JP4526593B2 - Anhydrous sodium sulfate-containing granular composition and process for producing the same - Google Patents

Description

  The present invention relates to a granular composition that can be used as an agrochemical formulation and the like, and more specifically, to a granular composition containing anhydrous sodium sulfate and obtained by wet granulation. The present invention relates to a granule composition and a granule composition in which the dry state of the granule is improved, and a method for producing the same.

  Currently, there are dosage forms such as granules, powders, emulsions, wettable powders, flowable powders, and granular wettable powders as agricultural chemical preparations. Among these agrochemical formulations, granular compositions such as granules and granular wettable powders are not dusty when used and are highly safe for users, and must not contain organic solvents that adversely affect the human body or the environment. It is widely used for such reasons. In addition, this preparation is most suitable as a dosage form of a preparation containing a pesticidally active ingredient that contains less moisture and is susceptible to hydrolysis.

  For granular compositions such as granules and granular wettable powders, as fillers, non-water soluble extenders such as clay, bentonite, calcium carbonate, talc, potassium chloride, ammonium sulfate, ammonium chloride, sodium sulfate, sodium carbonate, etc. It is known that water-soluble extenders such as inorganic salts, sugars such as sucrose and lactose, and urea can be used. In fact, some of the granules or granular wettable powders use a water-soluble extender among these extenders, and preparations having good dispersibility and component diffusibility are commercially available.

  By the way, among the water-soluble extenders, anhydrous sodium sulfate is a suitable extender for agricultural chemical formulations because it has low metal corrosivity, is stably supplied as an industrial raw material, and is relatively inexpensive. However, it has been said that it cannot be used as a bulking agent for granular compositions such as granules and granular wettable powders obtained by wet granulation.

That is, a granular preparation such as a granule or a granular wettable powder is generally produced by adding a suitable amount of water and granulating it, that is, after wet granulation and then drying the moisture. However, when anhydrous sodium sulfate and sodium sulfate hydrate are used as extenders, especially when these contents are 30 % by mass or more in the composition, the obtained granulated product is dried with hot air of 40 ° C. or more. Then, there existed a problem that it became a molten state and a granular material could not be obtained.

  As described above, anhydrous sodium sulfate has a problem that it cannot be used in a granular composition obtained by wet granulation while having excellent properties as a bulking agent for agricultural chemical formulations, and this problem can be solved. It is the subject of the present invention.

  In view of the above circumstances, the present inventors have intensively studied to obtain a granular composition containing anhydrous sodium sulfate, and as a result, a specific compound has an action of inhibiting the formation of anhydrous sodium sulfate hydrate, It was found that if used as a formation inhibitor, the granular composition does not melt in the drying step after wet granulation, and a granular composition with excellent performance can be obtained, thereby completing the present invention.

That is, the present invention provides a granular composition containing an anhydrous sodium sulfate and a hydrate formation inhibitor and manufactured by a wet granulation method.
The present invention also provides a method for producing a granular composition in which water is added to a composition containing anhydrous sodium sulfate and a hydrated salt formation inhibitor and granulated, and then the granulated product is dried at 40 ° C. or higher. is there.

  The granular composition obtained by wet granulation of the present invention contains anhydrous sodium sulfate as a bulking agent, but the granulated composition is not melted during drying and can be dried as a normal granular material. is there. That is, the present invention provides a granular composition containing anhydrous sodium sulfate that can be widely used as an agrochemical formulation or the like.

The granular composition of the present invention can be obtained by wet granulating a composition containing anhydrous sodium sulfate and a hydrate formation inhibitor.
Here, wet granulation includes extrusion granulation, fluidized bed granulation, stirring granulation, and the like, and refers to a granulation method in which powder is adhered to each other with water interposed.

  In the granular composition of the present invention, anhydrous sodium sulfate, which is an essential component, is a crystalline water-soluble salt, and it is known to form a hydrate when water is added. In the present invention, anhydrous sodium sulfate alone or a mixture thereof with sodium sulfate hydrate can be used.

