JP5593043B2 - Coated granular composition - Google Patents

Description

  The present invention relates to a coated granular composition containing a bioactive substance.

2. Description of the Related Art Conventionally, coated granular compositions are known that can coat biologically active substances such as fertilizers, insecticides, and fungicides, and can control the elution of the biologically active substances.
Moreover, as a coating material used for this coated granular composition, if a material with poor biodegradability is used, the coating material that is not decomposed at the application site of the coated granular composition such as paddy field or upland remains for a long time after application. Therefore, a material excellent in biodegradability is desirable.

Patent Documents 1 to 6 disclose a coated granular composition containing a bioactive substance in which a specific urethane resin is used as a coating material for the coating layer.
And in the coated granular composition containing a bioactive substance described in Patent Document 1, it is possible to achieve both elution characteristics of bioactive substances and biodegradability.

  When spraying granular bioactive substances such as fertilizers, insecticides, and fungicides, it may be performed with a power spreader. The power spreader has a delivery part for sending out the granular biologically active substance and a tubular spraying nozzle, and the biologically active substance is sent from the delivery part to the spraying nozzle, Power is scattered by being ejected to the outside from the nozzle hole provided.

Some spray nozzles of a power spreader have a plurality of nozzle holes in the longitudinal direction and a collision plate arranged corresponding to the nozzle holes. By using such spray nozzles, when using a power spreader, a part of the granular bioactive substance that passes through the pipe collides with the collision plate to change the jet direction, and the jets are ejected from the respective nozzle holes. Can be spread over a wide area.
Such spray nozzles are disclosed, for example, in Japanese Utility Model Publication Nos. 59-17400 and 64-44060.

JP 2007-210960 A JP 2008-31012 A JP 2008-69068 A JP 2008-7370 A JP 2008-31034 A JP 2008-56555 A

By the way, when the coated granular composition is subjected to power dispersion using the above-described spraying nozzle, as described above, a part of the coated granular composition collides with the collision plate. For this reason, depending on the spraying conditions and the type of coating material, the urethane resin layer covered by this collision may be damaged.
When this coating is broken, the elution characteristics (elution profile) of the bioactive substance change due to easiness of elution from the damaged portion.

  In order to prevent damage to the coating, it is conceivable to provide a protective layer that protects the urethane resin layer that is coated. However, if the protective layer is simply provided, the elution characteristics may change such that the protective layer inhibits elution of the bioactive substance, and the target elution characteristics may not be obtained.

  Accordingly, the present invention provides a coated granular composition that can control the elution characteristics of a bioactive substance by a coating layer, and that the elution characteristics of a bioactive substance hardly change even when sprayed using a power spreader. Is an issue.

  As a result of intensive studies in such a situation, the present inventor contains a polyisocyanate component and a polyester polyol in a coated granular composition in which a coating layer is provided on the surface of a granular material containing a bioactive substance. By using a coating layer having a urethane resin layer containing a urethane resin obtained by polymerizing a polyol component, and a protective layer containing a hydroxy fatty acid having 10 to 24 carbon atoms provided outside the urethane resin layer, The present inventors have found that the above problems can be solved and have reached the present invention.

That is, the present invention includes the following inventions.
[Invention 1]
[Invention 1]
A coated granular composition comprising a coating layer on the surface of a granular material containing a bioactive substance,
The coating layer is
A urethane resin layer containing a urethane resin obtained by polymerizing a polyisocyanate component and a polyol component containing a polyester polyol;
A coated granular composition comprising a protective layer containing a hydroxy fatty acid having 10 to 24 carbon atoms and provided outside the urethane resin layer.
[Invention 2]
The coated granular composition according to invention 1, wherein the polyester polyol has an oxycarbonyl partial structure in the molecule at a ratio of 15% or more (weight conversion) with respect to the total amount of the polyester polyol.
[Invention 3]
The coated granular composition according to invention 1 or 2, wherein the polyisocyanate component contains an aromatic polyisocyanate.
[Invention 4]
The coated granular composition according to any one of Inventions 1 to 3, wherein the weight ratio of the polyisocyanate component to the polyol component is 5:95 to 60:40.
[Invention 5]
The coated granular composition according to any one of Inventions 1 to 3, wherein the weight ratio of the polyisocyanate component to the polyol component is 5:95 to 40:60.
[Invention 6]
The coated granular composition according to any one of Inventions 1 to 5, wherein the molar ratio of the isocyanate group in the polyisocyanate component and the hydroxyl group in the polyol component is 1: 0.9 to 1: 1.5.
[Invention 7]
The coated granular composition according to any one of Inventions 1 to 6, wherein the hydroxyl group equivalent of the polyester polyol is 200 to 1250.
[Invention 8]
The coated granular composition according to any one of Inventions 1 to 7, wherein the molecular weight of the polyester polyol is 300 to 5,000.
[Invention 9]
The coated granular composition according to any one of Inventions 1 to 8, wherein the polyester polyol is at least one selected from the group consisting of polyester diols and polyester triols.
[Invention 10]
The coated granular composition according to any one of Inventions 1 to 9, wherein at least one of the polyester polyols is a polycaprolactone polyol.
[Invention 11]
The coated granular composition according to invention 10, wherein the polycaprolactone polyol is polycaprolactone diol or polycaprolactone triol.
[Invention 12]
The coated granular composition according to any one of Inventions 1 to 11, wherein the polyol component further contains a polymethylene glycol having 2 to 8 carbon atoms.
[Invention 13]
The coated granular composition according to invention 12, wherein the polymethylene glycol having 2 to 8 carbon atoms is 1,4-butanediol.
[Invention 14]
The coated granular composition according to invention 12 or 13, wherein the content of the polymethylene glycol having 2 to 8 carbon atoms is 1 to 35% by weight based on the total amount of the polyisocyanate component and the polyol component.
[Invention 15]
The coated granular composition according to any one of Inventions 1 to 14, wherein the content of the polyester polyol is 15 to 80% by weight relative to the total amount of the polyisocyanate component and the polyol component.
[Invention 16]
The coated granular composition according to any one of Inventions 1 to 15, wherein the content of the aromatic polyisocyanate in the polyisocyanate component is 80 to 100 weight percent.
[Invention 17]
The coated granular composition according to any one of Inventions 1 to 15, wherein the total amount of the polyisocyanate component is an aromatic polyisocyanate compound in which all isocyanate groups are directly bonded to the benzene ring.
[Invention 18]
The coated granular composition according to any one of Inventions 1 to 17, wherein the content of the aromatic polyisocyanate is 10 to 50% by weight based on the total amount of the polyisocyanate component and the polyol component.
[Invention 19]
The coated granular composition according to any one of Inventions 16 to 18, wherein the aromatic polyisocyanate is diphenylmethane diisocyanate.
[Invention 20]
The coated granular composition according to any one of Inventions 1 to 19, wherein the content of the hydroxy fatty acid having 10 to 24 carbon atoms relative to the total coated granular composition is 0.1 to 10% by weight.
[Invention 21]
The coated granular composition according to any one of Inventions 1 to 20, wherein the hydroxy fatty acid having 10 to 24 carbon atoms is 12-hydroxystearic acid.
[Invention 22]
The coated granular composition according to any one of Inventions 1 to 21, wherein the urethane resin has a glass transition temperature of 20 ° C or lower.
[Invention 23]
The coated granular composition according to any one of Inventions 1 to 21, wherein the urethane resin has a glass transition temperature of -50 ° C or higher and 5 ° C or lower.
[Invention 24]
The coated granular composition according to any one of Inventions 1 to 23, wherein the urethane resin layer is a layer containing a hydrophobic liquid compound having a boiling point of 100 ° C or higher.
[Invention 25]
25. The coated granular composition according to invention 24, wherein the hydrophobic liquid compound is liquid paraffin.
[Invention 26]
26. The coated granular composition according to any one of Inventions 1 to 25, wherein the granular substance containing the bioactive substance is granular urea.
[Invention 27]
A plurality of nozzle holes in the longitudinal direction and a collision plate arranged in correspondence with the nozzle holes are sent out using a power spreader in which a tubular spraying nozzle formed in a pipe is connected, and the nozzles in the spray nozzle are 27. A method for applying a coated granular composition according to any one of inventions 1 to 26, comprising a step of colliding with a collision plate and dropping from a nozzle to a paddy field or a field.

