JP2000086404A - Agrochemical granular agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an agrochemical granular agent capable of efficiently controlling the release of the agrochemical active ingredient. SOLUTION: This agrochemical granular agent consists of granules each composed of inner nucleus and coating layer; wherein the inner nucleus comprises (a) an agrochemical active ingredient, (b) a fine powdery solid support, (c) a binder, and (d) a water-soluble matter solid at normal temperatures with a molecular weight of 50-700 which is dispersed in the inner nucleus.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a pesticide granule.

[0002]

2. Description of the Related Art
The dissolution of the pesticide is carried out by supporting the pesticide on the granular carrier with a binder (Japanese Patent Application Laid-Open No. 58-205536) or coating with a resin (Japanese Patent Publication No. 60-44967, Japanese Patent Application No. 64-4484, etc.). Pesticide granules that are controlled and have increased potency are known. However, in many cases, relatively large amounts of binders and resins are required in order to impart this effect, and it is desired to develop formulations that can achieve more efficient sustained release of pesticides. Was rare.

[0003]

Means for Solving the Problems As a result of repeated studies on pesticide granules, the present inventors have found that the pesticidal active ingredient, a finely divided solid carrier, a binder and a specific water-soluble substance, The present inventors have found that a pesticidal granule composed of particles having an inner core in which is dispersed and coated with a coating layer can control the dissolution of an active pesticide component extremely efficiently, and have reached the present invention. That is, the present invention is an agricultural chemical granule comprising particles composed of an inner core and a coating layer, wherein the inner core is (a) an agricultural chemical active ingredient, (b) a fine powder solid carrier, (c) a binder and ( d) molecular weight of 50 to 70
0, which contains a water-soluble substance which is solid at room temperature and wherein the water-soluble substance is dispersed in the inner core (hereinafter referred to as the present granule). It is.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION The granules of the present invention comprise particles whose inner core is covered with a coating layer. The inner core in the present invention is a granular structure containing an agricultural chemical active ingredient, and the coating layer is a film-like structure three-dimensionally surrounding the inner core. That is, the granule of the present invention is a granule containing particles composed of the inner core and the coating layer defined in the present invention, and may be composed of only the particles, or attain the object of the present invention. In the range, other agents depending on the use as appropriate, such as other pesticide granules,
It may contain granular agricultural materials such as granular fertilizer, granular soil, granular plant nutrient, granular plant preparation control agent, granular hormonal agent, seeds and the like. Note that, unless otherwise specified, in the present specification, the inner core, the coating layer, the pesticidal active ingredient, a fine powder solid carrier, a binder, a water-soluble substance, a film-forming substance, a surfactant, a solvent, a stabilizer, a coloring agent. When the content of the agent, flavor, etc. is described, "the content of ... in the granule of the present invention" or "the content of ... in the granule of the present invention" means the inner core and coating defined in the present invention. It means the value expressed as the average of the content in the particles based on the average of the particles comprising the layer.

[0005] The content of the inner core in the granules of the present invention is usually 50
-99.9% by weight, preferably 85-99.8% by weight. The inner core is a granular material containing an agrochemical active ingredient, a finely divided solid carrier, a binder, and a water-soluble substance specified in the present invention, and may have a uniform structure as a whole. The components may be unevenly distributed, for example, have a multilayer structure. However, the water-soluble substance specified in the present invention is dispersed in the inner core. Here, “dispersed in the inner core” means that the water-soluble substance is at least one of other components.
It refers to a state of being dispersed in a matrix composed of seeds, and preferable forms of dispersion include a form dispersed throughout the inner core and a form dispersed in the outermost layer in the case of a multilayer structure.

[0006] Examples of the pesticidal active ingredient in the present invention include the following compounds. Fenitrothion [O, O-dimethyl O- (3-methyl-4-nitrophenyl) phosphorothioate], phenthione [O, O-dimethyl O- (3-methyl-4- (methylthio) phenyl) phosphorothioate], diazinon [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 -Dimethylacetyl phosphoramidothioate], methidathion [S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazole-3-
Ylmethyl O, O-dimethyl phosphorodithioate],
Disulfoton [O, O-diethyl S-2-ethylthioethyl phosphorodithioate], DDVP [2,2-dichlorovinyldimethyl phosphate], sulfophos [O
-Ethyl O-4- (methylthio) phenyl S-propyl phosphorodithioate], cyanophos [O-4-cyanophenyl O, O-dimethyl phosphorothioate], dioxabenzophos [2-methoxy-4H-1,3,3. 2-benzodioxaphosphorin-2-sulfide], dimethoate [O, O-dimethyl-S- (N-methylcarbamoylmethyl) dithiophosphate], fentoate [ethyl 2-dimethoxyphosphinothioylthio (phenyl) acetate] , Malathion [diethyl (dimethoxyphosphinothioylthio) succinate], trichlorfon [dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate], azinephosphmethyl [S-3,
4-dihydro-4-oxo-1,2,3-benzotriazin-3-ylmethyl O, O-dimethylphosphorodithioate], monocrotophos [dimethyl-{(E) -1-)
Methyl-2- (methylcarbamoyl) vinyl) phosphate], ethion [O, O, O ', O'-tetraethyl-S, S'-methylenebis (phosphorodithioate)]
Organic phosphorus compounds such as

[0007] BPMC [2-sec-butylphenylmethylcarbamate], benfracarb [ethyl N- {2,
3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio} -N-isopropyl-β-alaninate, propoxur [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], ethiophenecarb [2- (ethylthiomethyl) phenylmethylcarbamate], aldicarb [2
-Methyl-2- (methylthio) propionaldehyde
O-methylcarbamoyl oxime], oxamyl [N,
N-dimethyl-2-methylcarbamoyloxyimino-
Carbamate compounds such as 2- (methylthio) acetamide] and phenothiocarb [S-4-phenoxybutyl-N, N-dimethylthiocarbamate];

[0008] 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], fenpropatrin [(R
S) -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], permethrin [3-phenoxybenzyl (1RS) -cis, trans-3-
(2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], cyhalothrin [(RS)
-Α-cyano-3-phenoxybenzyl (1RS, 3
Z) -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], cycloprothrin [(RS) -α-cyano-3- Phenoxybenzyl
(RS) -2,2-dichloro-1- (4-ethoxyphenyl) cyclopropanecarboxylate], fluvalinate [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 (1
R) -cis-3- (1,2,2,2-tetrabromoethyl) -2,2-dimethylcyclopropanecarboxylate], silafluofen [(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], cyphenothrin [(R
S) -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], acrinasulin [(S) -α-cyano-3-phenoxybenzyl (1R, 3Z) -cis-
(2,2-dimethyl-3- {3-oxo-3- (1,
1,1,3,3,3-hexafluoropropyloxy)
Propenyl @ cyclopropanecarboxylate], cyfluthrin [(RS) -α-cyano-4-fluoro-3-
Phenoxybenzyl 3- (2,2-dichlorovinyl)
-2,2-dimethylcyclopropanecarboxylate], 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-dimethylcyclopropanecarboxylate], tetramethrin [3,4,5,6
-Tetrahydrophthalimidomethyl (1RS) -cis, trans-2,2-dimethyl-3- (2-methyl-
1-propenyl) cyclopropanecarboxylate],
Allethrin [(RS) -2-methyl-4-oxo-3-
(2-propenyl) -2-cyclopenten-1-yl
(1RS) -cis, trans-2,2-dimethyl-3-
(2-methyl-1-propenyl) cyclopropanecarboxylate], prarethrin [(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) cyclopropanecarboxylate], imiprosulin [2,5-dioxo-3- (2-
Propynyl) imidazolidin-1-ylmethyl (1
R) -cis, trans-2,2-dimethyl-3- (2-
Methyl-1-propenyl) cyclopropanecarboxylate], d-framethrin [5- (2-propynyl) furfuryl (1R) -cis, trans-2,2-dimethyl-3- (2-methyl-1-pro Pyrenyloid compounds such as [(nyl) cyclopropanecarboxylate] and 5- (2-propynyl) furfuryl 2,2,3,3-tetramethylcyclopropanecarboxylate;