  On the other hand, the hydrate formation inhibitor, which is another component in the granular composition of the present invention, is a substance in which 10 g or more dissolves in 100 g of water at 20 ° C., and examples thereof include sodium carbonate, sodium acetate, Surface activity of organic or inorganic acid salts such as sodium chloride, potassium chloride, ammonium sulfate, ammonium bicarbonate, ammonium nitrate, ammonium sulfate, magnesium citrate, sodium bicarbonate, sodium acetate, sodium benzoate, and lignin sulfonate Agents, urea and the like. Of these, sodium carbonate, sodium acetate, sodium chloride, potassium chloride, and urea are preferable. These can be used alone, but two or more kinds may be mixed and used.

The content of the hydrate salt formation inhibitor in the granular composition of the present invention is about 2 % by mass (hereinafter simply indicated as “%”) or more with respect to anhydrous sodium sulfate in the composition. In particular, when the content of anhydrous sodium sulfate in the composition is as high as 30% or more, it is preferably 5% or more. The content of anhydrous sodium sulfate in the granular composition of the present invention is not particularly limited, but the present invention is particularly effective when it is 30% or more.

  The granular composition in the present invention is produced by adding water to the above composition containing anhydrous sodium sulfate and a hydrate formation inhibitor, followed by granulation, and then drying the granulated product at 40 ° C. or higher. The As this granulation method, known wet granulation methods such as extrusion granulation, fluidized bed granulation, stirring granulation and the like can be used.

  The method for producing the granular composition of the present invention will be described in more detail as follows. That is, first, a powder composition containing a hydrate formation inhibitor as an essential component in anhydrous sodium sulfate or a mixture of sodium sulfate and hydrate is prepared. The particle size of the powder of this composition is not particularly limited, but it is preferable that anhydrous sodium sulfate and a hydrate formation inhibitor are uniformly dispersed in the powder. Generally, the powder composition is obtained by dry pulverization. Prepare.

  Next, this powder composition is granulated by a wet granulation method. In the case of extrusion granulation, an appropriate amount of water is added to the aforementioned powder composition and kneaded, followed by extrusion from a plate having a hole of 0.1 mm to 20 mm and granulation. In the case of fluidized bed granulation, the aforementioned powder composition is put in a container, and the powder is blown up with warm air from below to create a fluidized state, and water is sprayed there. Thereby, powder particles adhere to each other, and grains are gradually formed. Furthermore, in the case of mixed granulation, the above-mentioned powder composition is put in a container and the container itself is rotated to move the powder, or the blade in the container is rotated to move the powder, Spray water with a spray. As a result, the powder particles adhere to each other, and grains are gradually formed.

  When both the fluidized bed granulation and the mixed granulation have reached a predetermined particle size, the spraying of water or the movement of the powder is stopped to obtain a granular composition.

  Finally, the granular composition obtained by wet granulation is generally subjected to ventilation drying with warm air or vacuum drying to reduce or remove moisture. Usually, the moisture in the granular composition after drying is 20% or less, but it is desirable to obtain a granular composition with a certain degree of hardness or to suppress decomposition of the pesticidal active ingredient that is susceptible to hydrolysis. Is 10% or less, more preferably 5% or less.

In the granular composition of the present invention, sodium sulfate can exist as an anhydride even when it contains moisture.
In this case, the presence of sodium sulfate as an anhydride in the granular composition can be easily discriminated by measuring with a powder X-ray diffraction apparatus after grinding with a mortar or the like. In some cases, the contained water can be converted into the amount of water added for wet granulation, and sodium sulfate hydrate can be used alone.

  The granular composition of the present invention obtained as described above can be applied to all granular preparations and granular compositions that are allowed to contain anhydrous sodium sulfate, and is expected to be used in a wide range of industrial fields. Especially for agricultural chemicals, it can be advantageously used as a granule and a granular wettable powder.

  When the granular composition of the present invention is used as an agrochemical formulation, the composition includes an essential component of the present invention, anhydrous sodium sulfate (and sodium sulfate hydrate if necessary), a hydrate formation inhibitor, In general, an agrochemical active ingredient, a surfactant, a bulking agent other than anhydrous sodium sulfate, other adjuvants and the like which are generally blended in an agrochemical formulation can be included.

