JPH0543651B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a colored natural marble-like crystallized glass and a method for producing the same.

[Prior art and its problems] Crystallized glass obtained by heat treating glass is
It is used in a variety of fields due to its excellent mechanical strength, thermal shock strength, and chemical durability, but recently it has become a preferred alternative to natural stone as a building material due to its excellent properties. I'm getting used to it. Patent Publication No. 47-1989, which was invented by the present applicant.
No. 2276, Special Publication No. 51-23966, Special Publication No. 53-39884
The crystallized glass introduced in Japanese Patent Publication No. 55-29018 is a typical example. On the other hand, in recent years, with the diversification of architecture, there has been a demand for diversification of building materials, and one direction of this diversification is the diversification of color tones. Generally, when coloring glass or crystallized glass, a method is known in which coloring additives such as Fe, Co, Cr, etc. are added to glass raw materials and the mixture is melted at high temperature to vitrify and further crystallize. However, the method of adding colored oxides to glass raw materials to obtain colored glass or colored crystallized glass is suitable for mass production of a small number of products when manufactured in a glass tank kiln, etc. It cannot be said that it is suitable, and the color tone is also blue, brown, etc.
It is limited to gray colors, etc., and in the case of crystallized glass, there is a problem that it is difficult to obtain a color tone close to the primary color due to the influence of crystal precipitation.

[Objective of the Invention] The present invention was developed in view of the above-mentioned problems, and is easy to manufacture, suitable for small-lot production of a wide variety of products, and is capable of producing natural marble-like materials colored in various tones, including tones close to primary colors. The object of the present invention is to provide a crystallized glass and a method for producing the same.

[Structure of the Invention] The present invention provides glass particles having the property that when heat treated at a temperature higher than the softening point, needle-shaped crystals are precipitated from the surface inward while softening and deforming in a direction substantially perpendicular to the surface. A dense glass article without air bubbles, which is obtained by softening and fusing a plurality of glass corpuscles and crystallizing the glass corpuscles to a required degree, wherein the needle-like crystals in the glass article are This gives the glass article a pattern based on the presence of needle-like crystals and the difference in their orientation, and a colored layer of inorganic pigments is formed on the interface of the glass bodies. It is a colored crystallized glass having a pattern characterized by being formed.

The method for producing colored crystallized glass of the present invention includes the steps of preparing a large number of glass bodies that have the property of precipitating crystals while softening and deforming when heat treated at a temperature higher than the softening point, and mixing the glass bodies and an inorganic pigment. preparing a mixture in which an inorganic pigment is attached to the surface of the glass bodies by mixing; and heat-treating the mixture at a temperature equal to or higher than the softening point of the glass to fuse the glass bodies together; The method is characterized in that it includes the step of precipitating crystals and exposing a colored layer of an inorganic pigment at the interface of each glass body.

The crystallized glass used in the present invention preferably has a known composition as described in the above-mentioned patent publication, but has the characteristic that crystals precipitate while being softened and deformed when heat treated at a temperature higher than the softening point. Any crystallized glass can be used.

In addition, the inorganic pigment used in the present invention is an oxide having a desired color, has excellent heat resistance, and does not ionize or change color even when heat treated with crystallized glass and remains as an oxide. . In this way, inorganic pigments include NiO, MnO ₂ ,
Single colored oxides such as CoO, Fe ₂ O ₃ , Cr ₂ O ₃ or Zn-Cr-Ni-Al spinel, Sn-Si-Ca-
Cr−Zn sphene, Zr−Sr−Pr zircon, Zr−
Si-V-Pr zircon, Zr-Si-V zircon, Al
-Co-Cr-Zn spinel, Al-Zn-Fe-Cr spinel, Fe-Cr-Zn-Al spinel, Fe-Cr-Zn
Colored oxides based on components such as spinel and Fe-Cr-Ni-Mn spinel are suitable, and it is also possible to use a mixture of these.

The manufacturing method of the present invention will be explained in detail below.

First, a glass raw material mixture is prepared and melted so as to form a crystallized glass having the property of precipitating crystals while being softened and deformed when heat treated at a temperature higher than the softening point. This molten glass is directly poured into water to be rapidly cooled, and the resulting crushed glass, so-called glass bodies, are sufficiently dried and then weighed in an amount corresponding to the desired shape.
Next, select a desired color tone from among the inorganic pigments, weigh out a preferable amount of 0.1 to 10% based on the weight of the hydrated glass, depending on the shade of the desired color, and then add it to the weight of the hydrated glass. Preferably 0.1~
Add 5% of water and thoroughly stir and mix using a mixer such as a mixer. Here, the amount of inorganic pigment is
The reason why 0.1 to 10% is preferred is that if it is less than 0.1%, sufficient color development cannot be obtained, and if it is more than 10%, the softening and flow of the glass is significantly inhibited, making it difficult to obtain a smooth flat surface. In addition, the reason why the amount of water is preferably 0.1 to 10% is because if it is less than 0.1%, the particle size of the inorganic pigment and the particle size of the glass will be greatly different, so mixing will not be done sufficiently, and the inorganic pigment will adhere to the surface of the glass. Because it is difficult to color, the glass does not develop sufficient color after heat treatment.
Also, the color unevenness within one board becomes more intense. If it exceeds 5%, agglomeration of the inorganic pigment will occur, resulting in severe color unevenness similar to the above, which is not suitable. After stirring and mixing, the mixture is collected into a desired shape and heat-treated at a temperature equal to or higher than the softening point of the glass. As the temperature rises, the glass bodies fuse together and become integrated, and crystals precipitate within the glass.

