WO1997030952A1 - Ceramic granules - Google Patents

Abstract

Novel hollow spherical granules usable as excellent pharmaceutical industrial products, fertilizer products, food products, feed products, agricultural products, catalyst products, ceramic products, powder metallurgy products, detergent products, plastic products, bioindustrial products and the like as, for example, catalysts, lightweight materials, soundproofing materials, microcapsules, and lightweight aggregates. In particular, the ceramic granules comprising a spherical ceramic shell and a spherical space provided within the shell are usable as excellent catalyst products, ceramic products, bioindustrial products and the like. In particular, granules, whose shells are constituted of porous walls permit gas or liquid to gradually flow from inside the spherical spaces toward outside the shells or vice versa, enabling the gas or liquid filled inside to be gradually released toward outside, which renders the granules usable for various useful applications.

Description

 Description Ceramic granules Technical field

 The present invention relates to a novel granule, and more particularly to a granule having a hollow space inside a spherical shell. More preferably, the present invention relates to a novel ceramic granule, and more particularly to a ceramic granule having a spherical space (hollow portion) inside a spherical shell.

Background art

 Conventional granules include the pharmaceutical industry, fertilizer industry, food industry, feed industry, agriculture field, catalyst industry, color material industry, ceramic industry, ceramic industry, powder metallurgy industry, detergent industry, It is being widely used in the cosmetics, plastics, and biotechnology industries.

 The granules are obtained by rolling granulation, compression granulation, stirring granulation, extrusion granulation, crushing granulation, fluidized bed granulation, melt granulation, and spraying. Manufactured by dry granulation, liquid phase granulation, vacuum freeze granulation, submerged granulation, etc.

 However, it is not easy to obtain hollow granules by these granulation methods, and hollow granules are slightly obtained by spray drying granulation or the like. In particular, it has been difficult to provide granules having a hollow portion therein, particularly ceramic granules. Disclosure of the invention

As a result of research to solve the above problems, the present inventor has found that a method for easily producing a hollow granule having an arbitrary particle size, particularly a hollow granule having a spherical space inside a spherical porous shell. The present inventors have developed a method for producing a ceramic granule and the like, and have proposed a granule of the present invention. That is, the present invention

 (1) A granulated material characterized by having a spherical space inside a spherical powder solid shell,

 (2) The granule according to (1), wherein the powder is an organic material.

(3) The granule according to the above (1), wherein the powder body is an inorganic material,

(4) The granule according to any one of (1) to (3), wherein the powder contains a binder; and

 (5) The granulated product according to (3) or (4), wherein the inorganic material is a ceramic material. In yet another aspect, the invention provides a method comprising:

 (6) A ceramic granule characterized by having a spherical space inside a spherical ceramic shell,

 (7) A ceramic granule characterized by having a spherical space inside a spherical ceramic shell and being filled with a liquid in the spherical space.

 (8) A ceramic granule characterized by having a spherical space inside a spherical ceramic shell and being filled with a gas in the spherical space.

 (9) A ceramic granule characterized in that it has a spherical space inside a spherical ceramic shell, and the spherical space is filled with a solid that becomes a liquid or gas at high temperature.

(10) The ceramic granule according to any of (6) to (9), wherein the spherical ceramic shell is a sintered ceramic.

(11) The spherical particles of the superabsorbent polymer swollen by water absorption are brought into contact with the ceramic raw material powder to form a ceramic raw material powder layer on the entire surface of the spherical particles of the superabsorbent polymer swollen by water absorption. It is characterized by comprising a ceramic granule having a spherical space inside a spherical ceramic shell obtained by drying and firing. Ceramic granules,

 (12) The ceramic granule according to any one of the above (6) to (11), wherein the shell of the spherical ceramic granule is porous.

 (13) The ceramic granule according to any one of (6) to (12) above, wherein the raw material powder of the spherical ceramic granule contains a binder.

(14) The ceramic granule according to any one of (6) to (13), wherein the shell of the spherical ceramic granule contains a liquid.

 (15) The ceramic granule according to any one of (6) to (14), wherein the shell of the spherical ceramic granule contains a metal salt solution.

(16) The ceramic granule according to any one of (6) to (15), wherein the shell of the spherical ceramic granule contains a solid fine powder.

(17) Ceramic raw materials or ceramics, clay, clay minerals, chamotte, quartz sand, pottery stone, feldspar, alumina, magnesia, zirconia, silica, mullite, cordierite, blast furnace slag, shirasu, fly ash, fly ash, The ceramic granule according to any one of the above (6) to (16), wherein the ceramic granule is at least one selected from silicon carbide, aluminum nitride, and silicon nitride.

 (18) The ceramic raw material or ceramic is clay, clay mineral, chamotte, silica sand, pottery stone, feldspar, graphite, alumina, magnesia, mullite, cordierite, zirconia, silica, blast furnace slag, shirasu, fly ash The granulated ceramic according to any one of the above (6) to (17), which is a mixture of a binder and at least one selected from silicon carbide, aluminum nitride, and silicon nitride. Provide body. In another aspect, the present invention provides

(19) The ceramic granule according to any of (6) to (18), wherein the ceramic granule is a catalyst carrier. (20) The ceramic granule according to any one of (6) to (18), wherein the ceramic granule is an admixture for cement mortar or concrete.

 (21) The ceramic granule according to any one of (6) to (18), wherein the ceramic granule is a lightweight aggregate.

 (22) The ceramic granule according to any one of (6) to (18), wherein the ceramic granule is a fertilizer containing a fertilizer.

 (23) The ceramic granule according to any one of (6) to (18), wherein the ceramic granule is a soil improvement material containing a soil conditioner.

(24) The ceramic granule according to any one of (6) to (18), wherein the ceramic granule is a luminescent material containing a luminescent substance.

(25) The ceramic granule according to any one of (6) to (18), wherein the ceramic granule is a phosphorescence-generating material containing a phosphorescence-generating substance.

(26) The ceramic granule according to any one of (6) to (18), wherein the ceramic granule is a pH adjusting material containing a pH adjusting substance.

(27) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is a sublimable substance release containing a sublimable substance.

(28) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is a fragrance sustained-release product containing a fragrance.

(29) The ceramic granule according to any of (6) to (18), wherein the ceramic granule is an enzyme-containing product containing an enzyme.

(30) The ceramic granule according to any one of (6) to (18), wherein the ceramic granule is a bacteria-containing product containing bacteria. (31) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is a bactericide-containing product containing a bactericide.

(32) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is an insecticide product containing an insecticide.

(33) The ceramic granule according to any of (6) to (18), wherein the ceramic granule is a color material product containing a color material.

 (34) The ceramic granule according to any one of (6) to (18), wherein the ceramic granule is a digestive agent-containing product containing a digestive agent.

(35) The ceramic granule according to any of (6) to (18), wherein the ceramic granule is a fire extinguisher-containing product containing a fire extinguisher.

(36) The ceramic granule according to any of (6) to (18) above, wherein the ceramic granule is a surfactant-containing product containing a surfactant.

 (37) The ceramic granule according to any of (6) to (18), wherein the ceramic granule is a ferromagnetic material-containing product containing a ferromagnetic material. ,

 (38) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is a rare earth magnet material-containing product containing a rare earth magnet material.

 (39) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is a neutron absorbing material-containing product containing a neutron absorbing material.

 (40) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is a product containing a radioactive material containing a radioactive material. ,

(41) The method according to (6), wherein the ceramic granules are colored. ) Or ceramic granules according to any of (18),

 (42) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is an antibiotic-containing product containing an antibiotic.

(43) The ceramic granule according to any of (6) to (18), wherein the ceramic granule is a hormone-containing product containing a hormone substance.

 (44) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is a product containing a hydrogen storage substance containing a hydrogen storage substance.

 (45) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is a superabsorbent polymer-containing product containing a superabsorbent polymer.

 (46) The ceramic granule according to any of (6) to (27), wherein the spherical ceramic shell has a multilayer structure.

 (47) The ceramic granule according to any one of (6) to (38), wherein the spherical ceramic shell is an unsintered ceramic green material.

(48) The spherical particles of the superabsorbent polymer swollen by water are brought into contact with the ceramic raw material powder to form the same powder layer on the entire surface of the spherical particles of the superabsorbent polymer swollen by the water. A ceramic granule characterized by comprising an unfired ceramic granule having a spherical space inside a spherical unfired ceramic shell obtained by drying the ceramic granule. In yet another aspect, the invention provides a method comprising:

(49) The spherical particles of the superabsorbent polymer swollen by water are brought into contact with the ceramic raw material powder to form a powder layer on the entire surface of the spherical particles of the superabsorbent polymer swollen by the same water. A ceramic granule characterized by comprising an unsintered ceramic granule having a spherical space inside a spherical unsintered ceramic shell obtained by drying it after drying.

 (50) Contact the powder with the spherical particles of the superabsorbent polymer that has swollen to form a powder layer on the entire surface of the spherical particles of the superabsorbent polymer that have swollen and then dry it. Characterized by being a granulated body obtained by the above and having a spherical space inside a spherical solid shell,

 (51) A granulated body, characterized in that the granulated body according to any one of (1) to (50) is immersed in a liquid, and the shell of the granulated body is impregnated with the liquid.

 (52) The granulated product according to (51), wherein the liquid is a metal salt solution.

(53) The granulated product according to any one of (1) to (50) is immersed in a suspension of solid fine powder, dried, and mixed with the solid fine powder in the shell of the granulated product. Granules, characterized in that

 (54) A granulated body characterized in that the granulated body according to any one of (1) to (50) is immersed in a liquid, and the liquid is contained in an internal spherical space.

 (55) A granulated body characterized in that the granulated body according to any of the above (1) to (50) is left in a gas body, and the gas body is incorporated in an internal spherical space.

