WO2006035553A1 - Spherical capsule having outer coating layer and containing glazing material for forming glaze and coloring agent for coloring calcined glaze encapsulated therein - Google Patents

Abstract

It is intended to provide a spherical capsule having a seamless coating layer that is a spherical capsule comprising an inner layer constituting the core of the capsule and a seamless coating layer covering the inner layer, or a multilayered spherical capsule of a composite structure comprising an innermost layer constituting the core of the capsule, an intermediate layer formed, if desired, on the innermost layer and an outermost seamless coating layer made of a film-forming material, wherein an inorganic coloring agent employed in decorating ceramics is contained in at least one of the core material constituting the inner layer or the innermost layer, the material constituting the intermediate layer and the film-forming material constituting the coating layer and, moreover, a glazing material for forming the basic glaze is contained, either separately or together with the coloring agent for coloring the glaze, in the core material of the core, the material constituting the intermediate layer and/or the material constituting the coating layer. It is also intended to provide a method for producing ceramics having a pointillist-type decoration pattern by using the spherical capsule and a decoration method of forming a decoration pattern on the surface of heat-tolerant substrates including ceramics.

Description

 Specification

A spherical force psel having an outer coating layer and encapsulating a glaze raw material for producing soot and a colorant capable of coloring the fired soot and use thereof

Technical field

 The present invention has the application to create colored decorative patterns when fired on the surface of ceramic and other heat-resistant substrates and also produces more seamless seam coating layers. The present invention relates to a new product that is a spherical capsule with a two-layer or multi-layer structure containing a glaze raw material for use and a colorant capable of coloring the glaze upon firing. The present invention also includes a method for producing a ceramic having a colored decorative pattern by using such a spherical capsule, and a decorative method for creating a decorative pattern on the surface of a heat-resistant substrate including the ceramic.

Background art

 In making ceramics, it is well known to apply glaze, which is a glassy thin film layer that covers the surface of ceramics.

 Acupuncture is said to be a glaze in the field of ceramics in Japan. The glaze usually means a glaze coating fused to the surface of the ceramic, but glaze or glaze is a glaze-producing raw material that can be used to produce the glaze during firing. "Encyclopedia of Pottery and Porcelain J, 1800-1960, pp. 140-141, Sir Cameron, Facts On File Publications"; and Masanori Onishi "Ceramics glaze" New Edition, 2003 Page 10-10, 3rd edition, Science and Engineering).

A wide variety of moths The power of colorless and transparent base glazing (base glaze) includes limestone glaze, sodium: ¾ stone aze (sodium feldspathic glaze), potassium feldspar glazing (potassium feldspathic glaze) Ash glaze is known (rThe Japanese Pottery Handbook), p. 68, P.Simpson et al .; Kodansha International Inc., published in May 1979 “Industrial Encyclopedia” Vol. 17, pp. 470-473, Heibonsha, May 1962). Colored wrinkles made by blending inorganic colorants with colorless basic wrinkles are well known. Examples of inorganic colorants incorporated in such colored cocoons include various metal substances or It is well known that various metal compounds can be used (the above-mentioned “Ceramics glaze” written by Onishi, and the “Industrial Encyclopedia” Vol. 3, pp. 358-360, “Pigment”, Heibonsha, 1960 Issued in February).

 Typical examples of cocoons with colorants include Turkish Turquoise glaze with cupric oxide as a colorant, Black Tenmoku glaze with ferric oxide as a colorant, coloring Oil spot Tenmoku glaze containing ferric oxide as a colorant, Silver oil spot Tenmoku glaze containing a relatively large amount of ferric oxide as a colorant, and a wide variety of other Acupuncture is well-known (The above-mentioned “Powder of Ceramics”, 64-278, by Onishi; and “Encyclopedia of Pottery and Porcelain” 1800-: I960, by E. Cameron, 326, and “A Guide To The Pottery and Porcelain of the Far East, m The Department of Ceramics and Etlmography, ”published by British Musium., 1924, 20-: L33).

 In the production of ceramics with a glazed layer, a ceramic or magnetic earth molded product, for example, a dish-shaped molded product, is dried, then unglazed, and the resulting unglazed molded product (biscuit-fired body ) In addition, the slurry (glazed slurry or slip) of the glaze raw material for producing the glaze is applied by a wet method in which it is dipped, poured, smeared, blown, or blown out, or by a dry method in which fine powder glaze material is sprinkled. The dried glazed unglazed product is then placed in a kiln and fired in the kiln at a glazing temperature with a combustion flame and / or hot combustion gas, or by electrical heating. This is normal.

 In addition, colored decorative patterns are often painted on the surface of ceramics by brush or printing. On the unglazed substrate, a decorative pattern is drawn with a colorant for lower bran, and further, the slurry of the glaze raw material for the production of transparent straw with low heat is soaked, air dried, and 1000 ° C or less It is customary to apply a decorative pattern to ceramics by a method that consists of firing at a temperature of 5 ° C, painting a decorative pattern with the upper paint on the surface of the resulting fired product, and firing again.

Various types of paints containing various inorganic coloring agents are well known as top paints used to paint decorative patterns on ceramics. For example, “Golden Luster liquor” (also known as water gold) (oil-based preparation based on oil-soluble gold compound) “Primary Color Pottery Dictionary” 101 -102, 114-: L16, 279-280, 19 June 1978, 3rd edition, Awakosha). In addition, new methods for painting decorations on ceramics include fine particles mainly composed of colorants, glazes or glaze raw materials, binder resin and charge control agents (particle size is about 5-30 μm). Using the constructed toner, an image is formed on the transfer sheet by the electrostatic latent image developing method, and the image on the transfer sheet is transferred to a predetermined position on the surface of the ceramic unglazed molded product. A method for painting ceramics, which consists of burning images, has been proposed (Japanese Patent Laid-Open No. 8-11496).

 It is also known that the firing of glazed pottery ceramic products is a phenomenon called ki-en (yo-hen) (previously “primary color pottery dictionary”, pages 986-987, and “Pottery of ceramics” pp. 278-279). Kiln alteration refers to the generation of unexpected colors and mottles during the firing under the influence of the atmosphere in the furnace. Yo-hen (in the literal English translation "kiln-changes") means that 釉 shows the "hares-fur" effect spoken in English (Japanese Pottery Information Center) Internet website on the homepage

 “Http: 〃 www.e-yakimono.net/guide/htnil/tenrnoku.litml” Yohi “Tenmoku Kogo Intercense Box J Internet Website

 I http://www.fareastasianart.com/stores/japanesepottery/items/27496/item27 496 '' and Γ 前 記 GUIDE TO THE POTTERY & PORCELAIN OF THE FAR EAST, IN THE DEPAETMENT OF published by BRITISH MUSEUM

See pages 25-27 of CERAMICS AND ETHNOGRAPHYJ). The reasons for the kiln change phenomenon are often unknown. To change the kiln, use a glaze containing iron oxide or copper oxide or other metal compounds, adjust the firing temperature of the firing kiln, adjust the oxidizing atmosphere in the kiln, adjust the reducing atmosphere, It is said that it is necessary to perform firing by combining various conditions such as adjusting the cooling rate. However, there is still no way to reliably produce kiln changes by simply using the known glaze formulation or glazing method.

Various methods have been used for decorating colored decorative patterns on the surface of glazed ceramics since ancient times, but many of the traditionally used decoration methods are quite complicated and time consuming. is there. Compared to traditionally known decoration methods, glazed ceramics It has long been desired to provide a new and simpler method for creating colored decorative patterns on the vessel surface.

 On the other hand, it is known that pharmaceuticals, cosmetics, and foods are encapsulated in a spherical capsule having a seamless outer coating layer that is seamless. In addition, a spherical capsule with a seamless coating layer, which has been conventionally used for encapsulating pharmaceuticals, cosmetics, and foods, has a central core layer and an outer solid sheet covering the core layer. A spherical force pusher with a two-layer structure or a central core layer, one or more intermediate layers that enclose the core layer, and the intermediate layer from the outermost side. It can be a spherical multi-layered spherical force psel with at least three layers consisting of a solid seamless coating layer (for example, US Pat. No. 4,695,466 (published September 22, 1987)) 3-333338 (published on May 16, 1991), Japanese Patent Application Publication No. 41732 (published on May 27, 1992), Japanese Patent No. 2806564 (published on July 24, 1998), Japan Patent application published, JP 2000-4844 (published on January 11, 2000), Japanese patent application public , JP-A-11 one 79 964 No., each specification of its corresponding US Pat. No. 6,426,089 (July 30, 2003 publication) and Japanese Patent No. 3313124 (published May 31, 2002), reference).

For example, a double-layered nozzle consisting of an upright inner nozzle tube and an upright outer nozzle tube that coaxially and concentrically surrounds it, and the core of a two-layer spherical capsule to be manufactured The first liquid raw material or solid particles (core material) to be encapsulated as a partial layer are enclosed in an inner nozzle tube, extruded downward from the lower end nozzle hole of the inner nozzle, and the outer side of the capsule A second liquid raw material (solution containing a raw material for the film material) used to form a film layer and containing a gel-forming substance capable of forming a film is placed in the upper part of the outer nozzle tube, Then, the liquid is passed through a channel formed between the outer wall of the inner nozzle tube and the inner wall of the outer nozzle tube, and is extruded from the lower end nozzle hole of the outer nozzle, whereby the first liquid raw material or solid Particles form an inner layer and second liquid raw material Create a single liquid flow with a two-layer structure that forms the outer layer, and the liquid flow that exits from the outlet of the nozzle hole of the double tube nozzle is constricted naturally at the tip to form a round and liquid level one after another, An aqueous solution of a gelling agent capable of producing a falling double-layered round droplet and chemically gelling the raw material of the coating material in the outer layer of the droplet. In the solution bath, and the gel and the outer layer of the droplet are gelled in the aqueous gelling agent solution, thereby having a film layer made of the gelled solid substance and in the film layer. Since the first liquid raw material or the inner layer consisting of solid particles (core material) contained in the inner layer is formed into a seamless (seamless) spherical capsule with a two-layer structure, and these spherical capsules are recovered. There are known methods for producing spherical capsules having a two-layer structure (see, for example, the above-mentioned Japanese Unexamined Patent Publication No. 2000-4844 and US Pat. No. 4,695,466 and FIG. 3).

 It is also known that an aqueous solution containing sodium alginate or other gelling substance is used as a raw material for a material for forming a coating layer of a two-layered spherical capsule (US Pat. No. 6,426,089 and (See Japanese Patent No. 3313124, especially page 2).

Disclosure of the invention

 No simple method has yet been developed to form a glazed layer with various multicolored decorative patterns on the surface of the ceramic when firing the ceramic.

 In addition, in the production of ceramics, there has not yet been developed in the field of ceramics production that a simple and reliable method for producing ceramics with a glazed layer indicating a conventional kiln change has been developed.

 The first object of the present invention is to provide a new and beautiful monochromatic or multicolored decorative pattern or effect on the surface of a heat-resistant substrate including ceramics. If more of the performance that can be produced by a large number of combinations is desired, a large number of combinations of colored cocoon layers produced in the form of small island-like spots exhibiting beautiful A spherical solid force layer having a capability of generating a mottled pattern showing a solid layer on the ground layer, and a porous solid seamless skin layer that seamlessly surrounds a spherical capsule enclosure, and is covered with the skin layer. A central core layer and an intermediate layer provided as desired, and within the capsule, fine particles of a glaze raw material capable of producing colorless basic glaze, and colorless basic glaze during firing Encloses and contains inorganic colorants that can be colored 2 Or spherical capsule of a multilayer structure is to provide a novel industrial product.

The second object of the present invention is to provide fine particles of the above-mentioned glaze raw material that can produce colorless basic soot. And using a plurality of the above-mentioned spherical force pusels containing and containing the above-mentioned inorganic colorant, the surface is a beautiful and beautiful monochromatic or multi-colored decorative pattern or decorative effect, or a mottled effect with a kiln-changing effect. To provide a new method for manufacturing ceramics.

 Furthermore, a third object of the present invention is to use a plurality of the above-mentioned spherical capsules to create a new decorative pattern or decorative effect on the surface of ceramic or other heat-resistant substrate. It is to provide a method.

Still other objects of the present invention will be apparent from the following description provided herein. The inventors of the present invention have developed a new composition of glaze and a new glazing method, as well as glazing and coloring agents, in order to develop a technology that can create a kiln change in a ceramic glazing layer and a new overpainting technology for a ceramic glazing layer. We conducted a variety of research on new ingredients and formulations. One result of these studies is the generation of a known, colorless, transparent base glaze in a spherical capsule that is encapsulated in a seamless skin layer that seamlessly surrounds the spherical capsule. A spherical force Pseule that contains encapsulated glaze raw materials and known inorganic colorants that can be used to color such basic glazes during firing in various combinations. The inventors have obtained an idea. Based on this idea, the present inventors conducted the following first experiment. That is, in this first experiment, after obtaining a commercial product of a fine powdery mixture of glaze raw materials that can produce silver oil droplet Tenmoku, this fine powdery mixture can be used in a weight ratio of 60:40 to water. Mix to make a slurry (in the form of a slurry or slip) containing the glaze raw material, and mix this slurry with a sol solution containing 5% by weight of sodium alginate at a 1: 1 weight ratio to form a slurry mixture. (a) was prepared. This slurry-like mixture (a) was extruded downward through a single upright nozzle tube having a nozzle hole with an outlet hole diameter of 1.44 mm. The extruded liquid stream was naturally constricted at its lower end to form round droplets one after another (see, for example, FIG. 4 of the accompanying drawings of the aforementioned US Pat. No. 4,695,446). The round droplets thus formed were successively dropped at room temperature into a liquid bath composed of an aqueous solution containing 2% by weight of a salt calcium salt which acts as a gelling agent for sodium alginate. When held for about 5 minutes in this liquid bath, Ca ions penetrate into the surface layer of each droplet introduced into the liquid bath and react with sodium alginate. On the surface of the droplet, it was confirmed that a film layer containing a gel-like hardened calcium alginate was formed. As a result, a large number of seamless spherical capsule particles encapsulated with a gel-like surface film layer were formed from each of the round droplets dropped in the liquid bath. A number of spherical force pushel particles thus formed were removed from the liquid bath. When one of these spherical capsule fine particles is cut with a knife at the center, the surface layer of the spherical capsule cell is a film made of a gel-like cured product of Ca alginate, but is covered with the film of this gel-like substance. It was observed that the core layer remained a liquid of the slurry mixture (a). The spherical force pusher particles taken out in this way were sufficiently dried in a dry air flow at 20 ° C., including the core of the force pusher particles, until the particles were solidified. As a result, a large number of dry spherical capsule particles each having a particle size of about 1.0 mm were obtained (see Example 2, (a) and (i) below).