  Known herbicides, fungicides, insecticides, plant growth regulators and the like can be used as the agrochemical active ingredient.

  Among these, as herbicides, 2,4-dichlorophenoxyacetic acid (2,4-D), 2-methyl-4-chlorophenoxybutyric acid (MCPB), 2-methyl-4-chlorophenoxythioacetic acid- S-ethyl (phenothiol), α- (2-naphthoxy) propionanilide (naproanilide), methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate (biphenox), S- (4-chlorobenzyl) N, N-diethylthiocarbamate (bencho curve), S-benzyl = 1,2-dimethylpropyl (ethyl) thiocarbamate (esprocarb), S-ethylhexahydro-1H-azepine-1-carbothioate (molinate), S-1-methyl-1-phenylethyl = piperidine-1-carbothioate (dimethylpiperate), O-3-t ert-Butylphenyl = 6-methoxy-2-pyridyl (methyl) thiocarbamate (pyributycarb), 3,4-dichloropropionanilide (DCPA), 2-chloro-2 ′, 6′-diethyl-N- (butoxymethyl) ) Acetanilide (butachlor), 2-chloro-2 ′, 6′-diethyl-N- (2-propoxyethyl) acetanilide (pretilachlor), (RS) -2-bromo-N- (α, α-dimethylbenzyl)- 3,3-dimethylbutyramide (bromobutide), 2-benzothiazol-2-yloxy-N-methylacetanilide (mefenacet), 1- (α, α-dimethylbenzyl) -3- (paratolyl) urea (Dimron), methyl = Α- (4,6-Dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -O-Toluer (Bensulfuron methyl), 1- (2-chloroimidazo [1,2-a] pyridin-3-ylsulfonyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea (imazosulfuron), ethyl = 5 -(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -1-methylpyrazole-4-carboxylate (pyrazosulfuronethyl), 2methylthio-4,6-bis (ethylamino) -s-triazine (Cymetrin), 2-methylthio-4,6-bis (isopropylamino) -s-triazine (promethrin), 2-methylthio-4-ethylamino-6- (1,2-dimethylpropylamino) -s-triazine ( Dimetamethrin), 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-pyrazolyl-p-toluenesulfone (Pyrazolate), 2- [4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazol-5-yloxy] acetophenone (pyrazoxyphene), (RS) -2- (2,4-dichloro-m -Tolyloxy) propionanilide (chromeprop), 2- [4- [2,4-dichloro-m-toluoyl) -1,3-dimethylpyrazol-5-yloxy] -4'-methylacetophenone (benzophenap), S 2-benzenesulfonamidoethyl O, O-diisopropyl phosphorodithioate (benslide), α, α, α-trifluoro-2,6-dinitro-N, N-dipropyl-p-toluidine (trifluralin), S -(2-methyl-1-piperidyl-carbonylmethyl) -O, O-di-n-propyldithiophosphate (piperophos), S, S′-dimethyl = 2-difluoromethyl-4-isobutyl-6-trifluoromethylpyridine-3,5-dicarbothioate (dithiopyr), N- (1-ethylpropyl) -3,4-dimethyl- 2,6-dinitroaniline (pendimethalin), 2-chloro-N- (3-methoxy-2-enyl) -2 ′, 6′-dimethylacetanilide (tenylchlor), n-butyl- (R) -2- [4- (2-Fluoro-4-cyanophenoxy) phenoxy] propionate (cyhalohopbutyl), 1- (diethylcarbamoyl) -3- (2,4,6-trimethylphenylsulfonyl) -1,2,4- Triazole (cifentrole), N-{[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl]}-1-methyl-4- (2-methyl-2H-teto Razol-5-yl) (azimsulfuron), methyl 2-[(4,6-dimethoxypyrimidin-2-yl) oxy] -6-[(E) -1- (methoxyimino) ethyl] benzoate (pyriminoback Methyl) and the like.

