JP2003095781A - Method of manufacturing coated bioactive granule - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of stably manufacturing coated granules having specified functions by preventing the fluctuation and lack of the content of a small component of coating materials on the coated surface, when the coated bioactive granules is manufactured by spraying the liquid mixture dissolved and mixed many kinds of the coating materials components into a solvent on the surface of the granular bioactive substance. SOLUTION: The coated bioactive granules are manufactured by spraying the liquid mixture obtained by dissolving and mixing many kinds of the coating materials into the solvent on the surface. In the preparation of the liquid mixture the small component among the coating components are added, dissolved and mixed into the solvent in the state of previously filling the small component in the material soluble in the solvent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a coated granular bioactive substance. More specifically, when many kinds of coating material components are dissolved in a solvent, a small amount of the coating material component among the coating material components is sealed in advance in another material which can be dissolved in the solvent, and then the sealing is performed. The present invention relates to a method for producing a coated granular bioactive substance, which comprises coating the bioactive substance particles with a coating material dissolving mixed solution obtained by dissolving the above-mentioned material components in the solvent.

[0002]

2. Description of the Related Art Bioactive substances are used for the purpose of prolonging the effect (fertilizing effect, medicinal effect, etc.) of bioactive substances represented by fertilizers, pesticides, pharmaceuticals, bath salts, and supplemental foods, and improving the ease of handling. Bioactive substance particles (for example, granular fertilizers, pesticide granules, tablets, etc.) obtained by granulating substances are manufactured and used.

In addition, the efficacy of further bioactive substances (fertility,
For the purpose of prolonging the drug efficacy) and controlling the efficacy pattern, etc., coated granular bioactive substances (for example, coated fertilizers, coated agricultural chemicals, etc.) in which the surface of the bioactive substance particles are coated with a coating material are manufactured and used. There is. Among them, a coating material-dissolved mixed solution prepared by dissolving the coating material in a solvent is sprayed onto the surface of the bioactive substance particles to obtain a coating on the surface of the bioactive substance particles, which is obtained by a method for producing a coated granular bioactive substance. The coated granular bioactive substance has a high elution control function and is a material that has been drawing attention in recent years.

[0004]

The coated granular bioactive substance comprises:
Elution rate of bioactive substance, elution pattern, temperature dependence,
Many functions such as degradability of the coating material used are required.
Therefore, it has been practiced to use a coating material in which various types of coating material components are mixed. However, in this method, in the case of producing a large amount of coated particulate bioactive substance, among the various types of coating material components used, the coating material component with a small amount is used in a process of dissolving and mixing in a solvent,
A part of it may dissipate or adhere to the vessel wall of the melting tank, resulting in problems such as variations in the content of the minor component in the coating of the coated product or insufficient content, and It has been difficult to stably produce a functional coated product. In the present invention, the minor component means a coating material component whose content in the coating material is 10% by weight or less.

[0005]

The present inventor has conducted extensive studies to solve the problems of the prior art. As a result, when many kinds of coating material components are dissolved and mixed in a solvent, a small amount of the coating material component is weighed, and then the small amount of coating material component is sealed with a solvent-soluble material used for coating. When a coating material dissolving mixed solution is prepared by adding to a solvent and dissolving the mixture and spraying the coating material dissolving mixed solution onto the surface of the bioactive substance particles to form a film on the surface of the bioactive substance particles, a small amount is obtained. It has been found that it is possible to stably produce a coated product having a certain function by preventing the variation in the content of the components in the coating and the lack of the content, and completed the present invention based on this finding.

The present invention is shown in the following (1) to (6). (1) Coated granular organisms which form a film on the surface of bioactive substance particles by spraying a coating material dissolved mixed liquid obtained by dissolving and mixing various kinds of coating material components in a solvent In the method for producing an active substance, when dissolving the various kinds of coating material components in a solvent,
It is preferable to use a coating material solution mixture prepared by adding a small amount of the coating material component among the coating material components to a solvent that can be dissolved in the solvent in advance and dissolving and mixing the mixture. A method for producing a coated granular bioactive substance characterized by the above.

(2) The method for producing a coated granular bioactive substance according to the above item 1, wherein the material soluble in the solvent is a material containing a thermoplastic resin.

(3) The method for producing a coated granular bioactive substance according to the above item 2, wherein the thermoplastic resin is polyolefin.

(4) The method for producing a coated granular bioactive substance according to the above item 3, wherein the polyolefin is low density polyethylene.

(5) The first coating material dissolving mixed solution is a coating material dissolving mixed solution having a weight ratio of (material for enclosing a small amount of coating material component) / (total amount of coating material) of 10/200 or less. A method for producing a coated granular bioactive substance according to the item.

(6) The first coating material dissolving mixed solution is a coating material dissolving mixed solution having a weight ratio of (material for enclosing a small amount of coating material component) / (total amount of coating material) of 1/200 or less. A method for producing a coated granular bioactive substance according to the item.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The bioactive substance in the present invention means (A) agricultural products, useful plants,
What is used for the purpose of raising and protecting plants such as agricultural products, (B) What is used for raising and protecting animals including human beings, and (C) Used in the daily life of human beings and comes into direct contact with the skin. It is a thing.

(A) is for increasing the yield of crops, improving the quality of crops, controlling disease, controlling pests, controlling harmful animals, controlling weeds, and further promoting the growth, suppressing growth, dwarfing of crops, etc., depending on the purpose of use. Specifically, fertilizers, nitrification inhibitors, urease inhibitors, agricultural chemicals, microorganisms and the like can be mentioned. Particularly when used as a coated granular bioactive substance, if the bioactive substance is a fertilizer or a pesticide, a relatively high effect can be obtained for its intended purpose.

Specific examples of (B) include medicines such as tablets, pills, granules, and oral preparations, supplemental nutritional foods, livestock feed, and the like, and specific examples of (C) include:
Examples thereof include bath agents, laundry detergents, and molding detergents for drainage pipes and the like.