 In each of these dried and solidified spherical capsule particles with a two-layer structure, the seamless coating layer on its surface is a solid of fine particles of glaze raw material for the production of silver oil droplets and hardened calcium alginate. It has a porous structure with many pores generated by the evaporation of moisture, but the solid core layer encapsulated by the surface coating layer is the second layer of acid. It was found to consist of a solid mixture of glaze raw material for the production of silver oil droplet Tenmoku containing iron as a colorant and sodium alginate (a substance that acts as an organic binder).

On the other hand, a commercially available milky white sludge was dipped into a clay-glazed unglazed tile board and dried naturally. On the surface of the tile plate thus glazed and dried, the dried and solidified spherical force pushell particles of the two-layer structure obtained above (core composed of a solid mixture of glaze raw materials for producing silver oil droplets) Several spherical capsules having a partial layer were pasted with starch paste and further air-dried. In this way, the tile plate having the spherical force pouch bound thereto is put into an electric kiln and gradually heated, and the maximum temperature of 1235 ° C is set in the same manner as described in Example 2 (b) below. Firing in an acid atmosphere at the firing temperature. The baked Tainole plate has a milky white ground layer on the entire surface of the plate, and on the ground layer is a small island formed by melting each of the bound spherical force pusels. It was observed that several ridges in the form of spotted spots were formed in a slightly raised state from the ground layer. Moreover, the surface of each of the small island-shaped ridges of the small islands has a silver hue indicated by the silver oil droplet Tenmoku The appearance of iron crystals could be observed under a microscope. Therefore, in the fired tile board obtained in this way, a silver decorative pattern formed by a combination of small island-like spots made of silver oil droplet Tenmoku was created on the ground layer of milky white cocoon. Was recognized.

 Further, the present inventor conducted the following second experiment. In other words, in the second experiment, instead of the commercial product of the glaze raw material for producing silver oil droplet Tenmoku used in the first experiment, a fine powdery mixture of the glaze raw material that can produce Turkish blue glaze. Obtain a commercial product, mix this finely powdered powder mixture with water at a weight ratio of 60:40 to make a slurry, and apply a 5 wt% aqueous solution of sodium alginate (sol form) to this slurry as described below. As in Example 3, (a), a 1: 1 weight ratio was well mixed to prepare a slurry mixture (b). This slurry-like mixture (b) was extruded downward through a single upright nozzle tube having a nozzle hole with an outlet hole diameter of 1.44 mm in the same manner as in the first experiment. The liquid stream pushed out from the nozzle hole was naturally constricted at the lower end, forming rounds and droplets one after another. The round droplets formed in this way and composed of the above slurry mixture (b) (including glaze raw material for the production of Turkish blue glaze) are placed one after another in a liquid bath consisting of a 2 wt% zK solution of calcium chloride. The droplets dropped into the liquid bath were kept at room temperature for about 5 minutes. In this way, a large number of spherical capsule particles encapsulated by the surface film layer made of a gel-like substance, which are generated from the round slurry and droplets of the slurry-like mixture (b) described above, Formed in a liquid bath. The spherical capsule particles taken out from the liquid bath were solidified by drying in the same manner as in the first experiment. Using the dried solid capsule particles obtained in this way, the subsequent steps were carried out in exactly the same procedure as in the first experiment.

As a result, the fired tile board finally obtained has a milky white ground layer, and on the ground layer, small island-like spots generated by the melting of each of the spherical force pussels used. A plurality of ridges of shape were formed. The surface of the cocoon layer in the form of these small island-like spots had a blue-green color peculiar to Torco blue cocoons, and it was observed that copper crystals appeared in the cocoon layer of each spot. In the fired tile board obtained in this way, it was confirmed that a blue-green decorative pattern formed by a combination of small island-like spots of Turkish blue and blue was created on the ground layer of milky white cocoon. Furthermore, in the third experiment conducted, for example, a structure similar to the double tube nozzle provided in the multilayer capsule manufacturing apparatus shown in FIG. 1 of the attached drawing of US Pat. No. 4,695,466 was used. A double tube nozzle was prepared. In the inner nozzle tube of this double tube nozzle, a commercially available gold solution known as a ceramic paint was inserted, and the gold solution was extruded downward from the nozzle hole of the inner nozzle tube. At the same time, the slurry-like mixture (b) prepared in the second experiment (slurry consisting of a mixture of glaze raw material for producing Turkish blue glaze and aqueous sodium alginate solution) was added to the inner wall of the outer nozzle tube. And the outer wall of the inner nozzle tube are charged into a vacant chamber, and in the same manner as described in Example 1 (a) below, slurry is formed from the lower nozzle hole of the double tube nozzle. Mixture (b) was extruded downward. In the same manner as described in Example 1 and (a) described later, one liquid flow extruded from the lower nozzle hole was naturally constricted at the lower end to form rounds and droplets one after another. (See, for example, Figure 4 of the accompanying drawings of US Pat. No. 4,695,466). The round droplets thus formed had a two-layer structure in which the inner layer was made of a gold solution and the outer layer was made of the slurry-like mixture (b).

 Such round droplets having a two-layer structure were successively dropped in the same manner as in Example 1, (a) in a liquid bath composed of a 2% by weight aqueous solution of calcium chloride. When the droplets were held in the bath for 5 minutes, spherical force pushel particles with a two-layer structure were formed from each droplet. These two-layered spherical force cells were taken out of the liquid bath and sufficiently dried in a dry air stream in the same manner as in the first experiment to solidify the capsule layer of the spherical capsule. The core layer of the resulting two-layer spherical force pusher is made of the above-mentioned gold solution, and the coating layer is seamless (seamless). It was confirmed to have a porous structure consisting of a solid mixture with a cured product of calcium lginate.

Using the dried two-layer spherical capsule thus obtained, the subsequent steps were carried out in exactly the same procedure as in the first experiment. As a result, the finally obtained fired tile board is a small island-like spot-like layer formed by melting each of the double-layered spherical capsules on the milky white layer. Had multiple of. The surface of each of these small island-like spotted ridges shows a concentric, double-colored striped pattern similar to that described in Example 1 (b) below. Stripes It was blue and the inner stripes were purple with a purple color. Therefore, in the obtained baked tile plate, small island-like spots having the above-mentioned concentric double-colored striped pattern are generated on the ground layer of the milk white birch. It was recognized that the formed beauty and decorative patterns were created.

 In the fourth experiment, a triple tube nozzle having the same structure as the triple tube nozzle shown in FIG. 1 of US Pat. No. 4,695,466 was prepared. Then, in the same procedure as described in Example 6, (a), (i), O), and (iii) described later, a spherical force psel having a three-layer structure was manufactured, and Example 6, (b) In the same manner as described above, a painted ceramic dish was produced using the spherical capsule having the three-layer structure. As a result, in the baked pottery plate, small island-like spots with almost concentric double circle stripes with a red outer edge part and a yellow inner part on the milky white ground layer. It was observed that a plurality of shaped ridges were produced by melting each of the spherical force pusels, and that the fired tiles exhibited a beautiful decorative pattern composed of the aforementioned spot combinations.

 As described above, using a spherical force pusher manufacturing device with a single nozzle tube, a simple two-layer structure with only a core layer and a coating layer is produced. Using known technology, as well as seamless spherical force of three or more multilayer structures using double pipe nozzles, triple pipe nozzles or quadruple pipe nozzles Applying the known technology for producing seamless spherical capsules, and along with it, various types of glaze raw materials for the production of basic glaze to be produced in spherical capsules to be produced, and inorganic coloring departments to be blended A number of experiments were carried out to try to produce spherical force cells using various combinations of these materials and various types of film-forming substances used to form force-pelled film layers. . As a result of these series of experiments, a two-layer structure in which a glaze raw material for producing various basic glazes and various colorants capable of coloring the basic glazes are encapsulated, and having a core layer and a coating layer Seamless (seamless) spherical force pushell or core layer, one or more intermediate layers that envelop the core layer, and a multilayer structure that encloses the intermediate layer from the outermost side We have succeeded in manufacturing various types of spherical capsules that are seamless.

As a result, the core of the inner layer of the spherical capsule having the two-layer or multi-layer structure as described above is formed. The core material to be formed, the coating material constituting the coating layer provided on the outermost side of the capsule, and the intermediate layer or layers that can be provided between the inner layer of the core and the coating layer, if desired. At least one of the constituent materials forming the metal material is a metal material effective as a colorant having the effect of changing the kiln.A metal compound can optionally be contained if desired, and the core material of the inner layer. And at least one of the constituent material forming the intermediate layer and the coating material forming the coating layer separately from the glaze raw material for forming the basic soot and the coloring agent for coloring the soot, or A two-layer structure, a three-layer structure or more multilayers in which the glaze raw material and the colorant for coloring the glaze are contained together so that the glaze raw material and the colorant capable of coloring the glaze are enclosed Structure seamless sphere The present inventors have found that it can be manufactured.

 In the case of a capsule having a multilayer structure of two or more layers produced as described above, an appropriate decorative pattern is drawn on the surface of a ceramic glazed or unglazed product. Pasted with a heat-decomposable organic adhesive, for example, starch glue, and then put the capsules into a kiln and put them in a kiln. Heat gradually and finish at 1000 ° C or higher When firing in an acidic or reducing atmosphere at the firing temperature, each capsule melts, the organic substances in the capsules burn out, and the capsules The glaze material in the inside and the colorant for glaze melt together to produce a colored glaze layer, and the chemical composition of the substance contained in the capsule changes variously during the formation of this glaze layer. To undergo physical changes As a result, it was discovered this time that a cocoon layer in the form of beautifully colored small island spots can be created on the surface of the finished fired product. Based on the above findings, the present invention has been completed.

Therefore, in the first aspect of the present invention, the spherical capsule is composed of an inner layer that forms the core of the spherical capsule and a seamless film layer that covers the core from the outside, or the core of the spherical capsule An innermost layer that forms the innermost layer, a seamless coating layer that covers the spherical capsule from the outermost side, and an intermediate layer or layers that are provided between the innermost layer that forms the core and the coating layer A spherical composite cell having a multi-layered composite structure, and the coating material forming the coating layer is composed of a thermally decomposable organic substance capable of forming a film, or heat capable of forming the coating. Degradable organic substances and glazes below And / or a solid mixture with the colorant described below, and further, a core material forming the core, a coating material forming the coating layer, and forming the intermediate layer At least one of the material substances contains a glaze raw material for producing a basic glaze that can produce a transparent glaze layer upon firing, and the core material that forms the core part, and At least one of the coating material and the material forming the intermediate layer contains an inorganic colorant capable of coloring the transparent wrinkles produced during firing, and the core. At least one of the material substance, the coating material substance, and the material substance forming the intermediate layer is fired together with the glaze raw material for producing the basic soot capable of producing transparent soot. When generating small dots, spots or mottled patterns, showing kiln transformation effects Metallic material that can be effective as a colorant that can be formed on the eaves layer, and / or a force containing a metal compound, or the metal material or metal compound forms a core, an intermediate layer, and a coating layer, respectively. In addition, one or both of the core material and the material material forming the intermediate layer optionally further contains a thermally decomposable organic binder. Providing a spherical capsule that contains and encapsulates a glaze raw material for producing a transparent basic glaze that can produce a transparent glaze layer when fired, and a colorant that can color the transparent basic glaze. Is done.

 The capsule of the first aspect of the present invention can be in the form of a seamless spherical force psell composed of an inner layer that forms the core of a spherical capsule and a seamless film layer that covers the inner layer from the outside. . The spherical capsule of the first aspect of the present invention includes an innermost layer that forms the core of the spherical capsule, one, two, or three intermediate layers that enclose the core, and an intermediate layer that is wrapped from the outermost side. It can also be in the form of a seamless spherical capsule with a multi-layered composite structure composed of a seamless coating layer to cover.

In the spherical capsule without ridges (seamless) according to the first aspect of the present invention, the coating material for forming the capsule layer and the raw material for this is a thermally decomposable organic substance capable of forming a coating. Preferably, it is a protein such as gelatin, or a polysaccharide such as pectin, methoxy pectin, or alginic acid, but it is usually an organic material that can be gelled when treated with a gelling agent. Can be a substance. Alternatively, such a gelling organic substance can be included. Said tongue A hardened product of a protein or a polysaccharide is the main component contained in the capsule film layer, or the capsule film layer is formed by itself. The proteins and polysaccharides can be used alone or in admixture of two or more. The capsule film layer may contain a colorant.

 In general, the above-mentioned organic substances capable of forming a film are shown in US Pat. No. 4,695,466, a film-forming substance, and Japanese Patent No. 3313124, page 2 A coating material can be used. Film material raw material containing a gel-like cured product of calcium alginate produced by using sodium alginate aqueous solution as a raw material for the film material, contacting it with calcium chloride aqueous solution, reacting with Ca ions and ion crosslinking It is preferable to provide a spherical force layer with a solid film layer formed from the substance.

 In the spherical force pushell of the present invention, the heat-decomposable organic substance having a film-forming ability contained in the above-mentioned film material forming the force pushell film layer is a cured product of calcium alginate, pectin or methoxypectin. A polysaccharide, a protein such as a hardened material, a hardened gelatine or a hardened hardened material, and the coating layer is formed of a solid layer containing a large number of pores and having a porous structure. preferable.

 The core material forming the central core layer of the spherical capsule of the present invention may be liquid, semi-solid or solid. This core material can consist of only various colorants for ceramics (in the form of fine particles of colorant, or a dispersion of colorant fine particles in the form of an oily or aqueous slurry), or It can be a mixture with other ingredients. For example, the above-mentioned gold solution (also called water gold, which usually contains a flux) alone can form the core material. In the core material, an organic binder made of the above-mentioned gel-forming film-forming protein or polysaccharide can be blended as a main component. It is also possible to add a known colorant known in the art to be effective in creating kiln modifications in the core material.

If desired, a single or multiple intermediate layers may be interposed between the core layer and the coating layer of the spherical capsule of the present invention. The material that forms this intermediate layer is a koji made of a solid mixture of a coloring agent capable of coloring the basic soot when fired, fine particles of a glaze raw material for producing the basic soot, and a thermally decomposable organic binder, There Can comprise a solid mixture of the aforementioned colorants and organic binders. An organic binder such as the above-mentioned gelling protein or polysaccharide can be blended in a solution containing raw materials for the material substance forming the intermediate layer. In addition, for example, the intermediate layer can be composed only of a dry residue product of gold liquid, and it contains gold colloidal particles and gold ions that are effective as a coloring family that can cause kiln changes. it can.

 The constituent material forming one of the core layer, the intermediate layer, and the coating layer provided in the spherical force pushell of the present invention contains fine particles of the glaze raw material for generating basic glaze. it can. The basic agate can be a known glaze. The spherical capsules of the present invention can be produced by using a fine powder or an aqueous slurry (serum or slip) of the glaze raw material. It may be a self-made glaze material. Various types of glaze raw materials for producing various basic glazes can be used individually or in combination to prepare spherical capsules.