  Examples of bactericides include N-trichloromethylthiotetrahydrophthalimide (captan), tetrachloroisophthalonitrile (TPN), 4,5,6,7-tetrachlorophthalide (fusalide), O, O-diisopropyl- S-benzylthiophosphate (IBP), 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene (thiophanate methyl), methyl-1-butylcarbamoyl) -2-benzimidazole carbamate (benomyl), 3'-iso Propoxy-2-methylbenzanilide (mepronyl), α, α, α-trifluoro-3′-isopropoxy-O-toluanilide (flutranyl), 3,4,5,6-tetrachloro-N- (2,3 -Dichlorophenyl) phthalamic acid (teclophthalam), 1- (4-chlorobenzyl) ) -1-cyclopentyl-3-phenylurea (pencyclone), 6- (3,5-dichloro-4-methylphenyl) -3 (2H) -pyridazinone (dicromedin), methyl = N- (2-methoxyacetyl)- N- (2,6-xylyl) -DL-alaninate (metalaxyl), (E) -4-chloro-α, α, α-trifluoro-N- (1-imidazol-1-yl-2-propoxyethylidene) O-toluidine (triflumizole), kasugamycin, validamycin, 3-allyloxy-1,2-benzisothiazole-1,1-dioxide (probenazole), diisopropyl-1,3-dithiolane-2-ylidene-malonate (isoprothiolane) ), 5-methyl-1,2,4-triazolo [3,4-b] benzothiazole (tricyclazole), 1,2, , 6-Tetrahydropyrrolo [3,2,1-ij] quinolin-4-one (pyrrololone), 5-ethyl-5,8-dihydro-8-oxo [1,3] dioxolo [4,5-g] quinoline -7-carboxylic acid (oxolinic acid), (Z) -2′-methylacetophenone = 4,6-dimethylpyrimidin-2-ylhydrazone 4,5,6,7-tetrachlorophthalide (ferimzone), 3- ( 3,5-dichlorophenyl) -N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide (iprodione) and the like.

  Further examples of insecticides include O, O-dimethyl-O- (3-methyl-4-nitrophenyl) thiophosphate (MEP), (2-isopropyl-4-methylpyrimidyl-6) -diethylthiophosphate (diazinone). 1-naphthyl-N-methylcarbamate (NAC), O, O-diethyl = O-quinoxalin-2-yl = phosphorothioate (quinalphos), O, O-diethyl-O- (5-phenyl-3- Isoxazoyl) phosphorothioate (isoxathione), O, O-diethyl-O- (3-oxo-2-phenyl-2H-pyridazin-6-yl) phosphorothioate (pyridafenthione), O, O-dimethyl-O-3,5,6 -Trichloro-2-pyridyl phosphorothioate (chlorpyrifosmethyl), dimethyl-methylcarbamoylethyl Ruthioethyl phosphorothiolate (bamidithione), dimethyldicarbethoxyethyl dithiophosphate (marathon), O, O-dimethyl-S- (N-methylcarbamoylmethyl) dithiophosphate (dimethoate), 3- (dimethoxyphosphinyl) Oxy) -N-methyl-cis-crotonamide (monocrotophos), O, O-dipropyl-O-4-methylthiophenyl phosphate (propaphos), O, S-dimethyl-N-acetyl phosphoramidothioate (acephate) Ethylparanitrophenylthionobenzenephosphonate (EPN), 2-secondary-butylphenyl-N-methylcarbamate (BPMC), 3,5-xylyl-N-methylcarbamate (XMC), 2,3-dihydro-2, 2-Dimethyl-7-benzo [b] fura L = N-dibutylaminothio-N-methylcarbamate (carbosulfan), ethyl = N- [2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio] -N— Isopropyl-β-alaninate (benfuracarb), S-methyl-N [(methylcarbamoyl) oxy] thioacetimidate (mesomyl), 1- (6-chloro-3-pyridylmethyl) -N-nitroimidazolidine-2-H- Irideneamine (imidacloprid), (RS) -α-cyano-3-phenoxybenzyl = (RS) -2,2-dichloro-1- (4-ethoxyphenyl) cyclopropanecarboxylate (cycloprotorin), 2-isopropoxy Phenyl-N-methylcarbamate (PHC), 2- (4-ethoxyphenyl) 2-methylpropyl-3-phenoxybenzyl ether (ethofenprox), 1,3-bis (carbamoylthio) -2- (N, N-dimethylamino) propane hydrochloride (Cultap), 5-dimethylamino-1 , 2,3-trithian oxalate (thiocyclam), S, S′-2-dimethylaminotrimethylene di (benzenethiosulfonate) (bensultap), 2-tert-butylimino-3-isopropyl-5-phenyl -1,3,5,6 tetrahydro-2H-1,3,5-thiadiazin-4-one (buprofezin) and the like.