As fertilizers, nitrogenous fertilizers, phosphate fertilizers,
In addition to potassium fertilizers, fertilizers containing essential plant elements such as calcium, magnesium, sulfur, iron, trace elements and silicon can be cited. Specific examples of nitrogenous fertilizers include ammonium sulfate, urea, and ammonium nitrate, as well as isobutyraldehyde condensed urea, acetaldehyde condensed urea, and the like. Phosphoric fertilizers include superphosphate lime, fused phosphorus fertilizer, and calcined phosphorus fertilizer. Examples of the potassium fertilizer include potassium sulfate, chloride chloride, and silica silicate fertilizer, and the form thereof is not particularly limited. Further, advanced chemical fertilizer or compound fertilizer having a total amount of the three components of the fertilizer of 30% by weight or more, and further organic fertilizer may be used. Further, a fertilizer to which a pesticide, a nitrification inhibitor, a urease inhibitor, a trace element and the like are added may be used. Particularly when used as a coated granular bioactive substance, if the bioactive substance particles are urea, a relatively high effect is obtained for the purpose of use.

The pesticides include disease control agents, pest control agents,
Examples thereof include pest control agents, weed control agents, and plant growth regulators, and any of these can be used without limitation. The disease control agent is an agent used for protecting agricultural crops and the like from harmful effects of pathogenic microorganisms, and mainly includes bactericides. The pest control agent is a chemical agent for controlling pests such as agricultural crops, and is mainly an insecticide. The pest control agent is an agent used for controlling plant parasitic mites, plant parasitic nematodes, field worms, birds and other harmful animals that harm agricultural crops and the like. The weed control agent is a chemical agent used for controlling plants and plants that are harmful to agricultural crops and trees, and is also called a herbicide. The plant growth regulator is a drug used for the purpose of enhancing or suppressing physiological functions of plants.

The pesticide is preferably solid and powdery at room temperature, but may be liquid at room temperature. In the present invention, the pesticide may be water-soluble, sparingly water-soluble, or water-insoluble, and is not particularly limited. Specific examples of the pesticides are shown below, but these are merely examples and the present invention is not limited thereto. Also, even if there is only one pesticide,
It may be composed of two or more kinds of composite components.

For example, 1- (6-chloro-3-pyridylmethyl) -N-nitroimidazolidine-2-ylideneamine, O, O-diethyl-S-2- (ethylthio) ethyl phosphorodithioate, 1,3-bis. (Carbamoylthio) -2- (N, N-dimethylamino) propane hydrochloride, 2,3-dihydro-2,2-dimethyl-7-benzo [b] furanyl = N-dibutylaminothio-N-methylcarbamate , (2-Isopropyl-4-methylpyrimidyl-6) -diethylthiophosphate, 5-dimethylamino-1,2,3-trithian oxalate, O, O-
Dipropyl-O-4-methylthiophenyl phosphate,

Ethyl = N- [2,3-dihydro-2,2
-Dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio] -N-isopropyl-β-alaninate, 1-naphthyl-N-methylcarbamate, 2
-Isopropoxyphenyl-N-methylcarbamate,
Diisopropyl-1,3-dithiolane-2-ylidene-
Malonate, 5-methyl-1,2,4-triazolo [3,4-b] benzothiazole, 1,2,5,6-tetrahydropyrrolo [3,2,1-ij] quinoline-4-
On, 3-allyloxy-1,2-benzisothiazole-1,1-dioxide, sodium salt of 2,4-dichlorophenoxyacetic acid, dimethylamine salt or ethyl ester,

2-Methyl-4-chlorophenoxyacetic acid sodium salt or ethyl, butyl ester. 2-Methyl-4-chlorophenoxybutyric acid sodium salt or ethyl ester, α- (2-naphthoxy) propionanilide, S-1-methyl-1-phenylethyl = piperidine-1-carbothioate, S- (4- Chlorobenzyl) -N, N-diethylthiocarbamate, 5-tert-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazoline-2
-On,

2- [4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazol-5-yloxy]
Acetophenone, 4- (2,4-dichlorobenzoyl)
-1,3-Dimethyl-5-pyrazolyl-p-toluenesulfonate, 3-isopropyl-2,1,3-benzo-
Thiadiadinone- (4) -2,2-dioxide or its sodium salt, 2-chloro-4-ethylamino-6-
Isopropylamino-s-triazine,

2-methylthio-4-ethylamino-6-
(1,2-Dimethylpropylamino) -s-triazine, 2-methylthio-4,6-bis (ethylamino)-
s-triazine, 2-methylthio-4,6-bis (isopropylamino) -s-triazine, 1- (α, α-dimethylbenzyl) -3- (paratolyl) urea, methyl =
α- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -ο-toluate,

2-benzothiazol-2-yloxy-
N-methylacetanilide, 1- (2-chloroimidazo [1,2-a] pyridin-3-ylsulfonyl) -3-
(4,6-dimethoxypyrimidin-2-ylurea, S-
Benzyl = 1,2-dimethylpropyl (ethyl) thiocarbamate, 2-chloro-N- (3-methoxy-2-thenyl) -2 ′, 6′-dimethylacetanilide and the like can be mentioned.

Further, examples of pesticides include substances that induce phytoalexin, which is a low molecular weight antibacterial substance that is synthesized by plants after contact with plants and accumulates in the plants.

As the nitrification inhibitor, dicyandiamide, thiourea, 2-amino-4-chloro-6-methylpyrimidine, 2-mercaptobenzothiazole, sulfathiazole, guanylthiourea, N-2,5-dichlorophenylsuccinamide. Acid, 4-amino-1,2,4
-Triazole hydrochloride, 2-[(N-nitro) methylamino-1,3,4-thiadiazole, 5-mercapto-
Examples include 1,3,4-triazole, 2-chloro-6- (trichloromethyl) pyridine, trichloromethylmethylaminotriazine, 2,4-dichloroaniline, and 2-trichloromethylquinoline. Of these, dicyandiamide has a high solubility in water and is inexpensive, and thus can be preferably used in the present invention.

