JP2002114592A - Bioactive material particle, coated bioactive material, bioactive material composition containing the same, and method for manufacturing coated bioactive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide bioactive material particles which lessen powdering or atomizing even when the material particles receive physical force from outside in various scenes of storage, transportation and use after manufacture, and to obtain the coated bioactive material which lessens the degradation of the properties of films and the occurrence of the loss of an elution control function in consequence of the films intruded with the particulates and/or powder generated by the atomizing and/or powdering of the bioactive material particles which are the materials to be coated. SOLUTION: More than 70% of the bioactive material particles are formed as the particles included within a specific equivalent spherical diameter range, or the content ratio of water into the bioactive material particles is confined to <=1 wt.%. Further, the surfaces of such bioactive material particles are coated with film materials.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a bioactive substance particle,
The present invention relates to coated bioactive substances and bioactive substance compositions containing them.

[0002]

2. Description of the Related Art In order to prolong the efficacy (fertilization effect, medicinal effect, etc.) of biologically active substances represented by fertilizers, agricultural chemicals, medicines, bath additives, and supplemental nutritional foods, and to improve the ease of handling, the bioactive substances are used. Bioactive substance particles (for example, granular fertilizers, pesticide granules, tablets, etc.) obtained by granulating an active substance have been manufactured and used. Further, for the purpose of further prolonging the efficacy (fertilizer effect, medicinal effect, etc.) of the bioactive substance and controlling the effect expression pattern, the surface of the bioactive substance particles is coated with a coating bioactive substance (for example, Coated fertilizers, coated pesticides, etc.).

[0003]

The bioactive substance particles are produced after production.
In each case of storage, transportation, and use, a physical force is applied from the outside, and in some cases, some of the bioactive substance particles may be powdered or finely divided. In such a case, in the container or bag containing the bioactive substance particles, classification may occur between powdered or finely divided ones and those not.

In general, as a method for preventing the powdering or fine particle formation, a method of increasing the hardness of the particles themselves by using a binder such as bentonite, clay, molasses, and resin as a part of the particle raw material is adopted. Have been. However, some biologically active substances, which are the active ingredients, cause a chemical reaction with the binder.The purpose is to avoid this chemical reaction or to increase the content of the biologically active substance contained in the particles. When a binder is not used or its amount is reduced, a desired hardness may not be achieved in some cases. Further, even when a high hardness is achieved by using the binder, powdering or fine particle formation may occur depending on the degree of physical force received from the outside.

[0005] A coated bioactive substance represented by a coated fertilizer or a coated pesticide is obtained by coating the surface of bioactive substance particles with a coating material, and is widely used as a material capable of arbitrarily controlling the release of the bioactive substance. Widespread. The coating operation is generally performed by applying a liquid coating material to the surface of the biologically active substance particles in a state of rolling, flowing, or jetting by a physical external force, solidifying the coating material, and forming a coating film. I have.

During the coating operation, the bioactive substance particles are in a state of being continuously subjected to a physical external force. Or, powder was sometimes mixed into the coating. Further, the incorporation of the fine particles and / or the powder into the coating film may cause deterioration of the physical properties of the coating film and loss of the elution control function in some cases.

[0007]

In view of the above-mentioned problems of the prior art, the present inventors have conducted intensive studies. As a result, particles included in the following equivalent spherical circle diameter range (1) accounted for 70% of all particles.
% Of the bioactive substance particles having a water content of 1% by weight or less, compared with bioactive substance particles having the same hardness other than the present invention, and then stored and transported. In each case of use, even in the case of receiving a physical force from the outside, a part of the bioactive substance particles is less likely to be powdered or finely divided. In the case of a coated bioactive substance whose surface is coated with a coating material, the physical properties of the coating are reduced due to mixing of the fine particles and / or powder generated when the bioactive substance particles are finely divided and / or powdered into the coating. The present inventors have found that the occurrence of loss of the elution control function is small and have completed the present invention based on this finding. Equivalent sphere diameter range (1): (average equivalent sphere diameter x 0.7) to (average equivalent sphere diameter x 1.3)

The present invention is shown by the following (1) to (17). (1) Bioactive substance particles in which particles included in the following equivalent spherical diameter range (1) are 70% or more of all particles. Equivalent spherical circle diameter range (1): (average equivalent spherical circle diameter × 0.
7)-(Average equivalent spherical circle diameter x 1.3)

(2) Bioactive substance particles in which the particles falling within the equivalent spherical circular diameter range (1) described in the above item 1 are 90% or more of all particles.

(3) Bioactive substance particles in which the equivalent spherical diameter range (2) is at least 70% of the total particles. Equivalent spherical circle diameter range (2): (average equivalent spherical circle diameter x 0.8
5)-(Average equivalent spherical circle diameter x 1.15)

(4) Biologically active substance particles in which the particles falling within the equivalent spherical diameter range (2) described in (3) account for 90% or more of all particles.

(5) Bioactive substance particles having a water content of 1% by weight or less.

(6) Bioactive substance particles having a water content of 0.6% by weight or less.

(7) Biologically active substance particles in which particles falling within the range of equivalent spherical diameter described in the above item 1 are 70% or more of all particles and water content is 1% by weight or less.

(8) Biologically active substance particles in which particles falling within the equivalent spherical diameter range described in (1) account for 90% or more of all particles and water content of 1% by weight or less.

(9) Biologically active substance particles in which the particles falling within the equivalent spherical diameter range described in item 3 are 70% or more of all the particles and the water content is 0.6% by weight or less.

(10) Biologically active substance particles in which the particles falling within the equivalent spherical diameter range described in item 3 are 90% or more of all the particles and the water content is 0.6% by weight or less.

(11) The bioactive substance particles according to any one of (1) to (10), wherein the circularity coefficient represented by the following formula (1) is 0.85 or more. Formula (1): (4π × projected area of particle) / (length of contour of particle projected view) ²

(12) The bioactive substance particles according to any one of (1) to (11) above, wherein the bioactive substance is a fertilizer.

(13) The bioactive substance particles according to any one of the above items 1 to 11, wherein the bioactive substance is urea.

(14) The bioactive substance particles according to any one of (1) to (13) above, wherein the use is a core material of a coated bioactive substance.

(15) Any one of the above items 1 to 14
14. A coated bioactive substance, wherein the surface of the bioactive substance particles according to the above item is coated with a coating material.

(16) Any one of the above items 1 to 13
A bioactive substance composition comprising the bioactive substance particles according to claim 14 and the coated bioactive substance according to claim 14.

(17) 70% of all particles fall within the equivalent spherical diameter range (1) according to any one of the first to fourteenth aspects.
A method for producing a coated bioactive substance, comprising coating the surface of the above-mentioned bioactive substance particles with a coating material.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Bioactive substances include (A) those used for the purpose of growing and protecting plants such as crops, useful plants, and agricultural products;
(B) one used for the purpose of breeding and protecting humans and other animals, and (C) one used in human daily life and in direct contact with the skin.

In (A), the sales increase according to the purpose of use,
High quality of crops, disease control, pest control, pest control, weed control, furthermore, promotion of crop growth, growth suppression,
It brings effects such as dwarfing, and specifically, fertilizers, nitrification inhibitors, urease inhibitors, pesticides,
Microorganisms and the like can be mentioned. In particular, when used for coated bioactive granules, if the bioactive substance is a fertilizer or a pesticide, a relatively high effect can be obtained for the purpose of use.

Specific examples of (B) include medicaments such as tablets, pills, granules, and oral preparations, supplemental nutritional foods, and feeds for livestock. Specific examples of (C) include:
Examples include bath detergents, laundry detergents, and molded detergents for drainage pipes and the like.

