρ 〇' 2. 〇%, regret: G. 4 %, and (10) G Hui composition of the glass (four) ^ 15 = X After 16 hours of melting treatment, the glass will be melted in the water" and the glass will be mixed and classified, and then I can be a crystalline glass body. These crystallized glass bodies have a thermal expansion coefficient in the temperature range of heat treatment = second, and the mass percentages are Si〇2: 62. 0%, Α12〇3 · 9. 〇%, Ca0: q(10),

2^: 4δΓ〇'B 0〇4〇/* 6% 'NaZ〇: 5' 〇% ' Κ2° : 3* 〇% ' β2°3 : °· 5% ' ?2〇5°: ί ίΐ and (10): The glass raw material of the G· _ composition was subjected to 1501 TC X 16-hour melting treatment, and then formed into a plate shape by a press method, and then a five-person thick f-crystalline glass plate. This crystallized glass plate is thermally condensed on the surface of the crystallized glass plate in the temperature range of the processor. After the accumulation is completed: the upper body layer f degree is about 丨2_. Crystallization of the silk, the surface of the body layer = at the same time, to completely cover the 35-small body layer

The raft is placed on the surface of the crystalline glass body layer. Such a U, f raw glass body layer can be used as a sandwich in the use of 2 (four) crystalline glass plate to increase the temperature of the day, at 11GGX: after holding the temperature for 2 hours, 7 々 part to the temperature. Through such heat treatment, the crystalline glass plate can be softened by 23 200904769 to precipitate crystals to form the first crystallized glass layer B while being fused with the crystallized glass bodies, and a plurality of layers on the first crystallized glass layer B. The crystalline glass body can be fused while precipitating the crystal to form the crystallized glass layer A, and the crystalline glass plate can be softened while the crystallized glass plate A is precipitated to form a second crystallized glass. Layer B is simultaneously fused with the crystalline glass bodies. Therefore, a crystallized glass article formed of the first crystallized glass layer B, the crystallized glass layer A, and the second crystallized glass layer B can be obtained. The crystallized glass article obtained in this manner has a thickness of about i7 mm. Next, after the crystallized glass article is polished on both sides, the crystallized glass article is observed from the surface on which the crystallized glass layer B is laid, and the crystallized glass layer β having a thickness of three faces can form a translucent pattern, and at the same time, The crystallized glass layer β which is transparent and has a slightly blurred state, we can see the natural marble pattern on the surface of the crystallized glass layer. Since the translucent _ of the crystallized glass layer B and the crystallized glass layer A can be seen, in the second case, we can see the pattern which exhibits a subtle stereoscopic effect, and the surface from the side of the other crystallized glass layer B. Observing the gentleman's deuterated glass items, the results are the same. The reason why the gas, σ曰曰, and the 曰 呈现 呈现 呈现 呈现 呈现 呈现 呈现 呈现 呈现 呈现 呈现 呈现 之 之 之 之 之 之 之 之 之In addition, compared to

The natural marble day-to-day glass layer a of the produced crystallized glass article has almost the same color as the crystallized glass layer B, and the crystallized glass layer A is crystallized. The cross-section of the glass layer B. When the results of the peak-晦 electron microscope were observed in the thickness direction of the whole thickness of the crystallized glass _β, the crystals of the crystallization of the crystallization layer were precipitated, so that 'we can determine the degree of daily sputum Both reach the center of the section. 24 200904769 (Example 5) First, the mass percentage is Si〇2: 60. 〇%, Αΐ2α

MgO: 3.8%, BaO: 3. 5%, Zn〇: 6. 5%, Na2〇: 3. 8%, Μ, t/ ·, τ. 6%, I :, =: 〇.3% ,as well as_:. · 2°·成的璃璃二斗, after smashing and grading, then we can turn it into 曰^, ΪίΪ: This crystal is second, the percentage of mass is Si〇2: 6〇. 〇%, Ah〇3: 6. 〇%, (10)

MgO: 3.8%, BaO: 3·5%, ZnO: 6.5%, %2〇: 3·8%, M: 2·5%, ϊ.: Xt Ιδιο x 4lVjASf : 〇· 3〇/ 〇' Ni〇: °* Then I can w, umm linger. The plate = _ can be made into a diopside-based crystal after heat treatment, and (4) = the prepared crystalline glass body is layered in the coating layer. The crystallized glass cut completed by the product is about the thickness of the body, and the surface of the crystallized glass body layer which is finished after the completion of the film is flattened, and at the same time, the crystal layer of the glass layer is crystallized. The glass plate was placed on the surface of the crystalline glass body layer. Then, the temperature was raised at a rate of Got per hour, and after cooling for 2 hours, „5 small 5 was cooled to room temperature. Through such heat treatment, a plurality of crystalline glass domains and ruthenium are mutually fused and simultaneously precipitate crystals to form a crystallized glass layer A, and the crystallized glass sheet B can be softened while crystallizing glass = A while crystallizing to form crystals. The glass layer B j_ is simultaneously fused with the crystallized glass body, and therefore, the crystallized glass article formed by the crystallized glass layer A and the crystallized glass layer b can be used. The thickness of the crystallized glass article thus obtained was about 16%. Next, after crystallizing 25 200904769 = surface of the glass article, the glassy article B of the thickness of the l-thickened glass article B can be formed from the surface on which the crystallized glass layer B is laid, and a semi-transparent pattern can be formed. Through the crystallized glass layer B which exhibits a translucent and slightly blurred state, we can sharply see the natural marble pattern on the surface of the crystallized glass layer A. Since the translucent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer A can be simultaneously viewed, a natural marble pattern exhibiting a subtle three-dimensional feeling can be seen. Further, the reason why the crystallized glass layer β exhibits a translucent pattern is that the crystal grows from the surface of the crystallized glass plate to the inside due to heat treatment. Further, the crystallized glass layer has almost the same natural marble pattern as the natural marble pattern of the crystallized glass article produced by the accumulation method using almost the same heat treatment conditions as the above-mentioned crystallized glass body. In addition, the crystallized glass layer A and the crystallized glass layer B were each subjected to X-ray diffraction measurement, and it was found that the crystallized glass layer A and the crystallized glass layer B were precipitated by diopside as the main crystal. Further, when the cross section of the crystallized glass layer B was observed with the naked eye, it was found that cracking did not occur. When the cross section of the crystallized glass layer B was observed along the thickness direction of the crystallized glass layer B by a scanning electron microscope, it was found that crystals were precipitated in the entire thickness direction, so that 'the crystallized glass layer B can be determined. The degree of crystallization reaches the center of the section. (Example 6) First, the mass percentages are Si〇2: 62.0%, A12〇3: 9. 0%, CaO: 1%, %〇: 4.5%, BaO: 4.6%, Na2〇: 5·0%, Μ: 3. 0%, B2〇3: 〇· 5%, p2〇^ 2· 0%, Sb2〇3: 0. 4%, and C〇0: 0. 05% The glass raw materials were composed of 15 〇〇.匚 X After 16 hours of glutinous treatment, the glutinous rice glass is quenched in water to become a glass cullet, and the glass is pulverized, dried, and classified, and then a crystalline glass body having a particle diameter of 1 to 3 mm can be obtained. These crystallized glass bodies may be subjected to a diopside-based crystal after heat treatment, and a gray crystallized glass having a thermal expansion coefficient of 1 l〇' ° C in a temperature range of 30 to 380 C. x 26 200904769 _ ΐΐ =: 2.2%, ship: 5, maid (four), composed of glass materials ' · χ =, 6.f, and Zn〇: 5. 2% pressure forming into a plate shape, narrow five people can After n?, after the smashing of the 丨 曼 曼 了 侍 侍 侍 侍 侍 侍 侍 侍 侍 侍 侍 侍 侍 侍 侍 侍 侍This crystal ^ 0 can be a crystallized glass mainly composed of 10,000-stone. The crystallized glass plate obtained by the white chelate glass method with a coefficient of thermal expansion of 69 X 10 々 °c is used for the formation of crystallized glass layer C. Therefore, It can be combined with f 曰 Gan ^ to shape its domain without _ two kinds of crystalline glass plates. The product of the type of agent is coated with a cover, _, a body layer, and the crystallized glass is placed; The size of such a crystalline glass plate is fine: the four sides of the crystallized glass plate are spaced apart from the side walls of the refractory mold and placed on the upper surface of the crystalline glass body layer. The __ surface m formed by the accumulation of the crystallized glass body layer and the crystalline glassy layer is inserted in a 3 mm thick crystalline glass plate in the direction of the plate thickness direction parallel to the refractory mold, as shown in Fig. 2, crystallizing In addition, it will be between the end face of the laminate and the side wall surface of the refractory mold. This sand% and glass sheets are placed around the end faces of the laminates in a tightly bonded manner.蚀 ί , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , «layer A, in the crystallized glass ^ = ΐ glass plate β can be softened while precipitating crystals to form crystals ϊϊ ϊϊ f f simultaneously with the crystalline glass bodies, while crystallized glass layer B by crystal A Around the end face of the formed laminate, the crystal 1 plate c can be softened while precipitating crystals to form the crystallized glass layer C and at the same time 27 200904769 and the laminate are mutually fused. Therefore, it is possible to obtain a crystallized glass layer A and crystallize. The crystallized glass article formed by the glass layer B and the crystallized glass layer C. The thickness of the obtained crystallized glass article is about 16%. Secondly, the surface and the end surface of the crystallized glass article are polished. The surface of the crystallized glass layer B side is observed as a crystallized glass article, and the 3 mm thick crystallized glass layer β can form a translucent pattern while passing through a knot which exhibits a translucent and slightly blurred state. Glass layer Β 'We can see the natural marble pattern on the surface of the crystallized glass layer a. Since we can see the translucent pattern of the crystallized glass layer β and the natural marble pattern of the crystallized glass layer at the same time, we can watch Natural marble pattern to subtle three-dimensionality.

Further, the crystallized glass article was observed from the surface on which the thickened crystallized glass layer c was laid, and the result of crystallization was observed from the surface on which the crystallized glass layer B was laid. Further, the reason why the crystallized glass layer B and the crystallized glass layer c are present is because the crystal is long from the surface of the crystallized glass layer B and the crystallized glass layer c: f. In addition, the crystallized glass layer A has almost the same natural stone pattern as the natural crystal case of the crystallized glass article produced by the same heat treatment conditions. · Minutes, crystallized glass layer A, crystallized glass layer B, and crystallized broken glass 隹 线 线 线 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' The glass layer c is mainly composed of stone test stone. ^^ Columns | 'When the cross section of the crystallized glass layer β is observed with the naked eye, there is no trace of the cross section of the crystallized glass layer by the electron microscope. Turtle II's result _ whole thickness direction knot;::: The crystallization degree of δ crystallized glass layer δ reaches the center glass layer C of the cross section also has the same result. P , , , u a 曰 (Example 7) 28 200904769 First, the mass percentage is Si〇2: 62. 2%, Al2〇3: 5.9%, CaO: 13. 〇%,

Na2〇. 4. 5%, K2〇: 2.1%, Li2〇: 1. 〇%, Ba0: 6. 〇%, Zn〇: 5. 2%, and NiO.'OJ% of the glass raw material is 145〇 t: χ 16 hours of melt treatment, the molten glass is quenched in water to a glass cullet, and the glass is pulverized and dried, and the granules are granulated to form a crystalline lysate having a particle diameter of 3 to 7 mm. After the heat treatment, these knots can be made into a quartz crystal with a 0-downstone as the main crystal. The coefficient of thermal expansion is 69 χ忉'^, and the mass percentage is 62. 2%, Αΐ2〇3: 5 · 9%, Ca〇: 13.(10), ^2『n /%, K2〇: 2.1%, Uz〇: L 〇%, Ba0: 6. 0%, Zn0: 5. 2%, to connect, and into The glass material is melted at 145 ° C for 16 hours, and the glass shape is plate-shaped. Then we can obtain 2 thick crystallized A main sputum species, and the '3 crystal glass plate can be An untwisted crystallized glass having a thermal expansion coefficient of 69 X 10 VC in a temperature range of 3Q to 38Q °C without "矽灰石^二". The crystallized glass plate obtained by the method of the method is used to form the crystallized glass layer C. Therefore, we can cut it with the K inch. Two kinds of crystalline glass plates of different shapes. Fire; M · grip, 糸, the crystallized glass plate is placed on the surface coated with a release agent, ίίίΐΙ' Ξ 全 全 full coverage of the surface of the crystalline panel, crystallized glass small body crystallinity Glass plate surface. The crystallization of the accumulation is completed, and the degree is about 14 ugly. The crystallized glass body layer surface glass cup which has been accumulated is placed on the surface of the crystallized glass body layer so as to completely cover the surface of the crystallized glass body layer. After this configuration, the formed facet layer can be clamped on the ruler of two crystalline glass plates as in the case of three days. J4 The size of the crystalline glass plate is slightly smaller than that of the refractory mold placed on the glass plate of the surname. Each of the four 4th and the side wall of the fossil material mold has a distance of two sides, and the upper and lower sides of the small body layer of the day-breaking glass. 29 200904769 Integral crystallinity _ plate _ layer made of 结晶 之间 之间 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶As shown in Fig. 2, outside, the laminate_ is between the side wall surface of the refractory mold. This fried S and the glass plate are placed in close contact with each other around the end face of the laminated body. #用'Λ母人 tempering at 180°c, at 1〇5 (after rc holding for 2 hours, softening and B* folding, to temperature. Through this heat treatment, the crystalline glass plate can be twisted – The crystal is thoroughly smeared and _ and the crystallized glass λ! 'a plurality of crystallized glass on the first crystallization glass layer β simultaneously precipitates crystals to form crystallized glass w, and in the crucible-ΐ曰ΐ ί 结晶 crystallinity The glass plate can be softened while precipitating crystals to form f, , σ 曰曰 glass layer Β and simultaneously fused with the crystalline glass body. Meanwhile, the glass layer, and the first and second surfaces disposed on both sides thereof The crystallized glass layer is in the shape of a crucible, and the body is formed, and the crystalline glass plate c can be softened and simultaneously formed at the end face of the laminated body to form a crystallized glass layer c and simultaneously merge with the laminated body. The crystallized glass article formed by the second crystallized glass layer A, the crystallized glass layer β, and the crystallized glass layer c. Thus, the obtained crystallized glass article has a thickness of about 17 faces. Secondly, the crucible is formed. After the two surfaces and the end faces of the glass article are ground, the knot is laid from the paving Crystallization ^ Β 的 的 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察 观察Layers, we can see the natural marble pattern on the eight surfaces of the crystallized glass layer. Since we can see the translucent pattern of the crystallized glass layer and the natural marble of the crystallized glass layer, we can see A natural marble pattern that exhibits a subtle three-dimensional appearance. Further, 'the result of observing the crystallized glass article from the surface on the side of the crystallized glass layer c having a thickness of 2 mm and the surface of the crystallized glass from the side on which the crystallized glass layer B is laid is obtained. In the same way, along the interface between the crystallized glass _B and the crystallized glass layer c, the direction of the interface is observed, and we can see the line pattern of 30200904769 after the rib stretching. Layer B and the crystallized glass layer (the reason why the semi-transparent system is formed because the crystal is from the surface of the crystallized glass layer B and the crystallized glass layer c to the inside. The crystallized glass layer A has almost the same natural marble pattern as the natural marble pattern of the crystallized glass article produced by the accumulation method only by the heat treatment conditions of the crystallized glass body. The X-ray diffraction of the crystallized glass layer A, the crystallized Laminated layer B, and the crystallization layer c-ray was respectively measured, and as a result, the crystallized glass layer A, the crystallized glass layer B, and the B-deuterated glass layer were found, and the C system was The Wan-Shishi limestone is mainly composed of crystals.

Further, when the cross section of the crystallized glass layer β was observed with the naked eye, no turtle 4 was found: when viewed in the thickness direction by the surface of the glass layer B of the scanning electron microscope, the result was found in the entire thickness direction. Since crystals are precipitated, it is possible to confirm that the degree of crystallization of the crystallized glass layer B reaches the center and the portion of the cross section. The crystallized glass layer C also has the same result. (Example 8) First, the mass percentages were Si〇2: 65.1%, Al2〇3: 6.6%, Ca〇: 12. 〇%, ^3. Guan, Μ: 2·3%, Ba〇: 4.1%, and ZnO: 6.6% of the glass j is 15 〇 (TC X 16 hours of smelting treatment, the glazed glass is cooled in water, broken glass, and the glass is dried and graded. Then we can get crystallized glass bodies with a particle size of 1~3mm. These crystallized glass bodies can become the main crystal of asbestos after heat and treatment, and heat in the temperature range of 3〇~38 (rc temperature The number is 65 X HTVt: white crystallized glass. Secondly, the mass percentage is Si〇2: 65,1%, M2〇3: 6.6%, Ca〇: j2. 〇%, 3·3%, MH BaO: 4.1%, and ZnO: 6.6% of the glass 4 is subjected to 15G0 °C: X 16 hours of recording, and then formed into a large furnace by a furnace method, and then we can obtain a 2_thick crystalline glass plate. The crystallized glass can be a white crystallized glass with a thermal expansion coefficient of X 1〇-7/.匸 in the range of 30 to 380 gamma after the heat treatment, and the crystallized glass is mainly composed of 10,000-yttrium ash. Further, 31 20090476 9 This crystallized glass plate is cut and processed into a rod shape of 10 mm in width. Next, the prepared crystalline glass body is made into a refractory material mold of a layering agent. The crystallized glass is assembled. 15π^ι. However ^ 'The surface of the crystallized glass body layer which has been accumulated is finished +, and at the same time, the crystallized glass plate is placed on the surface of the crucible solar glass body layer.

C Then, the temperature was raised at a rate of 24 passages per hour, and after 1 hour of holding at 1 HKTC, it was cooled to room temperature for about 5 hours. Through the heat treatment, a plurality of crystalline glass bodies are mutually fused to each other to precipitate crystals to form a crystallized glass layer A, and a plurality of rod-like crystalline glass sheets β are fused to each other and precipitated simultaneously on the crystallized glass layer A. Crystallization is carried out to form a crystallized glass layer, and at the same time, it is fused with the crystallized glass body. Thus, it is possible to obtain a crystallized glass article from the crystallized glass layer A and the crystallized glass layer β. &~ Thus, the obtained crystallized glass article has a thickness of about 16%. Next, after crystallizing the surface of the glass article, the crystallized glass article is observed from the side where the crystallized glass layer B is laid, and the 2 mm thick crystallized glass layer β is lined up to form a translucent pattern. A crystallized glass layer having a slightly blurred state and exhibiting a slightly blurred state can be seen by a person who can see the natural Dali pattern on the surface of the crystallized glass layer a. Since the ruthenium line translucent pattern of the crystallized glass layer B and the natural marble pattern of the crystallized glass layer A can be simultaneously observed, we can see a natural marble pattern exhibiting a subtle three-dimensional feeling. Further, the reason why the crystallized glass layer B exhibits a translucent pattern is that the crystal grows from the surface of the rod-like crystalline glass sheet B to the inside due to heat treatment. Further, the crystallized glass layer A has almost the same natural marble pattern as the natural marble pattern of the crystallized glass article produced by the accumulation method using almost the same heat treatment conditions only by the crystallized glass body. Further, X-ray diffraction measurement of the crystallized glass layer A and the crystallized glass layer β was carried out, and as a result, it was found that the crystallized glass layer A and the crystallized glass layer β were precipitated by using a limestone as a main crystal. Further, when the cross section of the crystallized glass layer B was observed with the naked eye, no turtle 32 was found. 200904769 ^ The cross section of the crystallized glass layer B was observed by a scanning electron microscope, and it was found that crystals were precipitated throughout the thickness direction. , ^ to determine the degree of crystallization of the crystallized glass layer B to reach the center of the section. σ σ (Example 9) First, the mass percentages are Si〇2: 65.1%, Ah〇3: 6 =:3·3%, M: 2.3%, Ba〇: 4.1%, and Zn〇: 6 ^^成^^ Χ After 16 hours of county treatment, _ melted glass in water = become _ broken 'and the glass is broken, dried, graded, then d = ^ knot / f glass body. These crystallized glass bodies are subjected to , after, and after treatment, into a white crystallized crystal having a thermal expansion coefficient of 65 x 1 GVc. 38QC-degree-inside ^ times, the mass percentage is Si〇2:651% ' Κ1〇: 2· 3% ' Ba〇: 4·1% ' ^ c coefficient is 65 χ 1〇-rc white crystallization glass. The material of the type agent = the inner white glass body is layered and accumulated in the coating with the completion of the separation for the use of ^ 5 small days ^, 24Gc speed, after ll 〇 "C holding temperature for 1 hour, the small body Through such reduction, the crystals of the plurality of crystal-clear glass crucibles A are precipitated at the upper surface of the crystal layer A to form a crystallized glass layer A, and the crystallized glass is crystallized. The glass plate β is mutually fused and crystallized at the same time. In the form of a person, Jiang can be έ1 and the same day π and the crystalline glass body are fused together. Therefore, I crystallize the crystallized glass layer and the crystallized glass layer. The surface of the crystallized glass article is 16 faces. The crystallized glass layer which is semi-transparent and has a slightly blurred state is a natural marble pattern of the eight surfaces of the crystallized glass layer. Since it can be seen in the same way as the crystallized glass layer B (five) translucent ", I, layer A of natural marble, so that the two: the f-pattern and the natural marble of the glassy _ ° can be seen It shows that the semi-transparent pattern of the subtle three-dimensional series d匕B is caused by the heat treatment of the 匕曰 曰 曰 θ =1 plate β surface growth to the inside. In addition, compared to ii;, :?: Qiao, The crystallized glass layer A has a natural marble pattern by an accumulation method using almost the same heat treatment conditions. In addition, 'x-ray diffraction is performed on the crystallized glass layer a ΐ 层 layer β, respectively. As a result, it was found that the crystallized glass layer a, the aa-aluminized glass (five) layer B-series (9)-apatite was mainly crystallized and precipitated. When the cross section of the crystallized glass layer β was observed with the naked eye, no Cracking: When the section of the solar cell layer β is observed along the thickness direction by a scanning electron microscope, it is found that crystals are precipitated in the entire thickness direction, so that we can determine the crystallized glass layer. Crystallization process The center portion of the section was reached. (Comparative Example 1) First, the mass percentages were Si〇2: 65.1%, Α12〇3: 6.6%, Ca0: 12.0%, 0: 3·3%, Μ: 2. 3%, BaO: 4·1%, and ZnO: 6.6% glass raw material After 1500 CX 16 hours of melting treatment, the molten glass is quenched in water to become glass cullet, and the glass is crushed and dried. Grading, then we can obtain crystalline glass bodies with a particle size of 1~3mm. These crystallized glass bodies can be made into stone-stone-stone as the main crystal after heat treatment, in the temperature range of 30~380 °C White crystallized glass with a thermal expansion coefficient of 65 X 1〇7/°c. 34 200904769 Ζπο :ΐΐ; Sl〇2:51·〇%'Αΐ2〇3: 19· W--4 7%

At the same time as Ca 〇 : 2. 2% of the glass raw material is _: C χ 16 °; i after treatment 'by subtraction into a plate shape, then I J crystal glass plate. This kind of crystalline glass plate ^ J^^(forsterite, 2Mg0. shirt car = white crystallized glass with internal thermal expansion coefficient of 67 χ 1GVc._c

With the = input, the surname will be the surface of the crystallized glass body layer that has been accumulated, and the surface of the crystalline glass is cut, and the crystal layer is cut and the body layer is silk. The enemy is immersed in the knot _ 'heats up at 12G ° C per hour, at 11GGt: after holding for 2 hours, it is cooled to room temperature. Through this heat treatment, a plurality of crystalline glass fatigues are melted and the crystals are crystallized, and the crystallized glass plate can be softened while crystallizing to form crystals. The glass layer β and the crystallized glass body are mutually fused at the same time. Therefore, the crystallized glass material obtained by the crystallized glass layer and the crystallized glass can be obtained by ππ ° 曰, and the obtained crystal is obtained. The glass article has a thickness of about 16 mm. Next, after crystallizing the surface of the glass article, the crystallized glass article is observed from the surface on which the crystallized glass layer β is laid, and the crystallized glass layer of 3 mm thick is white, which is not transparent. The crystallized glass layer B cannot see the presence of the crystallized glass layer I. Further, the reason why the crystallized glass layer β exhibits a non-transparent white color is: "When the heat treatment is performed, the crystal does not grow from the surface of the crystallized glass sheet to the inside, and at the same time, from any of the crystallized glass sheets. The position grows. Also, when observing. When the crystallized glass article produced by the above-described crystallized glass body by the accumulation method under almost the same heat treatment conditions exhibits a natural marble pattern. According to the kind of 35 200904769, the crystallized glass layer β is transparent or translucent, so that it can be viewed. (4) = Do not align the crystallized glass layer and the crystallized glass layer β with X green = 疋 crystallized glass layer The stone is mainly set out.纟 "Crystalization_Layer B is analyzed by using magnesium bismuth as the main crystal. Going out of the sun (Comparative Example 2) w n First ^. Mouth mass percentage Wi〇2: 65.1%, A1 crystal: 6.6%, Ca〇: 12 〇. /,

: 2· 3%, _ : 4.1%, and Zn〇: 6. After breaking into 16 hours of smelting treatment from US 2 Jx, crush the broken glass in water, and let the glass be dried, graded, and then I can have a 3 glass body. These crystallized glass bodies are mainly crystals of Si «Li, and Shishi limestone, in the range of 30 to 38 (the temperature in the rc temperature range is 65 X urv. (10) White crystallized glass.

ZnO . 量 The percentage of the rate is 2: 51. (10), (4) 3:19 Summer Mg (): 4. 7%, 〇9 I '1〇2 : 2* 2% ' Zr〇2 : L 5% ' Β 2°3 : 6· 0〇/« ^ Na.0 : 8. 5% . °, and Ca0 : 0. 2% of the glass raw material is processed at 1500 ° C X 16 + inch ^ after forming into a plate by roll pressing Shape, then we can mm, 吉, crystal glass plate. This crystallized glass plate is subjected to heat treatment to be the main crystal of sapphire at 3Q~·. a white crystallized glass having a thermal expansion coefficient of g X /C in the temperature range. After that, the crystalline glass plate obtained by the rolling method is used to form the crystallized glass layer C in addition to the formation of the crucible=glass (five) layer B. Therefore, the size of the layer can be It is cut into two kinds of crystalline glass sheets having different shapes. In the secondary system, the prepared crystalline glass plate is placed in a mold of a refractory material coated with a release agent, and then the crucible glass body (10) is shaped into a crystal by completely covering the surface of the crystallized glass plate. The surface of the board. The accumulation is 曰曰, and the thickness of the glass body layer is about Umm. At the same time, the G surface of the accumulated glass layer is flattened. At the same time, the surface of the crystallized glass body layer is completely covered by the surface of the crystalline glass body layer. In this way, the crystallized glass body layer can be sandwiched between two sheets placed on the upper and lower sides of the crystalline glass body layer.柯^, _ soil surface distance 2 is deleted, and then, in the side wall surface of the crystallized glass body layer and the 砝曰 砝曰 ( ( ( ( ( ( 的 的 的 的 插 插 插 插 插 插 插 插 插 插 插 插 插 插 插 插 2 2 2 2 2 2 2 2 ^火巧^玻璃=located on the end face of the laminate and the side of the refractory mold; =The crystalline glass plate is placed in close contact with the end face of the laminate, and is heated at a speed of about m:, i2q c. (: After holding the temperature for 2 hours, L, p to room temperature. Through this heat treatment, the crystalline glass plate can be crystallized by the first crystallized glass layer β and simultaneously crystallized with the crystallized r Β The number of crystalline PMA bodies in the wall merges with each other and precipitates crystals at the same time to form crystallized glass, and in the case of ΤΤΛ n ώ, a brother-crystallized glass layer β and simultaneously melts with the crystalline glass body. In the past, the first and second crystallized glass layers were placed on both sides of the crystallized glass layer a to form a layered body, and the crystallized glass sheet G was softened and precipitated crystals to form a crystallized glass sheet G around the end surface of the layered body. The crystallized glass layer G and the laminated body are fused with each other, so that we can obtain the knot The crystallized glass article A, the crystallized glass layer β, and the crystallized glass layer C are formed of a crystallized glass article. Thus, the obtained crystallized glass article has a thickness of about 17. Further, on both sides of the crystallized glass article and After the end surface is polished, the crystallized glass article is observed from the surface on which the crystallized glass layer β or the crystallized glass layer (10) is laid, and the 2 swollen crystallized glass layer B and the crystallized glass layer C exhibit a non-transparent white color. The presence of the crystallized glass layer 无法 cannot be observed through the crystallized glass layer Β and the crystallized glass layer c. 200904769 The second glass layer β and the crystallized glass layer c are not treated: At the same time, the crystal does not grow from the surface of the crystalline glass to the inside, but at the same time, from the crystallized product, it will present a natural marble pattern. From this, it can be bright or translucent, and it can be seen as a stone. In order to pass through the glass crystal layer a, the crystallized glass layer b, and the crystallized gray stone as the main crucible, 3==glass, layer a is the peak stone (Comparative Example 3) Crystalline glass body layer The shape of the crystallized glass body layer is about 0, and the thickness of the crystalline glass body layer is about m. The surface of the crystallized glass body layer is flattened. ^11〇〇〇〇#^ 2 ^ The bodies are fused together; the complex f-solid, crystalline glass crystallization of the glass 2:::= The thickness of the bismuth glass is about 16 legs. Secondly, after the surface 5 of the knot is mirrored, 'observing the crystallized glass However, when the surface of the article can exhibit a surface with a ruthenium marble diameter of about ruthenium, we can observe that the glass material used for the production of the crystalline glass plate of Example 1 can be observed straight (Comparative Example 4). 15〇〇t 38 200904769 1=, =, then 'formed into a plate shape by roll pressing, and then we can give a crystalline glass plate. This crystallized glass plate is subjected to heat treatment, ϊΐΐ ϊΐΐ 灰 灰 为主 为主 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在The board is placed in the coating: After the temperature, the temperature is raised at the rate of bribes per hour, and it is cooled to room temperature in 1 _ for about 5 hours. Through this heat treatment, we can pay for the crystallized, plate-crystallized domain. Crystallization of the article. In this way, the obtained crystallized glass article has a thickness of about 10. Then, after grinding both sides of the glass article, observe the surface of the crystallized glass article to the sky. In addition, the crystallized glass article was subjected to ice-making and measurement, and it was found that it was made mainly of point-silver as a main crystal. ^ 'After cutting the crystallized glass article, observe the crystallized glass article. The surface of the crystallized glass article was cracked in the thickness direction. The result was that the crystallized glass material was observed in the thickness direction. Crystallization precipitates, and there is no crystal precipitation in the central portion of the thickness direction of about 4 mm in the thickness direction, so we can know that this portion is not crystallized. Although the present invention is directed to the preferred embodiment, it is understood by those skilled in the art. Various modifications, changes and variations of the present invention are possible without departing from the spirit and scope of the invention. However, such modifications, substitutions and changes are intended to come within the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1A to 1C are schematic cross-sectional views showing an example of a method for producing a crystallized glass article of the present invention; and FIG. 2 is a view showing another example of a method for producing a crystallized glass article of the present invention. Fig. 3 is a cross-sectional view showing a crystallized glass article obtained by heat treatment of the above plate glass. [Description of main components] 10 refractory mold 12 crystalline glass body layer 14 crystalline glass plate B 14A crystalline glass plate B 14B crystalline glass plate B 16 crystalline glass plate C 20 laminated body 20A laminated body 20B laminated body 20C laminated body 100 crystallization Crystallized glass article vitreous 110 120 130 No cracking crystallized glass body 40