Examples of urease inhibitors include N- (n
-Butyl) thiophosphoric triamide, N- (n-butyl) phosphoric triamide, thiophosphoryltriamide, phenylphosphorodiimidate, cyclohexylthiophosphoric triamide, cyclohexylphosphoric triamide , Folic triamide, hydroquinone, p-benzoquinone, ammonium thiosulfate, hexaamidocyclotriphosphazene, thiopyridines, thiopyridimines, thiopyridine-N-oxamides, NN-halo-2-imidazolidinone, N-halo -2-oxazolidinone, boric acid, N
-Hydrocarbyl thiophosphoric triamide,

N-hydrocalphosporic triamide, N-hydrocalphosporic trithioamide,
Metal nitrate, N-diamino (thio) phosphinyl sulfinamide, N-diamino (thio) phosphinyl sulfonamide, O-diaminophosphinyl oxime,
S-Hydrocarbyl diaminophosphoric acid thiolate Boric acid, borate, bromide-nitroalkanes, nitrates such as iron nitrate and aluminum nitrate, hydroxy acids, 3-alkyl-Rhodamine-5-acetic acid, calcium formate, calcium acetate, sodium And dithiocarbamates of copper, manganese, and zinc, immunoglobulins such as immunoglobulin G (IgG), and immunoglobulin Y (IgY). Among them, N- (n-butyl) thiophosphoric acid triamide is particularly effective.

Examples of the trace elements include iron, manganese, copper, zinc, molybdenum, boron, chlorine, silicon, sodium, cobalt, nickel, aluminum, and selenium.

As the microorganism, one having an effect of suppressing the propagation of pathogenic microorganisms can be used. Specifically, the genus Trichoderma (Trichoderma lignorum, Trichoderma viridi, etc.), the genus Gliocladium (Gliocladium virens, etc.), the genus Cephalosporium,
Filamentous fungi such as the genus Coniocillium, the genus Sporidesmium, the genus Laetitharia, the genus Agrobacterium (Agrobacterium radiobacter), the genus Bacillus (Bacillus subtilis), the genus Pseudomonas (Pseudomonas
Sepacia, Pseudomonas gourmet, Pseudomonas
Gladioli, Pseudomonas floressence, Pseudomonas aureofaciens, Pseudomonas putida, etc.), Xanthomonas spp., Erwinia spp., Arthrobacter spp., Corynebacterium spp.,

Enterobacter, Azotobacter,
Flavobacterium, Streptomyces (Streptomyces achromogenes, Streptomyces
Phaeo perculens, Streptomyces hygroscopicus, Streptomyces nitrosporens,
Streptomyces burnensis, etc.), Actinoplanes, Alcaligenes, Amorphosporangium, Cellulomonas, Micromonospora, Pasteuria, Hafnia, Rhizobium, Bradyrhizobium, Serratia, Lastonia Bacteria such as (Rustonia solanacearum) and actinomycetes can be mentioned.

Specifically, it is a Pseudomonas bacterium having a high antibacterial substance-producing ability. For example, as a strain producing an antibiotic, Pseudomonas cepacia, which produces the antibiotic pyrrolenitrin (against Japanese radish seedling wilt), and antibiotics are used. Substances Phenazine carboxylic acid (against wheat bacterial wilt), pyrrolenitrin, pioluteolin (against cotton bacterial wilt, cucumber bacterial wilt), cyanide (black tobacco root bacterium), diacetylfuroglucinol (against wheat wilt) Pseudomonas florescens, which produces bacteria, etc., as well as the iron chelating substance siderophore (pseudobactin, fluorescent siderophore: pioverdin), etc. Fluorescent Pseudomonas sp. (Pseudomonas putida, Pseudomona S flor essence, etc.).

Other microorganisms include growth-promoting rhizobacteria (PG) that produces growth-promoting substances such as Agrobacterium radiobacter, which produces the bacteriocin agrosin 84 (against rhizobia), and plant hormones.
Fluorescent Pseudomonas (PR)
Petitida, Pseudomonas floressence, etc.) and Bacillus. In particular, strains of CDU-degrading bacteria (Pseudomonas sp., Arthrobacter sp., Corynebacterium sp., Agrobacterium sp., Etc.) and Streptomyces sp. Strains (for example, Japanese Patent Publication No. 5-26462), Micromachine Research Deposit No. 10533. No.) has a remarkable deterrent against soil-borne pathogenic fungi and is preferably used.

The composition of the bioactive substance particles used in the present invention is not particularly limited as long as it contains at least one bioactive substance. The bioactive substance may be granulated alone, and granulated using a carrier such as clay, kaolin, talc, bentonite, or calcium carbonate, or a binder such as polyvinyl alcohol, sodium carboxymethyl cellulose, or starch. It can be one. Also, if necessary, for example, a surfactant containing polyoxyethylene nonylphenyl ether, molasses, animal oil, vegetable oil, hydrogenated oil, fatty acid, fatty acid metal salt, paraffin, wax, glycerin, etc. may be contained. I do not care.

The method of granulating the bioactive substance particles is as follows:
An extrusion granulation method, a fluidized bed granulation method, a tumbling granulation method, a compression granulation method, a coating granulation method, an adsorption granulation method and the like can be used.
In the present invention, any of these granulation methods may be used, but the extrusion granulation method is the simplest.

The particle size of the bioactive substance particles is not particularly limited, but in the case of fertilizer, for example, 1.
0 to 10.0 mm, 0.3 in the case of pesticides
It is preferably about 3.0 mm. By using a sieve, an arbitrary particle size can be selected within the above range.