Examples of the fertilizer include a nitrogenous fertilizer, a phosphate fertilizer, a potassium fertilizer, and a fertilizer containing essential elements such as calcium, magnesium, sulfur, iron, trace elements and silicon. Specific examples of the nitrogenous fertilizer include ammonium sulfate, urea, and ammonium nitrate, as well as isobutyraldehyde condensed urea and acetaldehyde condensed urea.Examples of the phosphate fertilizer include superphosphate lime, fused phosphorus fertilizer, and calcined phosphorus fertilizer. The potassium fertilizer includes potassium sulfate, potassium chloride, and silicic acid fertilizer, and the form thereof is not particularly limited. In addition, advanced chemical fertilizers, compound fertilizers, and organic fertilizers, in which the total amount of the three components of the fertilizer is 30% or more, further include fertilizers to which pesticides, nitrification inhibitors, urease inhibitors, trace elements, and the like are added. Can be. Particularly when used for coated bioactive granules, if the bioactive substance is urea, a relatively high effect can be obtained for the intended use.

As pesticides, disease control agents, pest control agents,
Pest control agents, weed control agents, and plant growth regulators can be used, and any of these can be used without limitation. Disease control agents are agents used to protect agricultural crops and the like from harmful effects of pathogenic microorganisms, and mainly include fungicides. Pest control agents are agents that control pests such as crops, and mainly include insecticides. Pest control agents are agents used to control plant parasitic mites, plant parasitic nematodes, wild boars, birds, and other pests that damage crops and the like. A weed control agent is an agent used for controlling plant plants that are harmful to crops, trees, and the like, and is also called a herbicide. A plant growth regulator is a drug used for the purpose of promoting or suppressing the physiological function of a plant.

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

For example, 1- (6-chloro-3-pyridylmethyl) -N-nitroimidazolidin-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-trithiane 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-methyl carbamate,
Diisopropyl-1,3-dithiolan-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, dimethylamine salt or ethyl ester of 2,4-dichlorophenoxyacetic acid.

Sodium salt of 2-methyl-4-chlorophenoxyacetic acid or ethyl, butyl ester. Sodium salt or ethyl ester of 2-methyl-4-chlorophenoxybutyric acid. α- (2-naphthoxy) propionanilide, S-1-methyl-1-phenylethyl piperidine-1-carbothioate, S- (4-chlorobenzyl) -N, N-diethylthiocarbamate, 5-tertiary 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-
Thiadiazinone- (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.

Further, examples of the pesticide include a substance that induces phytoalexin, a low-molecular-weight antibacterial substance that is synthesized by a plant after contact with the plant and accumulates in the plant.

Examples of the nitrification inhibitors include dicyandiamide, thiourea, 2-amino-4-chloro-6-methylpyrimidine, 2-mercaptobenzothiazole, sulfurthiazole, guanylthiourea, N-2,5-dichlorophenylsuccinamide. Acid, 4-amino-1,2,4
-Triazole hydrochloride, 2-[(N-nitro) methylamino-1,3,4-thiadiazole, 5-mercapto-
Examples thereof include 1,3,4-triazole, 2-chloro-6- (trichloromethyl) pyridine, trichloromethylmethylaminotriazine, 2,4-dichloroaniline, and 2-trichloromethylquinoline.

The 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, thiopyridines, thiopyridine-N-oxamides, NN-halo-2-imidazolidinone, N-halo -2-oxazolidinone, boric acid, N
-Hydrocarbyl thiophosphoric triamide,

N-hydrocarphophosphoric triamide, N-hydrocarphophosphoric trithioamide,
Metal nitrate, N-diamino (thio) phosphinylsulfinamide, N-diamino (thio) phosphinylsulfonamide, O-diaminophosphinyloxime,
S-hydrocarbyl diaminophosphate thiolate borate, borate, bromide-nitroalkanes, metal nitrates such as iron nitrate, aluminum nitrate, hydroxy acids, 3-alkyl-rhodamine-5-acetic acid, calcium formate, calcium acetate, sodium , Copper, manganese, zinc dithiocarbamates, and immunoglobulins such as immunoglobulin G (IgG) and immunoglobulin Y (IgY).

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

As the microorganisms, those having an effect of suppressing the propagation of pathogenic microorganisms can be used. Specifically, genus Trichoderma (Trichoderma lignorum, Trichoderma vilidi, etc.), genus Gliocladium (Gliocladium bilens, etc.), genus Cephalosporium,
Filamentous fungi such as Coniosilium, Spolidesmium, Laetizaria, Agrobacterium (Agrobacterium radiobacter), Bacillus (Bacillus subtilis), Pseudomonas (Pseudomonas sp.)
Sepacia, Pseudomonas Gourmet, Pseudomonas
Gradioli, Pseudomonas flouressence, Pseudomonas aureofaciens, Pseudomonas putida, etc.), Xanthomonas, Erwinia, Arthrobacter, Corynebacterium,

Enterobacter, Azotobacter,
Flavobacterium spp., Streptomyces sp. (Streptomyces achromogenus, Streptomyces sp.
Phaeopaperence, Streptomyces hygroscopicus, Streptomyces nitrosporence,
Streptomyces barnensis), Actinoplanes, Alcaligenes, Amorphosporangium, Cellulomonas, Micromonospora, Pasteuria, Hafnia, Rhizobium, Bradyrizobium, Serratia, Lastonia (Lastonia solanacearum) and actinomycetes.

Among these, those which can be preferably used include:
It is an antibacterial active substance producing bacterium. Specifically, it is a Pseudomonas bacterium having a high antibacterial substance-producing ability. Examples of the strains that produce antibiotics include Pseudomonas cepacia, which produces the antibiotic pyrrolnitrin (versus Japanese radish wilt fungus), and the antibiotic phenazinecarboxylic acid. (Against wheat wilt fungus), pyrrolnitrin, piorteolin (against cotton wilt fungus, cucumber young wilt fungus), cyanide (tobacco black root wilt fungus), diacetyl froglucinol (against wheat wilt fungus), etc. Pseudomonas flouressence, which is produced, and fluorescent Pseudomonas spp., Which produces iron chelate siderophore (pseudobactin, fluorescent siderophore: pioverdin), which makes it possible to use only iron plants in soil without using it in pathogens. Fungi (Pseudomonas putida, Pseudomonas florette) Sense, etc.).

Other microorganisms include Agrobacterium radiobacter, which produces the bacteriocin agrosine 84 (antifungal disease), and growth-promoting rhizosphere bacteria (PG) which produce growth-promoting substances such as plant hormones.
PR as fluorescent Pseudomonas (Pseudomonas
And Bacillus genus. In particular, CDU-degrading bacteria (Pseudomonas sp., Arthrobacter sp., Corynebacterium sp., Agrobacterium sp., Etc.) and Streptomyces sp. Strains (for example, microfabrication research deposit No. 10533 disclosed in Japanese Patent Publication No. 5-26462). No.) is preferably used because it has a remarkable deterrent against pathogenic fungi transmitted by soil.

The composition of the bioactive substance particles of the present invention is not particularly limited as long as it contains one or more bioactive substances. Alternatively, granulation may be performed using a carrier such as clay, kaolin, talc, bentonite, or calcium carbonate, or a binder such as polyvinyl alcohol, sodium carboxymethyl cellulose, or starch.
Further, the bioactive substance particles may contain a surfactant such as polyoxyethylene nonyl phenyl ether, molasses, animal oil, vegetable oil, hydrogenated oil, fatty acid, fatty acid metal salt, paraffin, wax, glycerin and the like, if necessary. It may be what you did.