  Furthermore, examples of plant growth regulators include 4′-chloro-2 ′-(α-hydroxybenzyl) isonicotinanilide (inabenfide), (2RS, 3RS) -1- (4-chlorophenyl) -4,4. -Dimethyl-2- (1H-1,2,4-triazol-1-yl) pentan-3-ol (paclobutrazol), (E)-(S) -1- (4-chlorophenyl) -4, 4-dimethyl-2- (1H-1,2,4-triazol-1-yl) pent-1-en-3-ol (uniconazole) and the like can be mentioned.

The disclosure of the above pesticidal active ingredient is merely an example and is not particularly limited thereto. Moreover, it cannot be overemphasized that these pesticidal active ingredients can be used individually or in mixture of 2 or more types.
The total blending ratio of these agrochemical active ingredients is usually 1 part by weight to 70 parts by weight with respect to 100 parts by weight of the composition, but this amount is not particularly limited.

  Examples of the surfactant that can be used when the granular composition of the present invention is used as an agrochemical preparation include, for example, polyethylene glycol higher fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene aryl phenyl ethers. , Nonionic surfactants such as sorbitan monoalkylate, acetylene glycol, polyoxyethylene acetylene glycol ether, alkyl aryl sulfonate, dialkyl sulfonate, alkyl sulfate ester salt, alkyl phosphate ester salt, alkyl aryl sulfate ester salt, Alkyl aryl phosphate ester salt, polyoxyethylene alkyl ether sulfate ester salt, naphthalene sulfonate and its condensate, lignin sulfonate, acrylic acid and italy Polycarboxylic polymer activity such as copolymer of acid or copolymer of methacrylic acid and itaconic acid, copolymer of maleic acid and styrene, copolymer of maleic acid and diisobutylene, and alkali metal salts thereof Anionic surfactants such as an agent, polyoxyethylene arylphenyl ether phosphate ester salt, polyoxyethylene arylphenyl ether sulfate ester salt and the like can be mentioned, but are not limited thereto. These surfactants can be used alone or in admixture of two or more.

  Furthermore, as a bulking agent other than anhydrous sodium sulfate (and sodium sulfate hydrate), a known water-soluble or water-insoluble substance can be used, or a combination thereof can be used. Examples of the water-soluble extender include saccharides such as sucrose and lactose. Examples of the water-insoluble extender include clays, calcium carbonate, bentonite, talc, diatomaceous earth, zeolite, attapulgite, gypsum, porcelain stone, white carbon, etc. Perlite made of pumice, wood powder, pearlite and obsidian, foamed shirasu made of shirasu, philite fired in aluminosilicate system, microballoon made of foamed sodium silicate or borax, cork powder, phenol microballoon made of phenol resin Examples include hollow bodies such as ecospheres made of epoxy resin, polyurethane foams made of polyurethane, and microspheres made of vinylidene chloride-acrylonitrile copolymer.

  As other adjuvants, for example, carboxymethylcellulose metal salt, polyvinyl alcohol, pregelatinized starch, dextrin, xanthan gum, guar seed gum, sucrose, polyvinylpyrrolidone, sodium polyacrylate, polyethylene glycol having an average molecular weight of 6,000 to 20,000, average Binders such as polyethylene oxide having a molecular weight of 100,000 to 5,000,000, solvents such as glycols, glycol ethers, aromatic hydrocarbons, silicone oils, physical property improvers such as sodium tripolyphosphate and calcium stearate, decomposition inhibitors, solids Anti-caking agents, melting point depressants and the like can be used. These components can be blended in appropriate amounts as necessary.