The shape of the bioactive substance particles is not particularly limited, but is preferably spherical in the present invention. Specifically, a circularity coefficient, which is a measure for knowing the circularity of particles, may be used, and is calculated by the formula {(4π × projection area of particles) / (contour length of particle projection diagram) ² }. The value is preferably 0.85 or more, more preferably 0.9 or more, still more preferably 0.93 or more. The maximum value of the circularity coefficient is 1, and as the value approaches 1, the particle approaches a perfect circle, and the circularity coefficient decreases as the shape of the particle collapses from the perfect circle.

The coating material used in the present invention uses a material capable of forming a film on the surface of the bioactive substance particles as a coating material component, but the material capable of forming a film is not particularly limited. is not. It is preferable to use an inorganic substance such as resin or sulfur.

The resin used for the coating material is not particularly limited, and examples thereof include thermoplastic resin, thermosetting resin and emulsion. As a thermoplastic resin,
Specific examples thereof include olefin polymers, vinylidene chloride polymers, diene polymers, waxes, polyesters, petroleum resins, natural resins, fats and oils and modified products thereof, and urethane resins.

As the olefin polymer, polyethylene, polypropylene, ethylene-propylene copolymer,
Ethylene-carbon monoxide copolymer, ethylene-hexene copolymer, ethylene-butene copolymer, ethylene-butadiene copolymer, polybutene, butene-ethylene copolymer, butene-propylene copolymer, polystyrene, ethylene- Examples of the vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid ester copolymer and the like, vinylidene chloride-based polymer, chloride A vinylidene-vinyl chloride copolymer can be illustrated. Here, polyethylene is high density polyethylene (HDP
E), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ultra-low-density polyethylene may be used, and the melt flow rate, molecular weight, molecular weight distribution, etc. are not particularly limited. Absent.

Examples of the diene polymer include a butadiene polymer, an isoprene polymer, a chloroprene polymer, a butadiene-styrene copolymer, an EPDM polymer and a styrene-isoprene copolymer.

Examples of the waxes include beeswax, wood wax, paraffin and the like, examples of the polyester include aliphatic polyesters such as polylactic acid and polycaprolactone and aromatic polyesters such as polyethylene terephthalate, and examples of the natural resin include: Examples thereof include natural rubber and rosin, and examples of fats and oils and modified products thereof include cured products, solid fatty acids and metal salts.

As the thermosetting resin, phenol resin,
Furan resin, xylene-formaldehyde resin, ketone formaldehyde resin, amino resin, alkyd resin, unsaturated polyester, epoxy resin, silicon resin, urethane resin, and drying oil can be mentioned. These thermosetting resins have many combinations of monomers, but the types and combinations of the monomers are not limited in the present invention. Further, in addition to a polymer of monomers, a polymer of a dimer or a polymer, or a mixture thereof may be used. Further, a mixture of a plurality of different types of resins may be used. Since the thermosetting resin does not dissolve in the solvent, when the thermosetting resin is used, the minor components are dissolved or mixed in the monomer of the thermosetting resin and then used for coating the particles of the bioactive substance.

As the phenol resin, phenol, o-
Phenols such as cresol, m-cresol, p-cresol, 2,4-xylenol, 2,3-xylenol, 3,5-xylenol, 2,5-xylenol, 2,6-xylenol, and 3,4-xylenol It is possible to use the one obtained by the condensation reaction of one or more selected from the above and one or more selected from the aldehydes represented by formaldehyde.

Typical furan resins are phenol-furfural resin, furfural-acetone resin,
And furfuryl alcohol resin. Xylene-formaldehyde resin is a condensation of at least one selected from xylenes such as o-xylene, m-xylene, p-xylene, and ethylbenzene with at least one selected from aldehydes typified by formaldehyde. What was obtained by the reaction can be used.

Examples of the ketone-formaldehyde resin include acetone-formaldehyde resin, cyclohexanone-formaldehyde resin, acetophenone-formaldehyde resin, and higher aliphatic ketone-formaldehyde resin.

As the amino resin, one obtained by a condensation reaction of at least one selected from amino group-containing monomers such as urea, melamine, thiourea, guanidine, dicyandiamide, guanamine, and aniline with formaldehyde is used. Can be mentioned.

The alkyd resin may be either non-converted or converted and is selected from polyhydric alcohols such as glycerin, pentaerythritol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, sorbitol, mannitol and trimethylolpropane. 1 or more and phthalic anhydride, isophthalic acid, maleic acid, fumaric acid, sebacic acid, adipic acid, citric acid, tartaric acid, malic acid, diphenic acid, 1,8-
Examples thereof include naphthalyl acid, terpene oil, rosin, and one obtained by condensing one or more selected from polybasic acids such as unsaturated fatty acid and an adduct of maleic acid.

The fatty oil or fatty acid used for modifying the alkyd resin includes linseed oil, soybean oil,
Mention may be made of perilla oil, fish oil, tung oil, sunflower oil, walnut oil, deer oil, castor oil, dehydrated castor oil, distilled fatty acids, cottonseed oil, coconut oil and their fatty acids or monoglycerides transesterified with glycerin. In addition, resin modified products such as rosin, ester rosin, copal, and phenol resin can also be used.

As the unsaturated polyester, maleic anhydride, fumaric acid, itaconic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, 3,6-
Endomethylenetetrahydrophthalic anhydride, adipic acid, sebacic acid, tetrachlorophthalic anhydride, and 3,
6-endodichloromethylene tetrachlorophthalic acid and one or more kinds selected from organic acids, ethylene glycol,
Diethylene glycol, 1,2-propylene glycol, dipropylene glycol, hydrogenated bisphenol A, 2,2-
Bis (4-oxyethoxyphenyl) propane, and 2,2-
Examples thereof include those obtained by subjecting one or more kinds selected from polyols such as bis (4-oxypropoxyphenyl) propane to a condensation reaction.

Further, for the purpose of accelerating the curing of the unsaturated polyester, styrene, vinyltoluene, diallyl phthalate, methyl methacrylate, triallyl cyanuric acid,
It is also possible to use those obtained by adding at least one selected from vinyl monomers such as triallylphosphoric acid during condensation.

