JPH0729802B2 - Method for producing a crystallized glass article having a pattern - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a crystallized glass part suitable for construction and decoration.

[Conventional technology]

One of the known methods for producing a pattern on crystallized glass is, for example, Japanese Examined Patent Publication Nos. 37-18063 and 46-432.
No. 38, JP-A-57-175751 and the like mainly have a method of coloring, but with this method, only a typical colored pattern is obtained, and the design effect of the appearance is poor. There was a problem.

Therefore, the aim was to obtain a very tasty and beautiful pattern that can have a natural stone-like appearance mainly due to the deep shade pattern caused by the crystal orientation and the mixture of the crystal and the matrix glass phase. The method is also Shokoku Sho53
-19607 and Japanese Patent Publication No. 55-29018.

However, in Japanese Examined Patent Publication No. 19607/1978, a flat patterned crystallized glass can be obtained only by completely grinding and removing the irregularities on the surface of the crystallized glass article obtained by heat treatment, and a mirror flat plate is obtained. However, there is a drawback in that much labor and time are required for the grinding / polishing process.

In the so-called sintering method typified by Japanese Patent Publication No. 55-29018, by collecting crystalline glass particles colored in various colors and then heat-treating them, the orientation of the crystals and the mixture of the crystals and the matrix glass phase can be obtained. Although it is possible to obtain a very beautiful crystallized glass that has a coloring design based on colored glass bodies in addition to the deep natural stone pattern caused by it.
The voids between the integrated crystalline glass bodies will always remain as pores in the final crystallized glass article, and the physical properties of the material will be impaired.

Therefore, the applicant of the present invention relates to a method for producing a crystallized glass article having the above-described deep and excellent design appearance, which does not require complicated finishing and has no internal pores. In order to improve the above-mentioned design effect by repeating various studies, in the heat treatment for crystallization, an interface that becomes a starting point of crystal precipitation / growth is preliminarily formed in the inside of the glass article before crystallization, and at the same time, pores etc. are formed. We paid attention to the fact that the cause of the problem should be avoided.

As one of such novel manufacturing methods, the present applicant has
A method in which a crystalline glass article before heat treatment (hereinafter, the one before heat treatment is referred to as crystallinity, the one after heat treatment is referred to as crystallization) is cracked and then heat treated (JP-A-61-201631),
(Hereinafter referred to as “cracking method”) is proposed.

Furthermore, the present applicant disperses a crystalline glass piece before heat treatment, a crystallized glass piece after heat treatment, or an amorphous glass piece in a melt of crystalline glass, and then forms the original crystalline glass. It proposes a method for producing a crystallized glass article (Japanese Patent Laid-Open No. 62-30630) which is characterized by heat treatment and can be easily subjected to a free coloring design.

[Problems to be Solved by the Invention] However, in the creation of a pattern by the conventional cracking method, it is not possible to predict the shape of the pattern that appears and it is difficult to repeatedly manufacture a product having the same pattern. In addition to the drawback, there is a need to grind the surface thickly in order to reveal a deep pattern.

In addition, in the method of dispersing the glass pieces, in addition to the laborious work of dispersing the glass pieces in consideration of the pattern in which the glass pieces are exposed, it is necessary to finally grind the surface thickly.

The object of the present invention is to make it possible to reveal a pattern on the crystallized glass by a simple manufacturing process, and to obtain the same pattern repeatedly, and to obtain even more depth by simply grinding the surface extremely thinly. It is an object of the present invention to provide a method for producing a crystallized glass article having a pattern, which can reveal a pattern.

[Means for Solving the Problems]

Means for achieving the object of the present invention are as described in each claim of the claims, and the crystalline glass used in the present invention has a known composition described in the above publication. May be other, may be other, the method of the present invention is not limited by the glass composition, and may be a crystalline glass colored with a known colorant Needless to say.

The method of the present invention will be described in detail below. First, by melting the crystalline glass, which has the property of acicular or dendrite-like crystals precipitating and growing from the surface to the inside by heat treatment, the plate is formed by conventional molding techniques such as roll-out method, pressing method, and casting method. Shaped into blocks or blocks. Next, water glass is applied to a part of the surface of the plate-shaped or block-shaped glass molded product thus obtained. As the water glass to be applied, No. 1, No. 2, No. 3 and No. 4 specified in JIS K1408 “Sodium silicate nNa ₂ O · mSiO ₂ ” are commercially available, but these may be applied as they are. However, it may be appropriately diluted with water and applied. As for the degree of dilution, even No. 4, which has the lowest concentration among Nos. 1 to 4, can be diluted to about 20 times and used. Further, crystals of sodium silicate having an effect equivalent to that of water glass may be dissolved in water and used, or so-called potash water glass may be used. As a coating method, a method of directly coating with a brush, a spray method, a screen printing method, or the like is applied. The thickness of water glass applied is about 0.1.
~ 1mm is desirable.

A glass molded article in which water glass is applied to a part of the surface by the above method is transferred to a heat treatment furnace for each refractory mold and heated, and the orientation and density of crystals in the water glass coated surface and the water glass non-coated surface The crystallized glass article has a pattern due to the difference in size and the like.

After that, an extremely thin surface-altered layer considered to be poor in physical properties such as chemical durability (a glass layer formed by a reaction between water glass and crystallized glass, and a cross-section of the obtained crystallized glass article is EPMA: Electron Probe X-ray Micro Ana
When analyzed with a lyzer, it was found that this layer was present only in a portion 0 to 0.5 mm from the surface. )
By removing by a method such as polishing, it is possible to combine the excellent physical properties originally possessed by crystallized glass with the above pattern.

The reason why the state of crystal growth is different between the surface coated with water glass and the surface not coated with water glass is presumed as follows.

Generally, when heat-treated, a crystallized glass having the property that crystals are precipitated and grow from the surface toward the inside,
Crystals grow like needles or dendrites vertically from the surface to the inside. Therefore, the surface not coated with water glass is
The surface of the crystallized glass is uniform. However, when water glass is applied to the surface of the crystalline glass in advance, the temperature of the water glass at the contact interface between the crystalline glass and the crystalline glass is lower than the temperature at which crystals start to precipitate from the surface (about 800 to 1000 ° C). It is considered that they are softened, fused, and integrated. However, at this time, there is a great possibility that a part of the Na ₂ O component in the water glass will diffuse into the surface layer of the crystalline glass, and the surface of the crystalline glass (that is, water glass and crystalline glass It is believed that the interface) will lose most of its ability as a starting point for crystal initiation where crystals can precipitate and grow.
Therefore, with the temperature increase during heat treatment on the water glass coated surface, only from a very limited portion near the surface of the crystalline glass (that is, the interface between the water glass and the crystalline glass),
Large crystals, with coarse (random orientation) coarse precipitation
It will grow.

On the other hand, as described above, on the surface not coated with water glass, crystals are uniformly deposited and grown vertically from the entire surface of the crystalline glass, so that the crystals on the surface coated with water glass and the surface not coated with water glass are Patterns appear due to differences in the orientation, density, size, and so on.

Therefore, when water glass is applied in the form of a picture, a character, etc. by a screen printing method or the like, the designed pattern appears due to the difference in the orientation, density, size, etc. of the precipitated / grown crystals.

On the other hand, when water glass is applied to the entire surface of the crystalline glass and heat-treated, large, random, and coarsely grown crystals themselves cause a deep pattern to appear.

Also, the area where the crystals are large and randomly grown roughly due to the application of water glass extends to the inside (about half of the thickness) of the crystallized glass, so after the heat treatment and crystallization, polishing etc. Even if the extremely thin surface-altered layer is completely removed by the method, the pattern does not disappear. That is,
The components of water glass are present only in the applied extremely thin surface-altered layer, and have the effect of growing crystals in a large, random, and coarse manner.For example, the components penetrate into the crystallized glass. In fact, it does not impair the physical properties of crystallized glass.

Also, if we focus on the above-mentioned principle, the temperature at which crystals start to precipitate from the surface of crystalline glass (about 800 to 1000 ° C)
At a lower temperature than that, it is softened, fused and integrated with crystalline glass,
It can be seen that the use of other substances that can lose the ability of the surface of the crystalline glass as the starting point of crystallization has the same effect as the water glass.

That is, print paint, low-temperature glaze, low-melting glass powder and the like are examples, and have the same effects as water glass, but water glass is most preferable in terms of economical efficiency and handling.

It is also possible to use a method of cracking in which the crystalline glass is cracked by thermal shock or mechanical shock before the water glass is applied. In this case, the surface of the crystalline glass coated with water glass loses most of its ability as a starting point of precipitation initiation of crystals due to the above-mentioned reason, while the crack entering the surface is a physical crystal. Since it retains the ability as a starting point of precipitation, crystals will grow preferentially from these cracks. Therefore, a wide band-shaped pattern appears with the cracks on the surface as a skeleton, and a crystallized glass article having a very tasty natural stone-like appearance can be obtained.

Example of Invention

 Examples of the present invention will be described below.

FIG. 1 (a) shows how the water glass 1 is applied to the entire upper surface of the crystalline glass article 5.

Drawing 1 (b) shows the state of the cross section of the crystallized glass article 4 obtained by heat-treating and crystallizing the crystalline glass article 5, and 2 shows the effect of the applied water glass.
Large, random, coarsely grown crystals 3 are crystals grown in an orderly and uniform manner from the surface to the inside, and 7 is an altered layer.

FIG. 2A shows a state in which the water glass 1 is applied to a part of the surface of the crystalline glass article 5, and FIG. 2B similarly depicts FIG. 2A from above.

Drawing 2 (c) shows the state of the cross section of the crystallized glass article 6 obtained by heat-treating and crystallizing the crystalline glass article 5, and 2 is large due to the effect of the applied water glass and is random. In the figure, coarsely-grown crystals are shown, and 3 is a crystal that is grown orderly and uniformly from the surface to the inside.
Similarly, (d) depicts the crystallized glass article 6 from above.

Example-1 Silica powder, aluminum hydroxide, zinc oxide, potassium carbonate, potassium nitrate, sodium carbonate, sodium nitrate,
Using magnesium oxide, magnesium hydroxide, and arsenous acid as raw materials, a glass batch is prepared so as to satisfy the following glass composition, put into a crucible, and melted in an electric furnace at a temperature of 1450 ° C. for about 6 hours.

_{SiO 2: 48.5wt%, Al 2} O 3: 21.5wt%, ZnO: 6.6wt%, K 2 O: 1.9wt%, Na 2 O: 4.0wt%, MgO: 17.0wt%, As 2 O 3: 0.5 wt%.

Pour the obtained molten glass into a metal mold, 300 × 300
After being molded into a plate shape of about × 20 mm, the plate-like crystalline glass article is obtained by gradually cooling to room temperature at a temperature falling rate that does not cause cracking.

Next, this glass molded product was transferred into a fire resistant mold whose inner surface was coated with a release agent powder, and water glass No. 1 specified in JIS K1408 was added to the entire upper surface of the glass molded product with water to give 10 parts. Dilute twice and apply by spraying method to a thickness of about 0.3 mm.

Then, the glass molded article coated with water glass is transferred to a heat treatment furnace together with the refractory mold, heated to a temperature of 1050 ° C at a rate of 200 ° C / hr, and held at 1050 ° C for 3 hours to perform heat treatment. It was

Water glass applied to the surface due to heat treatment is approximately 500-600 ℃
By the time it reaches
From around the temperature exceeding 900 ° C., needle-like crystals start to randomly precipitate near the fusion surface between the water glass and the crystalline glass. When the heat treatment is further continued, FIG. 1 (b)
Medium, as shown in appendix 2, it became a texture of large, roughly and coarsely grown acicular crystals. After the heat treatment, the crystallized glass article was observed to have a deep and beautiful pattern due to the above-mentioned large and randomly coarsely grown crystals. This pattern is made with a diamond grinder so that the water glass coated surface is 7 to 8 mm.
It did not disappear even after being ground and removed to some extent. On the other hand, the side surface of the crystallized glass article which is a non-coated glass surface,
From the bottom surface and the back surface, as shown by reference numeral 3 in FIG. 1 (b), needle-like crystals grew in an orderly and uniform manner from the front surface to the inside, and had a monotonous ceramic-like appearance.

The surface of the crystallized glass article after heat treatment was ground by about 0.5 mm to remove the altered layer on the surface, and immersed in an H ₂ SO ₄ aqueous solution of pH = 1 at room temperature for 24 hours. , Has been proved to have excellent chemical resistance inherent in crystallized glass. In addition, when the Vickers hardness, the bending strength, etc. were examined, the measured values were almost the same as the physical properties originally possessed by the crystallized glass. That is, the components of the water glass applied to the surface remain in the extremely thin surface-altered layer and do not impair the original excellent properties of crystallized glass under ordinary heat treatment conditions.

