JPH0450126A - Glass article having transparent layer on surface and production thereof - Google Patents

Abstract

PURPOSE:To obtain a glass article having a transparent feeling and deepness in pattern, etc., by making glass of structure wherein a transparent glass layer is formed on the surface and a translucent or patterned glass layer fused to the glass layer is made under the transparent glass layer. CONSTITUTION:This glass article 1 is a glass article wherein a transparent glass layer 2 is formed on the surface and a translucent or patterned glass layer 3 fused to the glass layer is made under the transparent glass layer 2 and integrated. The glass article is obtained by the following method. Namely, translucent glass granules, powder, plate material or nonwoven fabric or glass granules, powder, plate material or nonwoven fabric to be translucent is packed into a refractory mold or glass granules, powder, plate material or nonwoven fabric having two or more different colors is filled into the mold so as to make a pattern, transparent glass granules, powder, plate material or nonwoven fabric is filled to the outside of the material to make a laminate, heated, fused or fused and crystallized and integrated.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a glass article having a transparent layer on its surface, which is used as an exterior material for construction, an interior material, a furniture material, etc., and a method for manufacturing the same. The present invention relates to a glass article having a transparent layer on its surface and a glittering part below the transparent layer, and a method for manufacturing the same.

[Conventional technology]

Crystallized glass in which acicular β-wallasnite crystals are precipitated and grown from the surface to the inside has a beautiful appearance with a pattern similar to natural stone such as marble, so it is highly effective for fire and noncombustibility of buildings. Glass has attracted attention for its use as a wall material, and various methods of producing glass with a marble-like pattern have been studied, one of which is known as an accumulation method.

In this method, molten glass is first granulated by means such as water pulverization, then placed in a mold, heated, and fused together.
(Japanese Patent Publication No. 5529018).

It has also been proposed that by using glass with a specific composition, it is possible to easily produce marble-like crystallized glass by crystallizing molten glass formed into a plate shape using a roll-out method etc. (Unexamined Japanese Patent Publication No. Publication No. 6027622).

In addition, in order to form other patterns,
No. 51 and No. 60-166239 disclose island-shaped or mottled areas having a large number of microbubbles, matrices having a large number of microbubbles, located between the mottled areas, and having a different color tone from the mottled areas; This document discloses a multicellular glass body that has a mottled pattern made of glass and aims at the light scattering effect of air bubbles.

Furthermore, in order to give glass an emulsifying property or even coloring property, and to form a mottled pattern,
Publication No. 40 discloses a glassy fired body formed from glass powder, a heat-resistant inorganic oxide having a refractive index different from that of the glass powder, and a colored pigment, which has light-scattering mottled areas and a light-scattering area around them. A glass fired body with a mottled pattern is shown, which has colored mottled areas with poor scattering properties. This vitreous fired body scatters incident light based on the difference in refractive index with glass, thereby giving the fired body a milky white appearance.

[Problem to be solved by the invention]

Conventional methods used to obtain crystallized glass with a marble-like pattern, such as roll-out method, press method, and pouring method, are used to form glass and then heat-treat it to crystallize it. Since it precipitates and grows almost uniformly throughout, the appearance and pattern tend to be homogeneous and monotonous, making it difficult to obtain a transparent natural stone-like appearance.

In order to change the pattern, fine cracks are created in the crystalline glass molded into the desired shape, and then heat treatment is used to grow crystals from the crack interface towards the inside, thereby separating the crystals and the matrix glass phase. Method for producing crystallized glass articles having a beautiful natural stone-like appearance due to mixing and crystal orientation (Japanese Patent Application Laid-Open No. 61-201631
However, the transparency from the glass surface was not deep and it was difficult to obtain a tasteful appearance.

Furthermore, the mottled-pattern glass fired body disclosed in JP-A-1-172240 has a milky white appearance as a whole, and does not have a transparent natural stone-like appearance.

On the other hand, the above-mentioned crystallized glass articles having a natural stone-like appearance tend to have uneven surfaces and require a surface polishing step for finishing, but since crystallized glass is hard, polishing is time-consuming.

Furthermore, conventional porous glass bodies aimed at light scattering effects have a large number of fine pores throughout and have mottled areas, giving the overall impression of being cloudy. isn't it.