 (56) The powder is [1] pharmaceutical, [2] fertilizer, [3] food, [4] cement, (: 5) feed, [6] coloring material, [7] pesticide, [8] cosmetic, (9) enzyme-containing material, (10) surfactant, (11) semiconductor, (12) metal, (13) multi-capsule composition,

[14] Cermet, [15] Paint coating material, [16] Corrosion material, [17] Insulation material, [18] Sound absorbing material, [19] Radio wave absorbing material, [20] Light absorbing material, [21] Anti-reflective material Shooting materials, [22] Traffic sign display materials, [23] Ball bearings, [24] Bio-oritors, [25] Far-infrared radiation materials, [26] Electric heating materials, [27] Lightweight aggregates, [28] Ball game materials , [29] Dehumidifying material, [30] Furnace material, [31] Engine room wall material, (; 32] Gas turbine room wall materials, [33] Backing (lining) materials, [34] Ventilation materials, [35] Soil materials, [36] Biomaterials, [37] Inclined materials, [38] Apatite (39) Slow-acting material, (40) Plastic, (41) Photosensitive material, (42) Hydrogen storage material, (43) Musical instrument material, (44) Acoustic speaker material, (

45) Ozone decomposer, [46] Enamel, [47] Glaze, [48] Spacecraft, [49] Solar furnace, [50] Artificial teeth, [51] Tile, [52] Pigment, [53] Filling (54) adhesive main component, (55) ultrafine particle material, (56) permanent magnet material, and [57] shape memory material. ) To the granulated product according to any one of (55),

 (57) A mass formed by assembling and tying a large number of the granules according to any one of the above (1) to (56) to form a mass. body,

(58) A mass sintering process in which a large number of granules according to any one of the above (1) to (56) are sintered into a massive sintered body. Union,

(59) The granulation according to any one of the above (1) to (55), wherein the surface of the granulated body is coated with different powders to form a spherical multilayer solid shell. Body,

 (60) A mass formed by combining and combining a large number of the granules according to the above (59) into a mass,

 (61) a bulk sintered body obtained by sintering a large number of granules according to the above (59) to form a massive sintered body; and

 (62) The granules are (1) pharmaceutical, (2) fertilizer, (3) food, (4) cement, (5) feed, (6) coloring material, (7) pesticide, (8) cosmetics , (9) enzyme-containing material, (10) surfactant, (11) semiconductor, (12) metal, (13) multiple capsule composition,

[14] Cermet, [15] Paint coating material, [16] Suitable material, [17] Insulation material, [18] Sound absorbing material, [19] Radio wave absorbing material, [20] Light absorbing material, [21] Anti-reflective material Shooting material, [22] Traffic sign display material, [23] Ball bearing, [24] Biori Actor, [25] Far-infrared radiation material, [26] Electric heating material, [27] Lightweight aggregate, [28] Ball game material, [29] Dehumidifying material, [30] Furnace material, [31] Engine room wall material, [32] Gas turbine room wall material, [33] Backing (lining) material, [34] Ventilation material, [35] Soil material, [36] Biomaterials, [37] Inclined material, [38] Apatite G, (39) Slow-acting material, (40) Plastic, (41) Photosensitive material, (42) Hydrogen storage material, (43) Musical instrument material, (44) Acoustic speaker material, (45) Ozone decomposing material, (46) Enamel, [47] glaze, [48] space flight material,

(49) Solar furnace, (50) Artificial teeth, (51) Tile, (52) Pigment, (53) Filling material, (54) Adhesive main component, (55) Ultrafine particle material, (56) Permanent magnet material [57] The granule according to any one of [1] to [61], which is selected from the group consisting of shape memory materials.

 In yet another aspect, the invention provides a method comprising:

 (63) A viscosifier is applied to the surface of the spherical particles of the superabsorbent polymer that has swelled and absorbed, and after a powder is applied to the surface, it is dried and has a spherical space inside a spherical solid shell. The granulated product according to any one of the above (1) to (62),

(64) A binder is applied to the surface of the spherical particles of the superabsorbent polymer that has expanded and absorbs the powder, and then the powder is applied to the surface, dried, and then fired to form a solid inside the spherical solid shell. The granulated product according to any one of (1) to (62), wherein the granulated product has a spherical space.

 (65) A first powder layer is applied to the surface of the spherical particles of the superabsorbent polymer swollen by water absorption, and then one or more powder layers are applied thereon, and then dried to obtain a spherical multilayer solid. The granulated product according to any one of (1) to (64), wherein the granulated product has a spherical space inside the shell.

(66) A first powder layer is applied to the surface of the spherical particles of the superabsorbent polymer swollen by water absorption, and then one or more powder layers are applied thereon, dried, and then fired to obtain a spherical powder. Characterized by having a spherical space inside a multi-layered solid shell (1) Or the granulated product according to any of (6 4),

 (67) A mixed powder composed of two or more different kinds of powders is applied to the surface of the spherical particles of the water-absorbed and swollen superabsorbent polymer, and then dried to form a spherical solid shell composed of a combination of different kinds of powders. Characterized in that the granulated body has a spherical space inside the granulated body, wherein the granulated body according to any one of (1) to (66),

as well as

 (68) A mixed powder composed of two or more different kinds of powders is applied to the surface of the spherical particles of the water-absorbing and swollen superabsorbent polymer, dried, and then fired to form a composite of the different kinds of powders. The granulated product according to any one of (1) to (66), wherein the granulated product has a spherical space inside a spherical solid shell. BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 shows the appearance of the spherical granules obtained in Examples of the present invention.

 FIG. 2 shows the cross-sectional structure of the spherical granules obtained in the examples of the present invention.

 FIG. 3 shows a partial cross-sectional structure of a massive body obtained by bonding the spherical granules obtained in the example of the present invention by point bonding.

 FIG. 4 shows a cross-sectional structure of a spherical granule having a multilayer structure obtained by the present invention. FIG. 5 shows the appearance of a structure that is obtained by combining a large number of the spherical granules obtained in the example of the present invention and serving as a collecting / combining body.

 FIG. 6 shows an enlarged view of a part of the structure shown in FIG.

BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, the spherical particles of the superabsorbent polymer swollen with water are brought into contact with the powder to form a powder layer on the entire surface of the spherical particles of the superabsorbent polymer swollen with water, and then dried. Thereby, a hollow granule having an arbitrary particle size, that is, a granule having a spherical space inside a spherical solid shell can be easily obtained. Particularly preferably, the ceramic granule of the present invention has a spherical space inside a spherical ceramic shell. This is because a spherical particle of a superabsorbent polymer swollen by water is used as a ceramic raw material. The powder is brought into contact with the powder to form a ceramic raw material powder layer on the entire surface of the spherical particles of the superabsorbent polymer that has been swollen by water absorption, dried, and then fired.

 The superabsorbent polymer has a three-dimensional network structure in which a lightly cross-linking is introduced into a water-soluble electrolyte polymer having an ionic group. For example, a polyacrylate-based polymer, vinyl acetate ♦ Acrylate ester copolymers, starches • Acrylic acid graft polymers, etc. Examples of the superabsorbent polymer include, for example, a hydrolyzate of a starch-acrylonitrile graft copolymer, a neutralized product of a starch-acrylic acid graft base, and genification of an acrylate / vinyl acetate copolymer. Products, cross-linked poly (vinyl alcohol) modified products, cross-linked partially neutralized polyacrylate, cross-linked isobutylene-mono-maleic anhydride copolymer, cross-linked maleic anhydride-grafted polyvinyl alcohol, ethylene-vinyl alcohol-based polymer, etc. . Any of these superabsorbent polymers can be used, whether they have a uniform cross-link or have undergone a surface cross-linking treatment. Examples of superabsorbent polymers include, for example, Japanese Patent Publication No. 49-43995, Japanese Patent Publication No. 53-49619, Japanese Patent Publication No. 55-21041, Japanese Patent Publication No. 53-134995, Japanese Patent Publication No. 55-1923, Japanese Patent Publication No. 60-25045, Japanese Patent Publication No. 54-20093 Gazette, JP-A-55-184304, JP-A-56-91873, JP-A-56-93771, JP-A-56- Japanese Patent No. 1614408, Japanese Patent Application Laid-Open No. 58-71907, Japanese Patent Publication No. 56-36504, Japanese Patent Application Laid-Open No. 57-214405 , Japanese Patent Application Laid-Open No. 61-8

No. 770, JP-A No. 61-157, 513, JP-A No. 62-807, JP-A No. 2-490002, etc. , And Japanese Patent Application Laid-Open No. 58-1

Japanese Patent Application Laid-Open No. 08-233, Japanese Patent Application Laid-Open No. Sho 58-118172, Japanese Patent Application Laid-Open No. Sho 58-42602, and the like, are exemplified. . The water-swelled superabsorbent polymer used in the present invention preferably has a superabsorbent polymer to water ratio of 1:50 to 1: 500.

 The superabsorbent polymer is in the form of powder, and the particle size is preferably from 0.02 to 3.0 mm.The superabsorbent polymer immersed in water and swollen by water is a small spherical body. The particle size can be from 0.1 to 60.0 mm, preferably from 0.2 to 10 mm. The particle size can be selected by using a standard JIS standard screen, so by selecting an appropriate particle size as the superabsorbent polymer, the inside of the spherical solid shell of the granulated body can be selected. The spherical space of can be easily and arbitrarily adjusted.

 The superabsorbent polymer particles swelled by water absorption are brought into contact with a powder to form a powder layer on the surface of the superabsorbent polymer particles. In this step, generally, the powder body is spread on a plate to an appropriate thickness, and the superabsorbent polymer having an appropriate size is dropped on the plate, and then tumbled to form the superabsorbent polymer. This can be achieved by evenly coating the surface of the powder with a powder. However, the present invention is not limited to such a method, and any treatment that is substantially equivalent can be used without limitation. Here, the substantially equivalent treatment means a treatment in which a powder layer is formed on the surface of the superabsorbent polymer. The thickness of the powder layer can be appropriately selected depending on the type of the powder body and the properties required for the final granule. The amount of the powder used in this step is usually preferably large, so that the surface of the superabsorbent polymer can be sufficiently covered.

 The drying treatment can be selected from ordinary drying treatments, and preferably, infrared rays, microwaves, and the like can be used.