As the epoxy resin, bisphenol A is used.
Examples thereof include epoxy resins of the type, novolac type, bisphenol F type, tetrabisphenol A type, and diphenol acid type.

Further, it is also possible to use a compounded resin such as a urethane resinized polyester resin.

As the urethane resin, tolylene diisocyanate, 3,3'-bitrylene-4,4'-diisocyanate,
Diphenylmethane-4,4'-diisocyanate, polymethylene polyphenylene polyisocyanate, 3,3'-dimethyl-
Diphenylmethane-4,4'-diisocyanate, metaphenylene diisocyanate, triphenylmethane triisocyanate, 2,4-tolylene diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xy One or more selected from diisocyanates such as diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, and naphthalene-1,5-diisocyanate, and polyoxypropylene polyol, polyoxyethylene polyol , Acrylonitrile-propylene oxide polymer, styrene-propylene oxide polymer,
Polyoxytetramethylene glycol, adipic acid-ethylene glycol, adipic acid-butylene glycol,
Adipic acid-one obtained by polyaddition polymerization with trimethylolpropane, glycerin, polycaprolactone diol, polycarbonate diol, polybutadiene polyol, and one or more kinds selected from polyols such as polyacrylate polyol. You can

Particularly, in the case of a coated granular bioactive substance having a time-release type sustained release function, it is effective to form a film having low moisture permeability on the surface of the bioactive substance particles when a long release suppression period is required. Is. By forming a resin coating having a low moisture permeability on the surface of the particles, it is possible to gradually permeate the water present outside to the particles containing the bioactive substance.

For that purpose, it is effective to coat the particles with a coating material containing a thermoplastic resin having a low moisture permeability, and further, as the thermoplastic resin, an olefin polymer, an olefin copolymer or a vinylidene chloride polymer is used. It is effective to use a vinylidene chloride copolymer. In particular, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-carbon monoxide copolymer, ethylene-hexene copolymer, ethylene-butene copolymer, propylene-
Butene copolymers, ethylene-vinyl acetate copolymers and mixtures thereof can be mentioned as the most preferred resin component of the coating material component. If a film without pinholes or cracks is formed using these resin components, the amount of water permeation becomes extremely small.

In order to adjust the moisture permeability of the coating film, a resin having a high moisture permeability and a filler can be mixed and used as a coating material component. As the resin having high moisture permeability, polyethylene oxide, polypropylene oxide, a resin into which a polar group such as ethylene-vinyl acetate copolymer is introduced, ethylene-propylene copolymer, styrene-isoprene copolymer, polystyrene-polyisoprene-polystyrene. Examples thereof include rubber resins such as block copolymers, polystyrene-polybutadiene block copolymers, and polystyrene-polybutadiene block copolymer hydrogenated products.

As the coating material used in the present invention, in addition to the above-mentioned sulfur and resin coating material components, additives such as a filler and a surfactant for imparting hydrophilicity can be used. These fillers and additives are used together with coating material components such as resin components. Examples of the filler include talc, clay, kaolin, bentonite, sulfur, muscovite, phlogopite, mica-like iron oxide, metal oxides, metal salts of metals with organic acids or nitric acid, metal complexes, siliceous materials, glasses, alkalis. Examples thereof include carbonates or sulfates of earth metals, and celluloses, cellulose compounds, starches, and the like. Examples of the surfactants include nonionic surfactants represented by fatty acid esters of polyols. In the present invention, two or more kinds of the coating material components may be used in combination depending on the release function required for the coated granular bioactive substance.

In the coating material containing the resin, the content ratio of the resin is preferably in the range of 10 to less than 100% by weight, more preferably 20% by weight based on the coating material.
To less than 100% by weight. Further, in the coating material containing an inorganic substance such as sulfur, the content ratio of the inorganic substance is preferably 10 to 90% by weight, more preferably 20 to 80% by weight, based on the coating material. Is.

The coating ratio of the coating material in the coated granular bioactive substance of the present invention is 3 with respect to the coated granular bioactive substance.
It is preferably in the range of 20 to 20% by weight, more preferably in the range of 5 to 12% by weight.

Among the coating materials used in the present invention, a small amount of coating material components include metal oxides, metals and organic compounds which are additives for promoting photodecomposition, thermal decomposition, oxidative decomposition and biodegradation of the coating material. There are metal salts with acids and nitric acid, metal complexes, radical generators, photosensitizers, etc., other urease inhibitors, nitrification inhibitors, agricultural chemicals, trace element fertilizers, moisture absorbents such as calcium carbonate, water swelling agents, Surfactants, waxes such as beeswax, wooden wax, paraffin, fatty oils or fatty acids, isocyanates, amines, compatibilizers, biodegradable resins, and celluloses, glass fibers, starch, sulfuric acid as fillers added in a small amount. Examples thereof include fine powder particles such as potassium, cyclodiurea, and isobutylidene urea. In particular, the component added to accelerate the decomposition of the resin component in the coating material in the environment where the coated granular bioactive substance is used is often a substance that exerts an effect even in a trace amount,
The effect of the present invention is remarkable. Decomposition includes photodecomposition and thermal decomposition, and oxidative decomposition and radical decomposition are used. A metal compound is often used as a component used for these.

When a metal oxide is used as the metal compound, examples of the metal oxide include iron oxide, aluminum oxide, manganese oxide, calcium oxide and magnesium oxide. When a metal salt is used as the metal compound, examples of the metal salt include iron stearate, tin octylate, cobalt naphthenate, manganese naphthenate, ferrous sulfate, ferric sulfate, iron nitrate, and cobalt acetate. It is possible to use boron trifluoride and the like. When a metal complex is used as the metal compound, examples of the metal complex include iron acetylacetone, nickel dibutyldithiocarbamate and the like.