As a method for granulating the bioactive substance particles,
Extrusion granulation, fluidized bed granulation, tumbling granulation, compression granulation, bread granulation, coating granulation, adsorption granulation, 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. For example, in the case of fertilizer, 1.
It is preferably from 0 to 10.0 mm, and in the case of agricultural chemicals, it is preferably from 0.3 to 3.0 mm. By using a sieve, an arbitrary particle size can be selected within the above range.

The first invention is a biologically active substance particle in which particles included in the following equivalent spherical diameter range (1) are 70% or more of all particles. Equivalent spherical circle diameter range (1): (average equivalent spherical circle diameter × 0.
7)-(Average equivalent spherical circle diameter x 1.3)

The equivalent spherical diameter is the diameter of a perfect circle having the same area as the projected area of a particle.
(PIAS-IV, manufactured by Pierce Co., Ltd.) or other commercially available measuring instrument. The average equivalent spherical diameter is, specifically, an average value of the equivalent spherical diameter of 100 randomly selected bioactive substance particles.

The first invention is a bioactive substance particle in which particles having the above-mentioned equivalent spherical diameter range (1) are 70% or more of all the particles. When the measurement is difficult, it is possible to substitute the ratio of the particles included in the equivalent spherical circle diameter range to the 100 biologically active substance particles randomly selected when the average equivalent spherical circle diameter is obtained. it can. That is, the first invention rephrases bioactive substance particles in which the particles having the equivalent spherical diameter are 70% or more of 100 bioactive substance particles randomly selected for calculating the average equivalent spherical diameter. be able to.

In the case where the particles included in the above equivalent spherical diameter range (1) are the particles of the bioactive substance of the present invention which accounts for 70% or more of all the particles, they are included in the above equivalent spherical diameter range (1). Compared to bioactive substance particles of the same composition, in which the particles are less than 70% of the total particles, even if the external physical force is applied in each stage of production, storage, transportation, and use after the production, Part of the bioactive substance particles is less likely to be powdered or finely divided. Further, in the present invention, the proportion of particles included in the above-mentioned equivalent spherical circular diameter range (1) to all the particles is preferably 90% or more, and more preferably, all the particles are in the above equivalent spherical circular diameter range (1). Is included.

The above-mentioned equivalent spherical circle diameter range (1) is
In the present invention, the diameter is more preferably in the following equivalent spherical circle diameter range (2). Equivalent spherical circle diameter range (2): (average equivalent spherical circle diameter x 0.8
5)-(Average equivalent spherical circle diameter x 1.15)

The method for obtaining bioactive substance particles in which particles having the equivalent spherical diameter range (1) is 70% or more of the total particles depends on the type of the bioactive substance used and the composition of the bioactive substance particles, and is particularly limited. It is not something to be done. A bread granulation method can be cited as the method in which the kind of the bioactive substance to be applied and the range of the composition of the bioactive substance particles are relatively wide. In the bread granulation method, the equivalent spherical circle diameter range can be narrowed by using a multistage bread granulator or the like in order to classify the bread in the depth direction. The narrowing of the equivalent spherical diameter range is achieved by lengthening the granulation time.
Further, it is preferable that the bioactive substance particles obtained by the above-mentioned bread granulation method are fractionated using a sieve having a certain range of openings.

As a method of converting the bioactive substance particles granulated by the extrusion granulation method into bioactive substance particles in which particles having an equivalent spherical diameter range (1) are 70% or more of all the particles, there are extrusion methods. The bioactive substance particles granulated by the granulation method are shaped using a marmellaizer etc. to approximate a true sphere,
Further, there can be mentioned a method of sorting using a sieve having a certain range of openings. According to this method, it is easy to narrow the equivalent spherical circular diameter range of the bioactive substance particles granulated by the extrusion granulation method.

When the bioactive substance is a substance that is melted by heating and is dissolved in a highly volatile solvent, such as urea, it is preferable to granulate by the following method. First, molten urea is dropped into a cool air or a urea-insoluble solution from a dropping port having a constant diameter, and cooled and solidified to obtain a granular material.
Next, the granules are put into a bread granulator, and a urea-saturated methanol solution is sprayed while blowing hot air on the granules, and the granules are dried and granulated, whereby urea particles having a narrow equivalent spherical diameter range can be obtained.

The specific method for obtaining the bioactive substance particles in which the particles having the equivalent spherical diameter range (1) are 70% or more of the total particles is as described above. Whether the active substance particles have an equivalent spherical circle diameter range (1) of 70% or more of all particles is determined by Pierce-IV.
(PIAS-IV, manufactured by Pierce Co., Ltd.) or other commercially available measuring instruments.

The second invention is a bioactive substance particle having a water content of 1% by weight or less. When the water content ratio is 1% by weight or less, the case where physical force is applied from the outside in each scene of production, storage, transportation, and use as compared with the case where the water content exceeds 1% by weight. Also, the particles of the bioactive substance are less likely to be powdered or finely divided. In the present invention, the proportion is preferably 0.6% by weight or less.

Further, the biologically active substance particles of the second invention include:
More than 70% of all the particles are in the above equivalent spherical diameter range (1)
Preferably. Also in the second invention, as in the first invention, the equivalent spherical circle diameter range (1) is preferably the equivalent spherical circle diameter range (2), and the equivalent spherical circle diameter ranges (1) and (2) It is more preferable that the ratio of the particles to enter is 90% or more.

The water content in the present invention (hereinafter referred to as "water content") is determined by evaporating water by heating and measuring the weight change until the weight loss reaches a constant weight as the water content. Specifically,
2 g of the bioactive granular material was placed in a weighing bottle having a diameter of 5 cm and a height of 3 cm, dried at 100 ° C. for 2 hours, and the weight loss rate at this time was calculated.

However, when the biologically active substance is unstable to heating, it is preferable to appropriately adjust the drying temperature and the drying time to a drying condition which is not affected by the thermal decomposition.
The absence of the influence of the thermal decomposition means that the moisture content is measured five times and the standard deviation is 0.3 or less. For example, when the bioactive substance particles are urea particles, urea decomposes at 85 ° C., so it is preferable to dry at 75 ° C. for 4 hours.

The effect of the water content in the present invention is remarkable when the bioactive substance is a fertilizer component and when it contains a fertilizer component. Further, among the fertilizer components, particularly, in the case of bioactive substance particles containing highly hygroscopic urea, ammonium nitrate, etc., the effect of the present invention is greater. The effects of the first and second inventions can be obtained even if the bioactive substance particles are a mixture of different compositions or components.

In the present invention, the method of controlling the water content of the bioactive substance particles is not particularly limited, but specifically, it is preferable to control the water content by a moisture absorption prevention treatment or a drying treatment. The drying treatment method is not particularly limited, but specific examples thereof include hot air heating, drying gas ventilation, infrared heating, microwave, and vacuum drying.

The shape of the bioactive substance particles is not particularly limited, but is preferably spherical in the present invention. Specifically, it is preferable to use a circularity coefficient which is a measure for knowing the degree of circularity of the particles, and a value obtained by the following equation is preferably 0.85 or more, more preferably 0.9 or more. , 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 particle shape collapses from a perfect circle. Formula = (4π × projected area of particle) / (length of contour of particle projected view) ²

The use of the bioactive substance particles of the present invention is not particularly limited, and the use may be determined according to the type of the bioactive substance contained in the particles. The bioactive substance particles of the present invention have a smaller particle size even when they are subjected to a physical force from the outside, compared to bioactive substance particles having the same hardness other than the present invention. The bioactive substance particles are less likely to be formed or micronized, and if the bioactive substance particles are used as a core material of the coated bioactive substance and the surface is coated with a coating material, the bioactive substance particles Of the biologically active substance particles of the present invention, since the decrease in the physical properties of the coating and the loss of the elution control function due to the incorporation of the fine particles and / or the powder into the coating due to the formation of fine particles and / or powder are small. The application is preferably a core of a coated bioactive substance.