  By using the coated granular composition of the present invention, other applications such as nursery box application and side stripe application even when sprayed using a power spreader while controlling the elution characteristics of the contained bioactive substance Since the elution characteristics of the bioactive substance are not substantially changed as compared with the case of using in a form, it is possible to correspond to a desired application form.

  The coated granular composition of the present invention is a coated granular composition in which a coating layer is provided on the surface of a granular material containing a bioactive substance, and the coating layer contains a polyisocyanate component and a polyester polyol. It has a urethane resin layer containing a urethane resin obtained by polymerizing a polyol component, and a protective layer containing a hydroxy fatty acid having 10 to 24 carbon atoms provided outside the urethane resin layer. The coated granular composition.

  The particulate material containing the biologically active material used in the present invention may be a particulate material of the biologically active material itself or a particulate material formed by holding the biologically active material on a carrier. Furthermore, it is good also as a granular material formed by coat | covering the granular material formed by hold | maintaining the granular material of a biologically active substance or a biologically active substance with a support | carrier with another material.

  Specific examples of the bioactive substance used in the present invention include active ingredients of agricultural chemicals such as insecticides, fungicides, herbicides, plant growth regulators and repellents, and active ingredients of fertilizers.

Insecticides, fungicides, herbicides, and plant growth regulators used as biologically active substances include fenitrothion [O, O-dimethyl O- (3-methyl-4-nitrophenyl) phosphorothioate], fenthion [O , O-dimethyl O- (3-methyl-4- (methylthio) phenyl) phosphorothioate], diazinone [O, O-diethyl-O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate], chlorpyrifos [O, O-diethyl-O-3,5,6-trichloro-2-pyridyl phosphorothioate], acephate [O, S-dimethylacetylphosphoramidothioate], methidathion [S-2,3-dihydro-5-methoxy-2- Oxo-1,3,4-thiadiazol-3-ylmethyl O, O-dimethylphos Rothioate], Disulfoton [O, O-diethyl S-2-ethylthioethyl phosphorodithioate], DDVP [2,2-dichlorovinyldimethylphosphate], Sulphophos [O-ethyl O-4- (methylthio) phenyl S- Propyl phosphorodithioate], cyanophos [O-4-cyanophenyl O, O-dimethyl phosphorothioate], dioxabenzophos [2-methoxy-4H-1,3,2-benzodioxaphospholine-2-sulfide] Dimethoate [O, O-dimethyl-S- (N-methylcarbamoylmethyl) dithiophosphate], phentoate [ethyl 2-dimethoxyphosphinothioylthio (phenyl) acetate], malathion [diethyl (dimethoxyphosphinothioylthio) Succinate], triclo Hong [dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate], azine phosmethyl [S-3,4-dihydro-4-oxo-1,2,3-benzotriazin-3-ylmethyl O, O-dimethylphospho Rothioate], Monocrotophos [dimethyl-{(E) -1-methyl-2- (methylcarbamoyl) vinyl} phosphate], Ethion [O, O, O ′, O′-tetraethyl-S, S′-methylenebis (Phosphorodithioate)] and the like,
BPMC [2-sec-butylphenylmethylcarbamate], Benfuracarb [ethyl N- {2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio} -N-isopropyl-β-alaninate] Propoxyl [2-isopropoxyphenyl-N-methylcarbamate], carbosulfan [2,3-dihydro-2,2-dimethyl-7-benzo [b] furanyl N-dibutylaminothio-N-methylcarbamate], Carbaryl [1-naphthyl-N-methylcarbamate], mesomil [S-methyl-N- (methylcarbamoyloxy) thioacetimidate], etiophencarb [2- (ethylthiomethyl) phenylmethylcarbamate], aldicarb [2-methyl -2- (Methylthio) propyl Lopionaldehyde O-methylcarbamoyloxime], oxamyl [N, N-dimethyl-2-methylcarbamoyloxyimino-2- (methylthio) acetamide], phenothiocarb [S-4-phenoxybutyl-N, N-dimethylthiocarbamate], etc. Carbamate compounds,
Etofenprox [2- (4-ethoxyphenyl) -2-methyl-1- (3-phenoxybenzyl) oxypropane], fenvalerate [(RS) -α-cyano-3-phenoxybenzyl (RS) -2- (4-chlorophenyl) -3-methylbutyrate], esfenvalerate [(S) -α-cyano-3-phenoxybenzyl (S) -2- (4-chlorophenyl) -3-methylbutyrate], fenpropa Thrin [(RS) -α-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate], cypermethrin [(RS) -α-cyano-3-phenoxybenzyl (1RS) -cis , Trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], permetry [3-phenoxybenzyl (1RS) -cis, trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], cyhalothrin [(RS) -α-cyano-3-phenoxybenzyl ( 1RS, 3Z) -cis-3- (2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarboxylate], deltamethrin [(S) -α-cyano- 3-phenoxybenzyl (1R) -cis-3- (2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate], cycloprotorin [(RS) -α-cyano-3-phenoxybenzyl (RS ) -2,2-dichloro-1- (4-ethoxyphenyl) cyclopropanecarboxylate], fulvalinate [α-cyano 3-phenoxybenzyl N- (2-chloro-α, α, α-trifluoro-p-tolyl) -D-valinate], bifenthrin [2-methyl-3-phenylbenzyl (1RS, 3Z) -cis-3- (2-Chloro-3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylate], Halfenprox [2- (4-bromodifluoromethoxyphenyl) -2-methyl-1 -(3-phenoxybenzyl) methylpropane], tralomethrin [(S) -α-cyano-3-phenoxybenzyl (1R) -cis-3- (1,2,2,2-tetrabromoethyl) -2,2 -Dimethylcyclopropanecarboxylate], silafluophene [(4-ethoxyphenyl)-{3- (4-fluoro-3-phenoxyphenyl) Propyl} dimethylsilane], d-phenothrin [3-phenoxybenzyl (1R) -cis, trans-2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate], ciphenothrin [(RS ) -Α-cyano-3-phenoxybenzyl (1R) -cis, trans-2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate], d-resmethrin [5-benzyl-3 -Furylmethyl (1R) -cis, trans-2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate], acrinathrin [(S) -α-cyano-3-phenoxybenzyl (1R , 3Z) -cis- (2,2-dimethyl-3- {3-oxo-3- (1,1,1,3,3,3-hex) Safluoropropyloxy) propenyl} cyclopropanecarboxylate), cyfluthrin [(RS) -α-cyano-4-fluoro-3-phenoxybenzyl 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxyl Rate], tefluthrin [2,3,5,6-tetrafluoro-4-methylbenzyl (1RS, 3Z) -cis-3- (2-chloro-3,3,3-trifluoro-1-propenyl) -2 , 2-dimethylcyclopropanecarboxylate], transfluthrin [2,3,5,6-tetrafluorobenzyl (1R) -trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxyl Rate], tetramethrin [3,4,5,6-tetrahydrophthalimidomethyl (1RS) -cis Trans-2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate], alletrin [(RS) -2-methyl-4-oxo-3- (2-propenyl) -2 -Cyclopenten-1-yl (1RS) -cis, trans-2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate], praretrin [(S) -2-methyl-4 -Oxo-3- (2-propynyl) -2-cyclopenten-1-yl (1R) -cis, trans-2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate] , Empentrin [(RS) -1-ethynyl-2-methyl-2-pentenyl (1R) -cis, trans-2,2-dimethyl-3- (2-methyl-1-propenyl) si Clopropanecarboxylate], imiprosulin [2,5-dioxo-3- (2-propynyl) imidazolidin-1-ylmethyl (1R) -cis, trans-2,2-dimethyl-3- (2-methyl-1- Propenyl) cyclopropanecarboxylate], d-flamethrin [5- (2-propynyl) furfuryl (1R) -cis, trans-2,2-dimethyl-3- (2-methyl-1-propenyl) cyclo Propanecarboxylate], pyrethroid compounds such as 5- (2-propynyl) furfuryl 2,2,3,3-tetramethylcyclopropanecarboxylate,