Example-2 A crystalline glass article molded in the same manner as in Example-1 was transferred into a fire resistant mold whose inner surface was coated with a release agent powder, and a part of the upper surface of the glass molded article was subjected to JIS K1408. The prescribed water glass No. 3 is applied as it is to a circular shape as shown by reference numeral 1 in FIGS. 2 (a) and 2 (b) with a brush to a thickness of about 1 mm.

When this is heat-treated in the same manner as in Example-1, as shown by reference numeral 2 in FIG. 2 (c), in the lower part of the water glass application portion, it becomes large up to about half the thickness of the crystallized glass article and randomly roughened. Crystals were precipitated and grown on the surface, and a beautiful pattern with a depth as shown by the reference numeral 2 in FIG. 2 (d) was observed. As shown, needle-like crystals grew in an orderly and uniform manner from the surface to the inside, and exhibited a monotonous ceramic-like appearance as shown by reference numeral 3 in FIG. 2 (d). That is, due to the difference in crystal growth direction, density, size, etc. between the water glass coated portion and the water glass non-coated portion, FIG.
A crystallized glass article having a circular pattern as shown in FIG.

Furthermore, by applying water glass on the surface of the crystalline glass article in a predesigned character or intricate pattern by a screen printing method or the like, as shown in FIG. It was possible to obtain a crystallized glass article having a deep and beautiful pattern as designed due to the difference in the crystal growth direction, density, size, etc., from the portion not coated with water glass.

The surface of the crystallized glass article after the heat treatment was ground by about 0.5 mm to remove the altered layer on the surface, and the physical properties as shown in Example-1 were examined. As a result, the original crystallized glass was excellent. The physical property values are shown.

Example-3 Silica powder, aluminum hydroxide, zinc oxide, potassium carbonate, potassium nitrate, sodium carbonate, sodium nitrate,
Using magnesium oxide, magnesium hydroxide, and cerium oxide as raw materials, a glass batch is prepared so as to satisfy the following glass composition, which is put into a crucible and melted in an electric furnace at a temperature of 1450 ° C. for about 6 hours.

_{SiO 2: 57.5wt%, Al 2} O 3: 12.1wt%, ZnO: 8.4wt%, K 2 O: 1.2wt%, Na 2 O: 7.0wt%, MgO: 13.3wt%, CeO 2: 0.5wt% .

Pour the obtained molten glass into a metal mold, 300 × 3
It is formed into a plate with a size of about 00 x 20 mm.

This glass molded product is kept at 650 ° C for 30 minutes in a slow cooling furnace, then cooled to 300 ° C at a rate of 1 ° C / min, coated with a release agent powder and immediately transferred to a fireproof mold. Then, water is applied to the molded glass article to subject it to thermal shock and cracks. Next, the cracked glass molded product is dried together with the fireproof mold, and water glass No. 2 specified in JIS K1408 is applied to the entire upper surface thereof with a brush to a thickness of about 0.5 mm.

After that, the cracked glass molded product coated with water glass is transferred to a heat treatment furnace together with the refractory mold and heated to a temperature of 1050 ° C for 200
The temperature was raised at a rate of ° C / hr and the temperature was maintained at 1050 ° C for 3 hours to perform heat treatment.

Water glass applied to the surface due to heat treatment is approximately 500-600 ℃
By the time the temperature reaches, the crystalline glass is softened, fused and integrated, and then the cracks inside the glass molded product start to fuse due to softening of the glass from around the temperature of 800 ° C. In parallel with the fusion, from near the temperature of over 900 ℃, from the cracked glass molded product surface and the crack boundary surface existing inside the molded product,
Needle-like crystals start to grow densely and radially, and if the heat treatment is continued, the spikes of a gama with each crack on the surface as a skeleton or the tip of a brush used when washing a test tube Became the crystal structure of. When this was observed from the upper surface side, it had a wide band-like pattern centered on the cracks on the surface. On the other hand, in the part away from the crack, a deep and beautiful pattern was observed near the fusion surface between the water glass and the crystalline glass, which was caused by the crystals that grew large randomly. That is, in addition to the wide band-shaped pattern due to the densely grown crystal starting from the crack boundary surface, with the deep pattern due to the large and randomly grown crystal in the part apart from the crack, A crystallized glass article was obtained that has a very beautiful natural stone-like appearance, as if it were mistaken for natural stone.

Further, the surface of the crystallized glass article was ground by about 0.5 mm to remove the altered layer on the surface, and the same properties as in Example-1 were examined. As a result, excellent physical properties of the original crystallized glass were shown.

In addition, with the simple cracking method, it was necessary to grind high hardness crystallized glass by about 1 to 3 mm in order to reveal a natural stone pattern, but according to this method, it is extremely thin 0 to 0.5 mm.
It suffices to grind a moderately deteriorated layer, and the polishing cost was greatly reduced.

〔The invention's effect〕

According to the present invention, crystals which are easy to handle before heat treatment, and which are very inexpensive, for example, are simply applied to the surface of the crystalline glass to form large, random, and crystals with a tasty pattern due to coarsely grown crystals. Frozen glass articles can be manufactured. Further, when a coating agent such as water glass is applied to a part of the surface of the crystalline glass, a pattern caused by the difference in crystal size, density, etc. between the surface coated with water glass and the surface not coated with water glass appears. Therefore, by applying water glass in advance in the form of letters, patterns, etc., it is possible to make the final crystallized glass article show the pattern as it is as designed. Furthermore, the components of the applied water glass remain only in the extremely thin surface-altered layer even after the heat treatment / crystallization, and for example, under the ordinary heat treatment conditions, the components of the water glass penetrate into the crystallized glass. Thus, the excellent physical properties inherent in crystallized glass are not impaired. Therefore, after the heat treatment / crystallization, the extremely thin degenerated layer on the surface is removed by a method such as polishing to combine the above-mentioned very tasty pattern or designed pattern with the excellent physical properties of crystallized glass. be able to.

As described above, the method of the present invention is epoch-making in that a very tasty and designable pattern can be exhibited on the crystallized glass by the extremely simple process without deteriorating the excellent physical properties of the original crystallized glass. However, its usefulness is extremely large.

[Brief description of drawings]

FIG. 1 (a) is a side view showing a state in which water glass is applied to the entire upper surface of crystalline glass before heat treatment, and FIG. 1 (b).
FIG. 3 is a cross-sectional view showing how crystals grow in a crystallized glass article after heat-treating crystalline glass. 2 (a) and 2 (b) are a side view and a plan view showing a state in which water glass is applied to a part of the surface of the crystalline glass before the heat treatment, and FIGS. 2 (c) and 2 (d) are crystalline. FIG. 3 is a cross-sectional view and a plan view showing how crystals grow in a crystallized glass article after heat-treating glass. 1 ... Water glass 2 ... Large, randomly and coarsely grown crystals 3 ... Crystals uniformly grown from the surface 4,6 ... Crystallized glass article 5 ... Crystalline glass article, 7 ... Altered layer

Claims (3)

[Claims] 1. A glass molded article forming step of forming a crystalline glass having a property of crystal precipitation / growth from the surface toward the inside upon heat treatment into a desired shape, and crystal precipitation from the surface of the crystalline glass. The glass formed by the glass molding product forming step with an application agent having the property of softening and fusion-bonding with the crystalline glass at a temperature lower than the starting temperature to lose the ability as the starting point of the crystal initiation of the crystalline glass surface. A crystallized glass article having a pattern characterized by comprising a coating step of coating on a desired portion of the surface of a molded article and a step of crystallizing the glass molded article coated with the coating agent by heat treatment thereafter. Production method. 2. A glass molded article molding step of molding a crystalline glass having a property of crystal precipitation / growth from the surface to the inside upon heat treatment into a desired shape, and the glass molded article molding step. A cracking step of applying a thermal shock to a glass molded article to crack it, and softening and fusion-bonding the crystalline glass and the crystalline glass at a temperature lower than the temperature at which crystals start to precipitate from the surface of the crystalline glass. An application step of applying a coating agent having a property of losing the ability as a starting point of crystallization to a desired site on the surface of a glass molded article cracked, and then heat treating the glass molded article coated with the coating agent. A method for producing a crystallized glass article having a pattern, which comprises a step of crystallizing. 3. The method for producing a crystallized glass article having a pattern according to claim 1, wherein the coating agent is water glass.