The third invention is a coated bioactive substance in which the surface of the bioactive substance particles of the present invention is coated with a coating material.
The coating material is not particularly limited as long as it is a material capable of forming a coating on the surface of the biologically active substance particles.Specifically, an inorganic substance such as a resin or sulfur is used. It is preferred to use.

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

Examples of the olefin polymer include polyethylene, polypropylene, ethylene-propylene copolymer,
Ethylene-carbon monoxide copolymer, ethylene-hexene copolymer, ethylene-butadiene copolymer, polybutene,
Butene-ethylene copolymer, butene-propylene copolymer, polystyrene, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-
An acrylic acid copolymer and an ethylene-methacrylic acid ester copolymer can be exemplified. As the vinylidene chloride-based polymer, a vinylidene chloride-vinyl chloride copolymer can be exemplified.

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

As the thermosetting resin, a phenol resin,
Furan resin, xylene / formaldehyde resin, ketone formaldehyde resin, amino resin, alkyd resin, unsaturated polyester, epoxy resin, silicon resin, urethane resin, drying oil and the like can be mentioned. These thermosetting resins have many combinations of monomers, but in the present invention, types and combinations of monomers are not limited. 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.

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 And those obtained by a condensation reaction of at least one selected from aldehydes with at least one selected from aldehydes represented by formaldehyde.

As typical furan resins, phenol / furfural resin, furfural / acetone resin,
And furfuryl alcohol resin. The 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 represented by formaldehyde. Those 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.

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

The alkyd resin may be either non-inverted or inverted, and is selected from polyhydric alcohols such as glycerin, pentaerythritol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, sorbitol, mannitol, and trimethylolpropane. 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 those obtained by condensing naphthalylic acid, terpene oil, rosin, and one or more polybasic acids such as unsaturated fatty acids and adducts of maleic acid.

The fatty oils or fatty acids used in modifying the alkyd resin include 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.

The unsaturated polyesters include maleic anhydride, fumaric acid, itaconic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, 3,6-
Endomethylene tetrahydrophthalic anhydride, adipic acid, sebacic acid, tetrachlorophthalic anhydride, and 3,
One or more organic acids such as 6-endodichloromethylenetetrachlorophthalic acid and 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 a condensation reaction with at least one selected from polyols such as bis (4-oxypropoxyphenyl) propane.

Further, in order to accelerate the curing of the unsaturated polyester, styrene, vinyl toluene, diallyl phthalate, methyl methacrylate, triallyl cyanuric acid,
And those obtained by adding at least one kind selected from vinyl monomers such as triallyl phosphoric acid at the time of condensation can also be used.

As the epoxy resin, bisphenol A
Type, novolak type, bisphenol F type, tetrabisphenol A type, and diphenolic acid type epoxy resins.

Further, it is also possible to use a composite resin such as a urethane-modified polyester resin.

Examples of the urethane resin include 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 At least one member selected from the group consisting of diisocyanates, dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, and diisocyanates such as naphthalene-1,5-diisocyanate, and polyoxypropylene polyols and polyoxyethylene polyols , Acrylonitrile-propylene oxide polymer, styrene-propylene oxide polymer,
Polyoxytetramethylene glycol, adipic acid-ethylene glycol, adipic acid-butylene glycol,
Adipic acid-trimethylolpropane, glycerin, polycaprolactone diol, polycarbonate diol, polybutadiene polyol, and one or more selected from polyols such as polyacrylate polyol, and those obtained by polyaddition polymerization. Can be.

In order to obtain a long-term sustained release function and a timed release type sustained release function, it is possible to completely cover the surface of the particles with a resin having low moisture permeability and to suppress moisture permeation to a very small extent. It is necessary to form a proper coating. That is,
It is important to form a film without pinholes and cracks.

In the present invention, the time-release type sustained release function means a period from application to water or soil until 10% by weight of the total bioactive substance contained in the coated bioactive granules is released (release suppression period). ) And 90% after 10% by weight release.
The ratio (release inhibition period / release period) to the period until the weight% is released (release period) is in the range of 0.2 to 4.

In particular, when a long release suppression period is required in the time-release type sustained release function, it is effective to form a small moisture-permeable film on the surface of the particles. By coating the surface of the bioactive substance particles of the present invention with a resin film having low moisture permeability, moisture existing outside can be gradually penetrated into the particles over time.

For this purpose, it is effective to coat the particles with a coating material containing a thermoplastic resin, and further, as the thermoplastic resin, an olefin polymer, an olefin copolymer, a vinylidene chloride polymer, or a vinylidene chloride copolymer. It is effective to use a polymer. Particularly preferred coating materials are polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-carbon monoxide copolymer, ethylene-hexene copolymer, ethylene-butene copolymer, propylene-butene copolymer and mixtures thereof. It can be mentioned as. If a film without pinholes or cracks is formed using these film materials, the amount of permeation of moisture becomes extremely small.

As the coating material used in the present invention, in addition to the above-mentioned sulfur and resin, fillers and surfactants for imparting hydrophilicity can be exemplified. Examples of the filler include talc, clay, kaolin, bentonite, sulfur, muscovite, phlogopite, mica-like iron oxide, metal oxide, siliceous material, glass, alkaline earth metal carbonate, sulfate, and starch. Nonionic surfactants represented by fatty acid esters of polyols can be given as examples of surfactants. In the present invention, these coating materials may be used in combination depending on the release function required for the coated bioactive substance.

In the resin-containing coating material, the content of the resin is preferably in the range of 10 to 100% by weight, more preferably 20 to 100% by weight, based on the coating material.
% By weight. In the coating material containing an inorganic substance, the content ratio of the inorganic substance is 1 to the coating material.
It is preferably in the range of 0 to 100% by weight, and more preferably in the range of 20 to 80% by weight.

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

The coating of the coating material on the surface of the bioactive substance particles of the present invention may be achieved by any method. Specifically, the molten coating material is sprayed on the surface of the bioactive substance particles. A method, a method of spraying a coating material dissolving solution obtained by dissolving a coating material in a solvent onto the surface of the bioactive substance particles, a method of adhering a powder of the coating material to the surface of the bioactive substance particles, and then melting the monomer, A method of spraying on the particle surface and reacting on the surface of the bioactive substance particles to form a resin (forming a film).
A dip method in which the bioactive substance particles are immersed can be exemplified.

The effect of the present invention is remarkable when the surface of the biologically active substance particles is coated by a coating method in which the force applied to the biologically active substance particles to be coated is large. As a coating method in which a large force is applied to the biologically active substance particles to be coated, specifically, a coating material is coated on the surface of the biologically active substance particles in a flow, jet, or rolling state. In particular, when the coating material is coated on the surface of the biologically active substance particles in either a flowing state or a jet state, the effect of the present invention is remarkably exhibited.

As a method of coating a coating material containing a resin on the bioactive substance particles, a coating material solution, which is dissolved in a solvent capable of dissolving the resin in the coating material, is sprayed on the surface of the bioactive substance particles. To form a film (hereinafter referred to as "solution spraying method"), or a coating material melt obtained by melting the coating material by heating,
A method of forming a film by attaching the particles to the surface of the bioactive substance particles by spraying (hereinafter, referred to as a “melt spraying method”) can be exemplified.

The coated bioactive substance of the present invention may be obtained by either method. However, from the viewpoints of high production efficiency and uniformity of the obtained coating film, the tumbling or flowing state can be obtained. It is preferable to apply the solution of the coating material to the biologically active substance particles by spraying and then expose the solution to hot air to form a coating.