The high-frequency dielectric heating is preferably performed at a frequency of about 245 MHz, a power of 180 to 600 W, and a heating time of 10 to 60 minutes. Examples of the high-frequency dielectric heating device include a batch-type device, a roller-conveyor-type device, a decompression-type drying device, and a high-field-type waveguide-type drying device. High frequency induction heating equipment is And infrared ray drying and heating equipment can be obtained from Hitachi, Ltd., Toshiba Corporation, etc.

 Further, it is also preferable to form a sintered body by firing a spherical hollow granulated material which has been subjected to high frequency dielectric ripening and dried in a firing furnace. The dried spherical hollow granules can be further dried at lower temperatures, dried at higher temperatures, fired at lower temperatures, or melt fired at higher temperatures.

The powder used in the present invention may be an organic material, an inorganic material, or a mixture thereof. A binder may be blended in the powder. The binder can be selected according to the type of the powder material, and can be selected from those known in the art, but is not particularly limited thereto. Above [1] pharmaceutical, [2] fertilizer, [3] food, [4] cement, [5] feed, [6] coloring material, [7] pesticide, [8] cosmetic, [9] enzyme-containing material, [10] Surfactant, [11] Semiconductor, [12] Metal, [13] Multicapsule composition, [14] Cermet, [15] Paint coating material, [16] Appropriate material, [17] Insulation Materials, [18] sound absorbing materials, [19] radio wave absorbing materials, [20] light absorbing materials, [21] reflecting materials, [22] traffic sign display materials, [23] ball bearings, [24] bioreactors, [25] Far-infrared radiation material, [26] Electric heating material, [27] Lightweight aggregate, [28] Ball game material, [29] Dehumidifying material, [30] Furnace material, [31] Engine room wall material, [32] Gasta bin room Wall material, [33] Lining material, [34] Ventilation material, [35] Soil material, [36] Biomaterial, [37] Inclined Material, (38) apatite, (39) delayed-acting material, (40) plastic, (41) photosensitive material, (42) hydrogen storage material, (43) musical instrument material, (44) sound speaker material, (45) Ozone decomposer, [46] enamel, (47) glaze, [48] spaceflight, [49] solar furnace, [50] artificial tooth, [51] tile, [52] pigment, [53] filler, [54] adhesive main component, [55] ultra fine particle material, [56] permanent magnet material, and [57] The material selected from the group consisting of shape memory materials is not particularly limited as long as it is known in the art or obtained by improving them. Drugs include central nervous system drugs, allergy drugs (antihistamines), cardiovascular drugs, respiratory drugs, gastrointestinal drugs, hormonal drugs, metabolic drugs, antineoplastic drugs, antibiotics, and chemicals. Therapeutic agents, narcotics and the like. Central nervous system drugs include, for example, general anesthetics, hypnotics, sedatives, antiepileptics, antipyretic analgesics and anti-inflammatory drugs, antiepileptics, drugs for the psychiatric nerve, drugs for the peripheral nervous system, local anesthetics, skeletal muscle relaxants, There are autonomic nervous agents, anticonvulsants, etc. Cardiovascular drugs include, for example, cardiotonic, arrhythmic, diuretic, antihypertensive, vasoconstrictor (vasopressor), vasodilator, atherosclerotic, and other circulatory drugs (cerebral metabolism improver) And others). Respiratory drugs include, for example, antitussive expectorants and bronchodilators. Gastrointestinal drugs include, for example, peptic haematous agents, stomachic digesters, antacids, bile agents, intestinals, and other gastrointestinal drugs (such as antiemetic drugs). Examples of hormones include pituitary hormones, thyroid hormones, antithyroids, anabolic steroids, corticosteroids, male hormones, female hormones (estrogen, luteal hormone), There are other hormones. Metabolic drugs include, for example, vitamins, drugs for blood and body fluids, and other metabolic drugs (gout remedies, drugs for diabetes). Antibiotics include, for example, penicillins, cephalosporins, aminoglycosides, macrolides, tetracyclines, chloramphenicols, antifungal antibiotics, antitumor antibiotics, and other antibiotics and so on. Chemotherapeutic agents include, for example, sulfa drugs, antituberculous drugs, antiviral drugs, and other chemotherapeutic drugs. Fertilizers include potash fertilizers (for example, natural potassium salts or potassium ores, potassium chloride, potassium sulfate, etc.), lime fertilizers, fortress fertilizers, forsterite lime fertilizers, gay acid lime fertilizers, gay cal fertilizers, nitrogen fertilizers (for example, chloride Ammonium, ammonium sulfate Ammonia, ammonium nitrate, ammonium carbonate and other ammonium fertilizers, sodium nitrate, lime nitrate, potassium nitrate, lime nitrogen, etc., urea fertilizers (eg, urea, ureaform, isobutylidene urea, crotonylidene diurea, urezette (

Urea-Z), slow-release nitrogen fertilizers such as glycoperyl (acetylene urea), guanyl urea, oxamide, difurfurylidene triurea, and triazine compounds; nitrification inhibitors such as thiourea and dicyan diamide; and phosphoric acid Fertilizers (eg, superphosphate lime, masonry superphosphate, heavy superphosphate lime, precipitated phosphate lime, by-product phosphorus fertilizer, fused phosphorus fertilizer such as fused masonry phosphorus fertilizer, dehydrocalcified phosphate, etc. Calcined phosphorus fertilizer such as lime, tomato sulin fertilizer, etc.), organic fertilizers (eg, fish powder, bone meal, vegetable oil cake powder, etc.), calcareous fertilizers (eg, calcium carbonate, slaked lime, quick lime, etc.), gay acid fertilizers (eg, , Slags (gaycal fertilizers, etc.), fortified fertilizers (eg, magnesium sulfate, magnesium hydroxide, etc.), manganese fertilizers (eg, sulfuric acid) , Compound fertilizers (for example, compound fertilizers such as ordinary SB compound fertilizer, urea compound fertilizer, basic compound fertilizer, low-grade compound fertilizer, advanced compound fertilizer, etc.), trace element mixed fertilizer, pesticide Examples include fertilizers mixed with other substances and fertilizers mixed with soil conditioners. Food includes cereals, potatoes and starches, sugar and sweets, oils and fats, beans, fish and shellfish, veterinary whale meat, eggs, vegetables, fruits, mushrooms, algae, and favorite beverages. be able to. The fats and oils include vegetable fats and animal fats, and the vegetable fats include soybean oil, rapeseed oil, rice bran oil, cottonseed oil, sesame oil, castor oil, mustard oil, safflower oil, corn oil, safflower oil, olive oil Oils, coconut oil, seaweed oil, etc. Examples of animal fats and oils include body fat obtained from cattle, knees, chickens, etc., milk fat obtained from milk, goat milk, etc., di-cinnamon oil, sardine oil, mackerel oil , Saury oil and whale oil.

Sugars and other sugars include sucrose, glucose, fructose, maltose, lactose, honey, etc. Natural sweeteners, water sugar, powdered sugar, refined glucose, isomerized sugars and the like, and industrially obtained starch sugars and sugar alcohols such as mannitol.

 Examples of starches include those obtained from corn, potato, sweet potato, capsicum mackerel, wheat, sago, etc., dextrin, modified starch, amylose, pectin, esterified starch, etherified starch, crosslinked starch, alpha starch, etc. Is mentioned.

 Foods may also include amino acids, peptides, proteins, nucleic acids, protein hydrolysates, umami peptides, bitter peptides, sweet peptides, spices, organic acids, vegetable pigments, animal pigments, synthetic pigments, etc. it can. Foods further include food additives such as seasonings, sweeteners, flavors, colorings, antioxidants, coloring inhibitors, emulsifiers, pastes, preservatives, bleaches, and the like. Examples of cement include self-hardening cement, latent hydraulic cement, mixed cement, polymer cement, resin concrete, and the like. Self-hardening cements include, for example, Portland cements such as ordinary Portland cement, early-strength Portland cement, ultra-fast-strength Polynorethland cement, Nakakatsu hot boltland cement, sulfate-resistant Portland cement, white Portland cement, etc., alumina cement , Rapid-hardened high-strength cement, expanded cement, acid phosphate cement, colloid cement, calcined gypsum and the like. Examples of the latent hydraulic cement include lime slag cement, blast furnace cement, high sulfate slag cement, keince cement and the like. Examples of the mixed cement include lime-silicic acid cement, silica cement, lime-mixed cement such as fly ash cement, sodium gayate / potassium silicate, water glass, oxycyclolide cement, and phosphate cement. No.

Various admixtures can be added to the cement. Examples of such admixtures include water-reducing agents such as AE agents, water-reduction accelerators, water-reduction delay agents, and AE water-reducing agents. , High performance water reducing agents, retarders, accelerators, quickeners, waterproofing agents, foaming agents, foaming agents, thickeners, water retention agents, water inhibitors, hydration heat reducing agents, surfactants, etc. . Examples of the retarder include a saccharide, an oxycarboxylate, a polyhydroxy compound, a lignin sulfonate, and a silicofluoride.

 Examples of the polymer cement include rubber latex (styrene butadiene) cement, thermoplastic resin emulsion (ethylene vinyl acetate) cement, and T-acryl (polyacrylic ester) cement. Examples of the resin concrete include those made of a thermosetting unsaturated polyester resin, an epoxy resin, a fluorinated resin, a urethane resin, an acrylate ester, a methacrylate ester, and the like. Feed includes livestock feed, pet feed (eg, for dogs, cats, etc., as well as for ornamental fish, small birds, racing horses, zoo animals, etc., and farmed fish, etc.). Raw materials used for feed include, for example, cereals, legumes, potatoes, oil cakes, brassicas, brassica oleracea, and those of animal quality (for example, fish meal, white fish meal, fish soluble, meat meal, meat) Bone meal, frozen meal, silkworm oil cake, skim milk powder, dried whey, animal fats and oils), brewer's yeast, torula yeast, screening pellets, alfa alpha meal, orange peel, calcium carbonate, sodium chloride, sodium phosphate Lime, tricalcium phosphate and the like.

 As the feed, various vitamins, various amino acids, minerals, antibiotics, antibacterial substances, enzymes, fungicides, antioxidants, dye enhancers, sweeteners, flavors, hormones, etc. can be added.