A first object of the present invention is to provide a glass article that is transparent and has deep patterns.

A second object of the present invention is to provide a glass article that is transparent, has deep patterns, and has brilliance.

A third object of the present invention is to provide a method for manufacturing a glass article having a transparent glass layer on its surface.

A fourth object of the present invention is to have a transparent glass layer on the surface,
It is an object of the present invention to provide a method for manufacturing a glass article having a glittering part under the glass layer.

[Means to solve the problem]

The present invention has achieved the above object by the following means.

(1) A glass article having a transparent glass layer on its surface, and an opaque or patterned glass layer fused below the transparent glass layer.

(2) It has a transparent glass layer on the surface, and below the transparent glass layer there is an opaque or patterned glass layer fused to it, and there are many fine bubbles at the interface between both layers. A glass article in which an existing bright portion is formed.

(3) Filling a fire-resistant mold with opaque or opaque glass granules, powder, plates, or nonwoven fabric, or filling two or more types of glass granules or powder with different colors. body,
Filling a plate-shaped body or non-woven fabric so that a pattern is formed,
The outer surface is filled with transparent glass particles, powder, plates, or non-woven fabric in a laminated manner, and heated to fuse or fuse/crystallize and integrate. A method for producing a glass article having a transparent glass layer on its surface.

(4) Filling a fire-resistant mold with opaque or opaque glass granules, powders, plates, or nonwoven fabrics, or filling two or more types of glass granules or powders with different colors. body,
Filling a plate-shaped body or non-woven fabric so that a pattern is formed,
The outer surface is filled with transparent glass granules, powder, plates, or nonwoven fabrics whose melting point is lower than that of the glass described above, and is heated to fuse or fuse.
It is crystallized and integrated, and has a transparent glass layer on the surface.
A method for manufacturing a glass article, characterized in that a glittering part in which a large number of fine pores are present is formed at the interface between the glass layer and a lower glass layer.

The glass article of the present invention has a structure shown in the longitudinal cross-sectional view of FIG. 1, in which a surface layer 2 made of transparent glass and a lower layer 3 made of opaque or patterned glass are fused to each other. ing. 1 is a glass article.

Further, the glass article having a bright part of the present invention has a structure as shown in the vertical cross-sectional view of FIG. 2, and the surface layer 2 made of transparent glass and the lower layer 3 thereunder are fused to each other. Ori,
A large number of fine bubbles 5 exist at the interface 4 between both layers, forming a bright area.

1 represents a glass article.

The glass used in the present invention is a general term for all of crystallized glass, crystalline glass, and ordinary glass, and includes all of them.

Here, "crystallized glass" refers to glass in which crystals have already precipitated, and "crystalline glass" refers to glass in which crystals can be precipitated, but
It refers to glass in which crystals have not yet precipitated, and "ordinary glass" refers to general glass such as plate glass and colored glass. The specific contents will be described later.

Moreover, as the "transparent glass", it is preferable to mainly use colorless and transparent ordinary glass.

It is preferable to use glass for the lower layer 3 that has a pattern. The pattern may be a pattern composed of various colored parts, or may be formed by unevenness on the surface. Glass with a pattern made up of the various colored portions described above is produced by arranging glass powder of one color and glass powder of another color in a fire-resistant mold so as to form a pattern, heating them, and fusing them together. It may also be formed by In any case, the glass of the lower layer 3 is preferably colored.

There is a surface layer 2 made of transparent glass on top of the glass of the lower layer 3, so when viewed from above, the glass surface of the lower layer 3 can be seen through the surface layer 2, giving a sense of transparency. , it gives more depth.

In particular, when the lower layer 3 has a pattern, the three-dimensional effect of the pattern is enhanced.

Moreover, in the glass article of the present invention, it is also possible to form a bright area in which a large number of fine bubbles 5 exist at the interface 4 between the surface layer 2 and the lower layer 3, and in that case, the glass surface of the bubbles can form a transparent area. Light entering from the surface layer 2 is reflected in various directions, giving a strong brilliance and making the shape of the glass surface of the lower layer 3 look complex, giving it a beautiful appearance.

As the transparent glass used in the present invention, typically used ordinary glass such as soda glass can be used. From the viewpoint of production, it is preferable to use a material with a relatively low melting point.