In dispersing a filler in a resin-containing coating material, it is important that the filler is uniformly dispersed in the coating in order to control the elution of the bioactive substance. In the present invention, the state where the filler is uniformly dispersed in the coating means that the coefficient of variation obtained by the following method is 50% or less.
In the present invention, the coefficient of variation is preferably 35% or less.

The coefficient of variation is such that, in the cut surface of one-particle coating, the film thickness direction is vertical and the direction parallel to the film surface is horizontal, and the length × width = 20 μm from the cut surface of one-particle coating.
The area of m × 50 μm was observed at 10 locations with a scanning electron microscope, the number of fillers present at each location was measured, and the number of fillers was determined from the measurement result (the coefficient of variation = standard deviation / average × 1)
00). In order to obtain a film in which the filler is uniformly dispersed, it is preferable to produce the coated bioactive substance by a solution spraying method.

An example of a coating apparatus that can be used in the solution spraying method will be described with reference to the jet apparatus shown in FIG. In this method, in order to uniformly disperse a coating material insoluble in a solvent such as an inorganic filler in a coating material dissolving liquid, it is necessary to particularly strongly agitate the coating material dissolving liquid. The jet apparatus transports the coating material dissolving liquid to the particles 3 in a jet state via the pipe 5, sprays the solution with the spray nozzle 2, sprays the solution on the surface of the particles 3, and simultaneously and simultaneously coats the surface, A high-temperature gas flows into the jet tower 1 from below into the guide tube 6, and the high-speed hot air flow instantaneously evaporates and dries the solvent in the coating material dissolving solution adhering to the particle surface. The spraying time varies depending on the resin concentration of the coating material solution, the spray rate of the solution, the coverage, and the like, and these should be appropriately selected according to the purpose.

A coating apparatus other than the spout apparatus shown in FIG. 1 which can be used in the present invention is a fluidized bed type or spouted bed type coating apparatus disclosed in JP-B-42-24281 and JP-B-42-24282. And an apparatus for forming a fountain-type fluidized bed of particles with a gaseous substance and spraying a coating agent on a particle dispersion layer formed at the center of the apparatus. Examples of a rotary-type coating apparatus include JP-A-7-31914.
Publication No. 7-195007 and Japanese Patent Application Laid-Open No. 7-195007 discloses a method in which a granular material is transferred upward by a lifter provided on the inner periphery of the drum by rotation of the drum and then dropped, and a coating agent is applied to the surface of the falling granular material. And an apparatus for forming a film.

When the coated bioactive substance is obtained by the dissolving liquid spraying method, the solvent to be used is not particularly limited. However, since the dissolving characteristics for each solvent differ depending on the type of the resin used for the coating, the solvent is used. What is necessary is just to select a solvent according to resin. For example, when using an olefin polymer, an olefin copolymer, a vinylidene chloride polymer, a vinylidene chloride copolymer as a resin, a chlorine-based solvent or a hydrocarbon-based solvent is preferable, and among them, tetrachloroethylene,
When trichloroethylene or toluene is used, it is a particularly preferable solvent since a dense and uniform film can be obtained.

The fourth invention is a bioactive substance composition containing the bioactive substance particles of the present invention and the coated bioactive substance of the present invention. At that time, the type of the bioactive substance contained in the bioactive substance particles and the coated bioactive substance may be the same or different, and may be appropriately selected according to the purpose of use. Further, the ratio between the bioactive substance particles and the coated bioactive substance in the bioactive substance composition of the present invention is not particularly limited, and may be appropriately determined according to the purpose of use.

The bioactive substance composition of the present invention may contain substances other than the bioactive substance particles and the coated bioactive substance as long as the effects of the present invention are not impaired. As the substance, soil improvement materials, anti-caking agents and the like are used, and peat, humic acid materials, charcoal, diatomaceous earth fired granules, zeolite,
Examples include vermiculite, bentonite, lime, resins such as polyethyleneimine-based materials and polyvinyl alcohol-based materials, rice straw, straw, sludge, sludge compost, soil, sawdust, chaff, and bark. At that time, the content ratio of the substance is preferably 500% by weight or less based on the bioactive substance composition of the present invention.

The fifth invention is a method for producing a coated bioactive substance, characterized by coating the surface of the bioactive substance of the present invention with a coating material. The coating material used in the present invention is
What is necessary is just to use the same thing as what is used in the above-mentioned third invention, and a covering method, covering conditions, etc. may be the same as the third invention.

According to the production method of the present invention, the physical properties of the film are reduced and the elution control function is caused by the fine particles and / or the powder generated by the bioactive substance particles being finely divided and / or powdered. Coated bioactives with less loss can be easily manufactured.

[0103]

The present invention will be described below by way of examples. In the following examples, “%” is “% by weight” unless otherwise specified.

A. Production of Bioactive Substance Particles Comparative Example 1: Production of Bioactive Substance Particles 1 Production of Primary Granules Urea was charged into a heatable vessel and heated and melted at 130 ° C. (urea melt). After stirring the urea melt for 1 hour, the urea melt was heated from a height of 20 cm to 50 ° C. to a depth of 20 ° C.
Liquid paraffin in stainless steel container of 5 cm2
The mixture was dropped from a glass tube with a cock having a diameter of 2 mm while adjusting the flow rate so that the particle diameter became about 2 mm, to obtain a granular material. The granules are then washed with hexane and dried to a particle size of 1.5-1.5.
The mixture was passed through a 4.0 mm sieve to obtain primary granules.

Production of Secondary Granules Secondary granules were granulated using a coating device such as a jet stream. FIG. 1 shows the coating apparatus used. Tower diameter 250mm, height 200
High-temperature hot air flowed from the lower part to the upper part into the jet tower 1 having a shape of 0 mm, an air outlet diameter of 50 mm, and a cone angle of 50 degrees. The high-temperature hot air is blown from a blower 10, passes through an orifice flow meter 9, is heated to a high temperature by a heat exchanger 8, flows into a jet tower 1, and is discharged from an exhaust gas outlet 3 installed at an upper part of the jet tower 1. You. In the jet tower 1 in which the high-temperature hot air is circulating, the primary particulate matter is injected into the jet tower 1.
10Kg from the input port 2 installed on the side of
As shown in FIG. 1, the primary granular material 5 was in a jet state.
At this time, the flow rate and the hot air temperature were 70 ° C. ±
The temperature was adjusted to 2 ° C., and the flow rate was adjusted while measuring with an orifice flow meter. The hot air temperature was T1 hot air temperature, T2
And the exhaust temperature of T3 were measured and adjusted.

The production of the secondary granules was carried out at a flow rate (orifice flow meter 9) of 4 m ³ / min and a hot air temperature (hot air temperature T1) of 1.
00 ° C ± 2 ° C, primary granular material temperature (particle temperature T2) 70 ±
Performed at 2 ° C. On the other hand, urea 130-1
Melting was performed at 35 ° C. to obtain a urea molten liquid 12 for granulation.

The dissolving tank 11 was constantly stirred until the granulation was completed. The urea melt 12 for granulation is supplied by a pump 6 to a spray nozzle 4 which is a 0.8-mm full-con type one-fluid nozzle installed at the lower part of the jet tower 1 at a flow rate of 0.1 k.
g / min, and sprayed and sprayed on the primary granular material 5 in a jet state. At this time, the dissolving tank 11 and a pipe from the dissolving tank 11 to the spray nozzle 4 have a double structure so that the temperature of the urea melt 12 for granulation does not become 130 ° C. or lower, and steam is passed through. The coating material solution 12
Was transported with warming.

The above-mentioned granulation operation is started when the particle temperature T2 of the primary granules 5 in the jet state reaches 70 ° C. until the spray amount becomes 20% by weight of the injected primary granules. After spraying for a predetermined period of time, the blower 10 was stopped, and the primary particulate matter 5 was discharged from the outlet 7 at the lowermost part of the jet tower 1 to obtain a secondary particulate matter.