 Is the glaze raw material used to produce the transparent glaze layer that can be used in the spherical force process of the present invention to produce a transparent glaze layer, a known glaze raw material used to produce transparent lime glaze? Or a known glaze raw material used to produce clear ash glaze, or force that is a known glaze raw material used to produce transparent sodium feldspar or transparent power feldspar feldspar it can.

The above-mentioned glaze raw material for producing the basic cocoons capable of producing transparent limestone is potassium feldspar, stone, apatite, silica, and fine-grained material containing force olin. It is made of fine particles (iii) containing limestone, limestone and kaolin, or fine particles (iii) containing potassium feldspar, limestone, palium carbonate, silica and force olin. Further, the glaze raw material for producing the basic soot capable of producing the above transparent sodium feldspar is made of a particulate material containing sodium feldspar, palium carbonate, limestone, silica stone and lithium carbonate. The above-mentioned glaze raw material for producing the basic cocoons capable of producing the transparent power limestone feldspar is a fine particulate material containing potassium feldspar, limestone, silica, kaolin, dolomite, barium carbonate and zinc oxide. From those made. Furthermore, glaze material for production of basic glaze that can produce a clear Hai釉 said from particulate material containing a feldspar or pottery stone and wood ash It consists of.

 Typical examples of the preparation of the glaze raw material capable of forming the above transparent limestone are 37-40 parts by weight of potassium feldspar fine powder, 15-17 parts by weight of limestone fine powder, and 34-35 parts by weight of silica stone fine powder. Is mixed with 10 to 34 parts by weight of force oline and colloidal particles, and the resulting mixture is pulverized into finely divided material (0 or 16 to: L9 parts by weight of force Mix feldspar fine powder, 67-69 parts by weight porcelain stone powder, 16-18 parts by weight limestone fine powder, 4-6 parts by weight kaolin colloidal particles, and pulverize the resulting mixture It is the obtained particulate material (ii), or 39 to 41 parts by weight of feldspar fine powder, 9 to 11 parts by weight of limestone fine powder, 15 parts by weight of barium carbonate fine powder and 24 to 26 parts by weight. 9 to 11 parts by weight of force orin 'colloidal particles are mixed, and the resulting mixture is pulverized. Is a particulate material (iii).

 A typical example of the preparation of the raw material that can be formed from the transparent sodium feldspar is 39 to 41 parts by weight of sodium feldspar fine powder, 17 to 19 parts by weight of palium carbonate fine powder, and 10 to 12 parts by weight of powder. It was obtained by mixing limestone fine powder, 26-28 parts by weight of quartzite fine powder and 4-5 parts by weight of lithium carbonate (acting as a mineralizer), and grinding the mixture into fine powder It is a particulate material (see Onishi, “Ceramics glaze”, new edition, pages 41-230).

Any one of the core layer, the intermediate layer, and the coating layer of the spherical capsule of the present invention is a colorant conventionally known to have a function of causing a kiln change, such as a gold substance, a silver substance, an iron substance, or a copper substance. Such metal materials, or acids or salts of these metals, if desired, and can be colored separately from or in addition to such colorants. Of various common colorants such as ferric oxide, iron tetroxide, copper oxide, metal oxides such as cobalt oxide, or metal carbonates such as iron carbonate and copper carbonate, copper acetate Such as metal acetate, gold salt, silver salt. Therefore, an inorganic colorant that can be used in the spherical capsule of the present invention and can color the glaze layer produced when fired together with the glaze raw material for producing the basic glaze is oxidized. Metal oxide, which can also be cupric, ferric oxide, chromium oxide, manganese oxide, cobalt oxide, acid nickel, acid uranium, acid cerium, titanium oxide or neodymium oxide Is a known inorganic colorant in the form of Is a known inorganic colorant in the form of a metal carbonate, or a known inorganic colorant in the form of a metal silicate, chromate, or metal sulfide or selenide Or a known inorganic colorant in the form of metallic gold, metallic silver, metallic cadmium, metallic chromium or metallic selenium that can be colored in a dispersed state in the resulting soot layer.

 Furthermore, it is a colorant that can be arbitrarily blended with any of the substances forming the core layer, the intermediate layer, and the coating layer constituting the spherical capsule of the present invention, and has small spots, spots, or The metal substances or metal compounds described above, which can be used as a coloring agent capable of generating a mottled pattern on the generated glazing layer, are known as pigments used in ceramic upper and lower paints. Terpene oil soluble gold compound, especially gold salt of resin acid, gold colloid, silver, silver colloid, ferric oxide (Bengara), ferric carbonate, cupric oxide or cupric carbonate Or it can consist of two or more of these substances.

 The colorant may be a commercial product of pigments having various colors listed in Example 4, (a), (i) and (b) described later.

 Generally 0.1% to 20% by weight based on the total weight of the glaze ingredients contained in the capsule. /. The amount of the coloring agent can be added so that the soot layer can be colored. It is at the discretion of the person skilled in the art to properly adjust the amount of colorant to be added depending on the type of cocoon, the type of colorant, and the type of hue desired to color the cocoon. (Ceramic ceramic glaze, new edition, pages 64-70). For example, celadon porcelain can be colored with ferric oxide in an amount of 1-2% by weight as a colorant, and black tenmoku or oil-drop tenmoku can be colored with 8-10% by weight ferric oxide, Silver oil droplet Tenmoku can be colored with a combination of ferric oxide in an amount of 8 to 13% by weight and manganese carbonate (coloring aid) in an amount of !! to 3% by weight.

In the spherical capsule of the present invention, the thermally decomposable organic binder that can be optionally blended in the core material of the core of the capsule or in the material substance forming the intermediate layer of the force capsule is described above. It can be a thermally decomposable organic substance capable of forming a film, preferably a force that is a cured product of calcium alginate, or sodium alginate as an organic binder. The inner layer forming the core of a spherical force pusher with a core and a seamless coating layer according to the present invention comprises a transparent basic glaze, preferably a glaze raw material for producing lime glaze, and at least one that can color this basic glaze. Formed of a solid mixture of an inorganic colorant and an organic binder, preferably sodium alginate, or a thermally decomposable organic substance capable of forming a film, preferably a cured product of calcium alginate, and the capsule The coating layer is made of a glaze raw material for producing the basic soot, the colorant, and a thermally decomposable organic substance capable of forming a film, preferably a solid mixture of calcium alginate, or the film forming ability described above. It can be formed of a solid layer having a porous structure made of a thermally decomposable organic substance.

 According to the first preferred embodiment of the spherical force pushell of the present invention, the innermost layer forming the core of the spherical capsule having a multilayer composite structure is used for the production of a transparent basic cocoon, preferably a limestone cocoon. Formed from a solid mixture of a glaze raw material, at least one inorganic colorant capable of coloring the basic glaze, and a thermally decomposable organic substance capable of forming a film, preferably a cured product of calcium alginate, In addition, the one or more intermediate layers enveloping the core part may include another kind of inorganic colorant capable of developing a color different from the color developed by the inorganic colorant contained in the core part, Formed from a solid mixture of a raw material for forming a glaze and a thermally decomposable organic substance having a film-forming ability, preferably a cured product of calcium alginate, and further the intermediate layer from the outermost side. The film layer to be encapsulated is the film formation A heat-decomposable organic substance, preferably a force composed of a hardened calcium alginate, or a heat-decomposable organic substance capable of forming a film, preferably a solid mixture of calcium alginate and an inorganic colorant A spherical capsule having a multi-layered composite structure is provided (see Example 2 and Examples 4 to 7 below).

 In the present invention, among the substances forming the core layer, the intermediate layer, and the coating layer constituting the spherical capsule, the substance forming the layer containing the glaze raw material additionally contains a flux. You can also

According to a second preferred embodiment of the spherical force pushell of the present invention, it is a spherical capsule composed only of an inner layer forming the core of the spherical force pusher and a seamless film layer covering the inner layer, and The core material of the core is made up of small spots, spots, Is a terpene oil-soluble metal compound and gold colloidal fine particles, which can be effective as an inorganic colorant capable of forming a mottled pattern on the resulting cocoon layer, and The force formed by a commercially available gold solution containing a flux, or the core material comprises an inorganic colorant in the form of a metal compound and a transparent basic soot, preferably a glaze raw material for producing lime glaze and ( Or) a solid or semi-solid mixture containing a film-decomposable thermally decomposable organic substance, preferably a hardened calcium alginate, or a liquid mixture additionally containing a small amount of water. In addition, the film material forming the film layer is an inorganic colorant, preferably an acid cupric acid known as a colorant contained in Torco blue glaze, and a transparent basic glaze, preferably It consists of a solid mixture of a glaze raw material for the production of sodium feldspar and a maturation-degradable organic substance capable of forming a film, preferably a cured product of calcium alginate, and is a solid layer having a porous structure. A spherical force pushell is provided.

 In the spherical force pusell of the present invention, the entire three-dimensional form of the force pusell is slightly deformed from a perfect sphere, and the surface of the force pusell can have a small constricted portion or a small ridge, or a protruding portion. Or, a spherical capsule as a whole can have a shape close to an oval or teardrop shape. The amount of the constituent material of the coating layer is in the range of 5 to 15% by weight based on the total weight of one capsule.

 The average particle size of the spherical capsules of the present invention is in the range of 0.1 mm to 8 ran, preferably 0.5 mn! Can be in the range of ~ 3mm. If desired, the average particle size can be smaller than 0.1 mm, or larger than 8 mm. The amount of glaze material blended in the force psell can range from 80 to 95% by weight, and the colorant amount ranges from 5 to 15% by weight, based on the total weight of one force psell. There can be.

 Next, several methods for producing the first spherical capsule of the present invention will be explained. This method is similar to the method for producing the seamless spherical capsule shown in the aforementioned US patent and Japanese patent. .

An outline of a method for producing a spherical capsule having a two-layer structure when the core material forming the core portion of the force capsule is a liquid and is encapsulated with a solid coating layer will be described below. The

 Prepare a force psel manufacturing device with a double-pipe nozzle having the structure shown in the perspective view with the longitudinal section schematically shown in Fig. 3 of the accompanying drawings. From the upper part of the inner nozzle tube (4) of this device, the liquid raw material of the core material forming the core layer of the capsule is inserted into the inner nozzle tube (7). The liquid material of the core material is extruded downward from the nozzle hole (6) of the inner nozzle tube through the tip (5) of the inner nozzle tube (4).

 At the same time, a gelling liquid raw material of the film material for forming the capsule film layer is loaded into the supply chamber (1 ′) of the liquid material for forming the film layer provided in the capsule manufacturing apparatus. deep. The liquid material of the coating material is pumped through an intermediate channel (8) formed between the inner wall of the outer nozzle tube (1) and the outer wall of the inner nozzle tube. It should be noted that the opening position of the nozzle hole (6) of the inner nozzle tube should be stepped so that it is higher in the vertical direction than the opening position of the nozzle hole (3) of the outer nozzle tube. At the tip of the tip (2) of the outer nozzle tube (1), through the annular slit formed between the peripheral wall of the nozzle hole (3) of the outer nozzle tube and the nozzle hole (6) of the inner nozzle tube When the liquid material of the above-mentioned film material is discharged, the liquid material of the above-mentioned film material is in the form of a film around the liquid flow consisting of the nozzle hole (6) force of the inner nozzle tube. Enclosed, one liquid flow with inner and outer two-layer structure is formed near the outlet of the nozzle hole (3) of the nozzle hole of the outer nozzle. Then, when the liquid flow in the inner and outer two layers slightly flows down, the liquid flow naturally narrows and drops one after another (see FIG. 4 of US Pat. No. 4,695,466 or Japanese Patent No. 3313124). (See Figure 1). As a result, a plurality of round droplets of a two-layer structure composed of a round inner layer (core portion) made of a raw material of the core material and a film layer of the liquid raw material liquid of the above-mentioned film material covering the same Pieces are formed one after the other at the tip of the liquid flow coming out of the outlet of the outer nozzle tube (3).

Adjust the hole diameter of the nozzle hole (6) of the inner nozzle tube to 0.72 mm, for example, and adjust the hole diameter of the nozzle hole (3) of the outer nozzle tube to 1.43 mm, for example. The flow rate and the outflow rate of the liquid material of the film material are appropriately adjusted. By doing this, the weight of the inner layer (layer made of the liquid material of the core material) of the two-layer structure droplet and the coating layer (liquid of the coating material substance) per round droplet of the two-layer structure described above original While the average ratio to the weight of the layer made of the material can be kept substantially constant, many of the round droplets of the two-layer structure are formed one after another. The diameter and size of these round droplets vary somewhat from individual to individual, but are approximately the same.

 Two or more rounds formed one after another as described above! / Drop droplets one after another in an aqueous solution of a gelling agent that can gel the liquid raw material of the coating material. When the dropped droplet is held in the liquid bath composed of the gelling agent aqueous solution for about 5 to: L0 minutes, the gel-forming substance capable of forming a film contained in the coating layer of each droplet gels, and Harden. In this way, a large number of round capsule-like particles having a strong film are formed in the liquid bath.

 These many round capsule-like particles are separated from the liquid bath of the gelling agent aqueous solution and further washed with water at room temperature. Thereafter, the washed round capsule particles are dried in a stream of dry air. Dry thoroughly until the coating layer of force-pellate particles is solidified (see Example 1, (a) below).

 A dried round capsule-like particle with a solidified coating layer has a diameter in the range of 1.5 mm to 2.0 mm under the above conditions. It consists of an inner layer (core layer) and a coating layer surrounding it. It is a layered spherical force psell. A partial cross-sectional view of this spherical force psel and an illustration showing a perspective view of the half of the force psell are the same as in FIG. 1 showing the capsule obtained in Example 1 described later. This spherical capsule has an inner layer, that is, a core layer (1) and a skin layer (2).

Next, a method for producing a spherical capsule having a core layer made of a solid core material and a coating layer will be schematically described. First, spherical fine particles made of a solid core material are prepared in advance, and this is inserted into the inner nozzle tube of the force tube manufacturing apparatus with a double tube nozzle shown in FIG. Spherical fine particles are extruded one after another from the nozzle hole of the tube (see Example 1 (a), (i) to (v) below, and FIG. 3 of US Pat. No. 4,695,466) . At the same time, the gel material liquid raw material of the coating material is charged into the outer nozzle tube, allowed to flow down, and then extruded from the outlet of the nozzle hole (3) of the outer nozzle tube (3). Thus, the surface of the solid fine particles extruded one after another from the nozzle hole (6) of the inner nozzle is coated. In this way, solid fine particles provided with a coating layer made of a liquid raw material of the film material are formed. After that, the liquid core material mentioned above When a spherical capsule having an inner layer is processed in the same manner as in the latter half of the manufacturing method, a spherical capsule having a two-layer structure having a core layer made of a solid core material and a solid film layer made of a film material is obtained. Can be manufactured.