As the radical generator, benzoylper
Examples thereof include oxide, azobisisobutulonitrile, polyfuran, polyisoprene and the like. Examples of the photosensitizer include benzophenone, tetracyanobenzene, silver halide and chlorophyll. The urease inhibitor, nitrification inhibitor, pesticide, and trace element fertilizer are the same as those exemplified as the bioactive substance. Examples of the moisture absorbent include calcium carbonate, calcium chloride, calcium oxide, magnesium chloride and the like.

As the water-swelling material, an acrylate polymer (for example, Sumikagel (registered trademark) S, L, R types manufactured by Sumitomo Chemical Co., Ltd., Aqua Keep (registered trademark) manufactured by Sumitomo Seika Chemicals, Ltd.) ) 10SH, 10SHP, 10SH-NF
(20), SA60NTYPE2, Aquamate (registered trademark) AQ-200, A manufactured by Sekisui Plastics Co., Ltd.
Q-200B-02, Sunfresh (registered trademark) ST-500D, ST-500MP manufactured by Sanyo Chemical Industries, Ltd.
S), an isobutylene-based polymer (for example, registered trademark KI gel-201K, KI gel-201K manufactured by Kuraray Co., Ltd.)
-F2, KI gel solution system, KI gel compound), acrylic acid / vinyl alcohol copolymer, polyethylene oxide modified resin, starch graft polymer (for example, Sunfresh (registered trademark) ST-manufactured by Sanyo Kasei Co., Ltd.) 100, ST-500S, ST-100MP
S), starch (for example, potato starch, corn starch,
Examples include sweet potato starch, soluble starch), carboxymethyl cellulose (CMC), CMC metal salts and bentonite.

As the surfactant, higher fatty acid salts, higher alkyl dicarboxylic acid salts,
Anionic surfactants such as higher alcohol sulfate ester salts, higher alkyl sulfonates, higher alkyl disulphonates, sulfonated higher fatty acid salts, higher alkyl phosphate ester salts, higher alkyl amine salts, quaternary ammonium salts, etc. Cationic surfactant,
Examples thereof include fatty acid esters of polyols and nonionic surfactants such as polyethylene oxide condensation type.

Examples of the wax include dense wax, wooden wax, paraffin and the like. Examples of the fatty oil or fatty acid include linseed oil, soybean oil, sesame oil, fish oil, tung oil, sunflower oil, walnut oil, ochika oil, castor oil, dehydrated castor oil, distilled fatty acid, cottonseed oil, coconut oil, and those fatty acids, or Mention may be made of monoglycerides transesterified with glycerin. In addition, resin modified products such as rosin, ester rosin, copal, and phenol resin can also be used.

The isocyanates are the same as those exemplified for the urethane resin as the coating material component. It is used for the purpose of increasing the molecular weight of urethane resin or aliphatic polyester. Examples of amines include ethylenediamine and dicyandiamide.

Examples of the compatibilizer include styrene / ethylene / butadiene block copolymer, ethylene / methyl methacrylate block copolymer, polyethylene / polystyrene graft copolymer, polyethylene / polymethylmethyl methacrylate graft copolymer, ethylene / acetic acid. Vinyl copolymer, ethylene / propylene / diene copolymer,
Examples thereof include styrene / ethylene / butadiene / styrene copolymers. Examples of the biodegradable resin include polylactic acid and polycaprolactone. These minor constituent coating material components are appropriately selected and used according to the function required of the coated granular bioactive substance.

The coating of the coating material on the surface of the bioactive substance particles of the present invention is carried out by dissolving and mixing the coating material in a solvent.
A method of forming a coating film on the surface of bioactive substance particles by spraying a coating material dissolved mixed solution obtained by dissolving a small amount of coating material component in a solvent in a sealed state ( Hereinafter, the effect will be remarkable in the dissolution mixture spraying method). From the viewpoint of high production efficiency and uniformity of the obtained coating, the coating material dissolved mixed solution is sprayed onto the bioactive substance particles in a rolling or flowing state, and then the coating is exposed to hot air. The method of forming is preferred.

An example of a coating apparatus that can be used in the dissolved mixed solution spraying method will be described with reference to the jet apparatus shown in FIG. In this method, in order to uniformly disperse the solvent-insoluble coating material component such as an inorganic filler in the coating material dissolved mixed solution, it is necessary to strongly stir the coating material dissolved mixed solution. This jetting device transports the coating material-dissolved mixed solution to the jetted particles 3 through a pipe 5, sprays them with a spray nozzle 2, sprays them onto the surfaces of the particles 3, and simultaneously coats the surfaces. First, a high-temperature gas is caused to flow into the jet tube 1 from the lower part into the guide tube 6, and the solvent in the coating material-dissolved mixed liquid adhering to the surface of the particles is instantaneously evaporated and dried by the high-speed hot air flow. The spraying time varies depending on the resin concentration of the coating material-dissolved mixed solution, the spray rate of the solution, the coating rate, etc., but these should be appropriately selected according to the purpose.

As a coating apparatus other than the jet apparatus shown in FIG. 1 which can be used in the present invention, a fluidized bed type or jet layer type coating apparatus is disclosed in Japanese Examined Patent Publication Nos. 42-24281 and 42-24282. A device for forming a fountain-type fluidized bed of particles by a gas body and spraying a coating agent on a particle dispersion layer generated in the central part can be mentioned as a rotary type coating device.
Japanese Patent Laid-Open No. 7-195007 and Japanese Patent Laid-Open No. 7-195007, a lifter provided on the inner circumference of a drum by rotating the drum transfers the powder particles upward, and then drops the powder particles to apply a coating agent to the surface of the falling particles. However, an apparatus for forming a film can be used.

When the coated granular bioactive substance is obtained by the dissolution mixed solution spraying method, the solvent to be used is not particularly limited, but since the solubility characteristics for each solvent differ depending on the type of resin used for coating, The solvent may be selected according to the resin used. For example, when using an olefin polymer, an olefin copolymer, a vinylidene chloride polymer, a vinylidene chloride copolymer or the like as a resin, a chlorine-based solvent or a hydrocarbon-based solvent is preferable, and among them, tetrachloroethylene, trichloroethylene, and toluene are used. If it is present, it is a particularly preferable solvent because a dense and uniform film can be obtained.