Feeds include chicken feed (eg, chick feed, broiler feed, adult chicken feed, meat breeder feed, etc.), and pig feed (eg, piglet feed, pork fat feed, seeds). Feed for pig breeding, etc., feed for cattle (for example, feed for dairy cattle, feed for growing young cattle, feed for beef cattle fattening, etc.), feed for turkey, feed for quail, such as eel, Feed for farmed fish, such as koi, rainbow trout, eel, red sea bream, and yellowtail, and breeding for experimental animals.

Pesticides include fungicides, insecticides, fungicides, rodenticides, herbicides, plant growth regulators, attractants, repellents, chemical fertility, adjuvants, and the like.

 Agrochemicals include inorganic compounds, such as inorganic agents, mercury agents, zinc agents, iron agents, sulfur agents, arsenic agents, fluorine agents, phosphorus agents, chlorine agents, calcium agents, alkali agents, and the like; organic compounds such as nicotine agents, pyrethrins Agents, rotenone agents, machine oil agents, organic sulfur agents, organic mercury agents, organic chlorine agents, organic phosphorus agents, organic arsenic agents, nitro agents, phenol agents, triazine agents, quinone agents, antibiotics, etc .; microorganisms Or a toxin produced therefrom.

 Insecticides include pyrethrins (natural pyrethrins, synthetic pyrethroids and their derivatives), rotenones, nicotine, nornicotine, nerin toxin, parathion, malathion, diazinon, trichlorfon, fuenitrothion, teppu, sacrifipol, chlortipirophylchloride, chlortipirophylchloride , Fenthion, funtoate, methidathion, EPN, disulfoton, methyl parathion, etc., organophosphorus insecticides, MIPC, MTMC, MPMC, carbaryl, BPMC, propaoxalate, etc. , Heptachlor, endrin, chlordane, etc., organochlorine insecticides, dinitrophenol acaricides, chlorophyll acaricides (for example, chlorene benzylate, CPC BS, dicophor, bromopropylate, etc.), other acaricides, arsenic agents, nematicides and the like.

Examples of disinfectants include antibiotics, heavy metal disinfectants (eg, copper-containing agents such as bordeaux, organic mercury agents, organic tin agents, organic arsenic compounds, etc.), and sulfur disinfectants (eg, inorganic sulfur agents, dithione, Fungicide fungicide, organic sulfur fungicide, etc., organic phosphorus fungicide, aromatic fungicide (eg, PCP, DDC, PCNB, Zyklon) , TPN, etc.) and heterocyclic compound fungicides (eg, captan, triazine, quinomethionate, benomyl, fusaride, phenazine, hydroxy isoxazole).

 Examples of herbicides include phenoxy herbicides, phenol herbicides, diphenyl ether herbicides, aniline herbicides, urea herbicides, rubbamate herbicides, amide herbicides, and nitrile herbicides. Herbicides, bipyridillium herbicides, triazine herbicides, fatty acid herbicides, diazine herbicides and the like. Examples of cosmetics include basic cosmetics, makeup cosmetics, medicinal cosmetics, hair cosmetics, oral cosmetics, bath cosmetics, fragrances, and fragrances. Basic cosmetics include, for example, creams, emulsions, lotions, and the like. Make-up cosmetics include, for example, eye makeups such as white powder, lipstick, nail enamel, masquerade, and aisha dough. Examples include sunscreen products, suntan products, and deodorant cosmetics.

 Hair cosmetics include, for example, shampoo, cold water lotion, hair dye, pomade, hair liquid, etc. Oral cosmetics include toothpaste, mouth freshener, deodorant, etc. No. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.

 Examples of anionic surfactants include, for example, seggen, funnel oil, sulfate, alkylbenzene sulfonate, α-olefin sulfonate, polyaminosulfonate, dialkyl sulfosuccinate, Ν— (Ζ— Sulfo) ethyl-methylalkaneamide salt and the like.

Examples of the cationic surfactant include alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, and alkylpyridinium bromide. And alkylbenzyldimethylammonium chloride.

 Nonionic surfactants include, for example, alkyl polyoxyethylene ethers, alkyl phenyl polyoxyethylene ethers, alkylcarbonyloxypolyquineethylenes, N, N-di (polyoxyethylene) alkaneamides, fatty acid polyhydric alcohols Esters, fatty acid polyhydric alcohol polyoxyethylene ethers, fatty acid sucrose esters, N, N-di (alkanol) alkaneamides, polyoxyalkylene block copolymers, and the like.

Surfactants include detergents, wetting agents, penetrants, dispersants, flocculants, emulsifiers, demulsifiers, solubilizers, foaming agents, defoamers, smoothing agents, lubricants, softeners, Since it is used as an antistatic agent, a water repellent, a bactericide, and an antibacterial agent, it is expected that the same use of granules will be obtained. Examples of paints include synthetic resin paints, oil paints, spirit paints, and inorganic paints. Examples of the synthetic resin used for the synthetic resin paint include a thermoplastic resin and a thermosetting resin. Examples of the thermoplastic resin include an acrylic resin such as a thermoplastic acrylic resin and vinyl chloride-vinyl acetate. Polyvinyl resin such as polymer resin, vinylidene fluoride resin, polyolefin resin such as chlorinated polypropylene, polyvinyl alcohol, polyvinyl alcohol resin such as polyvinyl acetal 'butyral, vinyl acetate Resin, emulsion resin such as styrene butadiene resin, high molecular polyester, nylon and the like. Examples of the thermosetting resin include alkyd, epoxy resin, unsaturated polyester, thermosetting acrylic resin, melanin resin, urea resin, urethane prepolymer, silicon intermediate, phenol resin, xylene resin, and maleic resin. , Polybutadiene, petroleum resin and the like. The semiconductor is not particularly limited, such as a known semiconductor or an improved semiconductor. However, for example, a single element semiconductor, a binary alloy compound semiconductor combining two elements, a multi-element alloy compound semiconductor combining three or more elements (eg, II-IV-V, III, V, VII, etc.) Group IV elements such as Si, Ge, and Sn; combinations of IV-IV elements such as SiC; group VI elements such as Se and Te; and combinations of III-V elements ( For example, BP, A1P, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InP, InAs, InSb, etc., combinations of II-VI elements (eg, , ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, etc., and combinations of IV-VI elements (eg, PbS, PbSe, PbTe, SnTe, etc.) Stuff. The semiconductor may be doped with impurities or the like as necessary by doping or the like, such as a diffusion method, an ion implantation method, and an epitaxial growth method. Cermets include oxide cermets, carbide cermets, boride cermets, and nitride cermets. Is a cermet Bok ceramic components, for example, T i C, WC, C r 3 C 2, A 12 0 3, S i O 2 and the like can and Ageruko force, without being limited thereto, known as the ceramic It can be used from among those provided. The metal used for the thermistor is not particularly limited, and includes, for example, Ni, Mo, Fe, Cr, Co. Ag, Cu, Sn, etc., and further includes Cd〇, ZnO , and various metal oxides such as S n 0 ₂ may also and Ageruko. In the present invention, a ceramic granule is preferably obtained.

The ceramic raw material powder preferably has a particle size of several m to several hundred m. The ceramic raw material powder may be any that can be sintered at a high temperature, such as clayey clay, clay mineral, chamotte, silica sand, pottery stone, feldspar, alumina, magnesia, zirconia, silica, mullite, cordierite, Blast furnace slag, shirasu, fly ash And nitride, silicon carbide, aluminum nitride, silicon nitride, and the like, and are usually sintered at 1000 to 2000 ° C.

 In order to maintain the shape and strength during molding, drying and firing, low-temperature binders such as carboxymethyl cellulose, starch, water glass, etc. It is preferable to mix high temperature binders such as glaze frit, calcium fluoride, and glass frit to maintain the shape and strength during firing.

 It should be noted that a binder is not always necessary, and only ceramic raw material powder can be sintered without a binder.

 The sintering is preferably carried out at a suitable sintering temperature, so that the particles are joined by point contact, so that the sintered spherical ceramic shell becomes porous, that is, a porous shell wall of communicating pores. Through the spherical porous shell wall, gas and liquid flow can be realized between the inner spherical space and the outside.

 This flowability allows various functions and effects to be exhibited since the flow is usually gradually performed through the communicating pores, and enables the provision of various use products.

 For example, the gas filled in the internal spherical space, for example, germicidal gas such as chlorine and reactive gas gradually flows and flows out.

In addition, the liquid filled in the inner spherical space, for example, a pH adjuster such as a fragrance, an alkali solution, an acid solution, a disinfectant solution, a metal salt solution, an organic solvent, etc., gradually flows and flows out. In addition, solids, such as camphor, solid fragrance, tasting material, fertilizer, etc., which are filled into the inner spherical space are gradually released. The fertilizer and the like in the ceramic granules of the present invention buried in the soil gradually elute into the soil due to the intrusion of rainwater and the like, and become a long-lasting fertilizer. In addition, as a method for introducing a liquid, a gas, or the like into the internal spherical space, for example, the granulated material of the present invention is placed in a vacuum chamber, the internal spherical space is evacuated, and the periphery of the granulated material is cleaned. It can be easily implemented by surrounding with liquid or gas and returning to normal pressure. It is easy to introduce solids by surrounding the granules of the present invention in a vacuum chamber with metal such as tassel, aluminum, tin, etc. liquefied by high-temperature heating, returning to normal pressure, and cooling. Can be introduced. Further, it is preferable that the shell of the spherical ceramic granule contains a solid fine powder. For example, vanadium oxide, platinum, manganese oxide, silver, or the like as a catalyst substance is preferably supported to be used as a catalyst for decomposing automobile exhaust gas.

 Further, it is also preferable to use a filler filled with an admixture for cement mortar or concrete, such as a high-performance water reducing agent or a fire retardant.

 Ceramic granules include lightweight aggregates, soil improvement materials, luminescent materials containing luminescent substances in spherical spaces or shells, phosphorescent generating materials containing phosphorescent substances, iodine, mercury, camphor, etc. Sublimate-releasing material containing sublimable substance, sustained-release product containing fragrance, enzyme-containing products such as protease, starch-degrading enzyme, various bacteria, bacteria It is also preferable that the product be a bacterial-containing product, a fungicide-containing product containing a fungicide, or an insecticide product containing an insecticide.