3) Production of tertiary granules The secondary granules are supplied to a rotating disk type granulator (Malmerizer QJ400, manufactured by Fuji Paudal Co., Ltd.), and the circularity coefficient is 0.7 or more under the following operating conditions. Until smoothing was performed. After the treatment, the secondary granules are dried at 50 ° C. for 3 days using a circulating hot air drier, further dried at 75 ° C. for 4 hours, and sieved with a 1.0-4.0 mm sieve to classify the tertiary granules (biologically active substance). Particles 1) were obtained. Operating condition of rotating disk sizing machine Operating method: Batch type Operating time: 3 min Plate pitch: 1 mm Number of rotations: 788 rpm / min Charge: 3 kg (per time) Obtained bioactive substance particles 1 (tertiary granular material) The circularity coefficient is Pierce-IV (PIAS-I) manufactured by Pierce Co., Ltd.
V). The measurement was performed using 100 particles taken out at random. Table 1 shows the measurement results.

4) Powdering test 100 g of the obtained tertiary granular material (bioactive substance particles 1) was placed in a magnetic pot for ball mill (inner diameter 100 mm × inner depth 100).
mm), magnetic ball (diameter 30 ± 2 mm, weight 35 ±)
3 g) were selected into a pot so that the total weight became 105 g, and then the pot was rotated with a variable roller at 75 rpm for 15 minutes. Thereafter, the particles were sieved through a 1.5 mm sieve, and the particles that passed through were crushed. The weight percentage with respect to the test amount of the powdered product was determined and is shown in Table 1 as the powdered degree.

5) Measurement of Content in the Equivalent Spherical Circle Diameter Range 100 tertiary granules were randomly selected and pierced-IV
(PIAS-IV, Pierce Co., Ltd.) was used to measure the equivalent spherical diameter of each grain. The equivalent spherical diameters of 100 grains were averaged to obtain an average equivalent spherical diameter. The ratio of particles having the above equivalent spherical diameter range (1) to all particles was determined, and is shown in Table 1 as the content ratio within the range.

Example 1 Production of Biologically Active Substance Particles 2 1) Production of Primary Granular Material The primary granulated product is “Comparative Example 1: Production of biologically active substance particles 1”.
It was manufactured in accordance with "1) Production of primary granules". 2) Production of Secondary Granules 1 kg of the primary granules was put into a sugar coating machine having a diameter of 45 cm shown in FIG. 2 and used for producing the primary granules while rolling the primary granules at a rotation speed of 30 rpm. Urea melt 0.
5 kg was made into a saturated solution with methanol and sprayed on the primary granules to obtain secondary granules. Spraying of the urea melt is performed by blowing air at 25 ° C. from the air outlet having a diameter of 5 cm to the primary granules from about 20 cm above the rolling surface so that the temperature of the primary granules does not exceed 50 ° C. went. 3) Production of Tertiary Granules Bioactive substance particles 2 were produced according to Comparative Example 1, except that the tertiary granules were classified with a 1.5-4.0 mm vibrating sieve.

The circularity coefficient of the obtained bioactive substance particles 2 was measured by Pierce-IV (PIAS-IV) manufactured by Pierce Co., Ltd.
It measured using. The measurement was performed using 100 particles taken out at random. Table 1 shows the measurement results. The liquefaction test was performed in accordance with the liquefaction test in Comparative Example 1, and the measurement of the content within the range of the equivalent spherical diameter was performed as described in “5) Measurement of the content within the range of the equivalent spherical diameter” in Comparative Example 1. The results are shown in Table 1.

Example 2 Production of Bioactive Substance Particles 3 Bioactive substance particles 3 were produced in accordance with Example 1, except that the tertiary granules were classified with a 2.0-4.0 mm vibrating sieve. The circularity coefficient of the obtained bioactive substance particles 3 was measured using Pierce-IV (PIAS-IV) manufactured by Pierce Co., Ltd. The measurement was performed using 100 particles taken out at random. Table 1 shows the measurement results. The crushing test was carried out in accordance with the crushing test in Comparative Example 1 except that the amount of crushing was determined using a 2.0 mm sieve. The measurement was carried out in accordance with “5) Measurement of content rate within equivalent spherical diameter”, and the measurement results are shown in Table 1.

Example 3 Production of Bioactive Substance Particles 4 Bioactive substance particles 4 were produced in the same manner as in Example 1 except that the tertiary granules were classified with a 2.5 to 4.0 mm vibrating sieve. The circularity coefficient of the obtained bioactive substance particles 4 was measured using Pierce-IV (Pias-IV) manufactured by Pierce Co., Ltd. The measurement was performed using 100 particles taken out at random. Table 1 shows the measurement results. The crushing test was carried out in accordance with the crushing test in Comparative Example 1 except that the amount of crushing was determined with a 2.5 mm sieve. The measurement was carried out in accordance with “5) Measurement of content rate within equivalent spherical diameter”, and the measurement results are shown in Table 1. The equivalent spherical circle diameter range in the measurement of the content rate within the equivalent spherical circle diameter range is the equivalent spherical circle diameter range (2).

Example 4 Production of Bioactive Substance Particles 5 Bioactive substance particles 5 were produced according to Example 1 except that the tertiary granules were classified with a 3.0-4.0 mm vibrating sieve. The circularity coefficient of the obtained bioactive substance particles 5 was measured using Pierce-IV (Pias-IV) manufactured by Pierce Co., Ltd. The measurement was performed using 100 particles taken out at random. Table 1 shows the measurement results. The crushing test was carried out in accordance with the crushing test in Comparative Example 1 except that the amount of crushing was determined with a 3.0 mm sieve. The measurement was carried out in accordance with “5) Measurement of content rate within equivalent spherical diameter”, and the measurement results are shown in Table 1. The equivalent spherical circle diameter range in the measurement of the content rate within the equivalent spherical circle diameter range is the equivalent spherical circle diameter range (2).

Example 5: Production of Bioactive Substance Particles 6 Bioactive substance particles 6 were produced in accordance with Example 1, except that the tertiary granules were classified with a 3.4 to 4.0 mm vibrating sieve. The circularity coefficient of the obtained bioactive substance particles 6 was measured using Pierce-IV (PIAS-IV) manufactured by Pierce Co., Ltd. The measurement was performed using 100 particles taken out at random. Table 1 shows the measurement results. The crushing test was carried out in accordance with the crushing test in Comparative Example 1 except that the amount of crushing was determined with a sieve of 3.4 mm. The measurement was carried out in accordance with “5) Measurement of content rate within equivalent spherical diameter”, and the measurement results are shown in Table 1. The equivalent spherical circle diameter range in the measurement of the content rate within the equivalent spherical circle diameter range is the equivalent spherical circle diameter range (2).

[0118]

[Table 1] Urea: reagent product

Comparative Example 2: Production of Bioactive Substance Particles 7 The bioactive substance particles 6 were opened and stored indoors for 3 days to obtain bioactive substance particles 7. Next, 2 g of the particles were weighed to four decimal places, placed in a weighing bottle having a diameter of 5 cm and a height of 3 cm, dried at 75 ° C. for 4 hours, measured for weight loss, and measured for water content. The results are shown in Table 2. Indicated. The water content was calculated based on the following equation. (Weight of bioactive substance particles [g] −weight of bioactive substance particles after drying [g]) / (weight of bioactive substance particles [g]) ×
100 The crushing test was carried out in accordance with the crushing test in Comparative Example 1 except that the amount of crushing was determined with a 3.4 mm sieve. The measurement was carried out in accordance with “5) Measurement of content within equivalent spherical diameter” in Table 2 and the measurement results are shown in Table 2.