In the conventional dissolution mixed solution spraying method, in the step of dissolving the coating material in the solvent, a small amount of the coating material component is singulated by vaporization due to heating of the solvent or moisture absorption in the air, or is dissolved in the dissolution container. In some cases, the content of minor components was not constant in the product due to adhesion. Especially when a plurality of coating material components are mixed and used, when a small amount of coating material component is weighed simultaneously with a large amount of other coating material components, and mixed and dissolved, a small amount of coating material component may scatter. It was difficult to reliably add, dissolve, and mix a fixed amount.

The present invention makes it possible to dissolve and mix the small amount of the coating material component at a constant concentration with little variation in the coating material solution, and to add a small amount in the process of mixing the coating material with the solvent. The coating material component as a component is pre-encapsulated in a material that can be dissolved in the solvent, and is added to the solvent to be dissolved and mixed, whereby a small amount of the coating material component is uniformly mixed.

The solvent-soluble material for enclosing the minor constituent coating material component is not particularly limited as long as it is a material soluble in the solvent used for coating, and a material soluble in the solvent used can be selected. It is preferred that the material used for encapsulation is completely dissolved within the time during which the coating material components other than the encapsulation material are dissolved in the solvent during the dissolution operation. Moreover,
It is preferable that the material that does not affect the control of elution even when the material encapsulating the coating material component of the minor component is mixed in the formed film. For that purpose, it is preferable that one of the coating material components and the material encapsulating the coating material component of the minor component are the same. When a resin is used as one of the coating material components, when the resin is an olefin polymer, an olefin copolymer, a vinylidene chloride polymer, a vinylidene chloride copolymer, etc., the resin is also used as an encapsulating resin. The resin is preferable because it is easy to form a film into a packaging material, and since it is the same as the resin used for the coating material, it does not affect the function of the coating film after dissolution.

The amount of the material for enclosing the minor coating material component is preferably 10% by weight or less, more preferably 5% by weight or less, based on the total amount of the coating material. It is preferable to select the same resin as the resin used for the coating material as the material for encapsulating the minor constituents of the coating material component in the coating by the dissolution mixed solution spraying method, especially since the packaging material is desired to be easily completely dissolved.

As the solvent used for dissolving and mixing the coating material, it is preferable to select a solvent which easily dissolves the material components enclosing a small amount of the coating material component. The fact that the material encapsulating a small amount of the coating material component is easily dissolved means that the coating material is in an intended normal state of dissolution, mixing or dispersion in the apparatus for dissolving the coating material and the dissolution conditions thereof. If the material for encapsulating the coating material component of the minor component is a material that can be completely mixed with the coating material by dissolution, the number of manufacturing operations is reduced, and there is little influence on the control of the elution of the coated granular bioactive substance, which is a preferable material. is there.

The method of encapsulating a small amount of coating material component is not particularly limited. Although any method can be used as long as it can be packaged so that the coating material component of the minor component does not scatter, a method of putting the measured minor component coating material component in a packaging material and sealing it by heat sealing,
Examples thereof include a method of using a packaging material with a zipper and a method of sealing with an adhesive. As the packaging device, the one used as an automatic weighing and packaging device for internal medicine can be used. It is preferable to use an olefin polymer because it can be sealed by heat sealing.

[0078]

EXAMPLES The present invention will be described below with reference to examples. In addition, "%" in the following examples is "% by weight" unless otherwise specified.

Examples 1 to 5 A method of coating using granular urea classified with a sieve having a particle size of 2.5 to 3.5 mm will be described. The coating device used is shown in FIG. Tower diameter 250 mm, height 2000 m
m, the diameter of the air outlet was 50 mm, and the hot hot air flowed from the lower part to the upper part into the jet tower 1 having a shape of a cone angle of 50 degrees. The high-temperature hot air is blown from the blower 10, passes through the orifice flow meter 9, is heated to a high temperature by the heat exchanger 8 and flows into the jet tower 1, and is discharged from the exhaust gas outlet 3 installed at the upper part of the jet tower 1. It Inside the jet tower 1 in which this high-temperature hot air is circulated, 10 kg of bioactive substance particles are introduced from an inlet 2 installed on the side surface of the jet tower 1, and as shown in FIG. To flow. At this time, the flow rate of hot air and the hot air temperature need to be appropriately adjusted for each granular fertilizer, and the flow rate is adjusted while measuring with an orifice flow meter, and the hot air temperature is T1 hot air temperature, T2 granule temperature, Adjust while measuring the exhaust temperature of T3.

In the present embodiment, the flow rate (orifice flow meter 9) 4 m ³ / min, hot air temperature (hot air temperature T1) 10
0 ° C ± 2 ° C, granular urea temperature (particle temperature T2) 70 ± 2 ° C
It was carried out in. On the other hand, polyethylene (low density polyethylene d = 0.918 [g / cm ³ ] (density JIS K67
60), MI = 22 [g / 10min] (melt index
JIS K6760)) 60 parts by weight, ethylene-vinyl acetate copolymer (MI = 20 [g / 10 min] (melt index JIS K6760), vinyl acetate content 30% by weight) 3
When 9.7 parts by weight of iron stearate (reagent product) and 0.1 parts by weight of the coating material are charged into the dissolution tank 11 into which 70 liters of toluene as a solvent has been charged in advance, Iron oxide is polyethylene (low density polyethylene d = 0.918 [g / cm ³ ] (density JIS K6760), MI =
22 [g / 10min] (melt index JIS K676
0)) thickness 0.1 mm × length 100 mm × width 10
A 0 mm film was sealed by a heat-sealed bag and put therein. The resin was dissolved by mixing and stirring at 100 ° C. ± 2 ° C. to obtain 1.5 wt% of uniform coating material dissolved mixture solution 12.