 Further, a granulated ceramic material which is a coloring material product containing a coloring material is also preferable. It can also be used as a filtering material. For example, the ceramic granules are filled in a mesh container to form a filtering material layer, and the material to be filtered gas, liquid, solid suspended liquid is passed through the layer. It is also preferable to apply a treatment such as turbidity.

At this time, if the catalyst-supported ceramic granules are used as the base material, pollutant gases such as SOx and NOX and gases containing fine powder such as tobacco fumes can be purified. Ceramic granules with excellent heat resistance using alumina, thoria, magnesia, zirconia, etc. as main materials are useful as heat-resistant structural materials. Carbon, gay carbide, boron nitride, aluminum nitride, sialon, mullite, cordierite, Ceramic granules having excellent corrosion resistance using aluminum titanate as a main material are useful as structures. Ceramic granules with excellent heat insulation properties, mainly made of potassium titanate fiber, porous calcium gateate, mullite fiber, alumina fiber, etc., are useful as heat-resistant materials and non-combustible materials. Ceramic granules with excellent heat conductivity, mainly using beryllia, diamond, gayenium carbide, aluminum nitride, boron nitride, etc., are useful as heat dissipating materials.

 Hard materials using alumina, diamond, cubic boron nitride, boron carbide, tungsten carbide, titanium carbide, silicon carbide, titanium nitride, titanium boride, zirconium boride, etc. Abrasives, abrasives

It is useful as a cutting material, a wear-resistant material, and the like. Ceramic granules with high strength, mainly made of gay carbide, gay nitride, PSZ, alumina, etc. are useful as structural materials. Ceramic granules with excellent corrosion resistance using tempered glass, graphite fiber, whiskers, etc. as main materials are useful as machine parts.

_{A 12 O 3, B e 0} , _{diamond, Mg 2 S i O 4,} Mg S i O 3, co one de Ierai DOO, S i C, BN, A 1 N, mullite bets, and S i 0 ₂ main Ceramic granules with excellent insulating properties as useful materials are useful as insulator spark plugs, IC substrate package materials, and the like.

Barium titanate, titanate _{(B a 2 T i 9 O} 20), (Z r, S n) T i 4, Pb (Mg, Nb) 0 3, B a (Zn. Nb) 0 3 etc. of the main Ceramic granules with excellent dielectric properties as useful materials are useful as capacitors, resonators and the like.

PZT, _{quartz, L i Ta0 3, L i} Nb0 3, ZnO, B i 12 G e O 20. P b T i 0 3 system, Ceramic Zotsubutai having excellent piezoelectric properties KTN or the like as a main material Is useful as a resonator, a resonator filter, a delay element, an ignition element, a piezoelectric transformer, and the like. _{PZT, L i Ta0 3, P} b T i 0 3 Se Lami click Zotsubutai with excellent pyroelectric and as the main material is useful as an infrared detection element.

PLZT. ADP, KDP, L i Ta0 3, L i Nb0 3. KTP, B a B 2 O 4 , etc. The ceramic Zotsubutai with excellent electrical polarization characteristics as the main material, the image recording element, an electro-optical polarization element It is useful as such.

_{S i C, LaC rO 3,} MoS i 2, Z r0 2, Ceramic Zotsubutai with excellent resistance heating characteristics carbon or the like as a main material is useful as such as a resistance heating element. Manganese - Nickel cobaltous based _{oxides, Z r0 2, T i 0} 2, titanate burr © beam solid solutions of vanadium: Excellent ceramic Zotsubutai the resistance-temperature characteristic as the primary material such as titanium oxide is Sir It is useful as a mr (NTC), heating element (PTC), temperature element (CTR), etc.

 Ceramic granules that use zinc oxide-bismuth and SiC as main materials and have excellent nonlinear resistance characteristics are useful as voltage stabilizing elements and varistors.

SnO _2, ZnO, Ceramic Zotsubutai was excellent in _{T i O 2, Z r O} 2 resistance and gas resistance, etc. as the main material is useful as a gas centers.

_{MgC r 2 0 4 - T i} 0 2 _{system, ZnO- L i 2 0- V 2} 0 5 system, ceramic Zotsubutai with excellent resistance humidity characteristics L i ₂ OF e ₂ 0 ₃ system or the like as a main material Is useful as a humidity sensor.

 Ceramic granules with excellent thermopower using BP or BY materials as main materials are useful as thermoelectric devices.

 Ceramic granules with excellent ionic conductivity using β-alumina, zirconia, NASICON, lithium-containing glass, etc. as main materials are useful as solid electrolytes for batteries and sensors.

B a P b, - x B i x 0 3, L i T i 2 0 4, Pb, Μο β S 7, (. La B a) 2 C u0 4, B a 2 YC u 3 0 7, B i _{2 S r 2 C a 2 C} u 3 0 8 , such as the main Ceramic granules with excellent superconductivity as useful materials are useful as devices, cables, magnets, and so on.

_{B aT i 0 3, ZnT i} 0 3 ceramic Zotsubutai having excellent thermal emissive etc. as the main material is useful as a secondary electron emission element.

Ceramic granules having excellent secondary electron emissivity using La B ₆ , T i C and the like as main materials are useful as hot cathodes and the like.

_{7 -F e 2 0 3, F} e 3 0 4, B a (F e, Co, T i) 12 0 19, Μη-Ζη Fuwerai DOO, N i- Ζη Fuwerai DOO, including a major N i Fuwerai DOO Ceramic granules having excellent soft magnetic properties are useful as magnetic tapes, magnetic fluids, magnetic cores, magnetic heads, storage elements, magnetostrictive vibrators, and the like.

_{S rO * 6F 2 0 3,} B aO '6F e 2 0 3 ceramic Zotsubutai was superior to hard magnetic as the main material, etc., it is useful as a magnet class.

 Ceramic granules excellent in radio wave absorption using various types of flies as main materials are useful as radio wave absorbers and the like.

_{A 12 O 3, MgO, Υ} 2 0 3 ceramic granules excellent in light transmitting property as the main material, such as is useful as a heat-resistant corrosion-resistant light-transmitting material.

 Ceramic granules having excellent light guiding properties using silica, fluoride glass or the like as a main material are useful as light guiding materials and the like.

_{Sn0 2, ln 2 0 3,} T i N Ceramic Zotsubutai having excellent light reflectivity and the like as the main material, the infrared reflective glazing coating material, is useful as heat-resistant light reflected solar collectors .

_{C aWO 4, C sl, Na} l, L i F, Ca 10 (PO 4) 6 (F, C 1) 2, Y 2 0 3, B aMg 2 Α 1 1β 0 27, C eMg A 1 ,, Ο _{, β L a F 3:.} Yb, E r, Y 2 0 2 S, ZnO, Zn S, Z n 2 S i 0 4, Zn 3 (P0 4) including a main _2, G d ₂ 0 ₂ S Ceramic granules having excellent fluorescence as materials are useful as X-ray-ultraviolet-excited phosphors, infrared-excited phosphors, and power-excited phosphors. Ceramic granules excellent in photoconductivity and photovoltaic properties using CdS, PbS, InSb, HgCdTe, etc. as main materials are useful as light receiving elements and the like.

_{A 12 O 3: C r,} YAG: Nd, _{glass: Nd, B e A 1 2} O 4, G a A s, Ga P, GaA s P, GaA l P, such as a main G a A 1 A s Ceramic granules having excellent luminescence as a material are useful as lasers and the like.

 Ceramic granulation with excellent light emission using GaAlAs, GaInAsP, GaAlAsSb, GaInAs, GaInAsP, GaN, SiC, ZnS, etc. as main materials The body is useful as a light emitting diode and the like.

Ceramic granules having excellent luminous properties using BGO (Bi 4 Ge ₃ 0 ₁₂ ), Na I and the like as main materials are useful as materials for radiation detection and the like.

 Ceramic granules having excellent light emitting properties using ZnS, CaS, SrS, ZnSe and the like as main materials are useful as electroluminescent materials and the like.

_{B aT i O 3, S r} T i O 3, W0 3, Mo0 3, T i O 2 or a ceramic Zotsubutai excellent in to colorability the main material, useful as elect port Kuromitsuku material It is.

_{L i T a0 3, L i} Nb0 3, PLZT. BSO (B i 12 S i O 20), ceramic Zotsubutai is excellent in electro-optical properties and the like as the main material KTN, as such an electro-optical modulator element Useful.

L i Ta0 _3, L i Nb_〇 _3, P _bMo 0 _4, Te0 excellent ceramic Zotsubutai the acoustooptic properties ₂ or the like as main material, Ru der useful as acousto-optic deflector.

_{Y 3 F e 5 0 12,} Gd 2 B i F e 5 0, 2 and Ceramic were excellent in the magneto-optical properties as the main material Zotsubutai magneto-optical recording material is useful as.

_{Quartz, C aC0 3, T i 0} 2, mica, _{Sekkou, CdS, Gd 2 (Mo0 4} )

Ceramic granules with excellent birefringence, mainly using 3 etc. Useful.

 Ceramic granules with excellent biocompatibility using apatite, alumina, carbon, etc. as main materials are useful as artificial bones and artificial teeth.

 Ceramic granules having excellent adsorptivity using silica, alumina, zeolite, etc. as main materials are useful as immobilized enzyme carriers and the like. Ceramic granules excellent in catalyst and carrier properties using alumina, cordierite, titania, silica, zeolite, potassium titanate, vanadium oxide and the like as main materials are useful as catalyst carriers and catalysts.

 Ceramic granules having excellent corrosion resistance using alumina, zirconia, gay carbide, boron carbide, boron nitride, gay nitride, titanium nitride, etc. as main materials are useful as corrosion-resistant materials.

 Ceramic granules having excellent nuclear properties using uranium oxide and uranium carbide as main materials are useful as nuclear fuels and the like.

 Ceramic granules with excellent nuclear properties using graphite, gay carbide, etc. as main materials are useful as nuclear fuel cladding materials.