Example 6: Production of bioactive substance particles 8 The bioactive substance particles 6 were dried at 75 ° C for 1 hour to obtain bioactive substance particles 8. The water content was measured according to Comparative Example 2, and the results are shown in Table 2. The crushing test was carried out in accordance with the crushing test in Comparative Example 1 except that the amount of crushing was determined with a 3.4 mm sieve. 5) Measurement of Content within Equivalent Spherical Circle Diameter ”, and the measurement results are shown in Table 2.

Example 7: Production of Bioactive Substance Particles 9 Bioactive substance particles 6 were dried at 75 ° C. for 2 hours to obtain bioactive substance particles 9. The water content was measured according to Comparative Example 2, and the results are shown in Table 2. The crushing test was carried out in accordance with the crushing test in Comparative Example 1 except that the amount of crushing was determined with a sieve of 3.4 mm. The measurement was carried out in accordance with “5) Measurement of content within equivalent sphere diameter”, and the measurement results are shown in Table 2.

Comparative Example 3 Production of Biologically Active Substance Particles 1 kg of sulfuric acid potassium powder was placed in a sugar-coating machine having a diameter of 45 cm as shown in FIG. 1 kg was sprayed onto the sulfated potassium powder while controlling the spray amount to obtain a granular sulfated product (hereinafter referred to as “vulcanized granular material”). In the spraying operation, the spray amount and the spray interval were adjusted so that the vulcanized granular material was not dissolved and solidified, and the granulation time was 60 to 75 minutes. The operation was performed at room temperature. After spraying, the granules were dried at 100 ° C. for 30 minutes, and then dried for 1.5 minutes.
The fine powder was removed with a vibrating sieve of mm to obtain a bioactive granule 10.
The circularity coefficient of the obtained bioactive granular material 10 was measured using Pierce-IV (PIAS-IV) manufactured by Pierce Co., Ltd. The measurement was performed using 100 particles taken out at random. Table 1 shows the measurement results. 100 drying conditions
The water content was measured according to Comparative Example 2 except that the temperature was changed to 2 hours, and the results are shown in Table 2. The confusion test is 3.4m
m was measured in accordance with the crushing test in Comparative Example 1 except that the amount of crushing was determined with a sieve having a diameter of m. The measurement results are shown in Table 2.

Example 8: Production of bioactive substance particles 11 1 kg of sulfuric acid potassium powder was placed in a pan granulator having a diameter of 45 cm, and while rotating at a speed of 30 rpm, 0.1 kg of molasses solution (manufactured by Izumi Alcohol Company) was added. It was sprayed toward the sulfuric acid powder to obtain a granular sulfuric acid (hereinafter referred to as "sulfurized granular material"). In the spraying operation, the spray amount and the spray interval were adjusted so that the vulcanized granules were not dissolved and solidified, and the granulation time was 60 to 75 minutes. The operation was performed at room temperature. After the spraying, the granular material is heated at 100 ° C.
After drying for 0 minutes, the resultant was classified with a 3.4 to 4.0 mm vibrating sieve to obtain bioactive granules 11. The circularity coefficient of the obtained bioactive granular material 10 is Pierce-IV (PIA manufactured by Pierce Co., Ltd.).
S-IV). The measurement was performed using 100 particles taken out at random. Table 1 shows the measurement results. The water content was measured in the same manner as in Comparative Example 2 except that the drying conditions were changed to 100 ° C. for 2 hours, and the results are shown in Table 2.
The crushing test was carried out in accordance with the crushing test in Comparative Example 1 except that the amount of crushing was determined with a 3.4 mm sieve. The measurement was carried out in accordance with “5) Measurement of content rate within equivalent spherical diameter”, and the measurement results are shown in Table 2.

Example 9: Production of Bioactive Substance Particles 12 Production was carried out according to "Example 8" except that 980 g of potassium sulfate powder and 20 g of magnesium hydroxide were used.
After removing the dust with a 4.0 mm sieve, drying was performed at 100 ° C. for 2 hours to obtain bioactive substance particles 12. The circularity coefficient was measured using Pierce-IV (PIAS-IV) manufactured by Pierce Co., Ltd. Measurements were taken of particles 10 taken out at random.
This was performed using 0 pieces. Table 2 shows the measurement results. The water content was measured in the same manner as in Comparative Example 2 except that the drying conditions were changed to 100 ° C. for 2 hours, and the results are shown in Table 2. The obfuscation test is
Except that the amount of comminuted was obtained with a sieve of 3.4 mm, it was carried out in accordance with the comminution test in Comparative Example 1. Measurement in Content of Circular Diameter ”, the measurement results are shown in Table 2.

Example 10: Production of biologically active substance particles 13 Bioactive substance particles were produced in the same manner as in Example 1 except that dicyandiamide was added so as to have a ratio of 10% to urea. Material particles 13 were obtained. The circularity coefficient of the obtained bioactive substance particles 15 was measured using Pierce-IV (PIAS-IV) manufactured by Pierce Co., Ltd. The measurement was performed using 100 particles taken out at random. Table 2 shows the measurement results. The water content was measured according to Comparative Example 2, and the results are shown in Table 2. The crushing test was carried out in accordance with the crushing test in Comparative Example 1 except that the amount of crushing was determined using a 2.0 mm sieve. The measurement was carried out in accordance with “5) Measurement of content within equivalent sphere diameter”, and the measurement results are shown in Table 2.

B. Measurement of equivalent spherical diameter of biologically active substance particles 100 randomly from each of biologically active substance particles 1 to 15
After taking out the grains, the equivalent sphere diameter is measured by piercing-IV (PIAS-IV, manufactured by Pierce Co., Ltd.), and the equivalent sphere diameter range occupying the 100 grains is divided into two types as follows.
Proportion of bioactive substance particles falling within the range (particle rate within range)
Was calculated. The results are shown in Tables 1 and 2. Equivalent spherical circle diameter range (1): (average equivalent spherical circle diameter × 0.
7) to (average equivalent spherical diameter × 1.3) equivalent spherical diameter range (2): (average equivalent spherical diameter × 0.8)
5)-(Average equivalent spherical circle diameter x 1.15)

[0127]

[Table 2] Urea: Reagent product Sulfate Kari: Reagent product Magnesium hydroxide: Reagent product

C. Production of coated bioactive substance Comparative Examples 4 to 6, Examples 14 to 23: Production of coated bioactive substance Bioactive substance particles 1 obtained in "A. Production of granular fertilizer"
A method of coating each of Nos. To 15 will be described.
FIG. 1 shows the coating apparatus used. High-temperature hot air flowed from the lower part to the upper part into the jet tower 1 having a tower diameter of 250 mm, a height of 2,000 mm, an air outlet diameter of 50 mm, and a cone angle of 50 degrees. The high-temperature hot air is blown from a blower 10, passes through an orifice flow meter 9, is heated to a high temperature by a heat exchanger 8, flows into a jet tower 1, and is discharged from an exhaust gas outlet 3 installed at an upper part of the jet tower 1. You. The particles to be coated are introduced into the jet tower 1 in which the high-temperature hot air is circulated from the inlet 2 provided on the side of the jet tower 1 by 10 kg.
Then, the particles 5 to be coated are caused to flow as shown in FIG. At this time, the flow rate 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. The hot air temperature is T1 hot air temperature, T2 granule temperature, and T3 temperature. Adjust while measuring the exhaust temperature.