 Note that a two-layer spherical capsule having a solid core layer and a coating layer can be produced using a single nozzle tube in the same manner as in the first experiment described above (described later). Example 2, (a), (i), see).

 Furthermore, a method for producing a multilayer capsule having a core layer made of a solid core material, an intermediate layer, and a coating layer will be described.

 First, spherical fine particles made of a solid core material are prepared in advance, and the liquid material of the material material that forms the intermediate layer is sprayed on the entire surface of such fine particles by spraying, dripping or other suitable coating. Each fine particle having a surface coating made of the raw material of the constituent material forming the capsule intermediate layer is formed by the method. The fine particles obtained in this manner are dried, and fine particles having a dried coating layer are produced. Next, the solid fine particles having such a coating layer are charged into the inner nozzle tube of the force tube manufacturing apparatus with a double tube nozzle shown in FIG. 3, and the subsequent steps are the above-described solid core. It is processed in the same way as the manufacturing method of the spherical force process with a core layer made of material. In this way, a desired multi-layered spherical capsule can be produced (see Example 2 (a) below).

 Furthermore, a method for producing a multilayer structural force cell having a core layer, an intermediate layer, and a coating layer will be described.

 That is, in the force pusher manufacturing apparatus with a double tube nozzle pipe shown in FIG. 3, instead of the double pipe nozzle comprising the inner nozzle pipe and the outer nozzle pipe, the inner pipe provided coaxially is provided. Prepare a capsule manufacturing device equipped with a triple tube nozzle consisting of a nozzle tube, an intermediate nozzle tube and an outer nozzle tube (see FIG. 1 of US Pat. No. 4,695,466 and FIG. 5 of the accompanying drawings of the present application). The inner nozzle tube (4) is charged with the liquid material of the core material, and the intermediate nozzle tube is charged with the liquid intermediate layer material that can be gelled, and the outer nozzle tube (1 ) In the inside, a gel-like liquid raw material of the coating material is charged. Thereafter, when the same procedure as in the capsule manufacturing method is performed, a spherical force psel having a desired multilayer structure can be manufactured.

To produce a ceramic with a decorative pattern using the spherical capsule of the first invention Do not place a plurality of the spherical capsules of the present invention on the glazed or unglazed surface of a ceramic or magnetic earth molded product in a desired arrangement that allows a dot-drawn decorative pattern to be drawn. Arrange them as they are and attach them with a heat-decomposable adhesive. Starch glue is suitable for such adhesives. The glazed or unglazed unglazed product with a spherical capsule bound is then placed in a kiln and gradually heated to finish firing under the firing conditions used in the production of ceramics. Commercial electric kilns can also be used, depending on the type of glaze raw material used, the type of colorant used, and the type of hue to be developed with the colorant, in an oxidizing or reducing atmosphere, or in these atmospheres Under the combination, it can be fired in a conventional manner at a firing temperature of 1200 to 1300 ° C.

 Accordingly, in the second aspect of the present invention, a large number of the spherical capsules of the first aspect of the present invention described above are applied to the glazed surface or the unglazed surface of the ceramic unglazed molded article with their force pussel as desired. The dot-patterned decorative patterns are arranged so as to be scattered in the positions to be drawn, and the force pussels are bonded to the glazed or unglazed surface with a thermally decomposable organic adhesive, and then the capsules are attached. The bonded unglazed molded product is gradually heated to melt the glaze raw material in the power vessel and to fire it in an oxidizing atmosphere or reducing atmosphere at a firing temperature at which it can be applied or in an oxidizing atmosphere. Next, firing in a reducing atmosphere, melting the bound capsule during the firing, and burning the organic substance component and the adhesive in the capsule, the surface of the fired product obtained above Power A colored small island-shaped cocoon layer formed by melting each of the psel is formed, a colored decorative pattern composed of a combination of these colored small island-shaped cocoon layers is created, and then the product is slowly cooled. Further, there is provided a method for producing a ceramic having a decorative pattern composed of a combination of small island-shaped cocoon layers on the glazed surface, which comprises cooling the fired product to room temperature. Provided.

 Firing is performed by a method commonly used in the production of ceramics. In the case of using an electric kiln for firing, the oxidizing atmosphere can be created by high-temperature air. In a reducing atmosphere, a gas burner is provided in the electric kiln, and the combustion gas containing carbon monoxide and the like is insufficient under the condition that incomplete combustion of the fuel gas containing gaseous hydrocarbons occurs. It can be made by generating.

Furthermore, instead of the unglazed substrate of the above-mentioned ceramic or magnetic earth molded products, A base made of iron, an iron alloy, or a base made of heat-resistant glass, and the spherical capsule of the first invention is adhered to the surface of the heat-resistant base in an arrangement facing a desired decorative pattern, Furthermore, it can be fired in the same manner as in the production of ceramics. When fired in this manner, a colored cocoon layer in the form of a large number of small island spots formed by roasting each of the spherical capsules can be formed on the surface of the heat-resistant substrate. It was recognized that the large number of colored small island-shaped cocoon layers formed as described above can produce a kind of decorative pattern by combining them.

Accordingly, in the third aspect of the present invention, a large number of spherical capsules described in the first aspect of the present invention are prepared in combinations with different types of colorants contained in the capsules. It is a specification that becomes a combination of capsules that can draw a single color or a point drawing style pattern with different colors, assuming the color that the colorant contained in the color develops after firing, Select a plurality of various spherical capsules containing the same or different types of colorants, and select a plurality of the various spherical capsules so selected for the surface of the heat-resistant substrate, in particular for ceramics. Glazed or unglazed surface, surface of heat-resistant glass molded product, enamel-coated surface, surface of molded product made of iron or iron alloy, surface of molded product made of copper or copper alloy, aluminum Are arranged side by side on the surface of an aluminum alloy molded product or other heat-resistant material base in the same way as a dot-drawn decorative pattern is drawn with these capsules, and the capsules are arranged in this way. In the arrangement, after firing the plurality of arranged force pusels, the various colors shown by the many colored islet-shaped cocoon layers formed from the melting of each of the force pusels and formed on the substrate surface are Take care so that you can draw and create a decorative pattern of your favorite point drawing style composed of a combination of small island-like cocoon layers, and a number of the above-mentioned force pussels arranged to draw a decorative pattern as described above The base material surface is bonded with a thermally decomposable organic adhesive, and the base material having the bonded capsules on the surface is melted with the capsule-containing glaze raw material at an oxidative atmosphere at a firing temperature at which glazing can be applied. Baked in a reducing atmosphere or baked in a reducing atmosphere followed by an oxidizing atmosphere to melt the bound capsule, and the organic substance component in the capsule and the adhesive were baked. On the surface of the resulting baked product to form a large number of colored islet-like cocoon layers produced by melting each of the capsules, and The base comprising: creating a dot-drawn decorative pattern composed of a combination of small island-like cocoon layers on the surface of the fired product, then gradually cooling the fired product, and further cooling the fired product to room temperature. There is provided a decoration method for creating a colored decorative pattern on the surface of a heat-resistant substrate, which is composed of a number of combinations of colored small island-like cocoon layers generated on the surface.

 Also in the method of the third aspect of the present invention, the firing step can be carried out in accordance with a method commonly used in the method for producing ceramics.

Brief Description of Drawings

 FIG. 1 is a partial cross-sectional view of a spherical capsule manufactured in Example 1 to be described later, and is a perspective view schematically showing the outer shape of a half portion of the capsule.

 FIG. 2 is an illustrative view of a central cross section of a multi-layered spherical capsule manufactured in Example 2 described later.

 FIG. 3 is a partial longitudinal sectional view of a capsule manufacturing apparatus equipped with a double tube nozzle that can be used for manufacturing a spherical capsule according to the present invention and a perspective view schematically showing the outer shape of a half of the apparatus.

 Fig. 4 shows the results of Example 4, (d) described later, and a plurality of the spherical capsules of the present invention are connected to the unglazed surface of a porcelain earthen dish so as to draw a landscape including mountains and clouds in a dot-drawn style. It is an illustration depicting the situation when worn.

 FIG. 5 is an illustrative view showing a longitudinal section of a force capsule manufacturing apparatus equipped with a triple tube nozzle that can be used for manufacturing the spherical capsule of the present invention.

 FIG. 6 is a perspective view schematically showing a partial fracture surface and a capsule outer shape of a spherical capsule of the present invention produced in Example 6 described later.

BEST MODE FOR CARRYING OUT THE INVENTION

 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

Example 1

 (a) Spherical force having a core made of a gold solution containing a colorant for ceramics, and a film layer made of a solid mixture of the colorant for glaze, glaze raw material and film material Preparation of pursell

A commercially available gold solution that is commonly used as a paint on ceramics was prepared. This gold solution (7 (Also referred to as gold) is a viscous oily preparation containing oil-soluble gold compound and gold colloid as the main components of colorant, and also containing flux and turpentine oil. It is a gold solution marketed under the name Gold Solution N-9. In addition, a commercial product of a slip of a glaze raw material for producing Turkish blue glaze that can form a Turkish blue glaze layer known as a glaze for ceramics. (It is called mud of glaze raw material for the production of Turkish blue glaze). This slurry of glaze raw material for producing Turkish blue glaze is a slurry mixture containing fine particles of cupric oxide as colorant, fine particles of glaze raw material for producing sodium feldspar and water, The mixture has a water content of about 40% by weight.

 1 part by weight of the slurry of the glaze raw material for producing Turkish blue glaze is a 5% by weight aqueous solution of sodium alginate (which acts as a binder for the fine particle component of the glaze raw material and also as a raw material for the organic coating). A slurry A mixture A was prepared by mixing well with 1 part by weight of the sol.

 Fig. 3 of the attached drawing schematically shows a capsule manufacturing device equipped with a double pipe nosole, with a device structure represented by a perspective view schematically showing the central longitudinal section of the capsule manufacturing device and the outline of half of the entire device. Prepared. The gold solution was charged from above the circular inner nozzle tube (4) having a cross section provided in this device into the inner lumen (7) of the inner nozzle tube. The gold liquid was extruded downward from the nozzle hole (6) of the inner nozzle through the tip (5) of the inner nozzle pipe (4).

 At the same time, the slurry mixture passes through a supply pipe (9) into a supply chamber () for a liquid raw material for forming a capsule film layer having a cylindrical peripheral wall (Γ) provided in the capsule manufacturing apparatus. A (ie, a 1: 1 mixture of a slurry of a glaze raw material slurry and an aqueous sodium alginate solution for the production of Turkish blue glaze). Then, the slurry-like mixture A was extruded downward through an intermediate channel (8) formed between the outer nozzle tube (1) and the inner nozzle tube (4) having a circular cross section. The outlet position of the outer nozzle hole (3) of the outer nozzle should be below the nozzle hole (6) outlet of the inner nozzle pipe (4).

Near the tip of the tip (2) of the outer nozzle tube (1), the peripheral wall surrounding the nozzle hole (3) of the outer nozzle tube, and the peripheral wall surrounding the nozzle hole (6) of the inner nozzle tube Formed during The slurry mixture A was extruded through the annular slit. As a result, the slurry mixture A surrounds the lateral surface of the gold liquid flowing out from the nozzle hole (6) of the inner nozzle in the form of a film, and the inner and outer two layers are surrounded. One liquid stream of structure was formed below the nozzle hole (3) outlet. Moreover, as the liquid flow flowed down, the liquid flow naturally narrowed into many round droplets. As a result, each of the two-layered round droplets composed of a round inner layer (core layer) made of a gold solution and a coating layer of the slurry mixture A that surrounds and coats the inner layer becomes an outer nozzle. It formed one after another at the tip of the liquid stream extruded from the nozzle hole (3) of the tube.

 Adjust the hole diameter of the nozzle hole (6) of the inner nozzle tube to 0.72mm, and adjust the hole diameter of the nozzle hole (3) of the outer nozzle tube to 1.43mm. The extrusion speed of the mixture A was appropriately adjusted. In this way, the weight of the inner layer (core part formed from the gold solution) of the two-layered droplet and the coating layer (layer consisting of the slurry-like mixture A) are per one of the two-layered round droplets. The above-mentioned two-layered round droplets were continuously formed, with an average ratio of about 25 to 75. The diameter and size of the many round droplets formed were found to be approximately the same, although each droplet varied somewhat.

 Many of the two-layered round droplets continuously formed as described above were dropped one after another in a liquid bath composed of a 2.0% by weight aqueous solution of rutile chloride at room temperature. When each dropped droplet is held in the above-mentioned aqueous solution of calcium chloride for 5 minutes, the sodium alginate contained in the coating layer of each droplet reacts with calcium ions that have penetrated into the coating layer and reacts with calcium ions. It was cross-linked with and hardened like a gel. In this way, a large number of round force pussel-like particles having a strong coating layer covering the gold liquid layer were formed. Many of these round force-pellate particles were separated from the aqueous sodium chloride solution and washed with water at room temperature. Thereafter, the washed force round particles were dried in a stream of dry air at 20 ° C. until the force capsule layer became a dry solid layer.

1.5mn dry round capsule particles! It is a capsule having a spherical structure having a diameter in a range of ˜2.0 mm and comprising an inner layer (core portion) and a solid film layer covering the inner layer. The inner layer of each capsule consists of a gold solution containing a gold compound and other metal compound components that act as colorants that can color the cocoon layer, and the coating layer is It consists of a solid mixture of fine particles of glaze raw material for the production of Turkish blue glaze, fine particles of cupric oxide (colorant), and solidified product of calcium alginate gel. This coating layer has a porous structure including pores generated by evaporation of water, and also includes a dispersed phase in the form of solid fine particles and a calcium alginate in the form of a dispersion medium that surrounds and bonds the dispersed phase. It was in the form of a dispersion consisting of a cured product. A perspective view schematically showing the partial cross section of this spherical force psel and the outer shape of the half of the force psel is shown in FIG. In FIG. 1, it is recognized that the spherical capsule has a core portion (1) made of a gold solution and a coating layer (2) covering the core portion.

 (b) Manufacture of pottery with colored decorative patterns on the earth layer

 The surface of the porcelain earthenware dish was dipped with a commercially available glaze raw material slip that was used to produce the Kurotenme candy and allowed to dry naturally. Obtained in Example 1, (a) at a position along a dotted line that draws a favorite dot-drawn pattern with a five-valve flower outline on the dried surface of the unglazed dish product thus glazed. Approximately 100 of the dried spherical capsules were arranged to depict many flower patterns. Separately, in another place on the glazed surface of the above-mentioned unglazed dish product, dozens of spherical capsules are scattered in a circular outline, and force pusels are concentrated in a part of the circular area. Arranged in such a state. Prior to the placement of these capsules, a pretreatment was performed in which a commercially available starch paste for spraying was sprayed as an adhesive at the capsule placement position. After that, spray the starch paste for spraying as an organic adhesive again on the surface of the glazed dish with the spherical force pusher arranged as described above, and then dry it naturally to make the spherical capsules of the unglazed dish. It was attached to the glazed surface. In this way, the unglazed dish having the above-mentioned spherical capsules is placed in an electric kiln (a product of Nidec Simpo Co., Ltd.) and gradually heated to a maximum glazing temperature of 1235 ° C. And fired in an oxidizing atmosphere made of air.