The dissolution tank 11 was constantly stirred until the coating was completed. The coating material-dissolved mixed liquid 12 is flown by a pump 6 to a spray nozzle 4 which is a 0.8 mm full-confluent type one-fluid nozzle installed at the bottom of the jet tower 1 at a flow rate of 0.1
It was transported at a rate of kg / min, and sprayed on the flowing granular urea 5 by spraying. At this time, the dissolution tank 11 and the dissolution tank 11 are kept so that the temperature of the coating material dissolution mixture 12 does not fall below 80 ° C.
The pipe from the nozzle to the spray nozzle 4 was made into a double structure, and the coating material-dissolved mixed liquid 12 was transported while heating while passing steam.

The above-mentioned coating operation is started from the time when the particle temperature T2 of the flowing granular urea 5 reaches 70 ° C. until the coating reaches 8.5% by weight based on the coated granular bioactive substance. After spraying for a period of time, the coated granular bioactive substance was maintained at 70 ° C. ± 2 ° C., while controlling the temperature of the hot air, drying was performed by blowing only hot air for 10 minutes. At the time of completion, the blower 10 was stopped, the coated granular bioactive substance 5 was discharged from the outlet 7 at the bottom of the jet tower 1, and Example 1 described in Table 3 was performed.
~ 5 coated granular bioactive substances were obtained.

Coating operation conditions One-fluid nozzle: outlet diameter 0.8 mm, full-corn type granular fertilizer: 10 kg Hot air temperature: 100 to 110 ° C. Hot air flow rate: 240 m ³ / hr Spray flow rate: 0.5 kg / min

Comparative Examples 1 to 5 Coated granular bioactive substances were prepared in the same manner as in Examples 1 to 5 except that iron stearate was not charged and directly charged into a dissolution tank.

Method for calculating theoretical iron content The iron content determined from the coating material composition ratio in 5 g of the coated granular bioactive substance of Example 1 and Comparative Example 1. Iron stearate [CH ₃ (CH ₂ ) ₁₆ COO] ₃ Fe:
Molecular weight 906.25 Atomic weight of iron: 55.85 Iron content theoretical value = (5.0 × 0.085 × 0.1 × 55.85 / 906.25) /5.0×10 ⁶ = 523.8 [ppm]

Method of Analyzing Measured Iron Content in Coatings 5 g of each of the coated granular bioactive substances prepared in Examples 1 to 5 and Comparative Examples 1 to 5 was dissolved in 100 ml of toluene, and the solution was contained by flame analysis. The iron content was measured and listed in Table 1.

[0087]

[Table 1]

As is clear from the results shown in Table 1, in Examples 1 to 5 in which a minor amount of coating material component was encapsulated, compared with Comparative Examples 1 to 5 in which no minor amount of coating material component was encapsulated. It was confirmed that it is possible to manufacture a product with little variation in the measured iron content in the coating and a small difference from the theoretical iron content.

[0089]

According to the manufacturing method of the present invention, a small amount of coating material components among various types of coating material components are encapsulated in a solvent-soluble material, and the other coating material components are dissolved in the solvent. By dissolving and mixing, it is possible to reduce the variation in the content of the minor component in the coating film of the obtained coated granular bioactive substance, and to provide the coated granular bioactive substance in a content having a small difference from the theoretical value. You can get it.

[Brief description of drawings]

FIG. 1 Diagram of a spouted bed flow sheet

[Explanation of symbols]

1. Spout tower 2. Bioactive substance particle input port 3. Exhaust gas outlet 4. spray nozzle 5. Bioactive substance particles 6. pump 7. Outlet 8. Heat exchanger 9. Orifice flow meter 10. Blower 11. Melting vessel 12. Dissolution mixture of coating material T1. Hot air thermometer T2. Granule thermometer T3. Exhaust thermometer SL. steam

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C05G 3/02 C05G 3/02 3/08 3/08 F term (reference) 4D075 AA01 BB16X CA31 DA11 DC30 DC38 EA07 EB07 EB08 EB13 EB14 EB15 EB19 EB22 EB32 EB35 EB36 EB38 EB43 EB56 EC30 EC54 4H011 AC01 BA01 BB09 BC01 BC06 BC14 BC19 DA04 DC10 DF06 DH02 4H061 AA02 BB01 BB21 BB51 CC01 CC15EE35 FF06 DD16 BBEE CCFF CC16 CC35 DD06 DD16

Claims (6)

[Claims] 1. A coating for forming a coating film on the surface of bioactive substance particles by spraying a coating material solution mixture obtained by dissolving and mixing various kinds of coating material components in a solvent, onto the surface of the bioactive substance particles. In the method for producing a granular bioactive substance, when dissolving the various kinds of coating material components in a solvent, a small amount of the coating material component among the coating material components is previously enclosed in a material that is soluble in the solvent. A method for producing a coated granular bioactive substance, which comprises using a coating material-dissolved mixed liquid prepared by adding to the solvent to dissolve and mix the solvent in the state. 2. The method for producing a coated granular bioactive substance according to claim 1, wherein the material soluble in the solvent is a material containing a thermoplastic resin. 3. The method for producing a coated granular bioactive substance according to claim 2, wherein the thermoplastic resin is polyolefin. 4. The method for producing a coated granular bioactive substance according to claim 3, wherein the polyolefin is low density polyethylene. 5. The coating material dissolving mixed solution is a coating material dissolving mixed solution having a weight ratio of (material enclosing a small amount of coating material component) / (total amount of coating material) of 10/200 or less. A method for producing a coated granular bioactive substance according to claim 1. 6. The coating material dissolving mixed solution is a coating material dissolving mixed solution having a weight ratio of (material for enclosing a small amount of coating material component) / (total amount of coating material) of 1/200 or less.
A method for producing the coated granular bioactive substance according to claim 1.