Thiadiazine derivatives such as buprofezin [2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-thiadiazin-4-one], nitroimidazolidine derivatives, cartap [S, S ′-(2-dimethylaminotrimethylene) ) Bis (thiocarbamate)], thiocyclam [N, N-dimethyl-1,2,3-trithian-5-ylamine], bensultap [S, S′-2-dimethylaminotrimethylenedi (benzenethiosulfonate) ], N-cyanoamidine derivatives such as N-cyano-N′-methyl-N ′-(6-chloro-3-pyridylmethyl) acetamidine, endosulfan [6, 7, 8, 9, 10,10-hexachloro-1,5,5a, 6,9,9a-hexahydro-6,9-methano-2, 4,3-benzodioxathiepine oxide], γ-BHC [1,2,3,4,5,6-hexachlorocyclohexane], dicofol [1,1-bis (4-chlorophenyl) -2,2,2 Chlorinated hydrocarbon compounds such as -trichloroethanol], chlorofluazulone [1- {3,5-dichloro-4- (3-chloro-5-trifluoromethylpyridin-2-yloxy) phenyl} -3 -(2,6-difluorobenzoyl) urea], teflubenzuron [1- (3,5-dichloro-2,4-difluorophenyl) -3- (2,6-difluorobenzoyl) urea], flufenoxuron [1- Benzoylsulfides such as {4- (2-chloro-4-trifluoromethylphenoxy) -2-fluorophenyl} -3- (2,6-difluorobenzoyl) urea] Nilurea compounds, amitraz [N, N ′-{(methylimino) dimethylidin} -di-2,4-xylidine], chlordimethyl [N ′-(4-chloro-2-methylphenyl) -N, N-dimethylmethyniimi Formamide derivatives such as damide], thiourea derivatives such as diafenthiuron [N- (2,6-diisopropyl-4-phenoxyphenyl) -N′-t-butylcarbodiimide], N-phenylpyrazole compounds,
Methoxadiazone [5-methoxy-3- (2-methoxyphenyl) -1,3,4-oxadiazol-2- (3H) -one], bromopropylate [isopropyl 4,4′-dibromobenzylate], tetradiphone [4-chlorophenyl 2,4,5-trichlorophenylsulfone], quinomethionate [S, S-6-methylquinoxaline-2,3-diyldithiocarbonate], propargite [2- (4-tert-butylphenoxy) cyclohexylpropiyl -2-ylsulfite], phenbutatin oxide [bis {tris (2-methyl-2-phenylpropyl) tin} oxide], hexothiazox [(4RS, 5RS) -5- (4-chlorophenyl) -N-chloro Hexyl-4-methyl-2-oxo-1,3-thiazolidine- -Carboxamide], clofentezin [3,6-bis (2-chlorophenyl) -1,2,4,5-tetrazine], pyridaben [2-tert-butyl-5- (4-tert-butylbenzylthio)- 4-chloropyridazin-3 (2H) -one], fenpyroximate [tert-butyl (E) -4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl) methyleneaminooxymethyl] benzoate], debufenpyrad [N-4-tert-butylbenzyl) -4-chloro-3-ethyl-1-methyl-5-pyrazolecarboxamide], polynactin complex [tetranactin, dinactin, trinactin], pyrimidifene [5-chloro-N- [ 2- {4- (2-ethoxyethyl) -2,3-dimethylphenoxy} Til] -6-ethylpyrimidin-4-amine], milbemectin, abamectin, ivermectin, azadirachtin [AZAD], 5-methyl [1,2,4] triazolo [3,4-b] benzothiazole, methyl 1- (buty Rucarbamoyl) benzimidazole-2-carbamate, 6- (3,5-dichloro-4-methylphenyl) -3 (2H) -pyridazinone, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H -1,2,4-triazol-1-yl) butanone, (E) -4-chloro-2- (trifluoromethyl) -N- [1- (imidazol-1-yl) -2-propoxyethylidene] aniline 1- [N-propyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] carbamoyl] imidazole, (E)- -(4-Chlorophenyl) -4,4-dimethyl-2- (1H-1,2,4-triazol-1-yl) -1-penten-3-ol, 1- (4-chlorophenyl) -4,4 -Dimethyl-2- (1H-1,2,4-triazol-1-yl) pentan-3-ol, (E) -1- (2,4-dichlorophenyl) -4,4-dimethyl-2- (1H -1,2,4-triazol-1-yl) -1-penten-3-ol, 1- (2,4-dichlorophenyl) -4,4-dimethyl-2- (1H-1,2,4-triazole -1-yl) pentan-3-ol, 4- [3- (4-tert-butylphenyl) -2-methylpropyl] -2,6-dimethylmorpholine, 2- (2,4-dichlorophenyl) -1- (1H-1,2,4-triazol-1-yl) Xan-2-ol, O, O-diethyl O-2-quinoxalinyl phosphorothioate, O- (6-ethoxy-2-ethyl-4-pyrimidinyl) O, O-dimethyl phosphorothioate, 2-diethylamino-5,6 -Dimethylpyrimidin-4-yl dimethylcarbamate, 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-pyrazolyl p-toluenesulfonate, 4-amino-6- (1,1-dimethylethyl) -3-Methylthio-1,2,4-triazin-5 (4H) -one, 2-chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) aminocarbonyl Benzenesulfonamide, 2-methoxycarbonyl-N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] benzenesulfur 2-methoxycarbonyl-N-[(4,6-dimethylpyrimidin-2-yl) aminocarbonyl] benzenesulfonamide, 2-methoxycarbonyl-N-[(4-methoxy-6-methyl-1,3, 5-triazin-2-yl) aminocarbonyl] benzenesulfonamide, 2-ethoxycarbonyl-N-[(4-chloro-6-methoxypyrimidin-2-yl) aminocarbonyl] benzenesulfonamide, 2- (2-chloro Ethoxy) -N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) aminocarbonyl] benzenesulfonamide, 2-methoxycarbonyl-N-[(4,6-dimethoxypyrimidine- 2-yl) aminocarbonyl] phenylmethanesulfonamide, 2-methoxycarbonyl-N-[( 4-methoxy-6-methyl-1,3,5-triazin-2-yl) aminocarbonyl] thiophene-3-sulfonamide, 4-ethoxycarbonyl-N-[(4,6-dimethoxypyrimidin-2-yl) Aminocarbonyl] -1-methylpyrazole-5-sulfonamide, 2- [4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-1H-imidazol-2-yl] -3 -Quinolinecarboxylic acid, 2- [4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-1H-imidazol-2-yl] -5-ethyl-3-pyridinecarboxylic acid, Methyl 6- (4-isopropyl-4-methyl-5-oxoimidazolin-2-yl) -m-toluate, methyl 2- (4-isopropyl-4-methyl-5-oxoi Dazolin-2-yl) -p-toluate, 2- (4-isopropyl-4-methyl-5-oxoimidazolin-2-yl) nicotinic acid, N- (4-chlorophenyl) methyl-N-cyclopentyl-N′- Phenylurea, (RS) -2-cyano-N-[(R) -1 (2,4-dichlorophenyl) ethyl] -3,3-dimethylbutyramide, N- (1,3-dihydro-1,1, 3-trimethylisobenzofuran-4-yl) -5-chloro-1,3-dimethylpyrazole-4-carboxamide, N- [2,6-dibromo-4- (trifluoromethoxy) phenyl] -2-methyl- 4- (trifluoromethyl) -5-thiazolcarboxamide, 2,2-dichloro-N- [1- (4-chlorophenyl) ethyl] -3-methylcyclopropanecarbo Cyamide, methyl (E) -2-2-2-6- (2-cyanophenoxy) pyrimidin-4-yloxy-phenyl-3-methoxyacrylate, 5-methyl-1,2,4-triazolo [3,4-b Benzothiazole, 3-allyloxy-1,2-benzisothiazole-1,1-dioxide, diisopropyl = 1,3-dithiolane-2-ylidene-malonate, O, O-dipropyl-O-4-methylthiophenyl phosphate, etc. Is mentioned.

  Moreover, as an active ingredient of the fertilizer used as a bioactive substance, various things, such as nitrogen, phosphorus, potassium, silicon, magnesium, calcium, manganese, boron, iron which are given to soil in order to give nutrients in plant cultivation Examples include substances containing elements, such as urea, ammonium nitrate, ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium phosphate, sodium nitrate, calcium nitrate, potassium nitrate, lime nitrogen, formaldehyde processed urea (UF), acetaldehyde processed urea (CDU), nitrogenous fertilizer components such as isobutyraldehyde processed urea (IBDU), guaneaure urea (GU); superphosphate lime, heavy superphosphate lime, molten phosphorus, humic acid phosphorus, calcined phosphorus, heavy calcined phosphorus, Magnesium superphosphate, ammonium polyphosphate, potassium metaphosphate, Phosphoric fertilizer components such as calcium tarpate, mafic phosphate, ammonium sulfate, potassium ammonium phosphate, ammonium phosphate; potassium chloride, potassium sulfate, potassium sulfate, potassium sulfate, potassium bicarbonate, potassium phosphate, etc. Potassium fertilizer components; Silicate fertilizer components such as calcium silicate; Magnesium fertilizer components such as magnesium sulfate and magnesium chloride; Calcium fertilizer components such as quick lime, slaked lime and calcium carbonate; Manganese sulfate, sulfated manganese manganese, mineral manganese, etc. Can be mentioned; fertilizer components such as boric acid and borate; iron-containing fertilizer components such as steel slag.

  Examples of the carrier that holds the bioactive substance include kaolin minerals such as kaolinite, montmorillonite, smectite, talc, wax, silica, hydrous calcium silicate, calcium carbonate, zeolite, acidic clay, and the like; cellulose, rice husk, Plant carriers such as starch and soy flour; water-soluble carriers such as lactose, sucrose, dextrin, sodium chloride, sodium tripolyphosphate; liquid carriers such as didecyl adipate, cottonseed oil, palm oil, etc. Can be used together.

  The size of the granular material containing the bioactive substance used in the present invention is not particularly limited, but is usually 0.1 mm to 15 mm, and the shape is preferably spherical, but other shapes such as a columnar shape are preferred. It may be a shape.

  The urethane resin layer used in the present invention is a layer containing a urethane resin obtained by polymerizing a polyisocyanate component and a polyol component containing a polyester polyol.

  Examples of the polyisocyanate component used in the present invention include aromatic polyisocyanates. Specifically, 4,4′-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI). , Tolidine diisocyanate (TODI), naphthalene-1,5-diisocyanate (NDI), tetramethylene xylylene diisocyanate (TMXDI), polymethylene polyphenyl polyisocyanate (polymeric MDI) or derivatives thereof (isocyanurate, biuret, uretdione) Etc.). In the present invention, the aromatic polyisocyanate is preferably an aromatic polyisocyanate in which an isocyanate group is directly bonded to the benzene ring at a ratio of one, and as such an aromatic polyisocyanate, specifically, MDI, Examples include TODI and polymeric MDI.

  The polyester polyol used in the present invention is a polyol containing an oxycarbonyl [—O—C (═O) —] partial structure, and examples thereof include the following polyester polyols.

As the polyester polyol used in the present invention, for example, a polyester polyol in which any terminal of the molecule has a structure of the following formula (1) or formula (2) can be mentioned.
— [O—C (═O) —CHR— (CH ₂ ) _p ] _m —OH Formula (1)
[Wherein, R represents a hydrogen atom or a methyl group, p represents an integer of 0 to 9, and m represents an integer of 1 or more. ]
- [O-C (= O ) -Q-C (= O) -O- (CH 2) r] n -OH Formula (2)
[In formula, Q represents a C1-C10 alkylene group or a phenylene group, r represents the integer of 1-10, n represents an integer greater than or equal to 1. ]

Examples of the polyester polyol having a structure represented by the formula (1) at any terminal of the molecule include a lactone polyester polyol obtained by ring-opening polymerization of a lactide monomer or a lactone monomer to a low molecular polyol.
As such a lactone-based polyester polyol, specifically, a lactone-based polyester obtained by ring-opening polymerization of β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone or the like to a low molecular weight polyol. A polyol is mentioned.

Examples of the polyester polyol in which any terminal of the molecule has the structure of the formula (2) include a condensed polyester polyol obtained by polycondensation of a low molecular diol and a dicarboxylic acid.
Specific examples of such condensed polyester polyols include low-molecular polyols such as ethylene glycol, 1,3-propanediol, and 1,4-butanediol, oxalic acid, succinic acid, glutaric acid, adipic acid, and pimeline. By polycondensing with aliphatic dicarboxylic acids such as acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid or aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid Examples thereof include the obtained condensed polyester polyol.

The polyester polyol contained in the polyol component is a polyester polyol having 2 to 3 terminal structures represented by the formula (1) or (2) in one molecule, that is, a ratio of 2 to 3 hydroxyl groups per molecule of the polyester polyol. It is preferable that it is the polyester polyol which it has.
The polyester polyol contained in the polyol component is preferably a polyester polyol having a molecular weight of 300 to 5,000.
In the present invention, the molecular weight in the mixture containing a plurality of types of compounds means the number average molecular weight. The number average molecular weight in the polymer can be determined by a general method such as gel permeation chromatography (GPC) or terminal group determination method.
Moreover, in this invention, the hydroxyl equivalent of the polyester polyol contained in a polyol component means the molecular weight of the polyester polyol per hydroxyl group. The hydroxyl equivalent can also be calculated from the hydroxyl value of the polyester polyol.

In the present invention, the polyester polyol contained in the polyol component is preferably a polycaprolactone polyol obtained by ring-opening polymerization of a low molecular weight polyol and ε-caprolactone.
Polycaprolactone polyols differ in the type of polycaprolactone polyol obtained depending on the type of low molecular polyol used as a starting material and the degree of polymerization of ε-caprolactone. A typical structure of a polycaprolactone polyol (polycaprolactone diol or polycaprolactone triol) having 2 or 3 hydroxyl groups in one molecule is shown below. The polycaprolactone polyol has one (1-oxohexa-1,6-diyl) oxy structure (—C (═O) —CH ₂ —CH ₂ —CH ₂ —CH ₂ —CH ₂ —O—) per molecule. It is a polyol having the above.

式（３）

〔上記の式中、ｍは０以上の整数、ｎは１以上の整数、Ｒ1は２価の有機残基（例えば、エチレン基、テトラメチレン基等）を表す。〕

Formula (3)

[In the above formula, m represents an integer of 0 or more, n represents an integer of 1 or more, and R 1 represents a divalent organic residue (for example, ethylene group, tetramethylene group, etc.). ]

式（４）

〔上記の式中、ｍおよびｐは０以上の整数、ｎは１以上の整数、Ｒ2は３価の有機残基（例えば、プロパン−１，２，３−トリイル基等）を表す。〕

Formula (4)

[In the above formula, m and p are integers of 0 or more, n is an integer of 1 or more, and R2 represents a trivalent organic residue (for example, a propane-1,2,3-triyl group, etc.). ]

  In the production of polycaprolactone polyol, a low molecular polyol used as a raw material is a compound having two hydroxyl groups in one molecule, such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, Examples include 1,6-hexanediol and 1,8-octanediol, and examples of the polyol having three hydroxyl groups in one molecule include 2-ethyl-2- (hydroxymethyl) -1,3-propanediol (common name: Trimethylolpropane), 2- (hydroxymethyl) -1,3-propanediol, glycerin, and triethanolamine. Examples of the compound having four or more hydroxyl groups include diglycerin and polyglycerin.

For example, the structure of polycaprolactone polyol obtained by ring-opening polymerization of 6 molecules of ε-caprolactone to 1 molecule of ethylene glycol is, for example, the following structure.
HO- [CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -C (= O) -O] ₃ -CH ₂ -CH _2- [OC (= O) -CH ₂ -CH ₂ -CH _2- CH ₂ -CH ₂ ] ₃ -OH
Formula (5)

The weight ratio of the oxycarbonyl [—O—C (═O) —] partial structure in this polycaprolactone polyol is 35%.
(44 × 6) / (62 + 114 × 6) = 0.354
[The molecular weights of ε-caprolactone and ethylene glycol were 114 and 62, respectively, and the oxycarbonyl partial structure was 44 in terms of molecular weight. ]

Moreover, the hydroxyl equivalent in this polycaprolactone polyol is 373.
(62 + 114 × 6) / 2 = 373
[The molecular weight of polycaprolactone polyol was divided by 2 of the number of hydroxyl groups. ]

  The molecular weight of the polycaprolactone polyol that can be preferably used in the present invention is not particularly limited, but is preferably 300 to 5000, and more preferably 400 to 2500. The hydroxyl group equivalent of the polycaprolactone polyol that can be preferably used in the present invention is 200 to 1250.

  In the present invention, when the polyester polyol contained in the polyol component is a polycaprolactone polyol, the polycaprolactone polyol is usually in the range of 10 to 90% by weight, preferably 30 with respect to the total amount of the polyisocyanate component and the polyol component. ~ 80% by weight.

式（６）
〔式中、Ｘは-CH₂-CH₂-又は-CH=CH-を表し、ｎは１、２又は３を表し、ｍは０、１又は２を表し、ｎ＋ｍは２又は３である。ｎ＋ｍが２である場合、ＡはＣ２−Ｃ８アルカンジイル基を表し、ｎ＋ｍが３である場合、ＡはＣ３−Ｃ８アルカントリイル基を表す。〕 Another example of the polyester polyol used in the present invention is a hydroxy fatty acid ester having a molecular weight of 300 to 5000 represented by the formula (6) (hereinafter referred to as the present hydroxy fatty acid ester).

Formula (6)
[Wherein, X represents —CH ₂ —CH ₂ — or —CH═CH—, n represents 1, 2 or 3, m represents 0, 1 or 2, and n + m represents 2 or 3. When n + m is 2, A represents a C2-C8 alkanediyl group, and when n + m is 3, A represents a C3-C8 alkanetriyl group. ]

In the present invention, the present hydroxy fatty acid ester is an ester compound produced by dehydrating condensation of ricinoleic acid or 12-hydroxystearic acid to a low molecular polyol, and ricinoleic acid or 12- Hydroxystearic acid is in a ratio of 1 to 3 molecules.
In the production of the present hydroxy fatty acid ester, the low molecular polyol used as a raw material is, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol as a compound having two hydroxyl groups in one molecule. 1,6-hexanediol, 1,8-octanediol, and as a polyol having 3 hydroxyl groups in one molecule, for example, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol (common name) : Trimethylolpropane), 2- (hydroxymethyl) -1,3-propanediol, 1,2,3-propanetriol (common name: glycerin).
In the formula (6), when the low molecular polyol used as a raw material is a compound having two hydroxyl groups in one molecule, n + m is 2, n is 1 or 2, and A is a C2-C8 alkanediyl group. (For example, ethane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group). When the low molecular weight polyol is a compound having three hydroxyl groups in one molecule, n + m is 3, n is 1, 2 or 3, and A is a C3-C8 alkanetriyl group (for example, propane- 1,2,3-triyl group).
Among the hydroxy fatty acid esters, ricinoleic acid triglyceride is a main component in castor oil, and ricinoleic acid can be obtained by hydrolyzing castor oil. Castor oil can also be used as the ricinoleic acid triglyceride. 12-hydroxystearic acid can be obtained by hydrogenating ricinoleic acid.
In the present invention, the hydroxy fatty acid ester is preferably ricinoleic acid triglyceride.
In the present invention, the hydroxy fatty acid ester is preferably 7 to 60% by weight, more preferably 10 to 60% by weight, and still more preferably 14 to 50% by weight based on the total amount of the polyisocyanate component and the polyol component. %.

  The polyester polyol used in the present invention preferably contains 15% or more of the oxycarbonyl [—O—C (═O) —] partial structure contained in the polyester polyol in terms of weight relative to the total amount of the polyester polyol.

  In the present invention, the molar ratio, which is the ratio of the number of moles of isocyanate groups in the polyisocyanate component and the number of moles of hydroxyl groups in the polyester polyol contained in the polyol component, is preferably 1: 0.9 to 1: 1.5. Yes, more preferably 1: 1 to 1: 1.2.

式（７）
〔式中、ＺはＺ¹又はＺ²ＣＯ₂ＣＨ₂を表し、Ｚ¹及びＺ²はＣ４〜Ｃ３０の鎖状炭化水素基を表す。〕 The polyol component used in the present invention may be only the above-described polyester polyol, or may further contain another polyol together with the polyester polyol.
Examples of other polyols include the following polyols.
A hydroxy fatty acid having 10 to 24 carbon atoms (hereinafter referred to as the present hydroxy fatty acid).
C 2-8 polymethylene glycol (hereinafter referred to as the present polymethylene glycol).
Diols shown below (hereinafter referred to as the present branched diol).

Formula (7)
[Wherein, Z represents Z ¹ or Z ² CO ₂ CH ₂ , and Z ¹ and Z ² represent a C4 to C30 chain hydrocarbon group. ]

When this hydroxy fatty acid is used as a polyol component, ricinoleic acid, 12-hydroxystearic acid, 11-hydroxyhexadecanoic acid, 16-hydroxyhexadecanoic acid, 16-hydroxyhexadecenoic acid, 2-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid 22-hydroxy docosanoic acid, 2-hydroxy tetracosanoic acid, dihydroxy myristic acid, dihydroxy palmitic acid, dihydroxy stearic acid, dihydroxy arachidic acid, trihydroxy palmitic acid and the like can be used.
In terms of producing a urethane resin, the hydroxy fatty acid having a lower melting point can be preferably used. In the present invention, the hydroxy fatty acid is preferably 12-hydroxystearic acid.
In this invention, when this hydroxyl fatty acid is contained in a polyol component, it is preferable that this hydroxy fatty acid is 1-30 weight% with respect to the total amount of a polyisocyanate component and a polyol component.

The present polymethylene glycol used as a polyol component has both ends of the polymethylene group being hydroxyl groups,
Structural formula HO— (CH ₂ ) _n —OH Formula (8)
[Wherein n represents an integer of 2 to 8. ].

Examples of the polymethylene glycol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,8-octanediol.
In the present invention, the polymethylene glycol is preferably 1,4-butanediol or 1,6-hexanediol.

The branched diol used in the present invention includes alkane-1,2-diol (for example, hexane-1,2-diol, heptane-1,2-diol, octane-1,2-diol, decane-1,2 -Diol, dodecane-1,2-diol, etc.), glycerin monofatty acid esters (eg glycerin monolaurate, glycerin monomyristic acid ester, glycerin monopalmitate, glycerin monostearate, glycerin oleate) It is done.
In this invention, Preferably this branched diol is 1-35 weight% with respect to the total amount of a polyisocyanate component and this polyol.
In the polyol component, the molar ratio of the polyester polyol and the branched diol is not particularly limited, but is preferably 9: 1 to 1: 9.

  Furthermore, examples of other types of polyol that can be used as the polyol component include fatty acid esters such as castor oil, polyether triols such as polyoxypropylene triol, and preferably castor oil.

  When the polyol component in the present invention is substantially composed of polycaprolactone polyol, the present polymethylene glycol and castor oil, the number of moles of hydroxyl groups in the polymethylene glycol is from 0.1 to 0.1, assuming that the number of moles of isocyanate groups in the isocyanate component is 1. 0.8, and the weight of the polycaprolactone polyol is preferably 0.3 times or more of the weight of castor oil.

The formation of the urethane resin layer is usually performed by reacting a polyisocyanate component and a polyol component in the presence of a catalyst as necessary on a granular material.
The reaction of the polyisocyanate component and the polyol component is not particularly limited. For example, a method in which all the polyisocyanate component and polyol component are mixed and cured and molded; the polyisocyanate component and a part of the polyol component are mixed in advance. And after preparing a polyisocyanate terminal prepolymer, it can carry out by methods, such as the method of mixing the remaining polyol component, hardening and shape | molding. Alternatively, a method in which a small amount of an organic solvent is mixed together and the reaction and solvent removal are simultaneously performed can also be performed. The reaction conditions can be arbitrarily selected. However, when the temperature is increased, the reaction rate between the hydroxyl group and the isocyanate group increases. Furthermore, the reaction rate can be accelerated by adding a catalyst.

Examples of the catalyst used in the formation of the urethane resin layer include potassium acetate, calcium acetate, stannous octoate, dibutyltin diacetate, dibutyltin dichloride, dibutyltin dilaurate, dibutylthiotinic acid, octylic acid primary tin, di- organic metals such as n-octyltin dilaurate, isopropyl titanate, bismuth 2-ethylhexanoate, phosphine, Zn neodecanoate, triethylamine, N, N, N ′, N′-tetramethylethylenediamine, triethylenediamine, N-methylmorpholine, N, N-dimethyldidodecylamine, N-dodecylmorpholine, N, N-dimethylcyclohexylamine, N-ethylmorpholine, dimethylethanolamine, N, N-dimethylbenzylamine, tetrabutyl tita Over DOO, oxy isopropyl vanadate, n- propyl zirconate, 2,4,6-tris (dimethylaminomethyl) include amine catalysts such as phenol.
In addition, before the diisocyanate group in the polyisocyanate component and the hydroxyl group in the present polyester polyol and the present hydroxy fatty acid sufficiently react, the polyisocyanate component, the present polyester polyol and the present hydroxy fatty acid (further added as necessary). A mixture having fluidity is also referred to as an uncured urethane resin.

  In the present invention, the urethane resin layer may contain other substances together with a urethane resin obtained by polymerizing a polyisocyanate component and a polyol component containing a polyester polyol. Examples of such other substances include hydrophobic liquid compounds having a boiling point of 100 ° C. or higher. Specific examples of such hydrophobic liquid compounds include chain hydrocarbons such as liquid paraffin, phenylxylylethane, and dihydrosilane. Aromatic hydrocarbons such as stilxylene, vegetable oils such as soybean oil and cottonseed oil.

  In the present invention, when a hydrophobic liquid compound having a boiling point of 100 ° C. or higher is contained in the urethane resin layer, the content is usually about 0.1 to 5% by weight based on the total amount of the coated granular composition of the present invention. As the addition method, for example, the granular material used in the present invention is rolled, a hydrophobic liquid compound having a boiling point of 100 ° C. or higher is added thereto in advance, and the polyisocyanate component and the polyester polyol are then added by the above-described method. A method of forming a urethane resin layer by polymerizing with a polyol component containing s.

The urethane resin has a glass transition temperature of preferably 20 ° C. or lower, more preferably −50 ° C. or higher and 5 ° C. or lower.
In the present invention, the glass transition temperature (Tg) of the urethane resin can be measured by a thermal analysis method such as differential scanning calorimetry (DSC). Since it is difficult to directly measure the glass transition temperature of a urethane resin coated with a bioactive substance, the same polyol component and isocyanate component are used in the same ratio as the urethane resin coated with the bioactive substance. Then, a urethane resin film is prepared, and the glass transition temperature is measured using the film. Depending on the type of urethane resin, when the glass transition temperature cannot be clearly measured by differential scanning calorimetry, the glass transition temperature can be measured by dynamic viscoelasticity measurement using the urethane resin film.
The glass transition temperature can be measured by differential scanning calorimetry using, for example, DSC8230 (manufactured by Rigaku Corporation).

  The thickness of the urethane resin layer used in the present invention is usually from 1 to 1000 μm, preferably from 8 to 400 μm, and usually from 1 to 20% by weight (relative to the coated granular composition of the present invention), preferably from 3 to 16 % By weight.

  In the present invention, a protective layer containing a hydroxy fatty acid having 10 to 24 carbon atoms is used. Specific examples of the hydroxy fatty acid having 10 to 24 carbon atoms include ricinoleic acid, 12-hydroxystearic acid, and 11-hydroxy. Hexadecanoic acid, 16-hydroxyhexadecanoic acid, 16-hydroxyhexadecenoic acid, 2-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 22-hydroxydocosanoic acid, 2-hydroxytetracosanoic acid, dihydroxymyristic acid, dihydroxypalmitic acid, dihydroxy Examples include stearic acid, dihydroxyarachidic acid, and trihydroxypalmitic acid, and preferably 12-hydroxystearic acid.

The protective layer is formed on the outside of the granular material in which the urethane resin layer is formed.
As a method for forming the protective layer, for example, a method in which a hydroxy fatty acid having 10 to 24 carbon atoms is heated to a temperature equal to or higher than the melting point and adhered to the outside of the urethane resin layer is used. It can also be done.
In addition, in order to form a more uniform protective layer, the one in which the urethane resin layer is formed on the outside of the particulate material is charged into a rotating tank, and the hydroxy fatty acid having 10 to 24 carbon atoms heated to the melting point or more while being in a rolling state is liquid. It can carry out by putting in a rotation tank in a state.

  The protective layer used in the present invention is usually 0.1 to 10% by weight (relative to the coated granular composition of the present invention), preferably 2 to 10% by weight.

The coated granular composition of the present invention thus produced can be applied to fields, paddy fields, etc. by using it in a form of application such as nursery box application or side stripe application, as in the case of normal agricultural chemical granular composition and granular fertilizer composition. Although applied, it is also possible to use a power spreader via a spray nozzle provided with a plurality of nozzle holes in the longitudinal direction connected to the power spreader and a collision plate arranged corresponding to the nozzle holes. All power application modes can also be applied.
In addition, the coated granular composition of the present invention has a bioactive substance elution characteristic as compared with the case where it is used in other application forms such as nursery box application and side stripe application even in the case of the above-mentioned power spraying. Since it does not change substantially, it can be applied to various application forms while maintaining the dissolution characteristics of the coated granular composition of the present invention.

  As shown below, the coated granular compositions of Comparative Examples 1 to 12 and Example 1 were produced, and elution characteristics were confirmed. In addition, this invention is not limited only to the Example shown below.

The coated granular composition of Comparative Example 1 was produced as follows.
Polycaprolactone diol having an average molecular weight of 1200 [manufactured by Daicel Chemical Industries, Ltd., trade name: Placcel 212] 1859.0 g heated and melted at 70 ° C. and heated to 70 ° C. [Toyoku Oil Co., Ltd., product Name: Industrial No. 1 castor oil] 1308.5 g and 1,4-butanediol [BASF Idemitsu Co., Ltd., trade name: 1,4-BDO] 279.5 g were mixed to obtain a polyol mixture. 50000 g of granular urea (large urea, particle size of about 3 mm, about 60 particles per gram) is charged in a rotating tank, brought into a rolling state, the granular urea is heated to about 66 ° C. with hot air, and then liquid paraffin [ Made by Matsumura Oil Research Co., Ltd., trade name: Moresco White P-260, kinematic viscosity: 56.0 mm ² / S] 500 g was added, and the rolling state was continued for 10 minutes. Next, 689.4 g of the aforementioned polyol mixture heated to 70 ° C. and 310.7 g of aromatic diisocyanate [manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Sumidur44S] heated to 70 ° C. were rapidly stirred and mixed. Cured urethane was added and the rolling state was maintained under heating conditions for 8 minutes or longer. Further, the addition of the uncured urethane resin and the maintenance of the rolling state under heating conditions were repeated until the total amount of the uncured urethane resin added reached 5000.5 g. Then, it cooled to room temperature vicinity and manufactured the coated granular composition of the comparative example 1.
In addition, the coating layer of the coating granular composition of the comparative example 1 is only a urethane resin layer, and the protective layer is not formed.

The coated granular composition of Comparative Example 2 was produced as follows.
11100.0 g of the coated granular composition of Comparative Example 1 was charged into a rotating tank and brought into a rolling state, and the coated granular composition was heated to about 70 ° C. with hot air and then melted at 80 ° C. [molecular weight of about 20000 , Melting point: about 56 ° C.] 200.0 g was added, and the rolling state was maintained under heating conditions for 5 minutes or more. Then, it cooled to near room temperature, and manufactured the coated granular composition of the comparative example 2.

The coated granular composition of Comparative Example 3 was produced as follows.
777.0 g of the coated granular composition of Comparative Example 1 was charged into a rotating tank, brought into a rolling state, the coated granular composition was heated to about 70 ° C. with hot air, and then melted at 80 ° C. 14.0 g of glycol [melting point: about 55 ° C.] was added, and the rolling state was maintained under heating conditions for 5 minutes or more. Then, it cooled to near room temperature, and manufactured the coated granular composition of the comparative example 3.

The coated granular composition of Comparative Example 4 was produced as follows.
A coated granular composition of Comparative Example 4 was produced in the same manner as in Comparative Example 3 except that polyoxyethylene polyoxypropylene glycol was changed to a tristyrenated phenol ethylene oxide adduct [melting point: about 38 ° C.].

The coated granular composition of Comparative Example 5 was produced as follows.
A coated granular composition of Comparative Example 5 was produced in the same manner as Comparative Example 3 except that polyoxyethylene polyoxypropylene glycol was changed to an ethylene vinyl acetate copolymer-containing paraffin wax [melting point: about 63 ° C.].

The coated granular composition of Comparative Example 6 was produced as follows.
777.0 g of the coated granular composition of Comparative Example 1 was charged into a rotating tank and brought into a rolling state, and the coated granular composition was heated to about 70 ° C. with hot air and then melted at 80 ° C. [melting point: About 70 ° C.] 28.0 g was added, and the rolling state was maintained under heating conditions for 5 minutes or more. Then, it cooled to room temperature vicinity and manufactured the covering granular composition of the comparative example 6.

The coated granular composition of Comparative Example 7 was produced as follows.
A coated granular composition of Comparative Example 7 was produced in the same manner as Comparative Example 3, except that polyoxyethylene polyoxypropylene glycol was changed to palmitic acid [melting point: about 63 ° C.].

The coated granular composition of Comparative Example 8 was produced as follows.
A coated granular composition of Comparative Example 8 was produced in the same manner as in Comparative Example 3, except that the polyoxyethylene polyoxypropylene glycol was changed to stearic acid [melting point: about 57.5 ° C.].

The coated granular composition of Comparative Example 9 was produced as follows.
A coated granular composition of Comparative Example 9 was produced in the same manner as in Comparative Example 3, except that polyoxyethylene polyoxypropylene glycol was changed to beef tallow [melting point: about 54 ° C.].

The coated granular composition of Comparative Example 10 was produced as follows.
A coated granular composition of Comparative Example 10 was produced in the same manner as in Comparative Example 3, except that polyoxyethylene polyoxypropylene glycol was changed to stearyl-2-hydroxystearate [melting point: about 70 ° C.].

The coated granular composition of Comparative Example 11 was produced as follows.
A coated granular composition of Comparative Example 5 was produced in the same manner as in Comparative Example 3, except that polyoxyethylene polyoxypropylene glycol was changed to propylene glycol mono-2-hydroxystearate [melting point: about 50 ° C.].

The coated granular composition of Comparative Example 12 was produced as follows.
A coated granular composition of Comparative Example 12 was produced in the same manner as in Comparative Example 3, except that polyoxyethylene polyoxypropylene glycol was changed to ethylene glycol-mono-2-hydroxystearate [melting point: about 65 ° C.].