[Example] Hereinafter, the present invention will be explained with reference to Examples. A state in which glasses 4 are integrated is shown.

Example 1 SiO ₂ 59.0%, Al ₂ O ₃ 6.8%, CaO 19.1%, by weight
_K2O1.7 %, _Na2O1.7 %, _{B2O3 0.6} %, ZnO6.8%,
A glass raw material mixture prepared to contain 4.3% BaO was melted at 1400 to 1500°C, and the pulverized glass was dried to prepare glass having a diameter of 1 mm or less. Next, 2% by weight of Sn--Si--Ca--Cr--Zn based suphene pigment was added to this glass, and 2% by weight of water was further added and mixed in a mixer. Approximately 5
After mixing for 1 minute, the mixture was concentrated in a refractory mold crusher coated with alumina powder as a mold release agent and heated to 1100°C.
By heat treatment at a temperature of 1 hour for 1 hour, β-wollastonite crystals were precipitated in the glass and the mixture was fused and integrated. When this was then slowly cooled and the surface polished, crystallized glass with a bright pink color was obtained.

Example 2 Crushed glass having the same composition as in Example 1 was dried to prepare glass having a diameter of 3 to 7 mm. Next, 1% by weight of an Al-Co-Cr-Zn spinel pigment was added to this glass, and 1% by weight of water was further added and mixed using a mixer. After mixing for about 5 minutes, the mixture was assembled in a refractory mold coated with alumina powder and heat treated at a temperature of 1100°C for 1 hour to precipitate β-wollastonite crystals in the glass. The mixture was fused together. After that, it was slowly cooled and the surface was polished, resulting in crystallized glass in which the glass part was marble-like white and the interface was colored blue, with a color tone and pattern that cannot be obtained with natural stone.

Example 3 By weight: SiO ₂ 61.6%, Al ₂ O ₃ 4.6%, CaO 12.9%,
_K2O1.2 %, _Na2O4.5 %, _{B2O3 0.5} %, ZnO6.3%,
A glass raw material mixture prepared to consist of 4.0% BaO, 4.0% Fe ₂ O ₃ , and 0.3% CoO is melted at 1400 to 1500°C, and the pulverized glass is dried to form a glass with a diameter of 3 to 7 mm.
prepared a glass. Next, Fe-Cr was applied to this glass.
3% by weight of -Zn-Al spinel pigment was added, and 1% by weight of water was further added and mixed using a mixer. After about 5 minutes of mixing, the mixture is collected in a refractory mold coated with alumina powder and 1080
By heat treatment at a temperature of 1 hour at .degree. C., β-wollastonite crystals were precipitated in the glass and the mixture was fused and integrated. When this was then slowly cooled and the surface polished, a crystallized glass was obtained in which the glass part was black and the interface was colored gold.

[Effects of the Invention] As described above, the colored crystallized glass of the present invention is suitable for production of a wide variety of products in small quantities, and the obtained crystallized glass is colored in various tones including those close to the primary colors. It is suitable as a diversifying building material.

[Brief explanation of the drawing]

The drawing is a cross-sectional view of a state in which granulated glass is accumulated within a refractory formwork. 1... Refractory formwork, 2... Application layer of mold release agent powder, 3... Inorganic pigment, 4... Crushed glass.

Claims (1)

[Scope of Claims] 1. A plurality of glass particles having the property that when heat treated at a temperature higher than the softening point, needle-like crystals are precipitated from the surface toward the inside while softening and deforming in a direction substantially perpendicular to the surface. A dense glass article without air bubbles, which is obtained by softening and fusing the glass particles and crystallizing the glass bodies to a required degree, wherein the needle-like crystals in the glass article have the shape of the glass bodies. As a result, the glass article is given a pattern based on the presence of needle-like crystals and the difference in their direction, and a colored layer of inorganic pigment is formed at the interface of the glass bodies. Colored crystallized glass with a pattern characterized by 2. A step of preparing a large number of glass corpuscles having the property of precipitating crystals while softening and deforming when heat treated at a temperature higher than the softening point, and mixing the glass corpuscles with an inorganic pigment to coat the surface of the glass corpuscles with inorganic pigments. preparing a mixture to which a pigment is attached, and heat-treating the mixture at a temperature equal to or higher than the softening point of the glass to fuse and integrate each glass body;
A method for producing colored crystallized glass comprising the steps of precipitating crystals and exposing a colored layer of an inorganic pigment at the interface of each glass body.