JPH02149440A - Production of crystallized glass article having pattern - Google Patents

Abstract

PURPOSE:To decorate a crystallized glass article with a pattern by a simple production process and to repeatedly impart the same pattern by combining a glass forming stage, a stage for coating the formed product, and a stage for crystallizing the formed product to cause a specified function. CONSTITUTION:Crystallizable glass, which deposits and grows crystals from the surface toward the inside when heat-treated, is formed into a desired shape in the glass article forming stage (A). The desired region of the surface of the article formed in the stage (A) is coated with a coating agent, which is softened and integrally fused to the crystallizable glass at a temp. lower than the temp. at which a crystal begins to deposit from the surface of the crystallizable glass and allows the crystallizable glass surface to lose a capacity as the starting point of crystallization, in the coating stage (B). The glass formed product coated with the coating agent is crystallized in the stage (C). The stages (A), (B), and (C) are combined to produce the desired glass article.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing crystallized glass parts suitable for architectural, decorative, etc. uses.

[Conventional technology]

One of the methods known so far for making a pattern appear on crystallized glass is typified by Japanese Patent Publication No. 37-18063, Japanese Patent Publication No. 4 [1-43238], and Japanese Patent Publication No. 57-175751. There is a method that mainly involves coloring, but this method only provides a superficial colored pattern;
The problem was that the design effect on the exterior was poor.

Therefore, there is a deep layer due to the orientation of the crystals and the mixture of the crystals and the matrix glass phase. Q? There is also a method that aims to obtain a very tasteful and beautiful pattern that has the appearance of a natural stone pillar, mainly using the 'A pattern.
Special Publication No. 53-191i07, Special Publication No. 55-29018
It is proposed by No.

However, in Japanese Patent Publication No. 53-19607, flat patterned crystallized glass can only be obtained by completely removing the unevenness on the surface of the crystallized glass product obtained by heat treatment, and a mirror-like flat plate can be obtained. The drawback is that the grinding and polishing process requires a lot of effort and time.

In the so-called sintering method, as typified by Japanese Patent Publication No. 55-29018, crystalline glass bodies colored in various colors are accumulated and then heat-treated to change the orientation of the crystals and the coexistence of crystals and matrix glass phases. Although it is possible to obtain a very beautiful crystallized glass that has a deep natural stone-like pattern as well as a colored design based on colored glass bodies, it is difficult to obtain the final crystal due to the voids between the accumulated crystalline glass bodies. Since it will always remain as pores in the converted glass product, the physical properties of the material will be impaired.

Therefore, the present applicant has proposed a method for producing a crystallized glass article that has the above-mentioned deep and aesthetically superior appearance, does not require complicated finishing processes, and has no internal pores. After various studies, in order to improve the above-mentioned design effect, it was found that during heat treatment for crystallization, an interface that serves as a starting point for crystallization and growth is formed in advance inside the glass article before crystallization, and on the other hand, pores are We focused on the fact that problems such as these could be avoided.

As one of such new manufacturing methods, the applicant has
A method of cracking a crystalline glass article before heat treatment (hereinafter referred to as "crystalline" before heat treatment and "crystallization" after heat treatment) and then heat treating it (Japanese Patent Laid-Open No. 61-20163
1) (hereinafter referred to as the "crack-filling method").

Furthermore, the applicant disperses crystalline glass pieces before heat treatment, heat-treated crystallized glass pieces, or amorphous glass pieces in a crystalline glass melt, and then molds the original crystalline glass. proposed a method for producing crystallized glass articles (Japanese Patent Application Laid-open No. 30630/1983), which is characterized by heat treatment and can easily be colored with any design.

[Problem to be solved by the invention]

However, creating patterns using the conventional cracking method has the drawback that the shape of the pattern that will appear cannot be predicted, making it difficult to repeatedly manufacture products with the same pattern, and creating deep patterns. In order to make it appear, it was necessary to grind the surface thickly.

Further, the method of dispersing the glass pieces requires a troublesome work of dispersing the glass pieces in consideration of the pattern in which they appear, and it is also necessary to grind the surface thickly at the end.

The purpose of the present invention is to make it possible to make a pattern appear on crystallized glass through a simple manufacturing process, to be able to repeatedly obtain the same pattern, and furthermore, to create an even deeper pattern by simply grinding the surface very thinly. An object of the present invention is to provide a method for manufacturing a patterned crystallized glass article that can make a certain pattern appear.