As the crystalline glass used in the present invention, any glass that has been known as a raw material for producing crystallized glass can be used. Examples of the glass include β-wollastonite (CaO・5i02)-forsterite (2MgO・SiO□), β-spodumene (Li
zO・Al z03 ・4Si02), ureimite (2ZnO・5iOz), gahnite (ZnO-A/
20. ) can precipitate crystals. There are a large number of basic glass compositions for such glasses, but the main ones that are used in practical use are LizO-u gos
-5iO□, Na20-A/ 203-5iOz, Mg
0-A/203-3ift, Na20-CaO-Mg
O3in□, PbO-Zn0-BzO3, Zn0-Bz
O3-5iOz series, etc., among which a suitable one is selected. A nucleating agent for crystallization may be added to these glasses, in which case the nucleating agent is Ti.
0z, ZrO□, FezO,, M2O3, NiO, C
Many materials are known, including oxides such as r2O3, fluorides such as CaFz, sulfides, and noble metals such as pt and Au.

In addition, the composition system of ordinary glass is Na20-CaO-
5iO□, NazO-BzO:+-5iOz, Ca0-
A/ zoz-3iOz, K2O-CaO5iO□, K
There are zO-PbO-5iO□ systems, etc.

When these glasses are made into colored glasses other than colorless, a coloring agent is added. Colorants include gold, silver,
In addition to metal colloids such as copper, Ni0 (brown, beige)
, Mn0z (green, reddish brown), Co.

(dark blue), FezO3 (blue, blue-green, yellowish brown), Cr
zOs (orange, yellow, green, dark green), Cub (green, red)
oxides such as Zn0-CrzO=(light yellow), ZnO
・Cr2O2HTie□ (brown orange/light brown), ZZnO
-5nu・Cr, 0. (Ocher/Ming brown yellow), (M
nSO4'4HzO)' Coos (cream color)
, MnO□.M2O5 (pale yellowish white), and other spinel type pigments can be used. The amount of coloring agent added is 0.1~
5% by weight is preferred.

The crystallized glass used in the present invention is obtained by crystallizing the above-mentioned crystalline glass, and the crystallization is performed by, for example,
A crystalline glass granule, powder, plate, or nonwoven fabric is heated to reach a nucleation temperature, maintained at that temperature for a predetermined period of time to generate crystal nuclei, and then further heated. The crystal growth temperature can be reached and crystallization can be performed.

To manufacture the glass article of the present invention, for example, crystallized glass granules or powder (hereinafter referred to as "granules") are placed in a fire-resistant mold.
Powder) is filled to a certain thickness to form a layer, and then transparent glass grains/powder are filled to a certain thickness to form a layer, and the layer is heated to raise the temperature. As the temperature increases, the transparent glass grains and powder begin to fuse together, and as the temperature rises further, the crystallized glass grains and powder begin to fuse, forming their own fused layers. At the same time, the two layers are also fused together to obtain a glass article having a transparent glass layer on the surface and a crystallized glass layer as the lower layer, similar to that shown in FIG. The underlying crystallized glass layer is itself opaque and may also have a pattern, which can be seen through the transparent glass layer.

Further, when transparent soda glass, for example, is used as the transparent glass, this soda glass has a low melting point and therefore melts first, forming a softened and fused layer on the top. At this time, the air retained in the gaps between the grains and powder of crystallized glass below this layer is blocked by the softened and fused layer above and stops at the bottom surface of the softened and fused layer. When the softened/fused layer and the fused body (layer) of crystallized glass are fused to each other, a large number of fine bubbles are formed at the interface between the two layers.

As the above-mentioned transparent glass, a material other than soda glass may be used, and the shape thereof may be, for example, a single plate.

Next, the method for manufacturing a glass having a transparent glass layer on its surface according to the present invention will be described in detail. As the crystallized glass or crystalline glass, the ones described above can be used.

Furthermore, the above-mentioned transparent glass can also be used.

When crystallized glass is used as the raw material for filling the lower layer in the manufacturing method of the present invention, it is sufficient to heat the crystallized glass so that the grains, powder, etc. of the crystallized glass fuse together. When crystallized glass is used and a layer of crystallized glass is formed, the heating conditions must be such that the glass is packed and crystallized after fusion.