The surface of the baked earthenware dish has a base glaze coating fused to it, and is arranged on the ground layer so as to delineate the petals. Each of the ridges in the form of small island spots (spots) generated by melting of the spherical capsules produced was slightly raised from the terrain. In addition, the entire image composed of a combination of these numerous spots is generated in the style of a petal stipple pattern. It was. In addition, dozens of spherical capsules arranged as described above in the above-mentioned circular outline are small island-like spots that are slightly raised by melting each of the spherical capsules.

(spots) form each of the cocoon layers, but some of these islet-like spots are associated with each other, and some of the specks are slightly larger in size. Was forming.

 Each of the slightly raised ridges in the shape of the small island-like spots formed by the melting of the spherical force psel shows concentric double-colored colored stripes on the upper surface. The outer fringes were bluish green, and the inner fringes were purple. When the inner stripes were viewed under a microscope, gold crystals appeared, and when the outer fringes were observed under a microscope, copper crystals were observed. Slightly raised small island-like speckled cocoon layers created by melting individual spherical capsules, when viewed collectively, show a variety of unique, subtle and beautiful hues, and decorative patterns that show kiln alteration effects. Was produced on a black ground that was fused to the entire surface of the pottery plate.

 (c) Manufacture of porcelain stone tiles with decorative patterns showing kiln modification effects

 A commercial product of a glaze raw material slip that is used to produce the Kurotenme candy was dipped into the surface of a ceramic clay glazed tile board, and then the tile board was air-dried. Spray starch paste was sprayed on the dried surface, and a number of spherical force pusels made in Example 1, (a) were placed on the dried surface so as to draw a decorative pattern and bound. The unglazed Tainole plate with the capsules attached in this way is placed in an electric kiln (manufactured by Nidec Simpo Co., Ltd.) and gradually heated to 1000-1200 in an oxidizing atmosphere consisting of air. Firing was performed at a temperature of 1250 ° C, followed by firing in a reducing atmosphere. The reducing atmosphere was created by incomplete combustion of the fuel gas from the gas burner installed in the electric kiln. Carbon monoxide and carbon dioxide, which are incomplete combustion components of the fuel gas, chemically react with oxygen in the metal oxide contained in the capsule, resulting in a metal oxide having a low oxygen content, or Converted to oxygen-free metal.

The surface of the fired tile plate has a black tenmoku ground layer fused to it, and on the black ground layer, the kiln change that was generated by melting each individual capsule. It was confirmed that a decorative pattern consisting of small island-like spots and mottles with dots that showed the effect and various shades of blue, purple, yellow, and red was generated.

Example 2

 (a) a glaze raw material for producing lime glaze, ferrous oxide (colorant) and a core composed of a solid mixture of sodium alginate as an organic binder, the glaze raw material, colorant and alginic acid A first intermediate layer formed of a solid mixture of calcium, a second intermediate layer of a gold solution dry residue product, and a solid film layer formed of a calcium alginate hard material. Of multi-layered composite spherical capsules containing

(0 A mixture of glaze raw materials capable of producing silver oil droplet Tenmoku, which is a mixture of glaze raw material for the production of lime koji, ferric oxide (colorant) and manganese oxide (coloring aid) (Hereinafter referred to as the product of Tsuji Seki Co., Ltd .; hereinafter, the slurry is simply referred to as a glaze for the production of silver oil drop Tenmoku) This commercially available slurry (slip) is a basic lime cake. particles of the particulate glaze material for generation of ferric oxide as a colorant 12 weight _^0/0, based on the total weight of the glaze material microparticles and 2% of the amount of manganese dioxide (coloring adjuvant) Is a slurry-like mixture containing water and about 40% by weight of water.

1 part by weight of a commercially available slip (slip) of glaze material for formation of the silver oil Tianmu glaze, 5 weight sodium alginate (as organic binder, also acts as a starting material for formation of the coating material substance) ⁰ A slurry-like mixture B was prepared by mixing well with 1 part by weight of a / ₀ aqueous solution (sol form).

This slurry-like mixture B is dropped in a liquid bath composed of a 2.0% by weight aqueous solution of calcium chloride through a nozzle tube having a nozzle hole outlet diameter of 1.44 mm. In this liquid bath, each droplet has a surface coating layer composed of a mixture of calcium alginate gel-like hard particles and fine particles of the solid component of the slurry, and a core made of the slurry-like mixture B. A large number of spherical capsule particles with a part were formed. These spherical force-psel particles were separated from the aqueous solution of calcium chloride solution, washed with water, and the washed capsule particles were sufficiently dried in a 20 ° C dry air stream. This drying was performed until the entire force pushell particles (including the core) were solidified. The round force pusher particles thus dried each had a particle size of about 1.0 mm. Looking at the internal structure of these dried capsule particles, each individual capsule particle is composed of solid fine particles, ferric oxide fine particles, manganese dioxide fine particles, sodium alginate (organic binder) ) And a few percent of water (in the form of a dispersion) and a substantially solid core layer composed of a solidified calcium alginate gel. Configured.

 (ii) 30 parts by weight of the dry round force Psel particles obtained in this way are immersed in 1 part by weight of the gold solution used in the Example, (a), and placed on the capsule particle surface. The gold solution was coated. Round capsule particles with a surface coating of gold liquor were then dried in a stream of dry air at 50 ° C to solidify the entire particle. Each of the dried round capsule particles thus obtained has a core portion (innermost layer) made of the above dispersion-type solid mixture, and is an intermediate layer covering the core portion, and solidifies calcium alginate. A dry residue product of a gold solution having a first intermediate layer made of a solid mixture of the product and the solid component fine particles of the glaze slurry (acting as a coloring agent) It is in the form of a spherical force psel with a composite structure of three layers with a thin V, coating layer consisting of colloidal gold particles and gold ions and various components.

 (iii) A force psell manufacturing apparatus having the same structure as that of the power psell manufacturing apparatus with a double tube nozzle having the apparatus structure shown in FIG. 3 and used in Example 1 was prepared. However, in the apparatus used here, the outlet hole diameter of the nozzle hole (6) of the inner nozzle pipe (4) is adjusted to about 1.2 mm, and the nozzle hole (3) of the outer nozzle pipe (1) is adjusted. The outlet hole diameter was adjusted to be about 1.5 mm.

In the lumen of the inner nozzle (4) of the capsule manufacturing apparatus having such a structure, the dried round capsule particles obtained in (ii) above (that is, having a thin surface coating layer made of a dry residue product of gold solution) A total of three-layered spherical capsule particles) were charged, and the capsule particles were pushed downward one after another through the nozzle hole (6) of the inner nozzle. On the other hand, 5 weight of sodium alginate, which is the raw material for forming the capsule coating layer, is passed through the channel (8) formed between the inner nozzle (4) and the outer nozzle (1). _^0/0 aqueous solution (sol) is extruded. The aqueous sodium alginate solution (sol) is extruded through an annular slit formed between the peripheral wall of the nozzle hole of the inner nozzle tube and the peripheral wall of the nozzle hole of the outer nozzle tube. In the above (ii) The ratio of the weight of the capsule of the total three-layer composite capsules extruded from the nozzle hole (6) to the weight of the sodium alginate aqueous solution extruded through the annular slit is approximately 60:40. As described above, the extrusion rate of the sodium alginate aqueous solution was adjusted.

 Each of the capsule particles exiting from the outlet hole of the inner nozzle tube (4) is surrounded by an aqueous sodium alginate solution extruded through the annular slit below the channel (8), and the outer nozzle tube. Under the outlet of the nozzle hole (3), the sodium alginate aqueous solution was taken into the liquid stream, and the nozzle hole (3) came out one after another as it was. Thus, a film layer of the aqueous sodium alginate solution (sol) was formed on the dried round force pusher particles. As a result, a core part (innermost layer) made of the dispersion-type solid mixture, and a first intermediate layer made of a mixture of a solidified calcium alginate gel enveloping the core part and solid component fine particles of glaze And a thin second intermediate layer made of a dry residue product of gold liquid (including gold colloidal particles, etc.) encapsulated thereon, and as the outermost surface layer encapsulating it, alginic acid A four-layered round capsule particle (generally in the form of a droplet) composed of a coating layer made of an aqueous sodium solution (sol) is the outlet of the nozzle hole (3) of the outer nozzle tube. It was formed one after another at the tip of the liquid flow extruded from and then dropped one after another.

 (iv) The composite capsule-shaped round capsule particles (in the form of the droplets) dropped as described above were successively dropped into a liquid bath of a 2.0 wt% aqueous solution of calcium chloride at room temperature. In the liquid bath, the droplet composed of the round capsule particles having the composite structure dropped was held in the aqueous solution of calcium chloride for about 5 minutes. In this way, the sodium alginate contained in the film layer of the droplets composed of these capsule particles reacts with calcium ions that have penetrated the film layer to become genore, and the calcium alginate produced thereby becomes a gel-like hardening. It changed into a thing. Thus, a large number of multi-layered composite force spherical particles with a strong coating layer completely encapsulating the capsule contents were formed.

Next, the spherical force psel-like particles having a large number of composite structures were separated from the aqueous solution of chloride chloride aqueous solution and further washed with water at room temperature. After that, water-washed spherical capsules The child was dried in a stream of dry air at 20 ° C until the particle coating layer was solid.

(V) The dried multi-layer composite spherical capsules thus obtained are each l.Omn in diameter! It had a diameter in the range of ~ 1.5rmn. Each spherical force pushell is a multi-layered spherical capsule composed of an innermost layer (core), two intermediate layers covering the innermost layer, and a coating layer covering the outermost layer. The core of each capsule, that is, the innermost layer is made of the above-mentioned dispersion-type solid mixture, and the first intermediate layer that initially covers the core is a hardened material of calcium alginate and a solid of glaze material. A coating composed of a solid mixture of fine particles and a colorant, and the second intermediate thin layer covering the first intermediate layer is made of a gold liquid dry residue product containing gold colloid and is covered most outwardly. It was a composite multi-layered capsule in which the layer was a porous solid layer made of hard calcium alginate. Figure 2 shows a schematic diagram of the central cross section of such a multilayer composite capsule. It is recognized that the capsule has a core (1), a first intermediate layer (3), a second intermediate layer (3,) and a coating layer (2).

 (b) Manufacture of pottery with colored decorative patterns on the earth layer

 The surface of the ceramic earthenware dish was dipped with a commercially available glaze raw material slip that was used to produce the Kurotenme candy, and then air-dried. Example 2 in the position along the dotted line that draws a desired dot-drawn pattern with the outline of a five-valve flower on the dry surface of the inner surface of the glazed dish thus glazed. Approximately 100 of the dried spherical force cells obtained in a) and (v) were arranged, and many of the dotted flower patterns were made. Separately, in another place on the inner surface of the glazed dish, the dozens of the spherical capsules are scattered in a circular outline, and the capsules are partially encapsulated in the circular area. Arranged in a dense state. Prior to arranging the capsules as described above, a pretreatment was performed in which starch paste was preliminarily sprayed on the position where the capsules were placed.

After that, again, sprayed commercially available starch paste as an organic adhesive from the surface of the glazed dish with the spherical force pussels arranged as described above, and then naturally dried to unglare spherical capsules. It was bound to the inner surface of the dish. In this way, the unglazed dish having the above-mentioned spherical capsules is placed in an electric kiln (a product of Nidec Shinpo Co., Ltd.), gradually heated, and a maximum of 1235 ° C. Glazed temperature And then fired in an oxidizing atmosphere consisting of air.

 The inner surface of the baked pottery plate has a base glaze coating fused to it, and is arranged on the ground layer to outline the petals. Each of the ridges in the form of small island spots produced by the melting of the individual spherical capsules produced in a slightly raised form from the terrain. The entire image composed of a combination of these spots was generated in the style of a petal pattern. Furthermore, dozens of spherical capsules arranged as described above in the above-mentioned circular outline are caused by melting of each of the spherical capsules, so that small island-like spots slightly raised.

Each of the soot layers in the form of (spots) was generated. In addition, some of these small island-like spots were associated with each other, forming a cocoon layer in the form of several specks with a slightly larger size.

 Each of the ridges in the shape of a slightly raised small island-like spot formed by melting of the spherical force psell shows a concentric double-colored striped pattern on its upper surface, and the outer edge of each spot is It was blue and the inner stripes were purple with a purple color. When the outer stripes were viewed under a microscope, gold crystals appeared, and when the inner stripes were viewed under a microscope, it was observed that iron crystals appeared. The overall image, which is composed of a combination of slightly raised island-like spots in the form of small island-like speckles caused by the melting of individual spherical capsules, has a variety of unique, subtle and beautiful colors. It was also recognized that a decorative pattern showing a kiln change effect was created on the earthen layer of the Kurotenmoku, where ceramic plates were fused.

 (c) Manufacture of porcelain stone tiles with decorative patterns showing kiln modification effects

 A commercial product of a glaze raw material slip that is used to produce the black tempered candy is dipped into the surface of a clay-glazed unglazed tile board, and then the tile board is air-dried. A spray starch paste was sprayed on the dried surface, and a large number of spherical force pusels made in Example 2, (a) were placed on the dried surface so as to draw a decorative pattern and bonded.

The unglazed tile board with the capsules attached in this way is placed in an electric kiln (a product of Nidec Simpo Co., Ltd.) and gradually heated, and then oxidized at 1000-1200 ° C with air. Baking under atmosphere and reducing atmosphere in the same manner as in Example 1, (c) It was fired at a temperature of 1250 ° C below.

 The surface of the fired tile plate has a black tenmoku ground layer fused to it, and on the black ground layer, a kiln deformed by the melting of individual capsules. It was confirmed that a decorative pattern consisting of small island-like spots and spots including dots that showed the effect and various colors of yellow, blue, purple, and red was generated.

Example 3

 (a) Instead of 1 part by weight of the glaze raw material slip for producing silver oil droplet Tenmoku used in Example 2, (a), (i), in Example 1, (a) The capsule manufacturing method described in Example 2, (a), (i) to (iv) was used using 1 part by weight of the glaze (slip) of the glaze raw material used to produce the Turkish blue koji used. According to the procedure, a large number of multi-layer composite structured spherical capsules were produced. The core of the composite spherical capsule obtained after the drying step (iv) is composed of fine particles of sodium feldspar glaze raw material, cupric oxide fine particles, sodium alginate ( It essentially consists of a solid mixture with (acting as a binder). The first intermediate layer surrounding the core of the spherical capsule is formed from a solid mixture of a hardened material of calcium alginate, fine particles of the glaze raw material, and cupric oxide fine particles, and the second intermediate layer is made of gold. The dry layer product of the liquid (containing colloidal gold particles and gold ions, etc.), and the coating layer that encloses the second intermediate layer from the outermost side, is made of hard calcium alginate. It was comprised with the solid layer of the porous structure which becomes.

 The resulting multi-layer composite structured spherical capsules had particles of 1.0-1.5 mm.

(b) In place of the composite structure spherical force obtained in Example 2, (a), (V), except that the composite structure spherical capsule obtained in Example 3, (a) above is used. In the same manner as described in Example 2, (b), the spherical capsules were bound to the inner surface of a ceramic dish glazed with black Tenmoku as the ground, and then fired in the same manner. Went. The glazed surface of the baked earthenware dish thus obtained has an earthen layer of Kurotenmoku, on which the spherical capsules arranged so as to outline the petals are melted. Each of the ridges in the form of small island spots was generated in a slightly raised form from the base ridge. Moreover, the entire image composed of a combination of these spotted cocoon layers was generated in the style of a petal pattern. Furthermore, in Example 2 above, (b) As shown, in one region of the glazed inner surface of the pottery plate, dozens of spherical capsules scattered or closely packed in a circular contour are each of their spherical force pouches. As a result of the melting, each of the ridges in the form of slightly raised small island-like spots (spots) was formed, but the young thousands of these small island-like spots became associated with each other. The specks were in the form of spiders in the form of specks. Each of the ridges of the slightly raised small island-shaped spots resulting from the melting of each of the spherical capsules shows a concentric double-colored colored striped pattern on the upper surface, and the inside of each spot The striped portion of the film exhibited a blue-green color, and the striped portion on the outer edge exhibited a gold color. When the outer fringes were viewed under a microscope, gold crystals appeared, and when the inner fringes were viewed under a microscope, copper crystals were observed. The overall image, which is composed of a combination of slightly raised island-like spots in the form of small island-like spots caused by the melting of individual spherical capsules, together with a variety of unique and subtly beautiful hues. It was confirmed that the decorative pattern showing the kiln change effect was created on the black ground layer of the Kurotenmoku, fused to the pottery plate.

Example 4

(a) From a core composed of a solid mixture of a colorant for ceramics and a glaze raw material for producing colorless lime glaze and sodium alginate (organic binder), and a calcium alginate coating material ■ (i) A commercial product of a bright yellow pigment known as a pigment for ceramics for top-painting (manufactured by Nippon Ceramics Co., Ltd.) was prepared. The main component of commercially available light-colored yellow pigment consists of fine powder of a homogeneous mixture of Jiriko Niumushiriketo ZrSiO ₄ and plug Seo Jiu arm silicate PrSi0 _4. In addition, we have prepared a commercial product (slip product) of glaze (slip), a glaze raw material for producing lime glaze that can produce an almost colorless and transparent lime glaze layer known as a basic glaze for ceramics. The commercially available slurry of glaze raw material for the production of lime glaze prepared here consists of fine particles of potassium feldspar, fine particles of calcium carbonate, fine particles of calcite (Al ₂ 0 ₃ '4Si0 ₂ ' H ₂ 0) , A colloidal particle of kaolin, and lithium feldspar Li ₂ 0 · AI2O3 · 8S1O2, a fine powdery mixture consisting of fine particles of a flux (flux). The product had a moisture content of about 40% by weight. A 1:29:10 fine powder of the above-mentioned commercial light yellow pigment, a 5 wt% solution of the above-mentioned glaze raw material slurry (for producing lime cake) and carboxymethylcellulose 'Natrium salt (binder) Mix well in the weight ratio, thereby preparing a slurry-like mixture. In addition, a 5 weight ⁰ / οτ (solution (sol-like liquid) of sodium alginate used as a raw material for the film material for forming the film layer of the spherical capsule to be produced was prepared. Furthermore, a capsule manufacturing apparatus with a double tube nozzle having the apparatus structure used in the steps of Example 1 and (a) and schematically shown in FIG. 3 was prepared. However, in the device used here, the inner diameter of the outlet of the nozzle hole (6) of the inner nozzle pipe (4)

Adjust to 0.77mm and adjust the inner diameter of the nozzle hole (3) of the outer nozzle tube (1)

Adjusted to 1.94mm.

 (ii) The slurry-like mixture E is charged into the inner nozzle tube (7) from the upper side of the inner nozzle tube (4) of the force tube manufacturing apparatus with the double tube nozzle. did. The slurry-like mixture E was extruded downward from the inner nozzle hole (6) of the inner nozzle tube through the tip (5) of the inner nozzle tube (4).

 Prior to this, the above-mentioned 5 wt% aqueous solution of sodium alginate (sol form) is loaded into the supply chamber (1,) for the liquid material of the material forming the spherical capsule coating layer provided in the capsule manufacturing apparatus. I left it. The aqueous sodium alginate solution was extruded through an intermediate channel (8) formed between the outer nozzle tube (1) and the inner nozzle tube. This extrusion was performed in the form of a slurry passing through the inner nozzle tube (4). Simultaneously with the extrusion of mixture E.

The position of the outer nozzle hole outlet of the outer nozzle is located below the nozzle hole outlet of the inner nozzle pipe, and at the tip of the tapered part (2) of the outer nozzle pipe (1), The aqueous sodium alginate solution was extruded through an annular slit formed between the peripheral wall of the nozzle hole (3) of the outer nozzle tube and the peripheral wall of the nozzle hole (6) of the inner nozzle tube. In this way, the aqueous sodium alginate solution surrounds the surface of the liquid flow composed of the slurry mixture E exiting from the nozzle hole (6) of the inner nozzle tube in the form of a film, and the liquid flow of the inner and outer layers 1 A book was formed below the nozzle hole outlet. Moreover, when the liquid flow slightly dropped, the phenomenon of natural constriction and successive droplets occurred as in Example 1, (a). As a result, round droplets of a two-layer structure composed of a round inner layer made of the slurry mixture E and a coating layer of the above-mentioned sodium alginate aqueous solution enveloping this are formed into the nozzle holes of the outer nozzle tube (1). Formed one after another at the tip of the liquid stream extruded from (3). The extrusion rate of the slurry-like mixture E and the extrusion rate of the aqueous sodium alginate solution were appropriately controlled. In this way, the weight of the inner layer (consisting of the slurry-like mixture E) and the coating layer (consisting of aqueous sodium anoleate solution) of each of the round droplets having the two-layer structure described above The above-mentioned double-structured round droplets were continuously formed one after another, with an average ratio with respect to weight of about 40:60. However, the diameter and size of these round droplets were found to be approximately the same, although they varied somewhat for each individual droplet.

 (iii) The two-layered round droplets formed one after another as described above were dropped one after another in a liquid bath composed of a 2.0 wt% aqueous solution of rutile chloride at room temperature. When the dropped droplets were held in the aqueous solution of calcium chloride for about 5 minutes, sodium alginate in the coating layer of the droplets reacted with calcium ions and hardened into a gel by ionic crosslinking. Thus, a large number of round capsule-like particles having a strong film covering the core of the slurry-like mixture E were formed.

 These many round force pussel-like particles were separated from the aqueous solution of calcium chloride solution and further washed with water at room temperature. Thereafter, the round capsule-like particles washed with water were dried in a dry air flow at 20 ° C. until the slurry-like mixture E at the core of the capsule particles was solidified.

The dry round force psell-like particles obtained in this way are 1.5mn! It is a capsule having a spherical structure having a diameter in a range of ˜2.0 mm and comprising an inner layer (core portion) and a coating layer covering the inner layer. The inner layer of each capsule consists of a solid mixture of a kind of yellow pigment for ceramics, a glaze pigment for producing lime glaze, and sodium alginate as the organic binder, and the capsule coating layer is a hard layer of calcium alginate. It was made of a porous solid material made of metal. The cross-sectional structure of this capsule is the same as that of the spherical capsule of Example 1, (a) shown in FIG. 1, and the capsule has an inner layer (1) and a coating layer (2). In these spherical capsules, the yellow color of the yellow pigment contained in the core through the film layer was slightly blurred. (b) A core composed of a solid mixture of a pigment having a color different from the light yellow pigment, a glaze raw material for producing lime glaze and sodium alginate, and hardening of calcium alginate as a coating material Preparation of Spherical Capsule with Film Layer Made of Product In place of the above-mentioned commercially available light yellow pigment (product of Nissho Sangyo Co., Ltd.) used in the steps of Example 4, (a) and (i) above Commercially available rose pink pigments (based on a dispersion of force domum particles in zirconium silicate), 'commercial green-blue pigments (Ginoleconium silicate and Panadium silicate and A main component is a homogeneous mixture of commercially available dark blue pigment (copper aluminate (Co) Al ₂ 0 ₄ and zinc aluminate (Ζη) 1 ₂ 0 ₄ ). ), Commercially available amber pigment (Zirco Nium, Vanadium and praseodymium Pr silicate complex), commercially available green pigment (mixed oxide of aluminum and chromium (Al, Cr) ₂ O ₃ ), commercially available chocolate color pigments (zinc, iron and chromium hybrid Sani匕物(Zn, Fe) (Fe, Cr) as a main component ₂ 0 _4), a commercially available golden brown pigment (zinc, as iron and chromium content is small) ), Commercially available pink pigment (based on a substance having the chemical composition CaO'SnO ₂ 'Si0 ₂ ' CrO ₃ ), commercially available peacock pigment (cobalt chromate CoCr ₂ 0 ₄ Main component), commercially available black raw materials (cobalt, iron and chromium mixed oxide (Co, Fe) (Fe, Cr) _{2 4 4} as main components), or commercially available white pigments (chemical composition) Sn0 ₂ -Si0 ₂ -B ₂ 0 ₃ -Na ₂ 0-CaO as a main component) or another commercially available white pigment (di Example 4 (a), (i) to (iii) above, using a ruthenium 'silicate as a main component) or red citrus red pigment (based on an acid 匕 manganese or cadmium red pigment). ) Was carried out.

 In this way, since 11 kinds of pigments were blended in the core of the spherical capsule, 11 kinds of spherical force pusels each capable of expressing 11 colors could be manufactured.

 (c) Manufacture of pottery with multicolor decorative patterns on the ground layer

A commercially available glaze material (slip) for producing milky white koji was dipped in a ceramic clay dish, and then air-dried. Various spherical capsules that can develop the various colors obtained in Examples 4, (a) and (b) above in the outline of the five-valve flower on the inner surface of the unglazed dish glazed with milky leopard Were arranged at appropriate locations with color combinations according to preference. Prior to arranging the capsules, the capsules are placed on the glazed surface. The starch paste was sprayed on the position. The arrangement of these various spherical force pusels was adjusted to create a painting pattern to draw the desired dot drawing.

 After that, spray the starch paste for commercial spraying as an organic adhesive from the top of the glazed dish on which the spherical capsules are placed, and bind the spherical force pouch to the glazed inner surface of the dish. It was. The unglazed dish having the spherical capsules bound in this manner is placed in an electric kiln (a product of Nidec Sympo Co., Ltd.) and gradually heated to a maximum glazing temperature of 1235 ° C. Then, it was fired in an oxidizing atmosphere made of air.

 The inner surface of the baked pottery plate has a milky white cocoon layer fused to it, and various spherical forces arranged on the ground layer so as to outline the petals. A small island-like spotted coral layer with different hues produced by the melting of each of the psel was generated, and in the form of a slightly elevated islet from the milky white ground layer. Moreover, the entire image composed of a combination of these spots was created with a petal pattern.

 As a result, on the surface of the baked pottery plate, a variety of petal-painted patterns were created on the surface of the milky leopard.

 (d) Manufacture of porcelain dishes that have a decorative pattern that depicts a landscape including mountains, clouds, and trees in a dot-drawing style on the blue layer of Turkey.

(The porcelain raw material glaze used in Example 1, (a) was dipped in a porcelain earthenware round dish and dried naturally. The dried surface of the dish thus glazed In the center of the inner surface of the plate, the small spherical capsule (a) containing the red-red pigment made in Example 4, (b) and the large-size containing the red-red pigment in the outline that shaped Mt. Fuji A large number of spherical capsules (a,) were arranged in the form of a point drawing, which was created in Example 4, (b) in the outline of a thin cloud layer that floated a little apart below Mt.Fuji. A number of spherical capsules (b) containing pink pigments were arranged in close proximity to each other, below the above cloud layer, and in the contours of another cloud layer flowing laterally, in Example 4, ( Many of the capsules (c) containing the white pigment made in b) were arranged close to each other. Below, large capsules containing green pigment (d) is allowed arranged along the wavy line. The position to be arranged in their capsule, a starch glue by spraying pre Ji Umate A pretreatment was carried out to prepare the arranged capsules to stick to the dish surface. After arranging the capsules on the dish surface, the dish was air dried. Arrangement of spherical force pusels in the front of the plate where various color force pusels arranged so as to draw a landscape including mountains, clouds, and trees in an abstract style Figure 4 of the attached drawing shows a schematic diagram that schematically depicts the appearance.

 (ii) Put the unglazed round dish with the various force pusels containing pigments of various colors as described above into an electric kiln, and the same procedure as described in Example 4, (c) Baked in.

 The upper surface of the round plate baked as described above is arranged so that the upper area of the plate surface has a blue ground layer of Turkish blue glaze, and Mt. The capsules (a) and (a,) have a dark red cocoon layer formed by melting the capsules, and in the area below the dish surface are capsules arranged to form a pink cloud layer. It has a white soot layer produced by melting (c) and a row of green round soot layers produced by melting capsules (d) arranged along the wavy line. The resulting baked round dish had a beautiful appearance with decorative patterns of various colors that painted a beautiful landscape in a dot-drawing style.

Example 5

 (a) A porous body having a capsule core portion made of a solid mixture of a low-fire-degree frit powder containing blue pigment, yellow pigment or red pigment and sodium alginate, and a hardened product of calcium alginate Preparation of spherical capsules with a structured solid film layer

 (i) Blue fine powder (a) (product of Santoku Kogyo Co., Ltd.) that is commercially available for glass crafts and contains a low-temperature frit kite containing a blue pigment and a low-temperature frit kite containing a yellow pigment Commercially available yellow fine powder (b) (manufactured by Santoku Industry Co., Ltd.) and low-heated frit rice cake containing red pigment (c) (manufactured by Santoku Industry Co., Ltd.) And prepared.

The commercially available blue fine powder (a) of frits with various colors as described above, the commercially available yellow fine powder of frits (b), and the commercially available red fine powder (c) of frits. each, 5 weight _^0/0 aqueous solution of sodium alginate (the sol) 1: well mixed by the weight amount ratio of 1, this Yotsute, and blue slurry mixture F, yellow slurry A -like mixture G and a blue slurry mixture H were prepared.