 Ceramic granules with excellent nuclear properties using graphite, boron carbide, etc. as main materials are useful as moderators and reflectors.

 Ceramic granules having excellent nuclear properties using boron carbide or the like as a main material are useful as control materials.

 Ceramic granules with excellent nuclear properties using graphite, gay carbide, boron carbide, gay nitride, etc. as main materials are useful as fusion reactor materials.

 Ceramic granules with excellent nuclear properties using solid lithium compounds as main materials

It is useful as a tritium parent material for nuclear fusion. Each of the above-mentioned ceramic granules of the present invention can be manufactured as follows. (1) Bringing the superabsorbent polymer particles swollen with water into contact with the ceramic raw material powder

After forming a ceramic raw material powder layer on the entire surface of the water-absorbed and swollen superabsorbent polymer particles, the ceramic raw material powder layer is dried, and then fired to form a ceramic material having a spherical space inside a spherical ceramic shell. A method for producing a granulated ceramic, comprising obtaining granules.

 (2) The superabsorbent polymer particles that have expanded and absorbed water are brought into contact with the ceramic raw material powder to form a ceramic raw material powder layer on the entire surface of the water absorbent and swollen superabsorbent polymer particles, and then dried, A method for producing a ceramic granule, comprising obtaining an unfired ceramic granule having a spherical space inside a spherical solid shell.

 (3) The powder body is characterized by containing a binder such as an adhesive material or the like at room temperature such as methylcellulose, for example, a high-temperature binder such as calcium fluoride or glass frit. The method for producing a ceramic granule according to the above (1) or (2),

 (4) The ceramic granulation according to any one of the above (1) to (3), wherein the drying or baking method is performed by dielectric heating in a high-frequency dielectric heating heater. How to make the body.

 (5) The ceramic granules obtained by the method according to any one of the above (1) to (4) are immersed in a liquid, and the shell of the ceramic granules is impregnated with the liquid. A method for producing a granulated ceramic.

 (6) The method for producing a ceramic granule according to (6), wherein the liquid is a metal salt solution.

 (7) The ceramic granules obtained by the method according to any one of the above items (1) to (4) are immersed in a suspension of a fine solid powder of a catalyst substance or the like, dried, and dried. A method for producing a ceramic granule, characterized by obtaining a ceramic granulate in which a solid fine powder is mixed in a shell of a ceramic granule.

(8) A cell obtained by the method according to any of the above (1) to (7). A method for producing a ceramic granule, characterized by immersing a mic granulate in a liquid to obtain a ceramic granule (microcapsule) containing the liquid in a spherical space inside.

. (9) A ceramic in which the ceramic granule obtained by the method according to any one of the above (1) to (7) is left in a gas body, and the gas body is incorporated in a spherical space inside. A method for producing a granulated ceramic body, comprising obtaining a granulated body.

 (10) The ceramic material according to any one of (1) to (9), wherein the superabsorbent polymer is a powder and has a particle size of 0.02 to 3.0 mm. Manufacturing method of granules.

 (11) The superabsorbent polymer that has expanded by water absorption is a small sphere, and has a particle size of 0.2 to 60.0 mm. A method for producing a ceramic granule.

 (12) The superabsorbent polymer that has been swollen by water has a superabsorbent polymer-to-water ratio of 1:50 to 1: 500, wherein A method for producing a ceramic granule according to the above. The high-frequency dielectric heating is preferably performed at a frequency of about 2450 MHz, a power of 180 to 600 W, and a heating time of 10 to 60 minutes.

 Furthermore, it is preferable that the spherical hollow unfired ceramic granules dried by high-frequency dielectric heating are fired in a firing furnace to obtain a sintered body.

 The ceramic raw material must be clay, clay mineral, chamotte, silica sand, pottery stone, feldspar, alumina, magnesia, mullite, zirconia, silica, filler, cordierite, apatite, blast furnace slag, shirasu, It is also preferable that the binder be a mixture of at least one selected from fly ash, silicon carbide, aluminum nitride, and silicon nitride and a binder.

Furthermore, the unfired ceramic granules obtained by the above method are coated with the same substance or another substance on the surface thereof by using a snowman forming method (snow-ba11 method) or the like. It is also possible to form a multi-layer ceramic granule by wrapping and forming a multi-layer unfired ceramic granule and further firing at high temperature. The granulated body having a spherical hollow obtained by the present invention can be formed as a porous body, and the granulated body is immersed in a liquid, and the shell of the granulated body is impregnated with the liquid. The granules can be obtained by immersing the granules in a suspension of solid fine powder and drying to obtain granules in which solid fine powder is mixed in the shell of the granules. The body can be immersed in the liquid to obtain a granulated body containing the liquid in the internal spherical space, or the granulated body can be left in the gas body, and the gas body can be built in the internal spherical space. Granules can also be obtained. The components impregnated in the granules and the components contained in the granules can be gradually released. Preferred examples of the base and the liquid for impregnating the granules include a metal salt solution.

 The granulated body having a spherical hollow obtained in the present invention is sintered at a higher temperature, for example, by melting and sintering, so that part or the whole of the shell is denatured to vitreous and non-porous. It is also possible to form as a body.

 Furthermore, the same substance or another substance may be laminated on the surface of the granules obtained by the above method by employing a snowman forming method (snow-ba 11 method). Further, a different powder layer may be formed on the surface of the granule by coating to form a granule having a spherical multilayered solid shell.

 A large number of the granules of the present invention can be assembled and combined into a mass, and thus a mass formed by combining a large number of granules is also provided. Further, a large number of the granules can be sintered into a massive sintered body to produce a massive sintered body formed by firing a large number of the granules.

In the present invention, a hollow sphere having a spherical wall can also be produced by applying a binder to the surface of the superabsorbent polymer particles swollen by water absorption, further applying a powder to the surface, and then drying the powder. In addition, a first powder layer is applied to the surface of the superabsorbent polymer particles that have swollen and absorbed water. Then, a second or further third powder layer is applied thereon, followed by drying to produce a hollow sphere having a spherical wall. Furthermore, a mixed powder composed of two or more kinds of different kinds of powders is applied to the surface of the spherical particles of the superabsorbent polymer that has expanded and absorbed, and then dried to form a hollow sphere having a spherical wall composed of a combination of different kinds of powders. It can also be manufactured.

 FIG. 1 shows the appearance of the spherical granulated body 1 obtained by the present invention. FIG. 2 shows a cross section of the spherical granule 1 shown in FIG. In the example shown in this figure, it can be seen that the spherical granules 1 have an infinite number of communication holes caused by the coagulation of many powders in a point contact state. For example, when the spherical granulated body 1 is constituted by using a ceramic raw material or the like as a powder body, a granulated body as shown in FIG. 2 can be obtained as a porous body. Therefore, a liquid or gas body can be built in the spherical space 10 in the center of FIG. 2, and various parts can be impregnated in the spherical granule. Understand. FIG. 3 shows a typical form in which a plurality of (three in the illustrated example) spherical agglomerates 1 shown in FIGS. 1 and 2 are assembled and combined into a lump. In Fig. 3, it can be seen that the spherical granules are connected to each other by point bonding 3 to form a lump. It can be understood that such a massive body also has a structure in which a large number of large voids 4 formed due to the point junctions 3 exist as large communication holes.

 FIG. 4 shows a cross-sectional structure of the spherical granule 1 having a multilayer structure obtained by the present invention. In principle, not only two layers, 11 and 12, but also multiple layers can be formed as needed. The layers to be formed may be made of different materials, may be made of the same material, or may be made of partially different materials. FIG. 5 shows an aggregate structure 2 formed by bonding a large number of the spherical granules 1 of the present invention. FIG. 6 shows a part of the structure 2 in an enlarged manner. In this figure, it can be seen that a large number of granules 1 ♦ · are assembled and combined, and a large number of communicating voids 4 exist between them.

In the figure, 1 is a spherical granule, 2 is a lump, 3 is a point joint, 4 is a void, 10 Indicates a spherical space (hollow portion), 11 indicates a spherical porous shell wall, and 12 indicates a second porous shell wall. Example

 Next, more specific embodiments of the present invention will be described with reference to examples. However, the present invention is not limited to these, and it will be understood by those skilled in the art that there are various embodiments.

Example 1:

 Spread 50 g of the dry clay powder on a plate to a thickness of 5 mm, drop 30 spherical particles of the superabsorbent polymer with a water-absorbing swelling of 8 mm in particle size below from above, roll, and roll on the surface The clay powder was evenly sprinkled to obtain a granule having a 1.5-mm-thick hydrated clay powder layer.

 [Production method of spherical particles of water-absorbing and super-absorbing polymer]: A polyacrylic acid-based super-absorbing polymer having a particle size of 1.5 mm is immersed in 150 times the volume of water to absorb water having a particle size of 8 mm. Swelled superabsorbent polymer spherical particles are obtained.

 Next, the granulated body comprising a water-absorbing clay powder layer whose surface shell is a spherical particle of a highly water-absorbing bolimer having a water-absorbing swelling inside was placed in a drying oven and dried at 110 ° C for 3 hours. Obtained unfired ceramic granules with 6 mm, shell thickness l mm, hollow inside diameter 4 mm ο

 Thereafter, the dried unfired ceramic granules were placed in a firing furnace and fired at 110 ° C. for 2 hours to obtain solid porous ceramic granules having a hollow inside. Its bulk specific gravity was actually measured as 0.78, and the water absorption was 33%. Example 2:

100 g of the dried clay powder was spread on a plate to a thickness of 5 mm, and 50 spherical particles of the water-absorbing and swollen superabsorbent polymer having a particle diameter of 8 mm used in Example 1 were dropped on the plate, and the mixture was rolled. Movement Then, the clay powder was evenly spread on the surface to obtain a granule having a 1.5-mm-thick hydrous clay powder layer.

 Next, the granules were transferred into a dielectric heating apparatus (microwave oven of high frequency output: 180 to 600 W, 245 MHz), and were heated by energization for 20 minutes. In this heating stage, the water in the spherical particles of the superabsorbent polymer swelled and absorbed rapidly evaporates, and the shell of the clay powder layer is dried and solidified to obtain a granulated product having the appearance shown in FIG. Was The cross section of the granule has a structure as shown in FIG.

 Thereafter, the dried green ceramic granules were placed in an electric furnace and fired at 115 ° C. for 2 hours.

 The porous ceramic granule obtained after firing is a lightweight ceramic granule that has almost the same appearance and cross-sectional shape as shown in Fig. 1, has a hollow inside, and has high hardness and strength. there were. Its bulk specific gravity was 0.6, and the heat-resistant temperature was 1,300 ° C. Example 3:

 Drying was performed in the same manner as in Example 1 except that a mixture of 25 g of chamotte powder and 25 g of clay was used instead of 50 g of the clay powder, and the dried granules obtained were placed in a gas firing furnace. At 130.degree. For 2 hours.

 The spherical porous ceramic granules obtained as a result of the firing were ceramic granules with a hollow inside and a porous shell, high hardness and strength, and could be used as lightweight aggregates. Its bulk specific gravity was 0.5, and the heat-resistant temperature was 1,400 ° C. Example 4:

Spread 50 g of alumina calcined powder containing 3% mixed sintering agent of 1_10 and ₁₀ % on a plate to a thickness of 5 mm, and the same as that prepared in Example 1 above from above 50 spherical particles of the superabsorbent polymer swollen by water with a particle size of 8 mm are dropped, rolled, and the alumina calcined powder is evenly spread on the surface, and the shell is made of 1.5 mm thick hydrous alumina. A granule having a calcined powder layer was obtained.

 Next, the granulated body composed of a layer of alumina calcined powder having a spherical surface of a superabsorbent polymer whose interior is made of water-absorbing and swelling and containing a surface shell containing water was placed in a drying furnace at 110 ° C. for 2 hours. As a result of drying, dried granules having a particle size of 6 mm, a shell thickness of l mm, and a hollow inner diameter of 4 mm were obtained.

 After that, the dried granules were placed in a firing furnace and fired at 150 ° C. for 2 hours to obtain solid alumina-based porous ceramic particles having a hollow inside.

 The alumina-based porous ceramic granules obtained as a result of the firing were lightweight ceramic granules having a high heat-resistant temperature, high hardness and strength.

Example 5:

 50 g of zirconia calcined powder containing 3% of Mg 0 sintering agent was spread on a plate to a thickness of 5 mm, and water absorption and swelling with the same particle diameter of 8 mm as that prepared in Example 1 was performed from above. 50 spherical particles of the superabsorbent polymer are dropped and tumbled to evenly coat the zirconia calcined powder on the surface, and the granules having a water-containing zirconia calcined powder layer having a shell thickness of 1.5 mm are formed. Obtained.

 Next, the granulated body consisting of the superabsorbent polymer particles whose inside was made of a water-absorbing zirconia calcined powder layer having a water-absorbing swelling was dried in a drying furnace at 110 ° C. for 2 hours. As a result, a dried granulated product having a particle diameter of 6 mm, a shell thickness of l mm, and a hollow inner diameter of 4 mm was obtained. After that, the dried granules were placed in a firing furnace and fired at 650 ° C. for 2 hours to obtain solid zirconia porous ceramic particles having a hollow inside. The zirconia porous ceramic granules obtained as a result of firing had a high heat-resistant temperature, high hardness and strength, and were tough, lightweight ceramic granules. Example 6:

Y 2 0 ₃ and C a O a mixed sintered material 5% aluminum nitride-containing calcine powder 5 0 g was spread on a plate to a thickness of 5 mm, and 50 spherical particles of the water-absorbing and swollen superabsorbent polymer having the same particle diameter of 8 mm as those prepared in Example 1 were dropped on the plate and tumbled. The aluminum nitride calcined powder was evenly spread on the surface to obtain a granule having a water-containing aluminum nitride calcined powder layer having a shell thickness of 1.5 mm.

 Next, the granulated body consisting of a powdery aluminum nitride calcined powder layer having a spherical surface of a superabsorbent polymer having a water-absorbing swelling inside and a surface shell containing water was placed in a drying furnace and dried at 110 ° C for 2 hours. As a result, a dried granulated product having a particle size of 6 mm, a shell thickness of lmm, and a hollow inner diameter of 4 mm was obtained.

 Thereafter, the dried granules were placed in a non-oxidizing atmosphere firing furnace and fired at 1820 ° C. for 2 hours to obtain solid aluminum ceramic porous ceramic particles having a hollow inside.

 The aluminum nitride porous ceramic granules obtained as a result of the firing were lightweight ceramic granules having high heat resistance, high hardness and strength, and high thermal conductivity. Example 7:

 1000 ml of the spherical ceramic granules obtained in Example 1 was immersed in 1500 ml of a slurry (clay 15%, water 85%) obtained by adding and suspending the same clay in water for 1 minute, and then taken out. Then, it was put into a sheath (content volume: 15 cm × 15 cm × 15 cm), dried, and fired at 1150 for 2 hours. As a result of the firing, a porous ceramic plate of 15 cm × 15 cm × 4 cm was obtained.

 In the porous ceramic plate, a large number of the same spherical ceramic granules as obtained in Example 1 were sintered in such a manner that particles contact each other via a thin clay-sintered layer derived from slurry at each contact portion. It became a lump.

Since the porous ceramic plate has air permeability due to voids formed between the granules, and air permeability due to the porous shell of each granule itself, the air permeability is high. Good It became a lightweight ceramic plate. The bulk specific gravity of this plate was actually measured as 0.89.

 The ceramic plate can be suitably used as a filter, a sound insulating plate, a heat insulating plate, and the like.

 In the same manner as in Example 1, 50 g of the dried clay powder was spread on a plate to a thickness of 5 mm, and 30 spherical particles of the water-absorbing and swollen superabsorbent polymer having a particle size of 8 mm described below were dropped on the dried powder. After rolling, the surface was evenly covered with clay powder to obtain a granulated body having a 1.5-mm-thick hydrous clayey powder layer.

 Next, the granules, each having a spherical particle of a superabsorbent polymer in which the inside was swollen by water absorption and whose surface shell was composed of a hydrous clay powder layer, were dried in a drying furnace at 110 ° C. for 3 hours. Obtained unfired ceramic granules with 6 mm, shell thickness l mm, hollow inside diameter 4 mm ο

 The unfired ceramic granules were filled into a 100 x 100 x 100 x 100 volume alumina ceramic porcelain to a thickness of 50 mm, placed in a firing furnace, and left at 125 ° C for 2 hours. When baked, an air-permeable plate-like block was obtained in which the porous ceramic-produced granules having a solid hollow inside were sintered by point bonding.

 The plate-like block had good air permeability and liquid permeability, and was excellent as a filter plate and a sound absorbing plate.

Industrial applicability

According to the present invention, novel spherical granules having a hollow interior are excellent fertilizer products, food products, feed products, agricultural products, catalyst products, ceramic products, ceramic products, powder metallurgy products, It can be used as detergent products, plastic products, bio-industrial products, etc., for example, as catalysts, lightweight materials, soundproofing materials, microcapsules, lightweight aggregates, etc. In particular, the novel ceramic granules having a hollow inside according to the present invention are excellent catalyst products, Can be used as ceramic products, ceramic products, bio-industrial products, etc.

 In particular, in a granulated body in which the shell of the granulated body is composed of porous walls, the gas and the liquid gradually flow between the inside spherical space and the outside, so that the gas and the liquid filled therein are gradually reduced. Since it is released to the outside, it can be applied to various useful applications.

Claims

The scope of the claims

 (1) A granulated product characterized by having a spherical space inside a spherical powdered solid shell.

 (2) The granule according to the above (1), wherein the powder is an organic material.

(3) The granule according to the above (1), wherein the powder is an inorganic material.

(4) The granule according to any one of the above (1) to (3), wherein the powder contains a binder.

 (5) The granulated product according to (3) or (4), wherein the inorganic material is a ceramic raw material.

 (6) A ceramic granule characterized by having a spherical space inside a spherical ceramic shell.

 (7) A ceramic granule characterized by having a spherical space inside a spherical ceramic shell and filling the spherical space with a liquid.

 (8) A ceramic granule characterized by having a spherical space inside a spherical ceramic shell and filling the spherical space with a gas.

 (9) A ceramic granule characterized by having a spherical space inside a spherical ceramic shell, and the spherical space being filled with a solid that becomes a liquid or gas at high temperature.

(10) The ceramic granule according to any one of (6) to (9), wherein the spherical ceramic shell is a sintered ceramic.

(11) The spherical particles of the superabsorbent polymer that has swollen and absorbed are brought into contact with the ceramic raw material powder to form a ceramic raw material powder layer on the entire surface of the spherical particles of the superabsorbent polymer that has swollen and absorbed. A ceramic granule characterized by comprising a ceramic granule having a spherical space inside a spherical ceramic shell, obtained by drying and then firing.

(12) The ceramic granule according to any one of the above (6) to (11), wherein the shell of the spherical ceramic granule is porous.

 (13) The ceramic granule according to any one of the above (6) to (12), wherein the raw material powder of the spherical ceramic granule contains a binder.

(14) The ceramic granule according to any one of (6) to (13), wherein the shell of the spherical ceramic granule contains a liquid.

 (15) The ceramic granule according to any one of (6) to (14), wherein the shell of the spherical ceramic granule contains a metal salt solution.

 (16) The ceramic granule according to any of (6) to (15), wherein the shell of the spherical ceramic granule contains a solid fine powder.

 (17) When the ceramic raw material or ceramic is clay, clay mineral, chamotte, quartz sand, pottery stone, feldspar, alumina, magnesia, zirconia, silica, mullite, cordierite, blast furnace slag, shirasu, fly ash, fly ash, The ceramic granule according to any one of the above (6) to (16), which is at least one selected from silicon carbide, aluminum nitride, and silicon nitride.

 (18) Ceramic raw materials or ceramics Clay, clay minerals, chamotte, silica sand, pottery stone, feldspar, graphite, alumina, magnesia, mullite, cordierite, zirconia, silica, blast furnace slag, shirasu, fly ash The ceramic structure according to any one of the above (6) to (17), wherein the mixture is a mixture of at least one member selected from the group consisting of silicon carbide, aluminum nitride, and silicon nitride and a binder. .

 (19) The ceramic granule according to any one of (6) to (18), wherein the ceramic granule is a catalyst carrier.

(20) The ceramic granule according to any one of (6) to (18), wherein the ceramic granule is an admixture for cement mortar or concrete.

(21) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is a lightweight aggregate.

 (22) The ceramic granule according to any one of (6) to (18), wherein the ceramic granule is a fertilizer containing a fertilizer.

 (23) The ceramic granule according to any one of (6) to (18), wherein the ceramic granule is a soil improvement material containing a soil conditioner.

(24) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is a luminescent material containing a luminescent substance.

 (25) The ceramic granule according to any one of (6) to (18), wherein the ceramic granule is a phosphorescence-generating material containing a phosphorescence-generating substance.

(26) The ceramic granule according to any one of (6) to (18), wherein the ceramic granule is a pH adjusting material containing a pH adjusting substance.

(27) The ceramic granule according to any one of (6) to (18), wherein the ceramic granule is a sublimable substance release containing a sublimable substance.

(28) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is a fragrance sustained-release product containing a fragrance.

(29) The ceramic granule according to any one of (6) to (18), wherein the ceramic granule is an enzyme-containing product containing an enzyme.

 (30) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is a bacteria-containing product containing bacteria.

(31) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is a bactericide-containing product containing a bactericide.

(32) It is noted that the ceramic granule is an insecticide product containing an insecticide. The granulated ceramic according to any one of the above (6) to (18).

 (33) The ceramic granule according to any one of (6) to (18), wherein the ceramic granule is a color material product containing a color material.

 (34) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is a digestive agent-containing product containing a digestive agent.

(35) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is a fire extinguisher-containing product containing a fire extinguisher.

(36) The ceramic body according to any one of (6) to (18) above, wherein the ceramic granule is a surfactant-containing product containing a surfactant.

 (37) The ceramic granule according to any one of (6) to (18), wherein the ceramic granule is a ferromagnetic material-containing product containing a ferromagnetic material. .

 (38) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is a rare earth magnet material-containing product containing a rare earth magnet material.

 (39) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is a neutron absorbing material-containing product containing a neutron absorbing material.

 (40) The ceramic granule according to any of (6) to (18), wherein the ceramic granule is a product containing a radioactive material containing a radioactive material. .

 (41) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is colored.

(42) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is an antibiotic-containing product containing an antibiotic.

(43) The ceramic body according to any one of (6) to (18), wherein the ceramic granule is a hormone-containing product containing a hormone substance.

 (44) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is a product containing a hydrogen storage substance containing a hydrogen storage substance.

 (45) The ceramic granule according to any one of the above (6) to (18), wherein the ceramic granule is a superabsorbent polymer-containing product containing a superabsorbent polymer.

 (46) The ceramic granule according to any one of (6) to (27), wherein the spherical ceramic shell has a multilayer structure.

 (47) The ceramic granule according to any of (6) to (38), wherein the spherical ceramic shell is an unsintered ceramic green material, and

(48) After the expanded spherical particles of the superabsorbent polymer are brought into contact with the ceramic raw material powder, the powder layer is formed on the entire surface of the spherical particles of the superabsorbent polymer that has swollen the water. A ceramic granule characterized by comprising an unfired ceramic granule having a spherical space inside a spherical unfired ceramic shell obtained by drying it.

 (49) The spherical particles of the superabsorbent polymer swollen by water are brought into contact with the ceramic raw material powder to form the same powder layer on the entire surface of the spherical particles of the superabsorbent polymer swollen by water. A ceramic granule characterized by comprising an unsintered ceramic granule having a spherical space inside a spherical unsintered ceramic shell obtained by drying the same.

(50) The spherical particles of the superabsorbent polymer swollen with water are brought into contact with the powder to form a powder layer on the entire surface of the spherical particles of the superabsorbent polymer swollen with water. Characterized in that it is a granulated body obtained by drying a granule and having a spherical space inside a spherical solid shell.

 (51) A granulated body characterized in that the granulated body according to any one of (1) to (50) is immersed in a liquid, and a shell of the granulated body is impregnated with the liquid.

 (52) The granulated product according to (51), wherein the liquid is a metal salt solution.

 (53) The granulated product according to any one of (1) to (50) is immersed in a suspension of solid fine powder, dried, and mixed with the solid fine powder in the shell of the granulated product. A granulated body characterized in that:

 (54) A granulated body characterized in that the granulated body according to any one of (1) to (50) is immersed in a liquid, and the liquid is contained in a spherical space inside.

 (55) A granulated body characterized in that the granulated body according to any one of the above (1) to (50) is left in a gas body, and the gas body is built in a spherical space inside.

 (56) The powder is (1) pharmaceutical, (2) fertilizer, (3) food, (4) cement, (5) feed, (6) coloring material, (7) pesticide, (8) cosmetic, 9) enzyme-containing material, (10) surfactant, (11) semiconductor, (12) metal, (13) multi-capsule composition,

[14] Cermet, [15] Paint coating material, [16] Proper material, [17] Insulating material, [18] Sound absorbing material, [19] Radio wave absorbing material, [20] Light absorbing material, [21] Reflecting material , [22] Traffic sign display materials, [23] Ball bearings, [24] Bio-oritors, [25] Far-infrared radiation materials, [26] Electric heating materials, [27] Lightweight aggregates, [28] Ball game materials, [ 29] Dehumidifying material, [30] Furnace material, [31] Engine room wall material, [32] Gas turbine room wall material, [33] Backing (lining) material, [34] Ventilation material, [35] Soil material , [36] Biomaterials, bioceramics, [37] Inclined materials, [38] Aperitite, [39] Slow-acting materials, [40] Plastics, [41] Photosensitive materials, [42] Hydrogen storage materials, [43] Musical instruments Material, [44] acoustic speaker material, [45] ozonolysis material, [46] enamel, [47] glaze, [48] U Flight material, (49) Solar furnace, (50) Artificial teeth, (51) Tile, (52) Pigment, (53) Filling material, (54) Adhesive main component, (55) Ultrafine particle material, (56) Permanent magnet material [57] The granule according to any one of [1] to [55], which is any one selected from the group consisting of shape memory materials.

 (57) An aggregate formed by combining a large number of the granules according to any one of the above (1) to (56) into a mass, and forming a mass. ,

(58) A mass sintering process in which a large number of granules according to any one of the above (1) to (56) are sintered into a massive sintered body. Union.

 (59) The method according to any one of (1) to (55), wherein a different powder layer is formed on the surface of the granulated body to have a spherical solid shell having a multilayer structure. Granules.

 (60) A mass formed by combining and combining a large number of the granules according to the above (59) into a mass.

 (61) A massive sintered body obtained by sintering a large number of the granules according to the above (59) to form a massive sintered body.

 (62) The granules are (1) pharmaceutical, (2) fertilizer, (3) food, (4) cement, (5) feed, (6) colorant, (7) pesticide, (8) cosmetic, (9) enzyme-containing material, (10) surfactant, (11) semiconductor, (12) metal, (13) multi-capsule composition,

[14] Cermet, [15] Paint coating material, [16] Moat material, [17] Insulation material, [18] Sound absorbing material, [19] Radio wave absorbing material, [20] Light absorbing material, [21] Reflection Materials, (22) traffic sign display materials, (23) ball bearings, (24) bioreactors, (25) far-infrared radiation materials, (26) electric heating materials, (27) lightweight aggregates, (28) ball game materials, [29] Dehumidifying material, [30] Furnace material, [31] Engine room wall material, (: 32) Gas turbine room wall material, [33] Backing (lining) material, [34] Ventilation material, [35] Soil material, [36] Biomaterial, bioceramics, [37] Inclined material, [38] Apatite, [39] Slow-acting material, [40] Plastic, [41] Photosensitive material, [42] Hydrogen storage material, [43] Musical instrument material, [44] Acoustic speaker material, [45] Ozone decomposition material, [46] Enamel, [47] Glaze, [48] Space flight material,

(49) Solar furnace, (50) Artificial teeth, (51) Tile, (52) Pigment, (53) Filling material, (54) Adhesive main component, (55) Ultrafine particle material, (56) Permanent magnet material [57] The granule according to any one of the above [1] to [61], which is selected from the group consisting of shape memory materials.

 (63) A binder is applied to the surface of the spherical particles of the superabsorbent polymer that has swelled and absorbed, and after a powder is applied to the surface, it is dried and has a spherical space inside a spherical solid shell. The granulated product according to any one of the above (1) to (62), wherein

(64) A binder is applied to the surface of the spherical particles of the superabsorbent polymer that has swelled and absorbed, and after a powder is applied to the surface, the powder is dried, and then calcined to form spherical particles inside the spherical solid shell. The granulated product according to any one of the above (1) to (62), having a space.

 (65) A first powder layer is applied to the surface of the spherical particles of the superabsorbent polymer swollen by water absorption, and then one or more powder layers are applied thereon, and then dried to obtain a spherical multilayer solid. The granulated product according to any one of (1) to (64), characterized by having a spherical space inside the shell.

 (66) A first powder layer is applied to the surface of the spherical particles of the superabsorbent polymer swollen by water absorption, and then one or more powder layers are applied thereon, dried, and then fired to obtain a spherical powder. The granulated product according to any one of (1) to (64), wherein the granulated product has a spherical space inside a solid shell having a multilayer structure.

 (67) A mixed powder composed of two or more different kinds of powders is applied to the surface of the spherical particles of the water-absorbing and swollen superabsorbent polymer and then dried to form a spherical solid shell composed of a combination of different kinds of powders. The granulated product according to any one of (1) to (66), which has a spherical space inside.

(68) A mixed powder consisting of two or more different kinds of powders is mixed with It is characterized in that it has a spherical space inside a spherical solid shell made of a combination of different kinds of powders after it is applied to the surface of one spherical particle, dried and then fired. The granulated product according to any one of (66) to (66).