The particle size of crystallized glass or crystalline glass particles/powder is as follows:
In the case of granules, the range is preferably 0.5 to 10 ms+,
In the case of powder, use one with a diameter of 0.5 mm or less.

The granules do not need to have a precise granule shape, and may be small plate-like bodies, and the size may be 10 ml or more. The plate-like bodies and nonwoven fabrics are also of a size suitable for use.

The same applies to the size of grains and powder of ordinary glass.

The size of the transparent glass particles, powder, plate, etc. is the same, but in this case, one plate may be used.

Furthermore, when filling the above-mentioned crystallized glass or crystallized glass particles/powder, etc. into a fireproof mold, for example, a non-combustible mold is inserted and crystallized glasses of different colors are placed in a pattern. It may be filled so as to be placed at each location so as to be formed. The fireproof frame may first be filled with crystallized glass or crystalline glass particles/powder, etc. so as to form a layer, or it may be filled with transparent glass particles/powder first. It's okay.

According to the manufacturing method of the present invention, for example, a patterned crystallized glass article having a transparent glass layer on the surface can be obtained. In the present invention, since the present invention can best be explained in the case where a crystallized glass layer is formed as the lower layer, this will be described in detail, but other glasses can be used as well. Since this glass article has a transparent glass layer on its surface, the pattern of the underlying crystallized glass can be clearly seen and has a transparent feel, and it also appears to stand out and has a three-dimensional effect. Since the transparent glass layer on the surface is once melted due to heating, a smooth surface is formed when it is filled and laminated as an upper layer, and no subsequent finishing work is required.

Note that some crystallized glass exhibits a marble-like pattern depending on the direction of the crystals grown, so such materials are also included in those with a pattern in the present invention.

Furthermore, in the manufacturing method of the present invention, if a layer of transparent glass grains/powder with a lower melting point than the glass filled below is filled, this glass will melt first and soften.・
In order to form a fusion layer, as mentioned before, a large number of fine air bubbles can be present at the interface between the transparent glass layer and the crystallized glass layer, and the layer has a transparent glass layer on the surface. ,
A patterned crystallized glass with bright areas is obtained. In particular, it is preferable to use a transparent glass plate. However, if the air in the gaps between the grains and powder of the crystallized glass in the lower layer is allowed to escape through the side walls of the fireproof mold, it is possible to eliminate almost all air bubbles.

Furthermore, if the viscosity of the upper transparent glass is sufficiently reduced at the heat treatment temperature, air bubbles can be removed from the glass body through the transparent glass layer. Transparent glass particles/powder may be first filled into a fireproof mold and then heated. In this case, it is possible to ensure that there are no air bubbles at the interface between the two layers, but in the manufactured product, the surface of the transparent glass layer will have a shape that corresponds to the bottom surface of the fire-resistant mold. Therefore, finishing by polishing may be required.

[For production]

In the glass article of the present invention having a transparent glass layer on the surface, the pattern of the underlying glass can be seen through the transparent glass layer, so it has a sense of transparency and the pattern has depth.

In addition, in the glass article with a glittering part of the present invention, a large number of fine bubbles exist at the interface between the transparent glass surface layer and the lower layer such as crystallized glass fused thereto. The surface of the bubbles reflects the light that has passed through the transparent glass in various directions, giving it a luminous appearance.
Additionally, by emphasizing the unevenness of the underlying crystallized glass, the patterns appear complex and three-dimensional, giving a beautiful appearance.

In the present invention, it is possible to use patterned crystallized glass having a transparent glass layer on the surface, which gives a sense of transparency and three-dimensionality, giving it depth and a smooth glossy surface that does not require finishing. can be taken as a thing.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples.

However, the present invention is not limited to this example.

Example 1 Granular bodies of white crystalline glass having the composition shown in Table 1 and having a particle size of 0.6 to 2.0+++ m were placed in a fire-resistant mold to a thickness of 3 cm.
Fill it so that it becomes m. Transparent glass particles having the composition shown in Table 1 and having a particle size of 0.6 to 2.0 suw are placed on top of the aggregate so as to have a thickness of 6 mm, and placed in an electric furnace.

Table 1 As shown in Figure 1, the obtained crystallized glass is a glass plate having transparent glass in the surface layer 2 and white crystallized glass in the lower layer 3. The shape of the body becomes uneven and remains as a pattern, increasing the three-dimensional effect,
It has a lot of depth. Note that the surface was extremely smooth and glossy, and no polishing was necessary.

Example 2 Granular bodies 7 of black crystallized glass having the composition shown in Table 2 (
As shown in Fig. 3, a transparent glass plate (3 cm thick) was filled into the mold 6 to a thickness of 3 cm, as shown in Fig. 3.
1nffl) was placed and heated.

The heating conditions are This is heated by the next heating step.

When held at 750°C for 2 hours, crystal nuclei were generated in the white crystalline glass, and the temperature was further raised to 1070°C for 2 hours.

In this example, since already crystallized glass granules were used, the steps of crystal nucleation and crystallization were omitted, and only fusion was performed to integrate them.

The obtained crystallized glass article having a transparent glass layer on the surface has the same effect as in Example 1, but as shown in FIG. Since the fine air bubbles 5 are localized at the interface between the two layers, they form a bright area, further emphasizing the pattern and three-dimensional effect. 4 is the interface between the surface layer 2 and the lower layer 3.

〔Effect of the invention〕

In the glass article of the present invention having a transparent glass layer on the surface, the underlying glass surface can be seen through the transparent glass layer, and the pattern of the underlying glass can be seen, so it has a sense of transparency and the pattern has depth. be.

In the glass article on which the glittering portion of the present invention is formed, the surface layer is made of transparent glass, and a large number of fine bubbles are present at the interface between the surface layer and the lower layer made of crystallized glass or the like that is fused to the surface layer. Because of this, the light that has passed through the transparent glass is reflected in various directions on the glass surface of the bubbles, creating a strong shine, which makes the patterns of the underlying crystallized glass appear complex, giving it a beautiful appearance. . Furthermore, since the surface layer is a transparent glass layer, there is a sense of transparency, and the pattern on the underlying glass surface has depth.

According to the method of manufacturing a glass article having a transparent glass layer on the surface of the present invention, it is possible to make a patterned glass article having a transparent glass layer on the surface, so it is possible to give a sense of transparency, and also to give crystallization. Patterns such as chemical glass appear to be floating, adding to the aesthetic appearance. In addition, since the transparent glass layer on the surface can be formed as a smooth one,
Surface polishing becomes unnecessary. In addition, when a transparent glass layer is formed as the lower layer in a fire-resistant mold, even if it is better to polish it for the finish, polishing the transparent glass is difficult because its hardness is lower than that of crystallized glass. ,
It is much easier than polishing crystallized glass.

[Brief explanation of drawings]

FIG. 1 is a longitudinal cross-sectional view of the glass article of the present invention, and FIG.
The figure is a longitudinal cross-sectional view of a glass article having a bright part according to the present invention, and FIG. FIG. 1...Glass article of the present invention 2...Surface layer 3...
・Lower layer 4...Boundary surface 5...Bubble

Claims (4)

[Claims] (1) A glass article having a transparent glass layer on its surface, and an opaque or patterned glass layer fused below the transparent glass layer. (2) It has a transparent glass layer on the surface, and below the transparent glass layer there is an opaque or patterned glass layer fused to it, and there are many fine bubbles at the interface between both layers. A glass article in which an existing bright portion is formed. (3) Filling a fire-resistant mold with opaque or opaque glass granules, powder, plates, or nonwoven fabric, or filling two or more types of glass granules or powder with different colors. body,
Filling a plate-shaped body or non-woven fabric so that a pattern is formed,
The outer surface is filled with transparent glass particles, powder, plates, or non-woven fabric in a laminated manner, and heated to fuse or fuse/crystallize and integrate. A method for producing a glass article having a transparent glass layer on its surface. (4) Filling a fire-resistant mold with opaque or opaque glass granules, powders, plates, or nonwoven fabrics, or filling two or more types of glass granules or powders with different colors. body,
Filling a plate-shaped body or non-woven fabric so that a pattern is formed,
The outer surface is filled with transparent glass granules, powder, plates, or nonwoven fabrics whose melting point is lower than that of the glass described above, and is heated to fuse or fuse.
It is crystallized and integrated, and has a transparent glass layer on the surface.
A method for manufacturing a glass article, characterized in that a glittering part in which a large number of fine pores are present is formed at the interface between the glass layer and a lower glass layer.