 Furthermore, a capsule manufacturing apparatus with a double tube nozzle having the apparatus structure used in the steps of Example 1 and (a) and schematically shown in FIG. 3 was prepared. However, in the device used here, the inner diameter of the nozzle hole (6) of the inner nozzle tube (4) is adjusted to 0.80 mm, and the inner diameter of the nozzle hole (3) of the outer nozzle tube (1) is adjusted to 2.10. It is adjusted to mm.

 (ii) The three-color slurry mixture F, G, or H was charged into the inner lumen (7) of the inner nozzle tube (4) of the capsule manufacturing apparatus.

 In addition, a 5 wt% aqueous solution of sodium alginate (sol form) was charged into the supply chamber () for the liquid raw material of the capsule film forming substance provided in the apparatus.

 In the same manner as described in Example 4, (a), (ii), the colored slurry mixture F, G, or H is extruded downward from the nozzle hole (6) of the inner nozzle tube (4), and algin. The aqueous sodium acid solution was extruded through an annular slit between the nozzle hole (3) of the outer nozzle tube and the nozzle hole (6) of the inner nozzle tube.

 In the same manner as described in Example 4, (a), (ii), double-structured round droplets were formed one after another. The average weight ratio between the inner layer of those round droplets formed (the inner layer consisting of the colored slurry mixture F, G or H) and the coating layer (the outer layer consisting of an aqueous sodium alginate solution) is approximately 45 : Adjustment was made to be 55.

 (iii) The round droplets were dropped and introduced one after another into a liquid bath of a 2.0% by weight aqueous solution of calcium chloride in the same manner as described in Example 4, (a), (iii).

 Many round capsule particles with a film made of calcium alginate gel-like hardened material were formed. These force-pseudo particles were taken out from a salt water solution and further washed at room temperature. The water-washed force pussel-like particles were thoroughly dried in a stream of dry air at 20 ° C and dried until the entire capsule solidified. This yielded many of the dried spherical capsules, which had diameters ranging from 1.7 mm to 2.4 mm.

The spherical capsules manufactured by the above processes have a porous core made of a hardened calcium alginate having a core made of a solid mixture F ′ of blue frit powder (a) and sodium alginate. Spherical Force Pseule with Solid Structure of Solid Film Layer (i), a solid mixture G 'of yellow frit fine powder (b) and sodium alginate, and a solid coating layer having a porous structure made of a hardened calcium alginate having a core portion made of G' Solid capsule of spherical structure (ii), a solid mixture of red frit powder (c) and sodium alginate, having a core part H ', and a porous structure of a hardened calcium alginate Spherical force process with layer

(iii) and three types.

 (b) Manufacture of heat-resistant glass molded products with multicolor decorative patterns on the surface

 On the side of a cylindrical glass cup made of heat-resistant palium glass, the blue, yellow and red spherical capsules (i), (ii) and (iii) obtained in Example 5, (a) above were Used in combination to arrange the pattern as desired. Prior to the arrangement of the capsules, pretreatment was performed by spraying a starch paste at the position where the capsules were placed. After the capsules were arranged, a commercially available starch starch was sprayed again and dried to attach the capsules.

 The glass cups to which the capsules were adhered were gradually heated in an electric kiln and baked in an acid atmosphere at a maximum temperature of 850 ° C.

 After firing, when the side of the glass scoop is viewed, blue islets, yellow islets, and red islets are produced slightly from the glass surface. It was formed in a raised state. In addition, each small island-like spot showed a three-dimensional effect, and it was recognized that a beautiful decorative pattern was created by looking at the entire image created by combining these spots.

Example 6

 (a) a core made of a solid mixture of a canary yellow pigment for ceramics and a lime glaze raw material and calcium alginate (which serves as an organic binder); Spherical multi-layer structure with an intermediate layer composed of a mixture of glaze raw material for producing lime glaze and calcium alginate, and a film layer composed of an organic coating material (formed from a cured product of calcium alginate) Capsule preparation

(i) Commercially available fine powder of canary yellow pigment, known as a base paint for ceramics, and commercial fine powder of dark red pigment (both are products of Nidec Shinpo Co., Ltd.) did. In addition, a commercially available product (slipper product) of a glaze raw material for producing lime glaze used in Example 4, (a), (i) was prepared. This glaze material has a water content of about 40% by weight.

Prepared canary yellow pigment (fine powder), glaze (slip) of glaze raw material for lime glaze production, and sodium alginate 2 weight ⁰ /. A slurry mixture J was prepared by thoroughly mixing the aqueous solution at a weight ratio of 1: 9: 5.

 In addition, 2 weights of prepared red pigment (fine powder), glaze (slip) of glaze raw material for producing lime glaze, and sodium alginate. /. A slurry mixture K was prepared by thoroughly mixing the aqueous solution at a weight ratio of 3: 7: 20.

 Separately, we prepared a force psel manufacturing device with a triple pipe nozzle having the device structure shown in the schematic view of the vertical section of the device shown in Figure 5 of the accompanying drawings. This capsule manufacturing apparatus with a triple pipe nozzle is a circular cross section around the outer nozzle (1) in the capsule manufacturing apparatus with a double pipe nozzle shown in Fig. 3 used in Examples 1 to 4. Except for the fact that a third outer nozzle (10) is coaxially mounted, it has substantially the same structure as the apparatus shown in FIG.

 (ii) Insert the slurry mixture J (including yellow pigment) into the inner nozzle tube (4) lumen (7) of the force tube manufacturing equipment with triple tube nozzle shown in Fig. 5. Then, the mixture J was extruded downward from the nozzle hole (6) at the tip through the tip (5) of the inner nozzle tube (4).

 Also, a supply chamber (Γ for the liquid material formed between the inner nozzle pipe (1) and the inner nozzle pipe (4) concentrically surrounding the inner nozzle pipe (4). ) The above slurry mixture K is charged through the supply pipe (9), and between the tapered part (2) of the intermediate nozzle pipe (1) and the inner nozzle pipe (4). After passing through the channel portion (8) formed in the above, the mixture K (containing red red pigment) was extruded downward from the nozzle hole (3) at the tip of the intermediate nozzle tube (1).

Furthermore, the ring-shaped supply chamber (13) for the liquid raw material formed between the outer nozzle pipe (10) and the intermediate nozzle pipe (1) passes through the supply pipe (15). A 5% by weight aqueous solution (sol form) of sodium alginate (raw material for the coating material for forming the force layer) is charged, and the tip of the intermediate nozzle tube (1) (2) And outside Square through channel (14) formed between the tapered portion (11) of the nozzle tube (10), Nozzle the lower end of the sodium alginate 5 weight _^0/0 aqueous solution of outer nozzle tube tapered portion (11) Extruded downward from hole (12).

 In this way, one liquid stream extruded from the nozzle hole (12) has a central layer with a circular cross section, an intermediate layer with an annular cross section surrounding it, and an outer layer surrounding the intermediate layer. It has a three-layered cross-sectional structure with two layers. The central layer of this one liquid stream is made of the slurry mixture J containing yellow pigment, the intermediate layer is made of the slurry mixture K containing dark red pigment, and the outer layer. The side layer is composed of the above-mentioned aqueous sodium alginate solution.

 The above-mentioned liquid stream extruded from the nose hole (12) is naturally narrowed at the lower end to form round three-layer droplets one after another.

 Adjust the inner diameter of the nozzle hole (6) of the inner nozzle pipe to 0.72mm, adjust the outlet inner diameter of the nozzle hole (3) of the intermediate nozzle pipe to 1.94mm, and adjust the nozzle hole (12) of the outer nozzle pipe. The inner diameter of the outlet was adjusted to 3.0 mm, and the outflow rate of the slurry mixture J and the mixture K and the outflow rate of the sodium alginate aqueous solution were appropriately controlled.

 Then, for each of the three-layered round droplets, the weight of the innermost layer (made of the mixture J) of the three-layered droplet, the weight of the intermediate layer (made of the mixture K), The aforementioned three-layered round droplets were formed successively one after another, with an average ratio of the coating layer (made of aqueous sodium alginate solution) to the weight of approximately 25:35:40. The diameter and size of these round droplets were found to be almost the same, although they varied somewhat from individual to individual.

(iii) The three-layered round droplets formed one after another as described above were successively dropped into a 2.0 wt% aqueous solution of calcium chloride at room temperature. When the dropped droplets are kept in the aqueous solution of chloride chloride for about 15 minutes, the sodium alginate in the coating layer of the droplets reacts with the permeated calcium ions and hardens in a gel-like form by ionic crosslinking. A large number of round force-pselled particles with a smooth coating were formed. In addition, most of the sodium alginate contained in the innermost layer and the intermediate layer of the droplets is converted into a calcium alginate gel by reaction with the Ca ions that have permeated the innermost layer and the intermediate layer. Turned into.

 These many round capsule-like particles were separated from the aqueous calcium chloride solution and further washed with water at room temperature. Thereafter, the washed round capsule-like particles were dried in a stream of dry air at 20 ° C. This drying was performed until the adhered water contained in each individual capsule-like particle was substantially lost and the entire particle including the core of the capsule-like particle was solidified.

 A dry round capsule-like particle is a spherical capsule with a three-layer structure having a diameter in the range of 2.0 to 2.5 mm, comprising a core, an intermediate layer surrounding the core, and a coating layer surrounding the core. is there. The innermost layer that forms the core of the spherical capsule is a solid in the form of a dispersion, which is a mixture of a glaze raw material for producing lime glaze, the canary yellow pigment of the lower paint, and a hard alginate of calcium alginate. It consists of a substance. The intermediate layer is also made of a solid material in the form of a dispersion, which is a mixture of a glaze raw material for producing lime glaze, a dark red pigment component of the base paint, and a cured product of calcium alginate, The coating layer was a solid layer having a porous structure made of a cured product of calcium alginate.

 A schematic diagram showing the external appearance of this three-layer spherical force psel in a perspective view is shown in Fig. 6 of the accompanying drawings. A cross section of a portion of this capsule is also shown in FIG. 6 as a perspective view. Each individual capsule has a core (1), an intermediate layer (3), and a coating layer (2).

 (b) Manufacture of painted ceramic using the three-layer capsule manufactured in (a) Above, a slip of glaze raw material for milk white rice cake was soaked in a porcelain clay pot. After glazing in this way, it was naturally dried. The spherical capsule (three-layer structure) manufactured in Example 6, (a) with an arrangement of a desired dot-drawn pattern with a triple circle outline at an appropriate location on the inner surface of the glazed dish. Of dried spherical capsules). Prior to arranging the capsules in such a manner, a pretreatment was performed by spraying starch glue on the position where the capsules were placed. Then again and sprayed with a commercially available spray starch paste, dried to bind the power psel to the glazed surface of the unglazed dish. The unglazed dish glazed product with the spherical force psel attached in this way is gradually heated in an electric kiln (manufactured by Nidec Shinpo Co., Ltd.) and fired in an oxidizing atmosphere at a glazing temperature of 1235 ° C maximum. did.

As a result, the inner surface of the baked pottery plate has a white layer of milk white glaze. On top of each layer, we were able to create a small island-shaped spotted cocoon layer from each capsule with a double-striped pattern of concentric circles with a yellow inner part and a red outer edge. It is a unique technique that cannot be imitated by edging or other painting techniques to paint ceramics with a dot-drawn decorative pattern consisting of a small island-shaped cocoon layer with a double circle (outer diameter 3 mm) stripe pattern. . Example 7

 (a) A glaze raw material for producing lime glaze, a core made of a solid mixture of ferric oxide (colorant), manganese oxide (coloring aid), and calcium alginate (binder), and a dried gold liquor residue Manufacture of a three-layer spherical force psel having an intermediate layer made of a solid product and a porous solid film layer made of a cured product of calcium alginate

 (i) A commercial product of glaze (slip), a glaze raw material that can produce the same silver oil droplet Tenmoku as used in Example 2, (a), (i), is prepared. did. This glaze raw material slurry is a slurry-like mixture containing fine particles of glaze raw material for producing lime glaze, fine particles of ferric oxide, fine particles of mangan oxide and water. Slurry mixture M was prepared by mixing slurry of glaze raw material for producing silver oil droplet Tenmoku with 10% by weight 7 solution of sodium alginate at a weight ratio of 2: 1.

 Also, as the gold liquid commercial product, the product name “gold liquid N-9J gold liquid (product of Noritake Co., Ltd.) used in Example 1 was prepared and mixed with turpentine oil at a weight ratio of 1: 1. An oily mixture L was prepared.

 In addition, sodium alginate 5 weight ° /. In the aqueous solution, 0.1% cobalt oxide fine powder, 0.1% manganese oxide fine powder and 0.05% nickel oxide fine powder based on the weight of the aqueous solution are mixed to form a suspension. A mixture O of was prepared. Separately, an apparatus similar to that used in Example 6, (a), and a capsule manufacturing apparatus with a triple pipe nozzle having the apparatus structure illustrated in FIG. 5 was prepared. However, in this case, the inner diameter of the nozzle hole (6) of the inner nozzle pipe (4) is adjusted to 0.72mm, and the inner diameter of the nozzle nozzle (3) of the intermediate nozzle pipe (1) is 1.94mm. The outlet inner diameter of the nozzle hole (12) of the outer nozzle tube (10) was adjusted to 3.0 mm.

(ii) The slurry-like mixture M (including the glaze raw material for producing silver oil droplets) is extruded from the nozzle hole (6) of the inner nozzle tube, and the slurry-like mixture L (including the gold liquid) The nozzle hole (3) of the intermediate nozzle tube (1) of the above apparatus is extruded, and the above mixing is performed. The object O is directed downward through the annular slit formed near the nozzle hole (12) between the peripheral wall of the nozzle hole (3) of the intermediate nozzle pipe and the tip of the outer nozzle pipe (11). Extruded. The extrusion speeds of the respective mixtures M, L, and O were adjusted to each other. In the same manner as described in Example 6, (a), (ii), a single three-layered liquid flow having a concentric cross section is formed below the outer nozzle hole (12). It was. In addition, this liquid flow was narrowed naturally at the lower end, generating three-layered round droplets one after another.

 In this way, the weight of the innermost layer (mixture M), the weight of the intermediate layer (mixture L), and the coating layer (alginic acid) of the three-layered round droplets Round droplets of the above three-layer structure were formed where the average ratio with the weight of the mixture O) containing the aqueous sodium solution was approximately 30:40:30. The diameter and size of these round droplets were found to be approximately the same, although they varied slightly for each individual.

 (iii) The three-layered round droplets formed one after another as described above were successively dropped into a 2.0 wt% 7 solution of calcium chloride at room temperature. When the dropped droplets are held in the aqueous solution of chloride chloride for about 15 minutes, the sodium alginate in the coating layer of the droplets reacts with calcium ions and hardens into a gel by ionic crosslinking, so it has a strong coating. A number of round capsule-like particles were formed. In addition, sodium alginate in the innermost layer of the particles reacted with calcium ions that had penetrated most of the particles, and gelled.

 These many round capsule-like particles were separated from the aqueous calcium chloride solution and further washed with water at room temperature. Thereafter, the washed round capsule-like particles were dried in a stream of dry air at 20 ° C. Drying was performed until all of the adhering moisture contained in each of these force-pessel particles was removed, that is, until the entire particle including the core of the capsule particles was solidified.

 The dried round capsule-like particles have a diameter in the range of 2.5 to 3.0 mm, and also have a three-layer spherical shape composed of an innermost layer, an intermediate layer surrounding the innermost layer, and a coating layer surrounding the innermost layer. It is a capsule.

Each of these spherical capsules is a solid of glaze raw material for the production of silver oil droplet Tenmoku, various metal compounds as colorants, and calcium alginate (which acts as a binder). A core made of a mixture, an intermediate layer made of a solid residue product of gold liquor, and oxides of cobalt, manganese, and nickel (acting as an adhesion enhancer to the iron surface and acting as a coloring department) A three-layer structure having a porous solid film layer made of a cured product of calcium alginate containing the above fine particles as dispersed particles was shown. The three-layer structure of the spherical capsule is the same as the three-layer structure of the capsule produced in Example 6 and shown in FIG.

 (b) Manufacture of painted iron dishes using the three-layered spherical capsule manufactured in (a) above

 The dried three-layer spherical capsules prepared in Example 7, (a) were arranged in an appropriate place on the surface of the iron plate in an arrangement for creating a favorite stipple pattern. Prior to arranging the capsules, a pre-treatment was performed in which the starch starch for spraying was preliminarily applied to the position where the capsules were placed. Then, it was air-dried and sprayed with a commercial spray paste from above again, dried, and the capsules were bound to an iron pan.

 The iron pan was gradually heated in an electric kiln (manufactured by Nidec Simpo Co., Ltd.) and baked in an acid atmosphere at a maximum temperature of 1250 ° C. As a result, on the surface of the baked iron dish, silver oil droplet Tenmoku mochi spots and mottled cocoon layers are produced by melting each capsule. A beautiful colored decorative pattern was created. The pattern showing the kiln modification effect had a beautiful and unique hue on the surface of the ironware, and it was observed under the microscope that bright gold crystals and iron crystals appeared in the pattern.

Industrial applicability

A two-layer or multi-layer spherical capsule provided by the present invention and encapsulating a glaze raw material for producing a basic glaze and a coloring agent for coloring a glaze is obtained by applying a plurality of the capsules to a ceramic unglazed product. Or, arrange on a non-glazed surface, attach with a heat-decomposable adhesive, and arrange a plurality of force pusels in the same way as creating a dot-like decorative pattern with the adhered capsule, When ceramic pottery products in which these force pusels are arranged and bonded are baked in the usual way, a decorative pattern composed of a combination of colored small island-like cocoon layers generated by melting each capsule is put on the ceramic baked product. Can be created. Therefore, the spherical capsule according to the present invention can be used for producing ceramics having a decorative pattern. Also, ceramic Alternatively, the capsule of the present invention can be used to make a decorative pattern on the surface of another heat resistant substrate.

Claims

The scope of the claims

1. A force that is a spherical force psel composed of an inner layer that forms the core of a spherical capsule and a seamless coating layer that covers the core from the outside, or an innermost layer that forms the core of a spherical force psel And a seamless film layer that encloses the spherical force psel from the outermost side, and one or a plurality of intermediate layers provided between the innermost layer that forms the core and the film layer. A multi-layered composite spherical capsule configured, wherein the coating material forming the coating layer is composed of a thermally decomposable organic substance capable of forming a film, or the thermally decomposable capable of forming the film. It consists of a solid mixture of an organic substance and a glaze material described below and / or a colorant described below, and further a core material that forms the core, a film material that forms the film layer, At least one of the material substances that form the intermediate layer One contains a glaze raw material for producing a basic glaze that can produce a transparent glaze layer upon firing, and the core material forming the core, the coating material, and the intermediate layer At least one of the material substances to be formed contains an inorganic colorant capable of coloring transparent wrinkles produced during firing, and the core material substance, the coating material substance, At least one of the material substances forming the intermediate layer exhibits a kiln modification effect when fired together with the glaze raw material for producing the basic soot capable of producing a transparent soot. A metal substance and / or a metal compound that can be used as a coloring agent capable of forming a dot, speckled or mottled pattern on the generated cocoon layer, or the metal substance or metal compound is Each core, intermediate layer and coating layer are shaped In addition, the core material and one or both of the material forming the intermediate layer may contain a thermally decomposable organic binder. A spherical shape containing and encapsulating a glaze raw material for producing a transparent basic glaze that can produce a transparent glaze layer when fired, and a colorant capable of coloring the transparent basic glaze, which can be optionally contained capsule.

 2. The spherical force pusher according to claim 1, which is in the form of a spherical force pushell composed of an inner layer forming the core of a spherical capsule and a seamless film layer covering the inner layer from the outside.

3. The innermost layer that forms the core of the spherical force psel, one, two, or three intermediate layers that envelop the core, and the seamless coating layer that encloses the intermediate layer from the outermost side. Consists of The spherical force pushell according to claim 1, which is in the form of a multi-layer composite structured spherical capsule.

 4. The film-forming heat-decomposable organic substance in the above-mentioned film material that forms the force-pelled film layer is a hardened calcium alginate, a hardened pectin or methoxypectin, a hardened gelatin or a hardened casein. The spherical force pusher according to claim 1, which is a polysaccharide or protein such as a product, and the coating layer is formed of a solid layer containing a large number of pores and having a porous structure. .

 5. The glaze raw material for producing the basic glaze that can produce a transparent glaze layer upon firing is the known glaze raw material used to produce clear stone ash glaze, or transparent sodium feldspar or Spherical shape according to claim 1, which is a known glaze raw material used to produce clear power ash feldspar, or a known glaze raw material used to produce transparent ash feldspar Force purse.

 6. The glaze raw material for producing the basic cocoons that can produce transparent limestone cocoons is composed of fine particles (i) containing potassium feldspar, limestone, silica stone, and strong olin, or brilliant feldspar and ceramic stone.ゝ consisting of fine particles (ii) containing limestone, limestone and strong oliline, or fine particles (iii) containing potassium feldspar, limestone, palium carbonate, quartzite and strong olin The spherical capsule according to claim 5.

7. The glaze raw material for producing the basic cocoon capable of producing transparent sodium feldspar is made of a particulate material containing sodium feldspar, carbonated palyme, limestone, silica and lithium carbonate. A spherical capsule as described in 1.

 8. The glaze raw material for the production of basic cocoons that can produce transparent force limestone feldspar consists of fine-grained material containing potash feldspar, limestone, quartzite, force olin, dolomite, palium carbonate and zinc oxide. The force purse according to claim 5, wherein

 9. The spherical force psenore according to claim 5, wherein the glaze raw material for producing the basic glaze capable of producing transparent ash glaze is made of a fine particle material containing feldspar or porcelain stone and wood ash.

10. Inorganic colorants that can color the glaze layer produced when fired together with the above glaze raw material for producing basic glaze are cupric oxide, ferric oxide (bengara), chromium oxide, oxidation Manganese, acid cobalt, nickel oxide, acid uranium, cerium oxide, It is a known inorganic colorant in the form of a metal oxide, which can also be titanium oxide or neodymium oxide, or a known inorganic colorant in the form of a metal carbonate, or a metal silicate, aluminate Force, which is a known inorganic colorant in the form of a salt, chromate, or metal sulphide or selenide, or metallic gold that can be colored in a dispersed state in the resulting soot layer, The spherical capsule according to claim 1, which is a known inorganic colorant in the form of metallic silver, metallic cadmium, metallic chromium or metallic selenium.

11. Coloring agent that can be arbitrarily added to any of the substances forming the core layer, intermediate layer, and film layer that make up the spherical capsule, and has small spots, spots or mottles that show kiln alteration effects. The metal substance or metal compound according to claim 1, which can be effective as a colorant that can be formed on the generated glazing layer, is known as a pigment in ceramic upper or lower paints. Terpene oil-soluble gold compound, especially gold salt of resin acid, gold colloid, silver, silver colloid, ferric oxide (Bengara), ferric carbonate, cupric oxide or cupric carbonate, or these Spherical capsule according to claim 1, which consists of two or more substances.

12. The thermally decomposable organic binder that can be optionally blended in the core material of the core of the capsule or in the material of the intermediate layer of the capsule has the above-mentioned film-forming ability. The spherical force pusher according to claim 1, which is a thermally decomposable organic substance, preferably calcium alginate, or sodium alginate as an organic binder.

13. The inner layer that forms the core of a spherical capsule having a core and a skin layer is made of a transparent basic glaze, preferably a glaze raw material for producing lime glaze, and at least one inorganic color that can color this basic glaze. And a solid mixture of an organic binder, preferably sodium alginate or a heat-decomposable organic substance capable of forming a film, preferably calcium alginate, and the film layer of the capsule comprises A force composed of a solid mixture of the glaze raw material for producing the basic soot, the colorant, and the heat-decomposable organic substance having the film-forming ability, preferably calcium alginate, or the film-forming ability The spherical force pusher according to claim 1, wherein the spherical force pushell is formed of a solid layer having a porous structure made of a thermally decomposable organic substance.

14. The innermost layer that forms the core of a spherical capsule with a multi-layered composite structure is a transparent basic basket, Preferably formed from a solid mixture of a glaze raw material for producing lime glaze, at least one inorganic colorant capable of coloring the basic glaze, and a thermally decomposable organic substance capable of forming a film, preferably calcium alginate And one or more intermediate layers enveloping the core portion are made of another kind of inorganic colorant capable of developing a color different from the color developed by the inorganic colorant contained in the core portion. Formed from a solid mixture of the glaze raw material for producing the basic soot and the heat-decomposable organic substance capable of forming a skin film, preferably calcium alginate, and the intermediate layer from the outermost side. The film layer to be encapsulated is a heat-decomposable organic substance capable of forming a film, preferably a force composed of calcium alginate, or a heat-decomposable organic substance capable of forming a film, preferably alginate. The spherical force pusher according to claim 1, which is a spherical capsule having a multi-layered composite structure, which is formed of a solid layer having a porous structure made of a solid mixture of Lucium and an inorganic colorant.

 15. Of the substances that form the core layer, intermediate layer, and film layer that make up the spherical capsule, the substance that forms the layer containing the glaze raw material additionally contains a flux. Spherical force pell described in 1.

16. A spherical capsule composed only of an inner layer that forms the core of a spherical capsule and a seamless coating layer that covers the inner layer, and the core material of the core is small and has a kiln-modifying effect. The metallic substance and metal compound shown in claim 1 that can be effective as an inorganic colorant capable of forming spots, spots, or mottled patterns on the generated cocoon layer. The force formed by a commercially available gold solution containing a gold compound and gold colloidal fine particles, and a flux, or the core material comprises an inorganic colorant in the form of a metal compound and a transparent basic glaze, preferably Formed as a solid or semi-solid or hydrous liquid mixture containing a glaze raw material for the production of limestone and / or a thermally decomposable organic substance capable of forming a film, preferably calcium alginate In addition, the coating material forming the coating layer is composed of inorganic colorants, preferably cupric oxide known as a colorant contained in Turkish blue glaze, and transparent basic glaze, preferably sodium feldspar glaze. A solid layer comprising a glaze raw material for production and a thermally decomposable organic substance capable of forming a film, preferably calcium alginate, and having a porous structure, according to claim 1. Spherical capsule.

17. The entire solid form of the spherical force psel is slightly deformed from a perfect sphere, and the surface of the force psel can have a small constriction or a small protrusion, a protrusion, or a spherical capsule. The spherical capsule according to claim 1, which has a shape close to an oval or a teardrop as a whole.

18. Place a large number of spherical capsules as claimed in claim 1 on the glazed or unglazed surface of a ceramic unglazed molded product in a position where they can be used to draw a decorative pattern in a dot-drawing style as desired. Then, the capsules are bound to the glazed or unglazed surface with a thermally decomposable organic binder, and then the unglazed molded product to which the capsules are bound is gradually heated. The ability to melt the glaze raw material in the capsule and fire it in an oxidizing atmosphere or reducing atmosphere at a firing temperature at which glazing can be performed, or in an oxidizing atmosphere and then in a reducing atmosphere, and during the firing The bonded capsules are melted, the organic substance components in the capsules and the adhesive are burned off, and the color generated by the individual dissolution of the force psenore on the surface of the obtained fired product A small island-shaped cocoon layer is formed, and a colored decorative pattern composed of a combination of these colored small island-shaped cocoon layers is created. Thereafter, the fired product is gradually cooled, and then the fired product is cooled to room temperature. A method for producing ceramics, comprising a plurality of colored small island-like cocoon layers and a decorative pattern composed of a combination of these small island-like cocoon layers on the glazed surface.

19. Prepare a number of spherical capsules as claimed in claim 1 in different combinations of colorants contained in the capsules, and fire the colorants contained in each of those capsules A specification that is a combination of capsules that can draw a point-drawn pattern with a single color or a different color as desired, assuming the color that will be developed later. Select a plurality of different spherical force pusels containing different types of colorants, and select a plurality of the various spherical force pusels so selected for the surface of a heat-resistant substrate, in particular a ceramic glazed surface or Unglazed surface, or heat-resistant glass molding surface, enamel-coated surface, iron or iron alloy molding surface, copper or copper alloy molding surface, aluminum or aluminum alloy molding On the surface of the product or on the surface of the substrate made of other heat-resistant material, arrange them in the same way as drawing a decorative pattern in the form of a point drawing with these force pushers. After firing multiple force pusels A variety of colored small island-shaped cocoon layers produced from the melting of individual capsules and formed on the surface of the substrate. A number of capsules arranged to draw a decorative pattern as described above are bonded to the surface of the substrate with a thermally decomposable organic adhesive. The substrate having the capsules on the surface is baked in an oxidizing atmosphere or a reducing atmosphere at a baking temperature at which the glaze raw material containing the capsules can be melted and glazed, or is subsequently reduced in an oxidizing atmosphere. Firing in the atmosphere, melting the bonded force psel as described above, burning the organic substance component in the force psell and the adhesive, and by melting each of the capsules on the surface of the resulting fired product The resulting colored small islands A dot-drawn decorative pattern composed of a combination of these many colored small island-like cocoon layers is formed on the surface of the fired product, and then the fired product is gradually cooled, and then the fired A decorative method for producing a colored decorative pattern on the surface of a heat-resistant substrate, comprising cooling a product to room temperature, comprising a plurality of combinations of colored small island-like cocoon layers formed on the surface of the substrate.