Claims (1)

200904769 X. Patent application scope: 1. A crystallized glass article having a pattern comprising: a crystallized glass layer A formed by merging a plurality of crystalline glass bodies and simultaneously crystallizing; and a crystal When the at least one surface of the crystallized glass layer A is in a fused state, the glass layer B is disposed on the at least one surface, and the 5 Å crystalline glass plate B is placed on the surface thereof. Crystallization is performed toward the center to reach the center portion, wherein the main crystal of the crystallized glass layer A is /3 - stone ash stone (/5 lollastonite 'β-CaO. Si〇2) and diopside (CaO · At least one of MgO.2Si〇2), and the main crystal of the crystallized glass layer B is at least one of 10,000-graystone and diopside, and the crystallized glass layer B has a thickness of about 〇.1 mm to about 6 mm. . 2. A crystallized glass article having a pattern as claimed in claim 1, wherein the crystallized glass layer A has a thickness of from about 0.1 mm to about 3 mils. 3. The crystallized glass article of claim 1, wherein the crystallized glass article has a thickness of from about 8 mm to about 3 Å. A crystallized glass article having a pattern according to the first aspect of the invention, wherein the crystallized glass layer B is disposed on the upper and lower surfaces when the upper and lower surfaces of the δ crystallized glass layer A are in a molten state. The crystallized glass article having the pattern of the patent scope of the invention, wherein the crystallized glass layer A and the crystallized glass layer β are in the range of 3 〇 38 38 (the absolute value of the difference in thermal expansion coefficient in the range of TC is 〇 χ χ 1 〇-7 /.匸. 6. A method for producing a crystallized glass article having a pattern, comprising a heat treatment step for heat-treating at least the laminate of the following 41 200904769: (1) from a plurality of crystallized glasses a small volume body layer and a layered body in which the crystal glass body is laminated and formed by a raw glass small B; the surface of the crystalline glass plate (2) is composed of a crystalline glass plate 3 and the number of crystals a crystalline surface body _ layered === 衩 - layered body; and sgf sloping 5 禹 small body layer composed of (3) from a first crystalline glass plate β, located on the community surface a plurality of crystalline glass bodies, a layer of B$ layer, and a layered body formed by laminating the crystal glass: a small glass plate β, θ, and a first crystallized glass The steps include: The plurality of crystalline glass bodies of the glass body layer towel are fused to each other to form the crystallized glass body layer and the crystallized second crystal glass plate B-phase stone 芏 two pairs of D ^ Xingbiandi and glass bodies And the crystallized glass plate material B is crystallization of the plurality of crystallized glass, cis β $ and the material - and the second day of the solar glass plate B is less than the small body layer, the w gray stone is precipitated The diopside to t crystal, and the crystalline glass crucible, or the first surface of the first surface, reaches the inside of the glass, and the diopside to the crystal, as a main crystal. The method for producing a crystallized glass article having a pattern, wherein the "thinous glass plate B has a thickness of about 0.1 mm to about 6 faces. 8:,. Γΐί ΐ ΐ = the crystal of the pattern The manufacturing method of the glass article /, the eight-in-one, the mouth-to-day slab slab and the second crystalline glass slab have a thickness of about 0. lmm to about 6 awake. The scope of the patent application is 6th jg eve g. According to the goods method, the crystal glass is made of R θ-like crystallized glass articles. 11 broken 璁 β β Ay Β Β, 5 玄 弟 一 一 一 一 一And the second crucible glass plate has a thickness of about Q1 to about - respectively. The manufacturing method of the crystallized glass article having the pattern of the sixth item is wherein the crucible glass body layer has about 〇 · lmm to about 30mm thick ^. Fang XI, schema · 43