The coated granular composition of Example 1 was produced as follows.
1650.0 g of the coated granular composition of Comparative Example 1 was charged into a rotating tank, brought into a rolling state, the coated granular composition was heated to 70 ° C. with hot air, and then melted at 100 ° C. 12-hydroxystearic acid [Ito Oil Manufacturing Co., Ltd., trade name: 12-hydroxystearic acid, melting point: about 78 ° C.] 135.0 g was added, and the rolling state was maintained under heating conditions for 5 minutes or more. Then, it cooled to near room temperature, and manufactured the coated granular composition of Example 1.

The urethane resin of the urethane resin layer of the coated granular composition of Example 1 is a polymer obtained by polymerizing a polyisocyanate component composed of an aromatic diisocyanate and a polyol component composed of polycaprolactone diol, castor oil and 1,4-butanediol. is there.
The polyester polyol in the polyol component of this urethane resin is polycaprolactone diol and castor oil, and the partial structure of oxycarbonyl [—O—C (═O) —] is a molecule with respect to the total amount of these polyester polyols. It has 28% (weight conversion).
The weight ratio of the polyisocyanate component to the polyol component in Example 1 is approximately 31:69.
The molar ratio of the isocyanate group of the polyisocyanate component and the hydroxyl group of the polyol component in Example 1 is 1.00: 1.04.
The hydroxyl group equivalent of the polyester polyol in Example 1 is 464. The hydroxyl equivalent was calculated from the hydroxyl equivalent (623.3) of the polycaprolactone diol used and the hydroxyl equivalent (351) of castor oil.
The average molecular weight of the polyester polyol in Example 1 is about 1134.6. The average molecular weight was calculated from the molecular weight (1200) of the polycaprolactone diol used and the molecular weight (1050) of castor oil.
In the polyol component in Example 1, 1,4-butanediol, which is a polymethylene glycol having 2 to 8 carbon atoms, is used, and 2 to 2 carbon atoms with respect to the total amount of the polyisocyanate component and the polyol component. The content of 8 polymethylene glycol is 5.6% by weight.
Content of the polyester polyol of Example 1 is 63.4 weight% with respect to the total amount of a polyisocyanate component and a polyol component. The breakdown is 37.2% for polycaprolactone diol and about 5.6% for castor oil.
The polyisocyanate component of Example 1 is only aromatic polyisocyanate, and its content is 100% by weight.
The content of the polyisocyanate component (aromatic polyisocyanate) in Example 1 is 31.1% by weight based on the total amount of the polyisocyanate component and the polyol component.
The content of 12-hydroxystearic acid in Example 1 is 7.6% by weight based on the total amount of the coated granular composition.
The glass transition temperature of the urethane resin of Example 1 is about −24 ° C.
The boiling point of the hydrophobic liquid compound (liquid paraffin) used in Example 1 is 350 ° C. or higher.

  Table 1 shows the contents of the coated granular compositions of Comparative Examples 1 to 12 and Example 1 produced as described above.

Test Example 1 (Confirmation of dissolution profile before power application)
2.5 g (60 to 80 grains) of each of the coated granular compositions of Comparative Examples 1 to 12 and Example 1 were placed in a sample bottle, added with 100 g of water, and allowed to stand at 25 ° C. After a predetermined time, 0.6 ml of water in the sample bottle was taken and the urea concentration was measured. The elution rate of urea was calculated from the measured urea concentration, and the elution profile was confirmed.

Test Example 2 (Confirmation of dissolution profile after power application)
200 g each of the coated granular compositions of Comparative Examples 1 to 12 and Example 1 in a sample bottle are placed in a vinyl bag together with 600 g of granulated fertilizer [manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumitomo Suzuran Stamped Chemicals No. 600] and mixed. did. The obtained mixture was sprayed by a power spreader [manufactured by Yanmar Co., Ltd., V-P3] equipped with a jetty for shores, and the sprayed samples in Table 1 were collected. 2.5 g (60 to 80 grains) of the samples shown in Table 1 were placed in the collected sample bottles, 100 ml of water was added, and the mixture was allowed to stand at 25 ° C. After a predetermined time, 0.6 ml of water in the sample bottle was taken and the urea concentration was measured. The elution rate of urea was calculated from the measured urea concentration, and the elution profile was confirmed.

In Test Example 1 above, the elution period when the elution rate of urea was 80% was measured, and the rate of change of the elution profile was determined by the following equation by comparison with the elution period in the coated granular composition of Comparative Example 1. Judgment was made according to the following criteria based on the rate of change.
In Test Example 2, the coated granular composition of Comparative Example 1 was measured in Comparative Example 1 by measuring the elution period in which the elution rate of urea was 80% in the test coated granular composition recovered after power spraying. The change rate of the elution profile was determined by comparison with the elution period in, and the determination was made from the change rate according to the following criteria.

Rate of change (%) = (D _S / D _b ) × 100


D _S : Time to 80% elution with the test coated granular composition D _b : Time to 80% elution with the coated granular composition of Comparative Example 1

[Criteria]
−: Change rate is over 95% and less than 105% +: Change rate is over 80% and 95% or less, or 105% or more and less than 120% ++: Change rate is 80% or less or 120% or more

  The test results are shown in Table 2.

Claims (11)

A coated granular composition in which a coating layer is provided on the surface of a granular material containing an active ingredient of agricultural chemical or an active ingredient of fertilizer ,
The coating layer is
A urethane resin layer containing a urethane resin obtained by polymerizing a polyisocyanate component and a polyol component containing a polyester polyol;
A coated granular composition comprising: a protective layer containing a hydroxy fatty acid having 10 to 24 carbon atoms provided on the outside of the urethane resin layer.   The coated granular composition according to claim 1, wherein the polyester polyol has in its molecule an oxycarbonyl partial structure in a proportion of 15% or more (weight conversion) with respect to the total amount of the polyester polyol.   The coated granular composition according to claim 1 or 2, wherein the polyisocyanate component contains an aromatic polyisocyanate. The coated granular composition according to any one of claims 1 to 3 , wherein at least one of the polyester polyols is a polycaprolactone polyol. The coated granular composition according to claim 4 , wherein the polycaprolactone polyol is polycaprolactone diol or polycaprolactone triol. The coated granular composition according to any one of claims 1 to 5 , wherein the total amount of the polyisocyanate component is an aromatic polyisocyanate compound in which all isocyanate groups are directly bonded to the benzene ring. The coated granular composition according to claim 6 , wherein the aromatic polyisocyanate is diphenylmethane diisocyanate. The coated granular composition according to any one of claims 1 to 7 , wherein a content ratio of the hydroxy fatty acid having 10 to 24 carbon atoms to the coated granular composition is 0.1 to 10% by weight. The coated granular composition according to any one of claims 1 to 8 , wherein the hydroxy fatty acid having 10 to 24 carbon atoms is 12-hydroxystearic acid. The coated granular composition according to any one of claims 1 to 9 , wherein the particulate substance containing an active ingredient of agricultural chemical or an active ingredient of fertilizer is granular urea. A plurality of nozzle holes in the longitudinal direction and collision plates arranged corresponding to the nozzle holes are sent out using a power spreader connected to a tubular spraying nozzle provided in the pipe. The method for applying a coated granular composition according to any one of claims 1 to 10 , further comprising a step of causing the impact plate to collide and dropping the impact plate to a paddy field or a field.