[Means to solve the problem]

The means for achieving the object of the present invention are as described in each claim, and the crystalline glass used in the present invention has a known composition described in the above publication. It goes without saying that the method of the present invention is not limited by the glass composition, and that crystalline glass colored with a known coloring agent may be used. stomach.

The method of the present invention will be explained in detail below. First, crystalline glass, which has the property of precipitating and growing needle-like, dendritic, etc. crystals from the surface to the inside, is melted by heat treatment, and conventional molding techniques such as the roll-out method, press method, and pouring method are used to melt the glass. It is formed into a plate or block shape. Next, water glass is applied to a part of the surface of the thus obtained plate-shaped or block-shaped glass molded product.

The water glass to be applied is JIS K1408 r.
Sodium silicate nNa2 (No. 1 specified in 1msi02 J).

No. 2, No. 3, and No. 4 are commercially available, and these may be applied as they are, or may be diluted with water as appropriate before application.

Regarding the dilution level, even in the case of No. 4, which has the lowest concentration among the above Nos. 1 to 4, it can be used after being diluted to about 20 times. Furthermore, crystals of sodium silicate having the same effect as water glass may be dissolved in water, or so-called potash water glass may be used. Application methods include direct molding with a brush and spraying.

Screen printing methods etc. are applied. The thickness of the applied filter water glass is preferably about 0.1 to 1 mm.

When the glass molded product whose surface is partially coated with water glass by the above method is transferred to a heat treatment furnace together with the refractory form and heated, the crystal orientation, density, and The resulting crystallized glass article has a pattern due to the difference in size, etc.

After that, an extremely thin surface-altered layer (a glass layer formed by the reaction between water glass and crystallized glass) that is considered to have poor physical properties such as chemical durability, and a cross section of the obtained crystallized glass article was subjected to EPMA: Electron Prob
e) When analyzed using an X-ray Micro Analyzer, this layer did not come off the surface, h)
It was found that it existed only in a 5 mm portion. ) by a method such as polishing, it is possible to have both the excellent physical properties that crystallized glass inherently has and the above-mentioned pattern.

The reason for the difference in crystal growth between the surface coated with water glass and the surface not coated with water glass as described above is presumed to be as follows.

Normally, when heat-treated crystalline glass has the property that crystals precipitate and grow from the surface to the inside,
Crystals grow vertically from the surface to the inside in a needle-like or dendritic shape. Therefore, the surface without water glass coating is
A uniform surface of crystallized glass is created. However, if water glass is applied to the crystalline glass surface in advance, the water glass will form at the contact interface between the crystalline glass and the crystalline glass at a temperature lower than the temperature at which crystals start to precipitate from the surface (approximately 800 to 1000°C). It is thought that it softens, fuses, and becomes a body. Furthermore, at this time, there is a high possibility that part of the Na2O component in the water glass in particular will diffuse into the surface layer of the crystalline glass, and eventually reach the surface of the crystalline glass (i.e., the interface between the water glass and the crystalline glass). It seems likely that the crystals will precipitate and grow and lose most of their ability as starting points for vine crystal initiation. Therefore, on the surface coated with water glass, as the temperature rises during heat treatment, large crystals and random (free This results in coarse precipitation and growth in the direction of

On the other hand, as mentioned earlier, on the water glass-uncoated surface, crystals precipitate and grow vertically and uniformly from the entire surface of the crystalline glass toward the inside. Patterns appear due to differences in orientation, density, size, etc.

Therefore, if water glass is applied in the shape of a picture or letter using a screen printing method, the designed pattern will appear due to the differences in orientation, density, size, etc. of the precipitated and grown crystals. do.

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

Furthermore, due to the application of water glass, areas where large, random, and coarse crystals have grown can be found within the crystallized glass (
The pattern will not disappear even if the extremely thin surface-altered layer is completely removed by polishing or other methods after heat treatment and crystallization. In other words, the components of water glass exist only in the extremely thin surface-altered layer on which it is applied, and have the effect of causing crystals to grow large, randomly, and coarsely. It does not penetrate into the crystallized glass and impair its original physical properties.