[0009] 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
-Trithiane-5-ylamine], neristoxin derivatives such as bensultap [S, S'-2-dimethylaminotrimethylenedi (benzenethiosulfonate)], N-cyano-N'-methyl-N '-( 6-chloro-
N-cyanoamidine derivatives such as 3-pyridylmethyl) acetamidine, endosulfan [6,7,8,9,1
0,10-hexachloro-1,5,5a, 6,9,9a
-Hexahydro-6,9-methano-2,4,3-benzodioxathiepine oxide], γ-BHC [1,2,2
3,4,5,6-hexachlorocyclohexane], dicophor [1,1-bis (4-chlorophenyl) -2,2,
Chlorinated hydrocarbon compounds such as 2-trichloroethanol] and chlorofluazuron [1- {3,5-dichloro-4]
-(3-chloro-5-trifluoromethylpyridine-2
-Yloxy) phenyl} -3- (2,6-difluorobenzoyl) urea], teflubenzuron [1- (3,
5-dichloro-2,4-difluorophenyl) -3-
(2,6-difluorobenzoyl) urea], flufenoxuron [1- {4- (2-chloro-4-trifluoromethylphenoxy) -2-fluorophenyl} -3-
(2,6-difluorobenzoyl) urea] and other benzoylphenylurea-based compounds, amitraz [N, N'-
{(Methylimino) dimethylidine} -di-2,4-xylidine], chlorodimform [N '-(4-chloro-2)
-Methylphenyl) -N, N-dimethylmethinimidamide and the like; diafenthiuron [N- (2,6-diisopropyl-4-phenoxyphenyl) -N'-t-butylcarbodiimide] and the like. Thiourea derivatives, N-phenylpyrazole compounds,

[0010] Methoxadiazone [5-methoxy-3- (2-
Methoxyphenyl) -1,3,4-oxadiazole-
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) cyclohexylprop-2-yl sulfite],
Fenbutatin oxide [bis {tris (2-methyl-2-phenylpropyl) tin} oxide], hexthiazox [(4RS, 5RS) -5- (4-chlorophenyl) -N-chlorohexyl-4-methyl-2-methyl-2-oxide] Oxo-1,3-thiazolidine-3-carboxamide], clofentezine [3,6-bis (2-chlorophenyl)
-1,2,4,5-tetrazine], pyridaben [2-t
tert-butyl-5- (4-tert-butylbenzylthio) -4-chloropyridazin-3 (2H) -one],
Fenpyroximate [tert-butyl (E) -4
-[(1,3-dimethyl-5-phenoxypyrazole-
4-yl) methyleneaminooxymethyl] benzoate], debufenpyrado [N-4-tert-butylbenzyl) -4-chloro-3-ethyl-1-methyl-5-
Pyrazolecarboxamide], polynactin complex [tetranactin, dinactin, trinactin],
Pyrimidifen [5-chloro-N- [2- {4- (2-
Ethoxyethyl) -2,3-dimethylphenoxydiethyl] -6-ethylpyrimidin-4-amine], milbemectin, abamectin, ivamectin, azadirachtin [AZAD], 5-methyl [1,2,4] triazolo [3,4] -B] benzothiazole, methyl 1- (butylcarbamoyl) 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) -1- (4-chlorophenyl) -4,4-
Dimethyl-2- (1H-1,2,4-triazole-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- (1
H-1,2,4-triazol-1-yl) pentane-
3-ol, 4- [3- (4-tert-butylphenyl)
-2-methylpropyl] -2,6-dimethylmorpholine, 2- (2,4-dichlorophenyl) -1- (1H-
1,2,4-triazol-1-yl) hexane-2-
All, 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]
Benzenesulfonamide, 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
-Chloroethoxy) -N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) aminocarbonyl] benzenesulfonamide, 2-methoxycarbonyl-N-[(4,6-dimethoxy Pyrimidin-2-yl) aminocarbonyl] phenylmethanesulfonamide, 2-methoxycarbonyl-N-[(4-methoxy-
6-methyl-1,3,5-triazin-2-yl) aminocarbonyl] thiophen-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-oxoimidazolin-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-dimethylbutylamide, 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-thiazol-carboxamide, 2,2-dichloro-N- [1- (4-chlorophenyl) ethyl] -3
-Methylcyclopropanecarboxamide, methyl (E) -2-6- (2-cyanophenoxy) pyrimidin-4-yloxy-phenyl-3-methoxyacrylate, 5-methyl-1,2,4-triazolo [ 3,4
-B] benzothiazole, 3-allyloxy-1,2-
Benzoisothiazole-1,1-dioxide, diisopropyl = 1,3-dithiolan-2-ylidene-malonate, O, O-dipropyl-O-4-methylthiophenyl phosphate and the like.

[0011] The pesticidal active ingredient may be contained alone or in combination of two or more in the particles composed of the inner core and the coating layer defined in the present invention. The content of the pesticidal active ingredient in the granules of the present invention is usually 0.1 to 90% by weight, preferably 0.2 to 70% by weight. The pesticidal active ingredient may be dispersed throughout the inner core, or may be located inside the inner core or on the inner core surface.

[0012] Examples of the finely divided solid carrier in the present invention include a mineral carrier, a vegetable carrier, and a synthetic carrier. As the mineral carrier, for example, kaolinite, dickanite, nacrite, kaolin minerals such as halosite, chrysotile, lizatite, antichorite, serpentine such as amesite, sodium montmorillonite, calcium montmorillonite, montmorillonite minerals such as magnesium montmorillonite, Smectites such as saponite, hectorite, sauconite, and hyderite;
Pyrophyllite, talc, roxite, muscovite, fengite, mica such as sericite and illite, silica such as cristobalite and quartz, hydrous magnesium silicate such as attapulgite and sepiolite, calcium carbonate such as dolomite and calcium carbonate fine powder, gypsum , Gypsum and other sulfate minerals, zeolite, zeolite, tuff, vermiculite, laponite, pumice, diatomaceous earth, acid clay, activated clay and the like.

[0013] Examples of the vegetable carrier include cellulose, chaff, wheat flour, wood flour, starch, bran, bran, soy flour and the like. As the synthetic carrier, for example, wet-process silica, dry-process silica, calcined product of wet-process silica, surface-modified silica,
Processed starch (Pine flow manufactured by Matsutani Chemical Co., Ltd.) and the like.

[0014] These fine powder solid carriers are usually contained in the granules of the present invention in an amount of 0.5 to 99.9% by weight, preferably 25 to 99.5% by weight. In the present invention, among these fine powder solid carriers, those having a low oil absorbing ability, specifically, a fine powder solid carrier having an oil absorbing capacity of 50 or less are preferably used, and a fine powder solid carrier of 30 or less is more preferably used. Used. Such a suitable finely divided solid carrier is, for example, kaolin (oil absorption capacity 3).
2 to 45), talc (oil absorption capacity 30 to 50), calcium carbonate (oil absorption capacity 16 to 30), and the like. Among them, calcium carbonate is particularly preferable. The oil absorption capacity of the finely divided solid carrier can be measured by the method described in JIS K-5101.

The average particle size of the finely divided solid carrier is usually 100 μm.
m or less, and a fine powder solid carrier having an average particle diameter of 2 to 30 μm is preferable in terms of low oil absorbing ability. Further, when the inner core is manufactured by the extrusion granulation method, it is preferable to use a montmorillonite mineral as the fine powder solid carrier because breakage of the extrusion net at the time of granulation can be reduced, and the montmorillonite mineral and other fine powder solid carriers are preferably used. More preferably, they are used in combination. When the montmorillonite mineral is used in combination with another finely divided solid carrier, the content of the montmorillonite mineral is:
Usually, it is 2.5 to 30% by weight, preferably 5 to 20% by weight, and the total amount of the fine powdery solid carrier is usually 0.5 to 99.
It is 9% by weight, preferably 25 to 99.5% by weight.

Examples of the binder in the present invention include synthetic polymers such as acrylic polymers, vinyl polymers, and polyoxyalkylenes, semi-synthetic polymers such as cellulose derivatives, processed starch, and lignin derivatives; And the like. Examples of the acrylic polymer include sodium polyacrylate and sodium polymethacrylate, and examples of the vinyl polymer include polyvinyl alcohol, polyvinyl pyrrolidone, and vinyl acetate copolymer.
Examples of the polyoxyalkylene include polyoxyethylene and polyoxypropylene.

Examples of the cellulose derivative include sodium carboxymethylcellulose, dextrin, hydroxypropylmethylcellulose, methylcellulose, methylethylcellulose, and hydroxypropylcellulose, and modified starches include modified starch, carboxymethyl starch, and soluble starch. Examples of the lignin derivative include sodium lignin sulfonate. Examples of the natural polymer include polysaccharides such as gum arabic, xanthan gum, tragacanth, guar gum, carrageenan, alginic acid, sodium alginate, and proteins such as casein, casein lime, gelatin, and collagen.

[0018] The content of the binder in the granules of the present invention is usually 0.1 to
It is 10% by weight, preferably 0.5 to 5% by weight. In the granules of the present invention, among these binders, polyvinyl alcohol, sodium carboxymethylcellulose and sodium ligninsulfonate are particularly preferably used. Although the molecular weight of the binder is not particularly limited, it is usually 5,000 to 300,000, preferably 1,000.
0 to 50,000. Also, as a binder, 20 ° C.
It is preferable that the viscosity of the 4% aqueous solution is 3 to 30 centipoise.

The water-soluble substance of the present invention has a molecular weight of 50 to 50.
700 and a water-soluble substance that is solid at room temperature (hereinafter, referred to as the present water-soluble substance), and usually does not have surface activity. Examples of the water-soluble substance include saccharides such as monosaccharides and oligosaccharides, urea, amino acids, oligopeptides, solid organic acids, water-soluble organic substances such as organic acid salts, and water-soluble inorganic substances such as solid inorganic salts. Can be

Examples of the monosaccharide include trisaccharides such as glyceraldehyde and dioxyacetone, tetracarbons such as threose and erythrulose, pentoses such as ribose, lyxose and xylulose, glucose, mannose, galactose and fructose. Examples thereof include hexoses such as sorbose and tagatose; heptose such as mannoheptose and sedoheptose; and derived monosaccharides such as sorbitol, mannitol, and glucuronic acid. As oligosaccharides, cellobiose,
Examples include disaccharides such as trehalose, lactose, and sucrose, trisaccharides such as maltotriose, and tetrasaccharides such as maltotetraose.

Examples of solid organic acids include cinnamic acid, crotonic acid, glycolic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid, terephthalic acid and the like. And organic acid salts include magnesium, calcium, sodium, potassium, lithium, iron, copper, zinc, nickel, aluminum, etc., formate, formate, propionate, butyrate, valerate, caproate. Acrylate, crotonate, cinnamate, glycolate, lactate, pyruvate, benzoate, oxalate, malonate, succinate, glutarate, adipate, pimelic acid Salt, maleate,
Fumarate, terephthalate, sulfonate and the like. Examples of the amino acid include glycine, alanine, valine, leucine, isoleucine, phenylalanine, tyrosine, serine, threonine, cystine, methionine, aspartic acid, asparagine, glutamine, glutamic acid, lysine, arginine, histidine, tryptophan, proline and the like.

[0022] Solid inorganic salts include magnesium, calcium, sodium, potassium, lithium, iron, copper, zinc,
Nickel, aluminum, ammonium chlorides, fluorides, bromides, iodides, sulfates, nitrates, phosphates, etc.
Borate, carbonate, aluminate, silicate and the like. The content of the water-soluble substance is usually 4 to 5 in the granules of the present invention.
0% by weight, preferably 8 to 30% by weight.

In the present invention, among the present water-soluble substances, those having a water solubility at 20 ° C. of 10% or more are preferable, and those having a water solubility of 20% or more are more preferable. Water solubility 2
Specific examples of the water-soluble substance of 0% or more include sugars such as sucrose, glucose, and dextrin, urea, calcium chloride, sodium hydrogen phosphate, sodium acetate, sodium nitrate, potassium carbonate, potassium pyrophosphate, magnesium nitrate, and nitric acid. Examples thereof include metal salts such as calcium and calcium chloride, and organic acids such as citric acid. Among them, saccharides, urea and metal salts are preferable, and urea and saccharides are more preferable. Further, when the granules of the present invention are produced by an extrusion granulation method, it is particularly preferable in terms of manufacturability to use the present water-soluble substance having good compatibility with a binder. Whether compatibility is good or bad
The determination can be made based on whether precipitation or aggregation of the binder occurs when the present water-soluble substance is added to the aqueous solution of the binder. As an example, as a preferred present water-soluble substance when polyvinyl alcohol is used as a binder,
Magnesium nitrate, calcium nitrate, calcium chloride,
Examples include urea, citric acid, and sucrose.

The core of the granules of the present invention contains an active ingredient of agrochemicals, a finely divided solid carrier, a binder, and a water-soluble substance. If necessary, a surfactant, a solvent, a stabilizer, It may contain coloring agents, fragrances and the like.

Examples of usable surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene lanolin alcohol, polyoxyethylene alkylphenol formalin condensate, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Ethylene glyceryl mono fatty acid ester, polyoxypropylene glycol mono fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene castor oil derivative, polyoxyethylene fatty acid ester, higher fatty acid glycerin ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxy Ethylene polyoxypropylene block polymer, polyoxyethylene fatty acid amide, alkylolamide, polyoxy Nonionic surfactants such as ethylene alkylamine; alkylamine hydrochloride such as dodecylamine hydrochloride; dodecyltrimethylammonium salt;
Cationic surfactants such as alkyl quaternary ammonium salts such as alkyldimethylbenzylammonium salts, alkylpyridinium salts, alkylisoquinolinium salts, dialkylmorpholinium salts, benzethonium chloride, and polyalkylvinylpyridinium salts; sodium palmitate, etc. Sodium fatty acid, sodium ether carboxylate such as sodium polyoxyethylene lauryl ether carboxylate, sodium lauroyl sarcosine,
Amino acid condensates of higher fatty acids such as sodium N-lauroylglutamate; higher fatty acid ester sulfonates such as higher alkyl sulfonates and lauric ester sulfonates; dialkyl sulfosuccinates such as dioctyl sulfosuccinate; Higher fatty acid amide sulfonates such as acids, sodium dodecylbenzenesulfonate, alkylaryl sulfonates such as diisopropylnaphthalene sulfonate, formalin condensates of alkylaryl sulfonates, higher alcohol sulfates such as pentadecane-2-sulfate Polyoxyethylene alkyl phosphates such as dipolyoxyethylene dodecyl ether phosphate; anionic surfactants such as styrene-maleic acid copolymer; Uriruaranin, N, N, N- trimethyl-aminopropionic acid, N, N, N- tri-hydroxyethyl amino propionic acid, N- Hekishiru N, N-
Examples include amphoteric surfactants such as dimethylaminoacetic acid, 1- (2-carboxyethyl) pyrimidinium betaine, and lecithin. The content of the surfactant in the granules of the present invention,
It is usually 0.1 to 40% by weight, preferably 0.1 to 10% by weight.

