JPH0442827A - Production of glass having pattern - Google Patents

Abstract

PURPOSE:To improve transparent feeling and solid feeling of a glass by arranging a mixture of transparent glass grains with opaque glass grains in a mold and integrating the mixture by heating. CONSTITUTION:A mixture of transparent glass grains and opaque glass grains is housed in a mold and fused or fused and crystallized by heating to integrate the glass 1 having a pattern in which opaque part 2 and transparent part 3 are mixed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing highly decorative patterned glass used as exterior materials for buildings, interior materials, furniture materials, and the like.

[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 marble or other natural stone, so it is suitable for fire-resistant and non-combustible buildings. This glass has attracted attention for its potential to be used as a wall material, and various methods of producing glass with marble-like patterns 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. 55-29018).

It has also been proposed to easily produce marble-like crystallized glass by crystallizing molten glass formed into a plate shape using a roll-out method or the like by using glass with a specific composition (Unexamined Japanese Patent Publication No. Publication No. 60-27622).

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. It shows a glassy fired body with a mottled pattern consisting of 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 the roll-out method, press method, and pouring method, are used to shape 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
The problem was that the transparency from the glass surface was not deep, making it 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.

The present invention eliminates the drawbacks of the conventional patterned crystallized glass or glass described above, and provides a patterned glass that is transparent, has a deep pattern, and has a beautiful pattern with a three-dimensional effect. The purpose is to

[Means to solve the problem]

The present invention provides a mixture of opaque glass particles and/or powder and transparent glass particles and/or powder in a mold, and heats the mixture to fuse or fuse.・
The above object has been achieved by a method for manufacturing patterned glass, which is characterized in that it is crystallized and patterned and integrated by mixing opaque areas and transparent areas.

The glass used in the present invention is a general term that includes all of crystallized glass, crystallizable glass, and ordinary glass. 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.

In the present invention, crystallization is carried out at a crystal nucleation temperature, e.g.
C. for a certain period of time to generate crystal nuclei, and then held at a crystal nucleus growth temperature of, for example, 1050 to 1070.degree. C. for a certain period of time.

The granular material and/or powder material (hereinafter referred to as "grain/powder material") used above includes not only granular shapes but also various shapes such as small plate-like materials, It is preferable to use a material with a shape suitable for pattern formation. These "granules/powders" are produced by, for example, melting crystalline glass, forming it into a plate by pouring it, heat-treating it to make a crystallized glass plate, and pulverizing it to make crystallized glass granules. Alternatively, it can be manufactured by creating crystalline glass granules by a water crushing method in which crystalline glass is melted and then poured into water.

The opaque glass particles/powder used may be colored, and various patterns can be formed depending on the color. Transparent glass is preferably colorless, or may be colored to some extent, since it forms a pattern with a three-dimensional effect.

Since the degree of thermal expansion of crystallized glass or crystalline glass and ordinary glass may differ greatly, in order to alleviate the difference in thermal expansion, a material with a coefficient of thermal expansion between the two is added to the surface of the glass grains/powder. A thin layer of material with a value of
D) or coating by physical vapor deposition (PVD) is preferred.

Examples of such materials include alumina (AA20s), zirconia (ZrO2), MgO-AI! 20. It is used in some way.

In addition, a thin layer of metals or metal oxides for coloring the surface of crystallized glass or crystalline glass particles/powder can be coated by chemical vapor deposition or physical vapor deposition,
When the thin layer serves to alleviate the difference in thermal expansion, it may serve both functions.

As the crystallized glass used in the present invention, one obtained by crystallizing the crystalline glass described below can be used. In addition, as crystalline glass, β-wollastonite (Ca
O-3102), forsterite (2MgO・5i
Oz), β-spodumene (L120/A120z/4
It can precipitate crystals such as SiO2), ureimite (2ZnO-8io2), and gahnite (ZnO.Al 203). There are a large number of basic glass systems for such crystalline glasses, but among them, the ones that have been put to practical use (7
) (7) Main thigh, L 120-Ai20*-3i
O! , NazO-A/zoa-3i02, Mg0-Af
t○3-3i02, Na20-CaO-MgO-3i
Ox, pb○-ZnO-BxOz, ZnOBtCL-3
i02 series, etc., but select a suitable one among them. A nucleating agent for crystallization may be added to these crystalline glasses, in which case the nucleating agent is TiO
2, ZrO2, Fe2O2, v205, Nip, Cr2
Oxides such as 0z, fluorides such as CaFz, sulfides,
Many materials are known, including noble metals such as PT and Au.