Also, if we pay attention to the above-mentioned principle, the temperature at which crystals start to precipitate from the surface of crystalline glass (approximately 800 to 100 m
Even if other materials are used that soften, fuse, and integrate with crystalline glass at temperatures lower than 0°C) and can cause the crystalline glass surface to lose its ability as a starting point for crystallization, the same effect as water glass is obtained. It can be seen that it has

That is, printed paints, low-temperature axes, low-melting point glass powders, etc. are examples, and although they have the same effect as water glass, water glass is the most preferable in terms of economy and handling.

Note that it is also possible to use a cracking method in which the crystalline glass is cracked by thermal shock or mechanical shock before applying the water glass. In this case, the crystalline glass surface coated with water glass loses most of its ability as a starting point for crystal precipitation due to the reasons mentioned above, but on the other hand, the cracks on the surface are caused by physical crystallization. Since it retains its ability as a starting point for precipitation, crystals preferentially grow larger from this crack. Therefore, a wide band-like pattern appears with the cracks on the surface as a skeleton, and a crystallized glass article having a very tasteful natural stone-like appearance is obtained.

[Embodiments of the invention]

Examples of the present invention will be described below.

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

Drawing 1 (b) shows the state of the cross section of crystallized glass article 4 obtained by heat treating and crystallizing crystalline glass article 5, and 2 shows the effect of the applied water glass.
Crystals 3, which have grown large, randomly, and coarsely, are crystals which have grown orderly and uniformly from the surface toward the inside, and 7 indicates an altered layer.

Drawing 2 (a) shows a state where water glass 1 is applied to a part of the surface of crystalline glass article 5, and the same <
(b) depicts (a) from above.

Drawing 2 (c) shows the state of the cross section of crystallized glass article 6 obtained by heat treating and crystallizing crystalline glass article 5, and 2 is large and random due to the effect of the applied water glass. 3 shows a crystal that grew coarsely, and 3 shows a crystal that grew orderly and uniformly from the surface to the inside. The same <(d) depicts the crystallized glass article 6 from above.

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

5i02: 48.5wt! k, Al2O3:
21.5wtk.

ZnO: 6.6wt96. K, O: 1.9w
T! k.

NazO: 4. Owt zero, MgO: 17. Ow
t zero.

AS20. : 0.5wt%;.

The obtained molten glass was poured into a metal mold, and
After forming into a plate shape of approximately x 300 x 20 mm, the product is slowly cooled to room temperature at a cooling rate that does not cause cracking to obtain a plate-shaped crystalline glass article.

Next, this glass molded product is transferred into a fire-resistant mold whose inner surface is coated with mold release agent powder, and the entire upper surface of the glass molded product is coated with water glass No. 1 specified in JIS K1408 for 10 minutes with water. Approximately 0.3++ by diluting it twice and spraying it.
Apply to a thickness of ++n.

Thereafter, the glass molded product coated with water glass was placed in a heat treatment furnace together with the refractory mold, and heated at 200°C to a temperature of 1050°C.
Heat treatment was carried out by increasing the temperature at a rate of 1,050° C. and holding it at 1,050° C. for 3 hours.

Due to heat treatment, the water glass applied to the surface is approximately 500 to 6
By the time it reaches 00℃, it softens, fuses, and integrates with the crystalline glass, and from the vicinity where the temperature exceeds 900℃, coarse needle-like crystals precipitate randomly near the fused surface of the water glass and crystalline glass. Begin to. When the heat treatment was further continued, a texture of large, randomly coarsely grown needle-like crystals as shown by reference numeral 2 in FIG. 1(b) was obtained. After the heat treatment, a deep and beautiful pattern was observed in the crystallized glass article, which was caused by the large, randomly and coarsely grown crystals. This pattern was created by cutting the water glass coated surface 7 times using a diamond grinder.
Even after grinding and removing it to about 8 mm, it did not disappear. On the other hand, from the side and back surfaces of the crystallized glass article, which are the surfaces to which water glass is not applied, needle-like crystals are orderly and uniform from the surface to the inside, as shown by reference numeral 3 in FIG. 1(b). It grew into a monotonous, ceramic-like appearance.

In addition, 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
When immersed in an O4 aqueous solution at room temperature for 24 hours, there was no change in appearance or pattern, proving that it had the excellent chemical resistance inherent to crystallized glass. Others, Vickers hardness 9
When the bending strength and other properties were also investigated, the measured values were almost the same as the physical property values originally possessed by crystallized glass.

In other words, the components of the water glass applied to the surface remain in an extremely thin surface-to-plane layer, and under normal heat treatment conditions, the excellent physical properties of crystallized glass are not impaired.

Example-2 A crystalline glass article molded in the same manner as in Example-1 was placed in a fire-resistant mold whose inner surface was coated with mold release agent powder, and a part of the upper surface of the glass molded article was coated with JIS. Figure 2 (a) is made by using a brush with water glass No. 3 specified in 1408.
It is applied to a thickness of about 1 mm in a circular shape as shown by reference numeral 1 in (b).

When this was heat treated in the same manner as in Example-1, it was shown in Figure 2 (C
), at the bottom of the water glass coated area, large and random coarse crystals precipitate and grow up to about half the thickness of the crystallized glass article, and as shown in code 2 in Figure 2(d), On the other hand, in the lower part of the area where water glass was not applied, needle-shaped crystals were arranged in an orderly manner from the surface to the inside, as shown in the symbol 3 of 2nd [g (C)]. It grew uniformly and exhibited an IL-like II porcelain-like appearance as shown by reference numeral 3 in FIG. 2(d). That is,
The crystal growth direction in the water glass coated area and the water glass non-coated area is 1w degree.

Due to the difference in size, etc., a crystallized glass article with a circular pattern as shown in FIG. 2(d) was obtained.

Furthermore, by applying water glass to the surface of the crystalline glass article in the form of pre-designed letters or complicated patterns using a screen printing method, etc., as shown in Figure 2 (tl), the water glass coated area is Due to the difference in the growth direction, density, size, etc. of the crystals in the area to which water glass was not applied, it was possible to obtain a crystallized glass article having a deep and beautiful pattern as designed.

Note that the surface of the crystallized glass article after heat treatment is 0.5+nm
The deteriorated layer on the surface was removed by grinding to a certain extent, and the physical properties as shown in Example 1 were examined, and as a result, it showed excellent physical property values that original crystallized glass has.

Example-3 Silica powder, aluminum hydroxide, zinc oxide, potassium carbonate, potassium nitrate, sodium carbonate.

Using sodium nitrate, magnesium oxide, magnesium hydroxide, and cerium oxide as raw materials, a glass batch is prepared so as to satisfy the following glass composition, and this is placed in a crucible and melted at a temperature of 1450° C. for about 6 hours in an electric furnace.

5in2: 57.5wtX, A4203: 12
．． 1wt96°ZnO: 8.4Wt96. 20 to 20
: 1.2wt96°NazO: 7. Owt zero, MgO: 13.3wHCe02: 0.5w
T! k.

The obtained molten glass is poured into a metal mold, and 30
Form into a plate shape of approximately 0x 300x 20+ nm.

After holding this glass molded product at 650°C for 30 minutes in a slow cooling furnace, the temperature was lowered to 300°C at a rate of 1°C/min.
Immediately transfer the glass molded product into a fire-resistant mold whose inner surface is coated with mold release agent powder, apply water to the entire glass molded product, and apply a thermal shock.
Put a crack in it.

Next, dry the cracked glass molded product together with the fireproof formwork.
On the entire upper surface, filter water glass No. 2 specified in JIS K1408 is applied to a thickness of about 0.5+nm using a brush.

Thereafter, the cracked glass molded product coated with water glass was placed in a heat treatment furnace together with the refractory formwork, heated at a rate of 200°C/hr to a temperature of 1050°C, and kept at 1050°C for 3 hours for heat treatment. I did it.

Due to heat treatment, the water glass applied to the surface is approximately 500 to 6
By the time it reaches 00°C, it softens, fuses, and integrates with the crystalline glass, and then, when the temperature exceeds 800°C, cracks inside the glass molded product start to fuse as the glass softens.

In parallel with fusion, needle-shaped crystals begin to grow in a dense radial pattern from the surface of the cracked glass molded product and from the crack interface existing inside the molded product from around 900°C.
When the heat treatment was continued, the crystal structure formed into a structure with each crack on the surface as a skeleton, resembling the ears of a clover or the tip of a brush used to wash test tubes. When this was observed from the top surface side, it exhibited a wide band-like pattern centered around the cracks on the surface. On the other hand, in the area away from the crack, a deep and beautiful pattern was observed near the fused surface of water glass and crystalline glass, which was caused by large, randomly grown crystals. In other words, in addition to the wide band-like pattern caused by crystals that have grown densely starting from the crack interface, there is also a deep pattern caused by large, random, coarsely grown crystals in areas away from the crack. A crystallized glass article having an extremely beautiful natural stone-like appearance that could be mistaken for natural stone was obtained.

In addition, 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 characteristics as in Example 1 were investigated, and the results showed that the excellent physical properties of the original crystallized glass were found. .

Furthermore, with the Hayabusa Naru cracking method, it was necessary to grind the highly hard crystallized glass to about 1 to 3 mm in order to create a natural stone-like pattern, but with this method, it is possible to grind extremely thin 0 to 0.0 mm.
It is only necessary to grind about 5 mm of the surface deterioration layer, and the polishing cost is significantly reduced.

(Effects of the Invention) According to the present invention, by simply applying water glass, which is easy to handle and very inexpensive, for example, to the surface of crystalline glass before heat treatment, it is possible to remove large, random, and coarsely grown crystals. It is possible to produce a crystallized glass article having a tasteful pattern. In addition, when a coating agent such as water glass is applied to a part of the surface of crystalline glass, a pattern appears due to the difference in crystal size, density, etc. between the surface coated with water glass and the surface not coated with water glass. Therefore, by applying water glass in the form of letters, pictures, etc. in advance, it is possible to make the final crystallized glass article appear in the same pattern as the design. Furthermore, even after heat treatment and crystallization, the applied water glass components remain only in an extremely thin surface altered layer; for example, under normal heat treatment conditions, the water glass components penetrate deep into the crystallized glass. Therefore, the excellent physical properties of crystallized glass are not impaired. Therefore, by removing the extremely thin altered layer on the surface by polishing or other methods after heat treatment and crystallization, it is possible to combine the very tasteful or designed patterns mentioned above with the excellent physical properties of crystallized glass. can be set.

In this way, the method of the present invention is revolutionary in that it is possible to create a tasteful and designable pattern on crystallized glass through an extremely simple process without impairing the excellent physical properties of crystallized glass. It is extremely useful.

[Brief explanation of the drawing]

Figure 1(a) is a side view showing water glass applied to the entire upper surface of the crystalline glass before heat treatment, and Figure 1(b)
1 is a cross-sectional view showing how crystals grow in a crystallized glass article after heat-treating the crystallized glass. Figures 2 (a) and (b) are a side view and a plan view showing water glass applied to a part of the crystalline glass surface before heat treatment, and Figures 2 (c) and (d) are crystalline glass. FIG. 2 is a cross-sectional view and a plan view showing how crystals grow in a crystallized glass article after heat-treating the glass. 1...Water glass 2...Large, randomly, coarsely grown crystals 3...
・Crystals grown uniformly from the surface 4.6... Crystallized glass article 5... Crystalline glass article 7... Altered layer and 4 others

Claims (1)

[Claims] 1. When heat treated, crystals precipitate from the surface toward the inside.
A glass molding process in which crystalline glass, which has the property of growing, is formed into a desired shape, and the crystalline glass is softened and fused together at a temperature lower than the temperature at which crystals start to precipitate from the surface of the crystalline glass. A coating step of applying a coating agent having a property of causing the crystalline glass surface to lose its ability as a starting point for crystallization to a desired portion of the surface of the glass molded product formed by the glass molded product molding step, and then by heat treatment. A method for manufacturing a crystallized glass article having a pattern, comprising the step of crystallizing the glass molded article coated with the coating agent. 2 When heat treated, crystals precipitate from the surface to the inside.
a glass molded product forming step in which crystalline glass having the property of growing is molded into a desired shape; a cracking step in which the glass molded product obtained in the glass molded product forming step is subjected to a thermal shock and cracked; A coating agent having the property of softening and melting and integrating with the crystalline glass at a temperature lower than the temperature at which crystals begin to precipitate from the surface of the crystalline glass and causing the surface of the crystalline glass to lose its ability as a starting point for crystallization is cracked. A patterned crystal comprising a coating step of applying the coating agent to a desired part of the surface of the glass molded article, and a subsequent step of crystallizing the glass molded article coated with the coating agent by heat treatment. Method for manufacturing a chemically converted glass article. 3. The method for manufacturing a patterned crystallized glass article according to claim 1 or 2, wherein the coating agent is water glass.