The granular composition of the present invention thus obtained can be produced by wet granulation, which has heretofore been difficult when anhydrous sodium sulfate is used, so that the particle size is relatively large and the apparent specific gravity is small. It can be obtained as a preparation.
Therefore, this composition can be advantageously used as an agrochemical formulation such as a flowable agent and a jumbo agent.

  EXAMPLES Hereinafter, although an Example and a test example demonstrate this invention further in detail, this invention is not restrict | limited to these Examples at all. In the following examples, parts represent parts by weight. The amount of water added in each example is the amount when viscoelasticity necessary for wet granulation is obtained. Since water added by drying evaporates, the total of each composition after drying is 100 parts.

Example 1
30 parts of anhydrous sodium sulfate, 0.6 part of sodium chloride, 10 parts of bentonite and 59.4 parts of calcium carbonate were mixed and pulverized to obtain a powder. After 14 parts of water was added to this powder and kneaded, it was extruded from a plate with a 1 mm hole and granulated. The obtained granulated product was dried by ventilation at a temperature of 80 ° C. to obtain a granular composition.

Example 2
80 parts of anhydrous sodium sulfate, 12 parts of urea and 8 parts of pregelatinized starch were mixed and pulverized to obtain a powder. After 15 parts of water was added to the powder and kneaded, it was extruded from a plate with a 1 mm hole and granulated. The obtained granulated product was dried by ventilation at a temperature of 80 ° C. to obtain a granular composition.

Example 3
70 parts of anhydrous sodium sulfate, 18 parts of ammonium sulfate, 3 parts of polyvinyl alcohol and 9 parts of clay were mixed and pulverized to obtain a powder. After 15 parts of water was added to the powder and kneaded, it was extruded from a plate with a 1 mm hole and granulated. The obtained granulated product was dried by ventilation at a temperature of 80 ° C. to obtain a granular composition.

Example 4
35 parts of sodium sulfate decahydrate, 0.5 part of sodium polyacrylate and 34.1 parts of calcium carbonate were mixed and pulverized to obtain a powder. This powder and 14 parts of pulverized urea were mixed and kneaded, and then extruded from a plate having a 1 mm hole and granulated. The obtained granulated product was dried by ventilation at a temperature of 80 ° C. to obtain a granular composition.

Example 5
75 parts of anhydrous sodium sulfate and 25 parts of lignin sulfonic acid sodium salt were mixed and pulverized to obtain a powder. This powder was put into a disk-shaped container, the container was rotated while being tilted to move the powder, and 12 parts of water was sprayed thereon to perform mixing granulation. After stopping the rotation of the container when the particle size of the granulated product became 1 mm to 3 mm, the resulting granulated product was dried by ventilation at a temperature of 80 ° C. to obtain a granular composition.

Example 6
Bensulfuron methyl 0.5 parts, pyriminobac methyl 0.3 parts, anhydrous sodium sulfate 50 parts, sodium acetate 2.5 parts, dextrin 2 parts, sodium tripolyphosphate 1 part, bentonite 10 parts and calcium carbonate 33.7 parts Were mixed and pulverized to obtain a powder. This powder was put in a container, the blade in the container was rotated to move the powder, and 18 parts of water was sprayed there to mix and granulate. After stopping the rotation of the container when the particle size of the granulated product became 1 mm to 3 mm, the obtained granulated product was dried by ventilation at a temperature of 70 ° C. to obtain a granular composition.

Example 7
Mix and grind 20 parts of tricyclazole, 50 parts of anhydrous sodium sulfate, 2.5 parts of potassium chloride, 3 parts of a copolymer of maleic acid and styrene, 2 parts of alkylaryl sulfate ester salt, 10 parts of lactose and 12.5 parts of clay. To obtain a powder. This powder was put into a container, and air at 60 ° C. was sent from a mesh plate under the container, and 50 parts of water was sprayed into a fluidized state by blowing up the powder, and fluidized bed granulation was performed. The particle size of the granulated product was 0.5 mm to 2 mm. After the spraying of water, the granulated product was fluidly dried in the container at the same temperature to obtain a granular composition.

Example 8
0.5 parts of bensulfuron methyl, 0.3 parts of pyriminobac methyl, 2.1 parts of caffrontrol, 81.1 parts of anhydrous sodium sulfate, 10 parts of sodium carbonate, 1 part of sodium polyacrylate, 3 parts of dialkyl sulfonate and 2 parts of alkyl sulfate ester salt was mixed and pulverized to obtain a powder. After 12 parts of water were added to the powder and kneaded, the powder was extruded from a plate with a hole of 1.5 mm and granulated. The obtained granulated product was dried by ventilation at a temperature of 80 ° C. to obtain a granular composition.

Example 9
2 parts of bensulfuron methyl, 1.2 parts of pyriminobac methyl, 66.3 parts of anhydrous sodium sulfate, 12 parts of urea, 2.5 parts of acetylene glycol, 2.5 parts of white carbon, 3 parts of polyoxyethylene arylphenyl ether, 0.5 parts of sodium polyacrylate and 10 parts of microspheres were mixed and pulverized to obtain a powder. After 15 parts of water was added to the powder and kneaded, it was extruded from a plate with a 5 mm hole and granulated. The obtained granulated product was vacuum-dried at a temperature of 50 ° C. under a reduced pressure of 100 Torr to obtain a granular composition.

Example 10
2 parts of bensulfuron methyl, 1.2 parts of pyriminobac methyl, 69.3 parts of anhydrous sodium sulfate, 6 parts of potassium chloride, 3 parts of polyoxyethylene arylphenyl ether, 3 parts of condensate of naphthalene sulfonate, polyacrylic acid 0.5 parts of sodium and 10 parts of microspheres were mixed and pulverized to obtain a powder. After adding 10 parts of water to this powder and kneading, it was granulated by extruding from a plate having a 0.8 mm hole. The resulting granulated product was dried by ventilation at a temperature of 60 ° C. to obtain a granular composition.

Example 11
2 parts of bensulfuron methyl, 1.2 parts of pyriminobac-methyl, 61.4 parts of anhydrous sodium sulfate, 6 parts of potassium chloride, 3 parts of polyoxyethylene arylphenyl ether, 3 parts of condensate of naphthalene sulfonate, polyacrylic acid 0.5 parts of sodium and 10 parts of microspheres were mixed and pulverized to obtain a powder. This powder was mixed with 17.9 parts of separately pulverized sodium sulfate decahydrate, kneaded, and then extruded from a plate with a 0.8 mm hole and granulated. The resulting granulated product was dried by ventilation at a temperature of 60 ° C. to obtain a granular composition.

Comparative Example 1
142 parts of water was added to the powder obtained by pulverizing 100 parts of anhydrous sodium sulfate and kneaded, and then extruded from a plate having a 1 mm hole and granulated. The resulting granulated product was dried by ventilation at a temperature of 80 ° C., but it was melted and no granular composition was obtained.

Comparative Example 2
Mix 90 parts of anhydrous sodium sulfate, 5 parts of sucrose and 5 parts of clay, put the powder obtained by pulverization into a disk-shaped container, rotate the container while tilting it, and move the powder to 127 parts of water Spray and mix granulation. After stopping the rotation of the container when the particle size of the granulated product became 1 mm to 3 mm, the obtained granulated product was dried by ventilation at a temperature of 80 ° C., but it was melted and a granular composition was obtained. There wasn't.

Comparative Example 3
35 parts of sodium sulfate decahydrate, 0.5 part of sodium polyacrylate and 14.5 parts of calcium carbonate were mixed and pulverized to obtain a powder. This powder and 50 parts of pulverized sucrose were mixed and kneaded, and then extruded from a plate having a 1 mm hole and granulated. The resulting granulated product was dried by ventilation at a temperature of 80 ° C., but it was melted and no granular composition was obtained.

Comparative Example 4
20 parts of tricyclazole, 50 parts of anhydrous sodium sulfate, 3 parts of a copolymer of maleic acid and styrene, 2 parts of alkylaryl sulfate ester salt, 10 parts of lactose and 15 parts of clay were mixed and pulverized to obtain a powder. This powder is put in a container, 60 ° C air is sent from the mesh plate under the container, and the powder is blown up and sprayed with water and fluidized bed granulated, but 80 parts are sprayed. As a result, it was melted and no granular composition was obtained.