In this embodiment, the flow rate (orifice flow meter 9) is 4 m ³ / min and the hot air temperature (hot air temperature T1) is 1
00 ° C ± 2 ° C, coated particle temperature (particle temperature T2) 70 ±
Performed at 2 ° C. On the other hand, polyethylene (low density polyethylene d = 0.918 [g / cm ³ ] (density J
IS K6760), MI = 22 [g / 10 min] (melt index JIS K6760)) 50 parts by weight, 4.9 parts by weight of corn starch, 45 parts by weight of talc (average particle diameter 10 μm),
A coating material having a ratio of 0.1 part by weight of iron stearate (reagent product) and toluene are charged, and the resin is dissolved by mixing and stirring at 100 ° C. ± 2 ° C. to obtain a uniform coating material of 1.5% by weight. A solution 12 was obtained.

The dissolution tank 11 was constantly stirred until the coating was completed. The coating material dissolving liquid 12 is supplied by a pump 6 to a spray nozzle 4 which is a 0.8-mm full-con type one-fluid nozzle installed at a lower portion of the jet tower 1 at a flow rate of 0.1 kg.
/ Min, and sprayed and sprayed on the flowing coated particles 5. At this time, the temperature of the coating material dissolving liquid 12 is 80 ° C.
In order to avoid the following, the dissolving tank 11 and the piping from the dissolving tank 11 to the spray nozzle 4 had a double structure, and the coating material dissolving liquid 12 was transported while being heated by passing steam.

The above-described coating operation is performed in the following manner.
Starting from the point at which the particle temperature T2 of the polymer reaches 70 ° C., spraying the coating for a predetermined time until the coating becomes 8.5% by weight of the coated bioactive substance, and then coating the coated bioactive substance at 70 ° C. ± 2 ° C.
Keeping the temperature of hot air
Drying was performed by blowing only hot air for 0 minutes, and when drying was completed, the blower 10 was stopped, and the coated particles 5 to be coated were discharged from the extraction port 7 at the lowermost part of the jet tower 1, and The coated bioactive substances 1 to 13 of Comparative Examples 4 to 6 and Examples 14 to 23 described in No. 3 were obtained.

D. Defective coating confirmation test Comparative Examples 4 to 6 and Example 14 in a 50 mL beaker
~ 23 coated bioactive substances in each 10 g,
Next, the ink (G9) previously placed in a 35 ° C.
620AN, Yokogawa Hokushin Electric Co.) diluent (2g / 1000ml pure water) is added until the coated bioactive substance is completely immersed.
It was left as it was for 2 hours. After 2 hours, the coated bioactive substance was collected by filtration. Subsequently, the ink adhering to the coated bioactive substance was washed with water, and then dried with warm air at 70 ° C. The coated bioactive substance colored with the ink and the coated bioactive substance in which the coating was disintegrated were removed and weighed. Then, the coloring ratio was calculated by the following equation. The results are shown in Table 2. Coloring ratio = (weight of colored particles) / (weight of test coated bioactive substance) × 100 In calculating the coloring ratio, the coloration ratio for each measurement was calculated by performing each measurement through five repeated experiments. The average value was used as the coloring ratio of the sample.

[0133]

[Table 3]

E. Preparation of Bioactive Substance Composition Comparative Example 7 A bioactive substance composition was prepared by blending 50 g of bioactive substance particles 1 and 50 g of coated bioactive granules 1. The powdering test was performed according to the powdering test in Comparative Example 1, and the measurement results are shown in Table 4.

Example 24 A bioactive substance composition was prepared by blending 50 g of the bioactive substance particles 9 and 50 g of the coated bioactive granules 9. The powdering test was performed in accordance with the dusting test in Comparative Example 1, and the measurement results are shown in Table 4.

[0136]

[Table 4]

[0137]

The biologically active substance particles of the present invention have a higher hardness than other biologically active substance particles having the same hardness.
After production, in each case of storage, transportation, and use, even if physical force is applied from the outside, a part of the bioactive substance particles rarely becomes powdered or finely divided. In addition, in the case of the coated bioactive substance of the present invention, the physical properties of the coating are reduced and the elution is caused by the incorporation of fine particles and / or powder into the coating when the bioactive substance particles are formed into fine particles and / or powder. Less loss of control functions. Furthermore, according to the production method of the present invention, the physical properties of the coating film are reduced and the dissolution control function is lost due to the contamination of the coating film with the fine particles and / or the powder generated by the micronization and / or pulverization of the bioactive substance particles. A coated bioactive substance with less generation of odor can be easily produced.

[Brief description of the drawings]

FIG. 1 is a sectional view of a spouted bed.

[Explanation of symbols]

 1. Spout tower 2. 2. Granule inlet Exhaust gas outlet 4. Spray nozzle 5. Particles 6. Pump 7. Outlet 8. Heat exchanger 9. Orifice flow meter 10. Blower 11. Dissolution tank 12. Mixed solution of coating material T1. Hot air thermometer T2. Granular thermometer T3. Exhaust thermometer SL. steam

FIG. 2 is a schematic diagram of a sugar coating machine.

[Explanation of symbols]

 1: liquid tank 2: piping 3: pump 4: rotating pan 5: spray nozzle 6: hot air blowing pipe

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C05G 3/00 101 C05G 3/00 101

Claims (17)

[Claims] 1. Bioactive substance particles wherein particles falling within the following equivalent spherical circle diameter range (1) account for 70% or more of all particles. Equivalent spherical circle diameter range (1): (average equivalent spherical circle diameter × 0.
7)-(Average equivalent spherical circle diameter x 1.3) 2. The equivalent spherical circular diameter range according to claim 1.
Biologically active substance particles in which 90% or more of the total particles are contained. 3. Biologically active substance particles wherein particles falling within the following equivalent spherical circle diameter range (2) account for 70% or more of all particles. Equivalent spherical circle diameter range (2): (average equivalent spherical circle diameter x 0.8
5)-(Average equivalent spherical circle diameter x 1.15) 4. The equivalent spherical diameter range according to claim 3 (2).
Biologically active substance particles in which 90% or more of the total particles are contained. 5. Bioactive substance particles having a water content of 1% by weight or less. 6. Bioactive substance particles having a water content of 0.6% by weight or less. 7. The equivalent spherical circle diameter range according to claim 1 (1).
Bioactive substance particles containing 70% or more of all particles and a water content of 1% by weight or less. 8. The equivalent spherical circle diameter range according to claim 1 (1).
Bioactive substance particles containing 90% or more of the total particles and a water content of 1% by weight or less. 9. The equivalent spherical diameter range according to claim 3 (2).
Bioactive substance particles containing at least 70% of the total particles and a water content of at most 0.6% by weight. 10. Biologically active substance particles in which the particles falling within the equivalent spherical diameter range (2) according to claim 3 are 90% or more of all particles and the water content is 0.6% by weight or less. 11. The bioactive substance particles according to claim 1, wherein a circularity coefficient represented by the following formula (1) is 0.85 or more. Formula (1): (4π × projected area of particle) / (length of contour of particle projected view) ² 12. The method according to claim 1, wherein the bioactive substance is a fertilizer.
12. The biologically active substance particle according to any one of items 11 to 11. 13. The method according to claim 1, wherein the bioactive substance is urea.
12. The biologically active substance particle according to any one of items 11 to 11. 14. The bioactive substance particles according to claim 1, wherein the use is as a core material of a coated bioactive substance. 15. A coated bioactive substance, wherein the surface of the bioactive substance particles according to any one of claims 1 to 14 is coated with a coating material. A bioactive substance composition comprising the bioactive substance particles according to any one of claims 1 to 13 and the coated bioactive substance according to claim 14. 17. The surface of a bioactive substance particle in which particles equivalent to the equivalent spherical diameter range (1) according to any one of claims 1 to 14 account for 70% or more of all particles is coated with a coating material. A method for producing a coated bioactive substance, comprising: