JPH06135740A - Color patterned crystallized glass article and production thereof - Google Patents

Abstract

PURPOSE:To provide an article having a high added value by reutilizing a glass such as used bottle glass or plate glass. CONSTITUTION:A color patterned crystallized glass article is obtained by filling >=2 kinds of glass coarse grain and/or powder, which have + or -10X10<-7>/ deg.C difference in thermal expansion coefficient and are different in color from each other, into a molding flask with partitioning so as to form a prescribed color pattern, heating to fire in accordance with a prescribed schedule, cooling to a temp. of slow cooling point in accordance with a prescribed schedule to form devitlite and crystobalite crystal and after that, slowly cooling.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a crystallized glass article having a color pattern and a method for producing the same.

[0002]

[Background Art] As for glass bottles, the usage rate of glass scraps (cullet) required for bottle production has increased and the use of returnable bottles has expanded, as stated in the guidelines in "Countermeasures for Waste Management and Recycling" promoted by the Industrial Structure Council. The recycling rate is not sufficient due to the large amount of emissions and the scattered ones, etc., but is it generally discharged as garbage? , Or even if it is collected, it is not used and is piled up as glass scraps (cullet), and bottle glass discharged as such dust and glass scraps (cullet) piled up not used are effectively reused. There is an urgent need to develop ways to do it. Further, like glass bottles, plate glass has a low recycling rate, and it has been desired to develop a method for effectively recycling this.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a product with high added value by reusing used glass such as bottle glass and plate glass.

[0004]

[Means for Achieving the Object] In order to achieve the above object, the present inventor has made various studies on bottle glass, and has obtained the following findings.

(I) According to the color tone standard value of the Japan Bottle Glass Association, there are more than a dozen types of bottle glass, but the thermal expansion coefficient of those glass types (glass types) is 86-9.
^Within the range of 4 × 10 ⁻⁷ / ° C., coefficient of thermal expansion: 90 × 10
^-7 / ° C. to to ± 4 × 10 ^-7 / lying within ° C. centered.

(Ii) Therefore, even if the glass bottles of different kinds are mixed and fired, the glass bottles are not broken by strain after firing and cooling due to the difference in thermal expansion coefficient between the respective glasses.

(Iii) In addition, the bottle glass has a liquidus temperature in the range of 1020 to 1070 ° C. at which crystallization of the glass begins, and each glass has a temperature between the liquidus temperature and the slow cooling point temperature for a certain period of time. When retained, crystals (devitrite and cristobalite crystals) are deposited in the glass to devitrify and become opaque.

(Iv) Further, each bottle glass has a unique color tone, but the color tone is changed by mixing an appropriate amount of another glass coloring material (color glass frit, cloisonne, mineral pigment, metal oxide, etc.). Be able to.

(V) However, when glass containing metal particles such as carbon, charcoal, Pb, Fe and Cu, such as tea bottle glass, is used as a colorant, it may be discolored due to its reducing power.

Although the above findings (i) to (v) are about the bottle glass, the present inventor has obtained the similar findings about the plate glass.

Based on the above findings, the present invention was conceived to regenerate a bottle glass or plate glass into a glass article with a color pattern, and as a result of further studies, the difference in coefficient of thermal expansion was ± 10 ×.
Within the range of 10 ⁻⁷ / ° C., two or more kinds of glass coarse particles and / or powders having different colors are divided into a predetermined color pattern, filled in a mold, and heated according to a predetermined schedule. After firing, the devitrite and cristobalite crystals are produced by lowering the temperature to the slow cooling point temperature according to a predetermined schedule, and then slowly cooling to obtain a predetermined color defined by crystallized glass of different colors. It has been found that a crystallized glass article having a pattern, and the crystallized glass in each section having a color shade of the same color resulting from the grain size of the glass coarse particles and / or powder used, can be obtained. Was completed.

Therefore, according to the present invention, the difference in coefficient of thermal expansion is ± 10 ×.
Precipitated crystals are devitrite and cristobalite, which are obtained by filling two or more kinds of glass coarse particles and / or powders having different colors in the range of 10 ⁻⁷ / ° C. and different colors, and then heating and firing the crystals. A crystallized glass article, wherein the crystallized glass article has a predetermined color pattern defined by being designed by crystallized glass of different colors, and the crystallized glass in each section is composed of the glass coarse particles and And / or a crystallized glass article with a color pattern, which is characterized by having the same color tone due to powder.

In the present invention, the difference in coefficient of thermal expansion is ± 10 × 1.
It is in the range of 0 ^-7 / ° C, and two or more kinds of glass coarse particles and / or powders having different colors are divided into a predetermined color pattern and filled in a mold, and heated according to a predetermined schedule. After firing, the devitrite and cristobalite crystals are produced by lowering the temperature to a slow cooling point temperature according to a predetermined schedule, and then slowly cooling, which is a method for producing a crystallized glass article with a color pattern as above. It is also something to do.

The present invention will be described in detail below. In the present invention, two or more kinds of glass coarse particles and / or powders having a difference in coefficient of thermal expansion of ± 10 × 10 ⁻⁷ / ° C. and different colors are used as the starting material. Such glass coarse particles and / or powders can be collected by separating the collected various bottle glasses and / or plate glasses by color and then washing to remove surface deposits and drying, and then mechanically using a hammer or a crusher. Although it can be obtained by crushing into water, a method of heating to a temperature of 400 to 500 ° C. or higher by means of a heating furnace or the like and then pouring into water to thermally crush may be employed. The particle size of coarse glass particles after crushing is 0.
It is generally set to 5 to 10 mm, but depending on the product specifications, the particle size may be larger than this. The particle diameter of the glass powder is generally 0.1 to 0.5 mm, but it may be smaller than this depending on the specifications of the product.

The crushed glass coarse particles and / or powders are
After drying, remove iron as necessary. This is because the iron content present in the glass coarse particles and / or powder and the iron content mixed during the crushing become black after heating and firing and crystallization, which is not preferable because a black spot is obtained when a white or light color product is obtained. . However, when obtaining a product with a dark color tone, the black stains are hidden and inconspicuous, so iron removal is not necessary.

The glass coarse particles thus obtained and /
Alternatively, the powder is sieved and sorted according to a predetermined particle size range.

Whether to use only glass coarse particles or powders or both glass coarse particles and powders as a starting material is appropriately selected depending on the kind and appearance of the product to be obtained. That is, when coarse glass particles are used, crystallization (devitrification) described later remains only on the surface portion, and a relatively transparent (translucent) product tinged with the color of the glass used is obtained. . On the other hand, when glass powder is used, crystallization (devitrification) occurs even in the inside thereof, and an opaque (non-translucent) product tinged with the color of the glass used is obtained. Furthermore, when both glass coarse particles and powder are used, transparent (translucent) portions and opaque (non-translucent) portions having similar color shades of the used glass are scattered, A product is obtained which has a texture similar to that of natural stone. The light transmittance of the obtained product can also be adjusted by appropriately controlling the crystallization temperature and time after heating and baking the glass,
Even when glass coarse particles are used, the crystallization temperature is 800 to 10
By setting the temperature to 00 ° C. and setting the crystallization time to a relatively long time, an opaque (non-translucent) product can be obtained.

In the present invention, it is essential to use two or more kinds of the above glass coarse particles and / or powders. However, when two or more kinds of glass coarse particles are used, two or more kinds of glass are used. It is meant to include both the case of using a powder and the case of using one or more types of glass coarse particles and one or more types of glass powder.

Further, two or more kinds of glass coarse particles and / or powders have a difference in coefficient of thermal expansion within a range of ± 10 × 10 ⁻⁷ / ° C.,
Also, it is an essential requirement that the colors are different. The difference in the coefficient of thermal expansion is set within the range of ± 10 × 10 ^-7 / ° C.
This is because, even in the case of containing fine glass powder, if it is within this range, cracking or breakage due to strain does not occur during cooling after heating and firing. Particularly preferred difference in thermal expansion coefficient is ± 5
It is within × 10 ^-7 / ° C. The reason why different colors of glass are used is that it is possible to form a designed predetermined color pattern by partitioning by different colors of glass, and the decorativeness of the product is improved.

The glass coarse particles and / or powders used are
Those obtained from bottle glass and / or sheet glass are preferable, but if the conditions that the difference in thermal expansion coefficient is within the range of ± 10 × 10 ⁻⁷ / ° C. and the color is different are satisfied, the bottle glass and / or sheet glass are Not limited, S
iO ₂ as a main component, Al ₂ O ₃ , CaO, MgO, N
a ₂ O, K ₂ O, Fe ₂ O ₃ , TiO ₂ , MnO ₂ , C
r ₂ O ₃ , NiO, CuO, CoO, Se, Nd
Any glass containing at least one selected from ₂ O ₃ , CeO ₂ , F and SO ₃ can be used.

The color tone of the coarse glass particles and / or powder used is colorless (white), amber, emerald green,
It is preferable that at least two kinds selected from black, Georgia green, light amber, blue, smoke (smoke color), pink, amethyst, yellow and opal are used, but colored glass frit, mineral pigment, cloisonne frit, gold dust or gold leaf. By adding mica, the color tone can be changed appropriately.

In the present invention, a mold is filled with two or more kinds of glass coarse particles and / or powders described above. It is preferable that the mold has an outer shape corresponding to the intended product and a depth that is at least twice the thickness of the product. Further, the material of the mold is one that can withstand heating and holding for a predetermined time at the crystallization temperature and can release the product as it is after cooling or through a mold release agent applied to the inner surface of the mold. Any type of special steel material, carbon material, refractory gypsum, and diatomaceous earth refractory material can be used, for example, when the product has a simple shape such as tile, brick, or paving stone. Further, when a product having a complicated shape such as an art product or a decorative product is obtained, it is preferable to use a fire-resistant gypsum because it is difficult to mold the special steel material and the carbon material and the cost becomes high. Since the mold made of refractory gypsum is fragile after cooling, it has an advantage that it can be easily collapsed to take out the product, and that it can be taken out more easily by putting it in water. When it is desired to give a desired unevenness pattern to a target product, an embossed pattern having a corresponding shape can be provided on the inner surface of the mold.

For filling two or more kinds of glass into the mold, a partition plate is provided in the mold so as to have a shape corresponding to the pattern desired to be given to the product, and a plurality of partitions formed by the partition plates. By pouring glass coarse particles and / or powder of different colors into each of the above. In this case, for example, one section may be filled with glass coarse particles or powder, the other section may be filled with glass coarse particles or powder, or one section may be filled with a mixture of glass coarse particles and powder and the other section. May be filled with glass coarse particles or powder. Furthermore, both the one compartment and the other compartment may be filled with a mixture of glass grit and powder. In this way, the form of the glass filled in each section can take various variations.

As the material of the partition plate, a paper (for example, a postcard) having a certain degree of elasticity, a plastic plate, a metal plate, etc. are used, and these partition plates are pulled out after glass filling and before heating and firing. In order to facilitate the withdrawal,
A lubricant may be applied to the surface of the partition plate. However, when the partition plate is formed of a material that melts and volatilizes during glass heating and baking (for example, wax), it is not necessary to pull out the glass before heating and baking glass. Wax also has an advantage that it can form a partition plate having a complicated shape.

As the color tone of the glass filled in the compartment formed by the partition plate is considerably different from the color itself of the bottle glass and the sheet glass as described above, various color tones can be used, but more abundant. If you want a different color tone, mix colored glass frit other than plate glass, plate glass, rock paint, cloisonne frit, gold powder or gold foil, mica, etc., and color (colorless bottle glass coarse particles, powder)
Color correction (for colored bottle glass coarse particles or powder) can also be performed. Even in the case of obtaining a three-dimensional object having a complicated shape, it is possible to obtain a product with adjusted coloring by providing a partition plate and filling glass.

In the present invention, coarse glass particles of different colors and / or different colors are provided in a plurality of sections formed in the mold by the partition plate.
Alternatively, after the powder is filled as described above, the glass coarse particles and / or powder are fired and integrated by heat treatment according to a predetermined schedule. The temperature-time schedule of this heat treatment is appropriately selected in consideration of the degree of firing of the target product and the degree of crystallization (devitrification) after firing,
It is desirable to set the temperature at 1000 ° C. for 30 minutes or more. In order to obtain a soft-textured surface appearance, it is better to bake so as to leave traces of coarse particles, and the temperature in that case may be around 850 ° C. High-temperature firing at 880 to 950 ° C. is good for sufficiently smoothing and grinding and polishing the surface to finish it like a natural stone. The holding time at the maximum firing temperature is controlled by the amount of coarse glass particles, the amount of powder and the product thickness. When it is desired to retain the transparency of the glass, it is better to use coarse particles and bake and cool in a short time. Further, the fired product may be subjected to hot decoration (for example, raster decoration) in the cooling step.

In the present invention, after the glass coarse particles and / or powder are heated and calcined, the temperature is lowered to the annealing point temperature according to a predetermined schedule to generate devitrite and cristobalite crystals. The slow cooling point temperature is the upper limit temperature of the slow cooling temperature range, and this temperature lowering treatment in the present invention is performed on a schedule such that the heating and firing temperature is lowered to the slow cooling point temperature over 1 hour or more. Preferably. In the case of the present invention, the temperature reduction treatment causes the above-mentioned crystals to precipitate in at least one of the two or more kinds of glasses to make them devitrified and opaque. Then, by gradually cooling in the same heating / melting furnace or another furnace set to the annealing point temperature in advance, it has a predetermined color pattern designed and designed by crystallized glass of different colors, The crystallized glass gives a crystallized glass article with a color pattern having a similar shade due to the glass coarse particles and / or powder used. The crystallized glass article after gradual cooling may be subjected to finish processing as necessary to give a smooth surface.

The material glass used in the production of the colored patterned crystallized glass article of the present invention is not limited to bottle glass and plate glass, and glass prepared therefor may be used. The crystallized glass article with a color pattern obtained by the present invention is not limited to this, but can be used for various applications such as tiles, paving stones, panel materials, interior and exterior building members, works of art, and ornaments. You can

[0029]

EXAMPLES The present invention will be further described below with reference to examples.

Example 1 A production example of a glass tile product with a pattern will be described in detail as one of the examples of the present invention. As shown in FIG. 1, when manufacturing a glass tile product 3 having a pattern 2 of a green color ginkgo (a symbol mark of Tokyo) on a white background 1, first, as shown in FIG. The combined formwork 4 is manufactured. In the case of this example, heat-resistant gypsum was used as the mold material, but in the case of a simple shape such as the tile in this example, isolite brick or carbon material, special steel was processed with a draft angle. It may be one. In order to make the depth of the formwork 4 twice as large as that of the tile product to be obtained, a clay or wood having a thickness twice the thickness of the tile and having the outer dimensions (vertical × horizontal) of the product. A plate is prepared, and gypsum slurry of appropriate viscosity which has been melted with water is coated on the plate to an appropriate thickness (7 mm or more). After the plaster is sufficiently solidified, a clay or wooden board is pulled out and sufficiently dried to obtain the mold 4.

On the other hand, a bottle glass having a required color tone is selected. For example, in the case of the white glass portion 1, glass bottles that are colorless and transparent are crushed to form glass particles that match the texture of the desired product. The size of the glass particles is selected by considering whether the texture (texture) of the dough should be a fine and flat surface or rough skin. If you use powder with a particle size of 0.1-0.5 mm,
It becomes a glass with a fine texture, and when using coarse particles of 0.5 to 10 mm, it gives a rough texture. When fine particles (powder) and coarse particles (coarse particles) are mixed, a pattern in which coarse and fine particles are mixed is obtained (in the case of colored glass, this pattern remarkably appears). The surface of the sintered glass that is in contact with the mold surface (the surface inside the mold) transfers the shape of the mold surface during sintering, so by applying the necessary pattern to the mold surface, the surface of the product that touches the mold surface is desired. Pattern can be added. Further, the texture of the free surface of the product that does not touch the mold surface can be changed depending on the size of glass particles and the degree of sintering (temperature and time). The powder produces a smooth surface and the coarse particles produce a rough surface.

In order to put the pattern 2 in the tile product 3, a partition plate 5 is formed by folding the outline shape with a postcard, and set in the mold 4. The partition plate 5 is a material that can be easily bent and worked and does not lose its shape.

Next, predetermined green (emerald green) glass particles 6 (coefficient of thermal expansion 89 to 92) are placed inside the partition plate 5.
× 10 ⁻⁷ / ° C., particle size 0.1 to 3 mm) and colorless (flint) glass particles 7 (coefficient of thermal expansion 86 to 88 × 10 ⁻⁷ / ° C., particle size 1 to 5 mm) on the outside of the partition plate 5. ) Is filled. The difference in thermal expansion coefficient between the former glass and the latter glass is 6
× 10 ⁻⁷ / ° C. In order to avoid the bending of the partition plate 5, it is preferable to fill the inside and outside of the partition plate with glass at the same level as much as possible. The filling amount of glass is determined in consideration of volume shrinkage due to sintering. The thickness shrinks by about 30% depending on the particle size of glass, the sintering temperature, and the time. The shrinkage in the width direction is extremely small and is only a few percent. After filling the mold 4 with a predetermined amount of glass, the partition plate 5 is gently pulled out. The mold 4 filled with glass is set in the baking furnace and the baking is started. The heating up to the maximum firing temperature is achieved by heating the mold to such an extent that it is not damaged by a sudden thermal shock. In the case of the present embodiment, a temperature gradient from room temperature to 850 with a temperature gradient of about 3 ° C./min.
The temperature was raised to ° C and the temperature was maintained for 1 hour. When kept for 30 minutes or more, the coarse particles and powder of the filled glass are sintered and solidified and integrated. When firing without applying a weight in the mold, the lower surface on which the weight of the glass is applied becomes denser.
In order to uniformly and densely sinter the whole, pressure may be applied from above during firing according to the mold material. After the completion of sintering, the temperature was lowered to the slow cooling point temperature (about 570 ° C.) over 5 hours. At this time, the holding time at the sintering temperature is short, and if the temperature is rapidly lowered to the annealing point temperature, crystallization does not occur. The sintered glass was devitrified (crystallized) to generate devitrite and cristobalite crystals, which became cloudy. The sintered glass was kept at 570 ° C. for 3 hours and then gradually cooled to 450 ° C. over 4 hours.
Slow cooling was performed with the sintered glass kept in the mold, but 570 ° C.
The temperature may be lowered back and forth, taken out from the mold, and put in an annealing furnace. The molded product that has been slowly cooled and released is then subjected to grinding / polishing and surface decoration (for example, raster decoration) to finish the tile product 3 according to the requirements of the intended product. The obtained tile product 3 has a soft surface peculiar to crystallized glass on the fired surface that takes advantage of the texture of the mold, and the ground and polished surface is a hard and refreshing surface with the surface gloss of glass and the texture of natural stone. Become. It is possible to obtain tile products with various color tones and patterns different from conventional tile products as floor tiles and decorative tiles, respectively.
Depending on the design, it can also be used as a wall picture tile.

Example 2 This example shows an example of manufacturing exterior and interior products having a relatively complicated pattern. It has a picture of a tree having plum petals 11, buds 12 and a trunk 13 as shown in FIG.
When manufacturing the panel board 16 housed in, first of all, the size corresponding to the outer dimensions of the target product (vertical x horizontal) and the height corresponding to the target product thickness (glass amount) are set. Produce a mold that has. This formwork has a pattern of petals, buds, and a texture of the trunk formed at predetermined positions on the formwork, assuming that the part in contact with the formwork (inner surface of the formwork) is the surface of the product. .

Next, partition plates (those preliminarily dipped in a wax solution to make them water repellent) bent to the contours of petals, buds and trunks were assembled and set so as to correspond to the predetermined positions. Thereafter, the petals, buds, and trunks were filled with glass having a difference in thermal expansion coefficient of a predetermined color and amount within 10 × 10 ⁻⁷ / ° C. The glass filled in the petals has a coefficient of thermal expansion of 86-8.
8 × 10 ⁻⁷ / ° C., particle size 0.1 to 2 mm, color tone is colorless (white), the glass filled in the bud has a thermal expansion coefficient of 86 to 88 × 10 ⁻⁷ / ° C., particles Diameter 0.1-2
mm, the color tone is pink, and the glass filled in the trunk portion has a coefficient of thermal expansion of 92 to 94 × 10 ⁻⁷ / ° C. and a particle size of 1 to
The color tone was 5 mm and the color tone was black. The pink glass is
It is a glass obtained by mixing colorless flint glass powder with gold-red glass frit.

On the other hand, the portion of the mold corresponding to the void 14 in FIG. 3 was not filled with glass, but the heat-resistant gypsum mud that had been thawed was poured and solidified until the required amount (height) was reached. When the heat-resistant gypsum solidified, the partition plate in contact with it was lightly peeled off the plaster skin using a thin spatula, and all the partition plates were gently pulled out.

After that, the mold filled with glass was heated to 880 ° C. at a temperature gradient of 3 ° C./min and kept at that temperature for 2 hours, after which the glass was baked, solidified and integrated. Next, the temperature was lowered to the slow cooling point temperature (570 ° C.) over 3 hours to devitrify (crystallize) to generate the tevitrite and cristobalite crystals. After gradually cooling to 450 ° C. for 6 hours, the mold and the gypsum in the voids are removed to release the mold, and as shown in FIG. 3, a tree having petals 11, buds 12 and trunks 13 is removed. A panel plate 15 having a pattern and having voids 14 was obtained. The panel plate 15 can be further processed and decorated as desired.

Before the slow cooling of the baked glass, it is necessary to take out the glass from the mold and cool only the glass.
In the case of a metal material or a part of refractory material, the portion of the void 14 needs to be a protrusion having a slope. If the mold material is heat-resistant gypsum, it can be released from the mold after firing and slow cooling.
No need for that. Therefore, the unevenness (cutting) of the void is possible to the extent that the see-through effect can be obtained. By applying the lost wax method and making a notch, it is possible to express the plum petals as if white and crimson overlap.

The obtained panel plate 15 can be used as a product such as a stained glass member, a panel for a balustrade, an interior member, or the like, or by utilizing the translucency of crystallized glass, as a light source and various illumination members.

[0040]

As described above, according to the present invention, it is possible to provide a crystallized glass article with a high value-added color pattern using glass, particularly bottle glass or plate glass which is industrial waste.

[Brief description of drawings]

FIG. 1 is a perspective view showing a product obtained in Example 1.

FIG. 2 is a perspective view showing a state where coarse glass particles and / or powder are filled in the mold in Example 1.

FIG. 3 is a perspective view showing a product obtained in Example 3.

[Explanation of symbols]

 1 White background 2 Design 3 Glass tile product 4 Formwork 5 Partition plate 6 Green glass particle 7 Colorless glass particle 11 Plum petal pattern 12 Bud pattern 13 Trunk texture 14 Void 15 Frame 16 Glass panel product

Claims (5)

[Claims] 1. After filling a mold with two or more kinds of glass coarse particles and / or powders having a difference in thermal expansion coefficient of ± 10 × 10 ⁻⁷ / ° C. and different colors, heating and baking, A crystallized glass article which is crystallized and whose precipitated crystals are devitrite and cristobalite, wherein the crystallized glass article has a predetermined color pattern defined by crystallized glass of different colors, A patterned crystallized glass article, characterized in that the crystallized glass in the compartment has a shade of the same color due to the glass coarse particles and / or powder used. 2. Two or more types of glass coarse particles and / or powders having a difference in coefficient of thermal expansion within a range of ± 10 × 10 ⁻⁷ / ° C. and different colors are divided into a predetermined color pattern. The method is characterized in that after filling into a mold and heating and firing according to a predetermined schedule, the devitrite and cristobalite crystals are produced by lowering the temperature to a slow cooling point temperature according to a predetermined schedule, and then slowly cooling. 1. The method for producing a crystallized glass article with a color pattern according to 1. 3. The method according to claim 2, wherein the glass coarse particles and / or powders are obtained from bottle glass and / or flat glass. 4. Two or more kinds of glass coarse particles having different colors and //
Alternatively, the color tone of the powder is two or more kinds selected from colorless (white), amber, emerald green, black, Georgia green, light amber, blue, smoke (smoked color), pink, amethyst, yellow and opal. The method described in 2. 5. Coarse glass particles and / or powders are SiO ₂
Al ₂ O ₃ , CaO, MgO, Na
₂ O, K ₂ O, Fe ₂ O ₃ , TiO ₂ , MnO ₂ , Cr
₂ O ₃ , NiO, CuO, CoO, Se, Nd ₂ O ₃ ,
The method according to claim 2, which comprises a glass containing at least one selected from CeO ₂ , F and SO ₃ .