In addition, the composition of ordinary glass is NaaOCaO-3
iO,, NaaO-B20s-3i O2, CaO-1
20,-3iO,,KzO-CaO-3iOx,K
There are 2O-PbO-3iOt 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)
, Mn 02 (green, reddish brown), C00 (dark blue)
, Feaos (blue, blue-green, tan), Crabs
(orange/yellow/green/dark green), oxides such as Cu0 (green/red), Zn○/Crabs (light yellow), Zn○"Cr2
O5”TiO2 (row type/four-row color), ZnO-8nO2・
Cr2O, (loess/four-striped yellow), (Mn SO4”
4 H2O) ” Cr 20z (cream color), M
n O2・A 1220. Spinel type pigments such as (light yellowish white) can be used. The amount of colorant added is 0
．． 1 to 5% by weight is preferred.

The particle size of the various glass grains/powder used here is preferably in the range of 0.5 to 10 mm in the case of granules, and 0.5 mm or less in the case of powder. Granules having a size larger than 10 mm can also be used.

As the transparent glass, ordinary glass is mainly used.

The mixing ratio of the opaque glass particles/powder and the transparent glass particles/powder can be set arbitrarily.

[For production]

In the present invention, for example, opaque glass granules such as crystallized glass granules whose surfaces are coated with a substance for reducing the difference in thermal expansion by physical vapor deposition are mixed with transparent glass granules, and the The mixture is placed in a fireproof mold and heated to fuse or fuse/crystallize and integrate.

When this is slowly cooled, a patterned crystallized glass as shown in the vertical cross-sectional view of FIG. 1, for example, can be obtained. In the figure, 1 is patterned crystallized glass, 2 is crystallized glass, and 3 is transparent glass. Because the crystallized glass visible under the glass has different tones, the pattern has depth and a three-dimensional feel.

By increasing the proportion of transparent glass particles/powder, etc.
When a portion of the crystallized glass 2 is not exposed on the surface as shown in the longitudinal cross-sectional view of FIG. 2, a smooth surface is obtained, so there is no need for polishing work for finishing.

When putting a mixture of crystallized glass grains/powder and transparent glass grains/powder into a mold, you can either put the mixture in advance or mix it inside the mold. You can do it like this.

〔Example〕

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

However, the present invention is not limited only to these examples.

Example 1 White crystallized glass granules having the composition shown in Table 1 below were coated with Al2O by physical vapor deposition, and transparent glass granules having the composition shown in the same table were mixed in a 50:50 ratio.
The mixture was used at a weight mixing ratio of . The particle size of the white crystallized glass granules is in the order of 2-3, and the particle size of the transparent glass granules is 5-6 InIII.

Both glass granules are mixed in a mixer for 2 hours, and this mixture is filled into a refractory mold and placed in an electric furnace. 100
Heat treatment is performed by increasing the temperature at a rate of °C/hr and holding at 800 °C for 3 hours.

The resulting glass plate had a deep pattern with a mixture of opaque and transparent areas, giving it a three-dimensional appearance and an excellent aesthetic appearance.

Example 2 Black crystalline glass granules (particle size 2 to 3 mm) and transparent glass granules (particle size 4 to 5 mm) having the compositions shown in Table 2 below.
InIn) were mixed at a weight ratio of 60:40, the mixture was put into a mold, the temperature was raised to 750°C over 6 hours, this temperature was maintained for 2 hours, and then the mixture was heated to 1070°C.
The temperature was raised over 6 hours until
It was slowly cooled.

As shown in the longitudinal cross-sectional view of Figure 3, the obtained patterned glass plate has a mixture of transparent and opaque areas, giving it a three-dimensional effect, and the color tone of the crystallized glass in the surface area and under the transparent area is particularly strong. It has a different, more aesthetically pleasing pattern.

〔Effect of the invention〕

According to the present invention, it is possible to make a glass product that includes a mixture of opaque glass parts and transparent glass parts,
This is a glass product with an excellent aesthetic appearance, as the opaque glass part has a pattern that gives it depth and stands out.

Various different patterns can be obtained by changing the size, shape, color, and arrangement of the opaque glass particles/powder used.

[Brief explanation of the drawing]

FIG. 1 is a longitudinal cross-sectional view of the patterned crystallized glass obtained by the present invention, and FIG. 2 is a longitudinal cross-sectional view of the patterned crystallized glass obtained by the present invention in which the crystallized glass portion does not appear on the surface. FIG. 3 is a vertical cross-sectional view of a patterned crystallized glass plate obtained in Example 2. 1... Patterned crystallized glass 2... Crystallized glass 3... Transparent glass (3 others)

Claims (1)

[Claims] A mixture of opaque glass particles and/or powder and transparent glass particles and/or powder is provided in a mold,
A method for manufacturing patterned glass, characterized in that by heating it, it is fused or fused/crystallized to be integrated, and a pattern is created by mixing an opaque part and a transparent part.