Examples of the solvent that can be used in the present invention include unsaturated aliphatic hydrocarbons such as hexane, decane, tridecane, hexadecane and octadecane, unsaturated hydrocarbons such as 1-undecene and 1-heneicosene, and Celeclor S45 (ICI (Manufactured and trade names), ketones such as methyl ethyl ketone and cyclohexanone, alcohols such as ethanol, butanol, octanol, ethyl acetate, dimethyl phthalate, methyl laurate, ethyl palmitate, octyl acetate,
Esters such as dioctyl succinate and didecyl adipate; alkyls such as xylene, ethylbenzene, octadecylbenzene, Solvesso 100 (trade name, manufactured by Exxon Chemical), dodecylnaphthalene, tridecylnaphthalene, and alkyl such as Solvesso 200 (trade name, manufactured by Exxon Chemical) Glycols such as naphthalenes, ethylene glycol and diethylene glycol, glycol ethers such as propylene glycol monomethyl ether and ethylene glycol monoethyl ether, fatty acids such as oleic acid, capric acid, and enanthic acid; N, N-dimethylformamide; Acid amides such as N-diethylformamide,
Olive oil, soybean oil, rapeseed oil, castor oil, linseed oil, cottonseed oil, palm oil, avocado oil, animal and vegetable oils such as shark liver oil, mineral oils such as machine oil, glycerin, and glycerin derivatives such as glycerin fatty acid ester.
The content of the solvent in the granules of the present invention is usually 30% by weight or less, preferably 0.1 to 20% by weight.

The stabilizer which can be used in the present invention includes:
For example, phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, ultraviolet absorbers, epoxidized vegetable oils such as epoxidized soybean oil, epoxidized linseed oil, epoxidized rapeseed oil, and isopropyl Acid phosphate, liquid paraffin, ethylene glycol and the like. The content of the stabilizer in the granules of the present invention,
It is usually 0.01 to 10% by weight, preferably 0.01 to 5% by weight.

Examples of the coloring agent that can be used in the present invention include rhodamines such as rhodamine B and solar rhodamine, and dyes such as yellow No. 4, blue No. 1, and red No. 2. , Ethyl acetoacetate,
Ester flavors such as ethyl enanthate, ethyl cinnamate and isoamyl acetate; organic acid flavors such as caproic acid and cinnamic acid; alcohol flavors such as cinnamon alcohol, geraniol, citral, and decyl alcohol; vanillin, piperonal, perillaldehyde, etc. Aldehydes, maltol, ketone-based flavors such as methyl β-naphthyl ketone, and menthol. The content of the coloring agent and the flavor is usually 0.01 to 5% by weight in the granules of the present invention.

[0029] The inner core of the granules of the present invention can be obtained, for example, by granulation by a granulation method usually used in the formulation of agricultural chemicals. Examples of the granulation method include an extrusion granulation method, a compression granulation method, a stirring granulation method, a fluidized bed granulation method, a fluidized bed granulation method, a tumbling granulation method, and a coated granulation method. ,
Among them, the extrusion granulation method is preferable. An example is shown below.

Agrochemical active ingredient, finely divided solid carrier and binder or agrochemically active ingredient, finely divided solid carrier, binder and the present water-soluble substance, if necessary, surfactant, solvent, stabilizer, A mixture is prepared by mixing a coloring agent, a fragrance and the like.
The mixer used at this time includes, for example, a ribbon mixer, a Nauta mixer, a Sugi mixer, a Henschel mixer, a Lady Ge mixer, and the like. next,
Water and / or an aqueous solution of the present water-soluble substance are dropped, sprayed or sprayed on the mixture, and the mixture is kneaded to prepare a kneaded product. Examples of the kneader used at this time include a Nauter mixer, a ribbon mixer, a Henschel mixer, and a kneader. When the aqueous solution of the water-soluble substance is added in the kneading, the concentration of the aqueous solution of the present water-soluble substance varies depending on the water-soluble substance to be used.
It is 5 to 85% by weight, preferably 20 to 70% by weight.
The amount of water used for kneading is usually 5 to 35% by weight, preferably 10 to 25% by weight based on the total weight of the core and the added water and / or aqueous solution of the water-soluble substance.
% By weight. Next, a granulated material is prepared from the kneaded material using a granulator. Examples of the granulator used in this case include, for example, a basket granulator, a screw granulator, an extrusion granulator such as a pelletizer, a compression granulator such as a roller compactor, and a stirring granulator such as a Henschel mixer and a Nauter mixer. Granulator such as a press, a pan granulator, and a fluidized bed granulator. The inner core in the present invention is obtained by subjecting the obtained granules to ordinary drying, sizing, and sieving processes. Examples of the dryer used at this time include a fluidized-bed dryer and a bed-type dryer. Examples of the sizing machine include a marmelizer, a pin mill, a crusher, and the like.
Examples of the sieving machine include a gyro shifter and an electromagnetic vibration type sieving machine. The average particle size of the inner core thus produced is generally about 0.1 to 5 mm, preferably about 0.5 to 3 mm. In addition, the particle diameter in the present invention means the maximum diameter of the inner core.

The content of the coating layer in the granules of the present invention is usually 0.1 to 50% by weight, preferably 0.2 to 15% by weight.
It is. The coating layer is mainly composed of a film-forming substance, and if necessary, contains a finely divided solid carrier, a surfactant, a solvent, a stabilizer, a coloring agent, a fragrance, and the like.

[0032] Examples of the film-forming substance include wax, thermoplastic resin, thermosetting resin, sulfur and the like. Examples of the wax include synthetic waxes such as carbowax, next wax, sucrose ester and fatty acid ester, natural waxes such as carnauba wax, beeswax and wood wax, and petroleum waxes such as paraffin wax and petrolactam.

Examples of the thermoplastic resin include polyolefins such as polyethylene, polypropylene, polybutene, and polystyrene, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polyacrylic acid, polymethacrylic acid, polyacrylate, and polymethacryl. Vinyl polymers such as acid esters, butadiene polymers, isoprene polymers, chloroprene polymers, butadiene-styrene copolymers, ethylene-propylene-diene copolymers, diene-based polymers such as styrene-isoprene copolymers, ethylene -Propylene copolymer, butene-ethylene copolymer, butene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid Ester copolymer, ethi Polyolefin copolymers such as ren-carbon monoxide copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, vinyl chloride copolymers such as vinyl chloride-vinyl acetate copolymer, vinylidene chloride-vinyl chloride copolymer Objects and the like.

[0034] Examples of the thermosetting resin include urethane resin, epoxy resin, alkyd resin, unsaturated polyester resin, phenol resin, urea / melamine resin, urea resin, and silicone resin.

The urethane resin is formed by reacting a polyisocyanate and a polyol in the presence of a curing agent such as an organic metal or an amine. Examples of the curing agent include organic metals such as dibutyltin diacetate, dibutyltin dichloride, dibutyltin dilaurate, dibutylthiostannic acid, stannous octylate, and di-n-octyltin dilaurate;
Triethylenediamine, N-methylmorpholine, N, N
-Dimethyldidodecylamine, N-dodecylmorpholine, N, N-dimethylcyclohexylamine, N-ethylmorpholine, dimethylethanolamine, N, N-dimethylbenzylamine, 1,8-diazabicyclo [5.
4.0] undec-7-ene, isopropyl titanate, tetrabutyl titanate, oxyisopropyl vanadate, n-propyl zirconate, 1,4-diazabicyclo [2.2.2] octane and the like. The polyisocyanate and the polyol which are monomers of the urethane resin are used in the form of a monomer alone, a solution, an aqueous emulsion or an organic solvent emulsion. Examples of the polyisocyanate include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate,
Isophorone diisocyanate, xylylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate and the like. The polyisocyanate may be a mixture of two or more. Further, instead of the polyisocyanate, a modified form of the polyisocyanate or an oligomer of the polyisocyanate can be used. Examples of the modified form include an adduct modified form, a biuret modified form, an isocyanurate modified form, a block modified form, a prepolymer modified form, a dimerized modified form and the like. As the polyol, a condensation polyester polyol, a polyether polyol, a polyacrylic acid polyol, a lactone polyester polyol, a polycarbonate polyol, a natural polyol or the like, or a modified product of the polyol is used.

The condensed polyester polyol is usually obtained by a condensation reaction between a polyol and a dibasic acid, and the polyether polyol is usually obtained by a polymerization reaction of a cyclic oxide. Poly (meth) acrylic acid polyol is usually obtained by a condensation reaction between poly (meth) acrylic acid and polyol, a condensation reaction between (meth) acrylic acid and polyol, or a polymerization reaction of (meth) acrylate monomer. . The lactone-based polyester polyol is usually obtained by ring-opening polymerization of ε-caprolactam using a polyhydric alcohol as an initiator. The polycarbonate polyol is obtained by reacting a polyol with a carbonate such as diphenyl carbonate.The polyol used in this case is usually methylene glycol, ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylenediol, trimethylolpropane, polymethyl Tetramethylene glycol, glycerin, pentaerythritol, sorbitol, sucrose, etc.
Alternatively, these oligomers and the like can be mentioned. Examples of the dibasic acid include adipic acid and phthalic acid. Such polyols are commercially available and include, for example, Sumiphen 3086, Sumiphen 3900, Sumiphen 5200, Sumiphen TS, Sumiphen TM, Sumiphen VN, SBU polyol 0248, SBU polyol 0363, SBU polyol 0474, SBU polyol 480J, SBU polyol 0480, SB
U polyol 0485, SBU polyol 0487,
SBU polyol 0248, SBU polyol 036
3. SBU polyol 0262, Desmophen 550
U, desmophen 900U, desmophen 1600U,
Desmophen 1900U (all are trade names of Sumitomo Bayer Urethane Co., Ltd.) and the like.

The epoxy resin is obtained by reacting phenols or alcohols with epichlorohydrin in the presence of a curing agent,
Reaction of carboxylic acids with epichlorohydrin in the presence of a curing agent, reaction of amines, cyanuric acid or hydantoin with epichlorohydrin in the presence of a curing agent, aliphatic cyclic epoxy compound in the presence of a curing agent such as peracetic acid It is formed by the reaction of Examples of the curing agent include diethylenetriamine, triethylenetetramine, metaxylylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, diaminodiphenylmethane, 1,3
-Bisaminomethylcyclohexane, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, disisisandiamide, organic acid dihydrazide,
Polyamide-modified polyamine, ketone-modified polyamine, epoxy-modified polyamine, thiourea-modified polyamine, Mannich-modified polyamine, Michael addition-modified polyamine,
Dodecenyl succinic anhydride, polyazelaic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, trimetic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid, tetrabromophthalic anhydride, heptic anhydride, Novolak-type polyphenol, polymercaptan, polyisocyanate, carboxylic acid-containing polyester resin, benzyldimethylaniline, 2,4,6-trisdimethylaminomethylphenol, 2-methylimidazole, 2-ethyl,
-Methyl-imidazole, 2-heptadecyl imidazole, aromatic sulfonium salt, aromatic diazonium salt, resole type phenol resin, methylol group-containing urea resin,
Methylol group-containing melamine resins and the like can be mentioned.

As the epoxy resin to be produced, bisphenol A type, bisphenol F type, brominated bisphenol A
Type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AF type, biphenyl type, naphthalene type, fluorin type, phenol novolak type, orthocresol novolak type, DPP novolak type, trishydroxyphenylmethane type, tetraphenylolethane type Glycidyl ether type epoxy resin such as glycidyl ether type epoxy resin, tetraglycidyl diaminodiphenylmethane type, triglycidyl isocyanurate type, hydantoin type, aminophenol type, aniline type, toluidine type etc., glycidylamine type epoxy resin, glycidylamine type epoxy resin, alicyclic epoxy Resins.

The alkyd resin is formed by a reaction between a polybasic acid and a polyhydric alcohol, if necessary, in the presence of a denaturing agent such as a natural vegetable oil or animal fat, a metal soap, and an anti-skinning agent. Examples of the polybasic acid include phthalic anhydride and maleic anhydride, and examples of the polyhydric alcohol include pentaerythol and glycerin. Examples of the denaturing agent include soybean oil, linseed oil, tung oil, safflower oil, coconut oil, palm oil, dehydrated castor oil and the like, and the metal soap is usually manganese, cobalt, zirconium, nickel, Examples include naphthenes such as iron and lead or octylic acids such as zirconium octylate, manganese naphthenate, cobalt octylate, and the like, and mixtures thereof. As the anti-skinning agent, dipentene, methoxyphenol, cyclohexanone oxime, methyl ethyl ketone oxime and the like, or a mixture thereof are usually mentioned.

[0040] The unsaturated polyester resin is produced by reacting an unsaturated dibasic acid and a dihydric alcohol in the presence of a vinyl monomer. Examples of the unsaturated dibasic acid include phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride. Acids, heptonic anhydride, endmethylenetetrahydrophthalic anhydride and the like. Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, Neopentyl glycol, triethylene glycol, hydrogenated bisphenol A, bisphenol dihydroxypropyl ether and the like can be mentioned. Examples of the vinyl monomer include styrene, vinyl toluene, chlorostyrene, diallyl phthalate, triallyl cyanurate, methyl methacrylate and the like.

[0041] The phenol resin is formed by reacting a phenol with an aldehyde in the presence of a catalyst such as hydrochloric acid, oxalic acid, hexamethylenetetramine and the like. Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, xylenol, p-te
rt-butylphenol, resorcinol and the like. In this reaction, a novolak-type phenol resin is obtained under an acidic catalyst, and a resol-type phenol resin is obtained under a basic catalyst.

The urea-melamine resin is formed by reacting urea or melamine with formalin in the presence of a basic catalyst. Silicon resin is formed by the reaction between silicon and a polyfunctional siloxane in the presence of a catalyst.

The film-forming material used for the coating layer in the present invention is preferably a thermosetting resin such as a polyurethane resin or an epoxy resin from the viewpoint of ease of handling of the monomer and the conditions of the curing reaction, and a urethane resin in terms of operability. Is more preferred.

As the fine powder solid carrier, surfactant, solvent, stabilizer, coloring agent, and fragrance, those mentioned in the section of the inner core can be similarly used.

The granules of the present invention can be obtained by coating the inner core with a coating layer. As a method of coating with a coating layer, for example, a film forming material is dissolved or dispersed in a solvent, and the solution is added to an inner core moving in a rotating pan, a rotating drum, a fluidized bed, a fluidized bed, or the like, and simultaneously heated with hot air. Drying to form and grow a coating layer to cover to a predetermined coverage (coating drying method), or to transfer the raw material of the film forming material to the inner core moving with a rotating pan, rotating drum, stirring mixer, etc. While adding, if necessary, while heating or cooling, a catalyst is added as necessary, the raw material of the film forming material is cured, and the coating layer is formed and grown, and coated to a predetermined coverage. Method (film curing method) and the like. Of these coating methods, the coating drying method is often used when coating a thermoplastic resin, and the coating curing method is often used when coating a thermosetting resin. In coating with wax or sulfur, both a coating drying method and a coating curing method are applied. In addition, when coating the inner core, if a large amount of the film forming material is added to the moving inner core at a time, the film forming material tends to become spine-like in the process of forming the coating layer, and the inner core is likely to be agglomerated. Therefore, it is preferable to add the film forming material intermittently in small units.

The average particle diameter of the particles composed of the inner core and the coating layer in the granules of the present invention is generally about 0.1 to 5 mm, preferably about 0.5 to 3 mm.

The granules of the present invention may be used, for example, in agricultural fields such as paddy fields, dry fields, nursery boxes, fields, orchards, mulberry fields, greenhouses, open fields, forests, lawns, etc. Non-cultivated land such as golf courses, street trees, roads, shoulders, wetlands,
It can be used in water systems such as ponds, reservoirs, rivers, waterways, and sewers. The granules of the present invention can be applied by a method to which pesticides are generally applied, for example, a method of directly spraying by hand, a baggage type granulator, a pipe granulator, an aerial granulator, a power granule. Examples of the method include a granulator, a seedling box granulator, a tractor-mounted granulator, a multi-mouth hose granulator, and a rice transplanter equipped with a granulator.

When the granules of the present invention are applied, they are preferably used in a situation where the sustained-release performance of the granules of the present invention can be utilized. For example, seedling box application, rice planting application, seedling application, sowing application, germination application, and the like, which is applied earlier than the time when a pesticide is usually applied, are suitable from the viewpoint of the characteristics of the granules of the present invention. . When the granules of the present invention are used in a nursery box,
The application amount is nursery box (usually, about area 0.16 m ²⁾ 1
Usually 10 to 200 g, preferably 25 to 10 per sheet
It is 0 g, and as an application method at that time, a method of applying directly by hand or a method of applying using a granulator for a nursery box is mentioned. When the granules of the present invention containing urea as the present water-soluble substance are applied to a nursery box, the content of urea is preferably 3 to 20% in the granules of the present invention.

When the granules of the present invention are used in paddy fields or upland fields, the application rate is usually 0.1 to 10 per are.
It is 10 kg, preferably 0.25 to 5 kg. In this case, the application method includes a method of directly spraying by hand, a baggage type granulator, a pipe granulator, an aerial granulator, a multi-mouth hose granulator. And a method using a rice transplanter equipped with a granulator, a tiller equipped with a granulator, and the like.

[0050]

Next, the present invention will be specifically described with reference to production examples and test examples.

Production Example 1 (1) N- (1,1,3-trimethyl-2-oxa-4
-Indanyl) -5-chloro-1,3-dimethylpyrazole-4-carboxamide 4 parts by weight and 0.8 part by weight of hydrous silicon dioxide were thoroughly mixed with a juice mixer,
It was pulverized with a pin mill. The average particle size of the obtained pulverized product was 6.4 μm (measured value by Coulter counter TA-II). 4.8 parts by weight of the pulverized product obtained above, 3 parts by weight of polyvinyl alcohol, 20 parts by weight of bentonite Fuji (manufactured by Toyohyun Yoko), 2 parts by weight of sodium dodecylbenzenesulfonate, and fine powder of calcium carbonate (average particle size 1)
(4.8 μm) and 65.2 parts by weight were mixed well with a juice mixer to obtain a powder mixture. Next, 5 parts by weight of urea was added to 1
It was dissolved in 5 parts by weight of water to prepare an aqueous solution containing urea. 20 parts by weight of the obtained aqueous solution was added to the powder mixture and kneaded well. The obtained kneaded material was granulated by a small extrusion granulator with a screen of 0.9 mmφ, sized, and then dried at 60 ° C. for 15 minutes to have a particle size of 1400 to 85.
An inner core of 0 μm was obtained. (2) Rotating 1000 parts by weight of the obtained inner core in a temperature-controllable inclined pan-type tumbling granulator equipped with a hot air generator, and keeping the temperature at 80 ° C., polymeric MDI (diphenylmethane diisocyanate). 6% by weight, 33.2% by weight of branched polyether polyol, 28.2% by weight of linear polyether polyol and 1.0% by weight of 2,4,6-tris (dimethylaminomethyl) phenol
(Hereinafter referred to as mixture A) (5 parts by weight) was added, and the mixture was kept at 80 ° C. for 5 minutes. The operation of adding 5 g of the mixture A and maintaining the mixture at 80 ° C. for 5 minutes were repeated 12 times, and finally the mixture was maintained at 80 ° C. for 10 minutes to obtain the pesticide granule (1).

Production Example 2 (1) Fine powder of calcium carbonate (average particle size 14.8 μm)
m) was 60.2 parts by weight, the amount of urea was 10 parts by weight, and the amount of the aqueous solution containing urea was 25 parts by weight. Diameter 1400
An inner core of ８850 μm was obtained. (2) The same experiment as in Production Example 1 (2) was performed except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 11 times, to produce an agricultural chemical granule (2).

Production Example 3 (1) Fine powder of calcium carbonate (average particle size 14.8 μm)
m) was 55.2 parts by weight, the amount of urea was 15 parts by weight, and the amount of the aqueous solution containing urea was 30 parts by weight. Diameter 1400
An inner core of ８850 μm was obtained. (2) The same experiment as in Production Example 1 (2) was carried out except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated eight times, to produce an agricultural chemical granule (3).

Production Example 4 (1) Fine powder of calcium carbonate (average particle size 14.8 μm)
m) was 50.2 parts by weight, the amount of urea was 20 parts by weight, and the amount of the aqueous solution containing urea was 35 parts by weight. Diameter 1400
An inner core of ８850 μm was obtained. (2) The same experiment as in Production Example 1 (2) was carried out except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 6 times, to produce pesticide granules (4).

Production Example 5 (1) The same experiment as in Production Example 1 (1) was carried out except that sucrose was used instead of urea, and an inner core having a particle size of 1400 to 850 μm was obtained. (2) The same experiment as in Production Example 1 (2) was carried out, except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 14 times, to produce an agricultural chemical granule (5).

Production Example 6 (1) The same experiment as in Production Example 2 (1) was carried out except that sucrose was used instead of urea, and an inner core having a particle size of 1400 to 850 μm was obtained. (2) The same experiment as in Production Example 2 (2) was performed except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 10 times, to produce an agricultural chemical granule (6).

Production Example 7 (1) The same experiment as in Production Example 3 (1) was carried out except that sucrose was used instead of urea, and an inner core having a particle size of 1400 to 850 μm was obtained. (2) The same experiment as in Production Example 3 (2) was carried out except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 11 times to produce an agricultural chemical granule (7).

Production Example 8 (1) The same experiment as in Production Example 4 (1) was carried out except that sucrose was used instead of urea, and an inner core having a particle diameter of 1400 to 850 μm was obtained. (2) The same experiment as in Production Example 4 (2) was carried out except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 10 times, to produce an agricultural chemical granule (8).

Production Example 9 (1) Fine powder of calcium carbonate (average particle diameter 14.8 μm)
Production example except that the amount of m) was 55.2 parts by weight, 10 parts by weight of urea and 5 parts by weight of sucrose were used instead of 5 parts by weight of urea, and the amount of the aqueous solution containing urea and sucrose was 30 parts by weight. The same experiment as in 1 (1) was performed, and the particle size was 1400 to 850 μm.
m were obtained. (2) Mixture A The same experiment as in Production Example 1 (2) was carried out except that the addition of parts by weight of the mixture A and the operation of keeping the mixture at 80 ° C. for 5 minutes were repeated eight times, to produce an agricultural chemical granule (9).

Production Example 10 (1) The same experiment as in Production Example 9 (1) was carried out except that the amount of urea was changed to 5 parts by weight and the amount of sucrose was changed to 10 parts by weight.
An inner core of 400-850 μm was obtained. (2) The same experiment as in Production Example 9 (2) was carried out except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 12 times, to produce an agricultural chemical granule (10).

Production Example 11 (1) Fine powder of calcium carbonate (average particle diameter 14.8 μm)
The same experiment as in Production Example 9 (1) was performed except that the amount of m) was 60.2 parts by weight, the amount of urea was 5 parts by weight, and the amount of the aqueous solution containing urea and sucrose was 25 parts by weight. , Particle size is 1
An inner core of 400-850 μm was obtained. (2) Mixture A The same experiment as in Production Example 9 (2) was performed except that the addition of parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 11 times, to produce an agricultural chemical granule (11).

Production Example 12 (1) The same experiment as in Production Example 9 (1) was carried out except that the amounts of urea and sucrose were both 7.5 parts by weight.
An inner core of 50 μm was obtained. (2) The same experiment as in Production Example 9 (2) was carried out except that the addition of the mixture A5 and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 7 times, to produce an agricultural chemical granule (12).

Production Example 13 (1) Fine powder of calcium carbonate (average particle diameter 14.8 μm)
m) was 50.2 parts by weight, the amounts of urea and sucrose were both 10 parts by weight, and the amount of the aqueous solution containing urea and sucrose was 35 parts by weight. An experiment was performed to obtain an inner core having a particle diameter of 1400 to 850 μm. (2) The same experiment as in Production Example 9 (2) was performed except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 6 times, to produce an agricultural chemical granule (13).

Production Example 14 (1) Fine powder of calcium carbonate (average particle diameter 14.8 μm)
Production Example 12 except that kaolin clay was used instead of m)
The same experiment as in (1) was performed, and the particle size was 1400 to 850 μm.
Got the inner core. (2) The same experiment as in Production Example 12 (2) was carried out except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated eight times, to produce an agricultural chemical granule (14).

Production Example 15 (1) The amount of bentonite Fuji (manufactured by Toyohyun Yoko) was 5 parts by weight, and calcium carbonate fine powder (average particle size: 14.8 μm)
Was carried out in the same manner as in Production Example 12 (1) except that the amount was 70.2 parts by weight to obtain an inner core having a particle diameter of 1400 to 850 μm. (2) The same experiment as in Production Example 12 (2) was carried out except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 8 times, to produce an agricultural chemical granule (15).

Production Example 16 (1) The amount of bentonite Fuji (manufactured by Toyoko Yoko Co., Ltd.) was adjusted to 10 parts by weight, and calcium carbonate fine powder (average particle size: 14.8 μm)
Production Example 12 (1) except that the amount of m) was changed to 65.2 parts by weight.
The same experiment as described above was performed to obtain an inner core having a particle diameter of 1400 to 850 μm. (2) The same experiment as in Production Example 12 (2) was conducted except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 8 times, to produce an agricultural chemical granule (16).

Production Example 17 (1) The amount of bentonite Fuji (manufactured by Toyohyun Yoko) was 30 parts by weight, and calcium carbonate fine powder (average particle size: 14.8 μm)
Production Example 12 (1) except that the amount of m) was changed to 45.2 parts by weight.
The same experiment as described above was performed to obtain an inner core having a particle diameter of 1400 to 850 μm. (2) The same experiment as in Production Example 12 (2) was conducted except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 8 times, to produce an agricultural chemical granule (17).

Production Example 18 (1) The same experiment as in Production Example 12 (1) was carried out except that sodium carboxymethylcellulose was used instead of polyvinyl alcohol, to obtain an inner core having a particle diameter of 1400 to 850 μm. (2) An agricultural chemical granule (18) was produced by conducting the same experiment as in Production Example 12 (2) except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 10 times.

Production Example 19 (1) The same experiment as in Production Example 12 (1) was carried out except that 1 part by weight of polyvinyl alcohol and 2 parts by weight of sodium carboxymethylcellulose were used instead of 3 parts by weight of polyvinyl alcohol. An inner core of ８850 μm was obtained. (2) The same experiment as in Production Example 12 (2) was carried out except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 10 times, to produce an agricultural chemical granule (19).

Production Example 20 (1) The same experiment as in Production Example 12 (1) was conducted except that 1 part by weight of polyvinyl alcohol and 2 parts by weight of sodium carboxymethylcellulose were used instead of 3 parts by weight of polyvinyl alcohol. An inner core of ８850 μm was obtained. (2) The same experiment as in Production Example 12 (2) was carried out except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated eight times, to produce pesticide granules (20).

Production Example 21 (1) The amount of polyvinyl alcohol was 1 part by weight, and the amount of calcium carbonate fine powder (average particle size: 14.8 μm) was 5 parts.
The same experiment as in Production Example 12 (1) was performed except that the weight was 7.2, and an inner core having a particle size of 1400 to 850 μm was obtained. (2) The same experiment as in Production Example 12 (2) was carried out except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 12 times, to produce pesticide granules (21).

Production Example 22 (1) The amount of polyvinyl alcohol was 2 parts by weight, and the amount of calcium carbonate fine powder (average particle size: 14.8 μm) was 5
The same experiment as in Production Example 12 (1) was performed except that the weight was 6.2, and an inner core having a particle size of 1400 to 850 μm was obtained. (2) The same experiment as in Production Example 12 (2) was carried out except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 12 times to produce pesticide granules (22).

Production Example 23 (1) The amount of polyvinyl alcohol was 5 parts by weight, and the amount of calcium carbonate fine powder (average particle size: 14.8 μm) was 5 parts.
The same experiment as in Production Example 12 (1) was carried out except that the weight was 3.2, and an inner core having a particle size of 1400 to 850 μm was obtained. (2) The same experiment as in Production Example 12 (2) was performed except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 6 times, to produce an agricultural chemical granule (23).

Production Example 24 (1) The amount of calcium carbonate fine powder (average particle size: 14.8 μm) was reduced to 7 without adding Bentonite Fuji (manufactured by Toyoko Junko).
An experiment similar to that of Production Example 12 (1) was performed except that the weight was 5.2, and an inner core having a particle size of 1400 to 850 μm was obtained. (2) The same experiment as in Production Example 12 (2) was performed except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 6 times, to produce an agricultural chemical granule (24).

Production Example 25 (1) Fine powder of calcium carbonate (average particle size 14.8 μm)
Production example except that the amount of m) was 56.2 parts by weight, the amount of polyvinyl alcohol was 2 parts by weight, calcium nitrate was used instead of urea, and an aqueous solution containing calcium nitrate was used instead of the aqueous solution containing urea. The same experiment as in 3 (1) was performed to obtain an inner core having a particle size of 1400 to 850 μm. (2) An agricultural chemical granule (25) was produced by conducting the same experiment as in Production Example 3 (2) except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 10 times.

Production Example 26 (1) Fine powder of calcium carbonate (average particle size 14.8 μm)
Production example except that the amount of m) was 61.2 parts by weight, the amount of polyvinyl alcohol was 2 parts by weight, dextrin was used instead of urea, and an aqueous solution containing dextrin was used instead of the aqueous solution containing urea. The same experiment as in 2 (1) was performed to obtain an inner core having a particle diameter of 1400 to 850 μm. (2) The same experiment as in Production Example 2 (2) was carried out except that the addition of 5 parts by weight of the mixture A and the operation of maintaining the mixture at 80 ° C. for 5 minutes were repeated 10 times to produce an agricultural chemical granule (26).

Production Example 27 (1) The same experiment as in Production Example 26 (1) was carried out except that glucose was used instead of dextrin and an aqueous solution containing glucose was used instead of the aqueous solution containing dextrin. Obtained an inner core of 1400 to 850 μm. (2) The same experiment as in Production Example 26 (2) was performed, and the pesticide granules (2
7) was manufactured.

Production Example 28 (1) Fine powder of calcium carbonate (average particle size 14.8 μm)
The amount of m) was 51.2 parts by weight, 20 parts by weight of magnesium sulfate was used instead of 10 parts by weight of dextrin, and 35 parts by weight of an aqueous solution containing magnesium sulfate was used instead of 25 parts by weight of an aqueous solution containing dextrin. Except for this, the same experiment as in Production Example 26 (1) was performed, and the particle size was 1400 to 85.
An inner core of 0 μm was obtained. (2) The same experiment as in Production Example 26 (2) was performed, and the pesticide granules (2
8) was produced.

Production Example 29 (1) The same experiment as in Production Example 25 (1) was carried out except that potassium carbonate was used instead of calcium nitrate and an aqueous solution containing potassium carbonate was used instead of the aqueous solution containing calcium nitrate. This was performed to obtain an inner core having a particle diameter of 1400 to 850 μm. (2) The same experiment as in Production Example 25 (2) was performed, and the pesticide granules (2
9) was manufactured.

Production Example 30 (1) Production Example 25 except that potassium pyrophosphate was used instead of calcium nitrate and an aqueous solution containing potassium pyrophosphate was used instead of the aqueous solution containing calcium nitrate
The same experiment as in (1) was performed, and the particle size was 1400 to 850 μm.
Got the inner core. (2) The same experiment as in Production Example 26 (2) was performed, and the pesticide granules (3
0) was prepared.

Production Example 31 (1) Production Example 25 except that ammonium nitrate was used in place of calcium nitrate and an aqueous solution containing ammonium nitrate was used in place of the aqueous solution containing calcium nitrate
The same experiment as in (1) was performed, and the particle size was 1400 to 850 μm.
Got the inner core. (2) The same experiment as in Production Example 25 (2) was performed,
1) was manufactured.

Production Example 32 (1) The same experiment as in Production Example 25 (1) was conducted except that citric acid was used instead of calcium nitrate, and an aqueous solution containing citric acid was used instead of the aqueous solution containing calcium nitrate. This was performed to obtain an inner core having a particle diameter of 1400 to 850 μm. (2) The same experiment as in Production Example 25 (2) was performed, and the pesticide granules (3
2) was manufactured.

Comparative Production Example 1 (1) N- (1,1,3-trimethyl-2-oxa-4
-Indanyl) -5-chloro-1,3-dimethylpyrazole-4-carboxamide 4 parts by weight and 0.8 part by weight of hydrous silicon dioxide were thoroughly mixed with a juice mixer,
It was pulverized with a pin mill. The average particle size of the obtained pulverized product was 6.4 μm (measured value by Coulter counter TA-II). 4.8 parts by weight of the pulverized product obtained above, 30 parts by weight of Bentonite Fuji (manufactured by Toyoko Yoko), 2 parts by weight of carboxymethylcellulose, 0.5 parts by weight of sodium hexametaphosphate and 60.7 parts by weight of kaolin clay were mixed with a juice mixer. After mixing well, the mixture was transferred to a mortar, water was added and kneaded well. The obtained kneaded material was granulated with a small extrusion granulator equipped with a screen of 0.9 mmφ, sized, and then dried at 60 ° C. for 15 minutes to obtain a particle size of 1400 to 850.
A μm inner core was obtained. (2) 1000 parts by weight of the obtained core was rotated in a temperature-controllable inclined pan-type rolling granulator equipped with a hot air generator, and the polymer MDI 35.9 was maintained at 80 ° C.
A mixture of 31.3% by weight of a branched polyether polyol, 31.3% by weight of a linear polyether polyol and 1.5% by weight of 2,4,6-tris (dimethylaminomethyl) phenol (hereinafter referred to as a mixture). B) was added, and the mixture was kept at 80 ° C. for 5 minutes. The addition of the mixture B and the operation of keeping the mixture at 80 ° C. for 5 minutes were repeated eight times, and finally the mixture was kept at 80 ° C. for 10 minutes to produce a comparative pesticide granule (1).

Comparative Example 2 (1) The same experiment as in Comparative Production Example 1 (1) was performed, and the particle size was 14
An inner core of 00 to 850 μm was obtained. (2) The same experiment as in Comparative Production Example 1 (2) was carried out except that the addition of 5 parts by weight of the mixture B and the operation of keeping the mixture at 80 ° C. for 5 minutes were repeated 20 times. Manufactured.

Test Example 1 In a 500 ml beaker, 300 m of the pesticide granules shown in Table 1
g and 300 ml of hard water three times were added, followed by gentle stirring.
The water temperature was set to 25 ± 1 ° C. and 1, 3, 7, 14, 21,
… (Hereinafter every 7 days) 1 ml collected from the center of the beaker after a day is analyzed by liquid chromatography,
The amount of the pesticide active ingredient is measured, and the dissolution rate is determined by the following formula,
The number of days required for 50% of the pesticidal active ingredient to elute was determined by interpolation. Table 1 shows the results.

[0086]

(Equation 1)

[0087]

【table 1】

[0088]

According to the present invention, the dissolution of the pesticidal active ingredient can be controlled very efficiently, so that a sustained release of the pesticidal active ingredient can be achieved for a longer period of time even with the same amount of coating layer as the conventional granules.

Claims (8)

[Claims] An agricultural chemical granule comprising particles composed of an inner core and a coating layer, wherein the inner core comprises (a) an agricultural chemical active ingredient, (b) a finely divided solid carrier, (c) a binder and d) molecular weight of 50 to 70
0. A pesticide granule comprising a water-soluble substance which is solid at room temperature and having the water-soluble substance dispersed in an inner core. 2. The pesticide granule according to claim 1, wherein (b) the finely divided solid carrier comprises two types. 3. The pesticide granule according to claim 1, wherein (b) the finely divided solid carrier contains a montmorillonite mineral. (D) a water-soluble substance having a molecular weight of 50 to 700 and being solid at room temperature having a solubility in water at 20 ° C. of 20;
% Or more of the pesticide granule according to claim 1. 5. The pesticide granule according to claim 1, wherein (d) the water-soluble substance having a molecular weight of 50 to 700 and solid at room temperature is at least one selected from urea and saccharides. . 6. The coating layer according to claim 1, wherein the coating layer is a thermosetting resin.
5. The pesticide granule according to any one of 5. 7. A pesticidal active ingredient, a finely divided solid carrier and a binder are mixed, and a water-soluble substance having a molecular weight of 50 to 700 and solid at ordinary temperature is added and kneaded, and the kneaded product is granulated. A method for producing pesticide granules comprising particles composed of an inner core and a coating layer, wherein a coating layer is formed by adding a film-forming substance after preparing the inner core. 8. The method according to claim 7, wherein the granulation is extrusion granulation.