Comparative Example 5
Bensulfuron methyl 0.5 parts, Pyriminobac methyl 0.3 parts, Caffentrol 2.1 parts, Anhydrous sodium sulfate 91.1 parts, Sodium polyacrylate 1 part, Dialkyl sulfonate 3 parts and alkyl sulfate 2 The parts were mixed and pulverized to obtain a powder. After adding 85 parts of water to this powder and kneading, it was extruded from a plate with a hole of 1.5 mm and granulated. The resulting granulated product was dried by ventilation at a temperature of 80 ° C., but it was melted and no granular composition was obtained.

Comparative Example 6
Bensulfuron methyl 2 parts, pyriminobac methyl 1.2 parts, anhydrous sodium sulfate 78.3 parts, acetylene glycol 2.5 parts, white carbon 2.5 parts, polyoxyethylene arylphenyl ether 3 parts, sodium polyacrylate 0.5 parts and 10 parts of microspheres were mixed and pulverized to obtain a powder. The powder was kneaded with 100 parts of water, and then extruded from a plate with a 5 mm hole and granulated. The obtained granulated product was vacuum-dried at a temperature of 50 ° C. under a reduced pressure of 100 Torr, but it was melted and a granular composition was not obtained.

Comparative Example 7
2 parts of bensulfuron methyl, 1.2 parts of pyriminobac-methyl, 75.3 parts of anhydrous sodium sulfate, 3 parts of polyoxyethylene arylphenyl ether, 3 parts of condensate of naphthalene sulfonate, 0.5 part of sodium polyacrylate And 10 parts of microspheres were mixed and pulverized to obtain a powder. After 10 parts of water was added to the powder and kneaded, it was extruded from a plate with a 0.8 mm hole and granulated. Although the obtained granulated material was dried by ventilation at a temperature of 60 ° C., it was melted and no granular composition was obtained.

Test example 1
The granular composition before and after drying obtained from Examples 1 to 11 and the granular composition before drying obtained from Comparative Examples 1 to 7 were ground in a mortar and analyzed by a powder X-ray diffraction apparatus. . As a result, sodium sulfate in the granular compositions before and after drying obtained from Examples 1 to 10 was anhydrous, but the granular composition before drying obtained from Comparative Examples 1 to 7 was 10%. It was a hydrate.

Test example 2
When the agrochemical herbicide granular composition obtained in Examples 6 and 8 to 11 was sprayed onto a paddy field, the grains disappeared in an extremely short time and showed excellent diffusibility.
Moreover, when the agrochemical fungicide granular composition obtained in Example 7 was added to water, the particles disappeared in an extremely short time, and a spray liquid with good suspension was able to be prepared.

more than

Claims (5)

Next component (A), component (B) and component (C)
(A) anhydrous sodium sulfate having a content of 30 % by mass or more in the composition;
(B) at least one hydrate formation inhibitor selected from the group consisting of sodium chloride, urea, ammonium sulfate, lignin sulfonic acid sodium salt, sodium acetate, potassium chloride, and sodium carbonate, and (C) a fungicide as an agrochemical active ingredient (However, ionene polymer is excluded).
A pesticidal granular composition that contains sucrose and is produced by a wet granulation method. The agrochemical granular composition according to claim 1, wherein the ratio of the hydrate formation inhibitor to anhydrous sodium sulfate is 2 % by mass or more.   3. The agrochemical granular composition according to claim 1 or 2, which is a granule or a granular wettable powder. (A) 30 % by mass or more of anhydrous sodium sulfate, (B) Formation of at least one hydrate salt selected from the group consisting of sodium chloride, urea, ammonium sulfate, sodium lignin sulfonate, sodium acetate, potassium chloride and sodium carbonate It is characterized by adding water to a composition containing an inhibitor and (C) a fungicide (excluding ionene polymer) as an agrochemical active ingredient, and then granulating the granulated product, followed by drying at 40 ° C. or higher. A method for producing a granular composition for agricultural chemicals. The method for producing a pesticidal granular composition according to claim 4, wherein the ratio of the hydrate formation inhibitor to anhydrous sodium sulfate is 2 % by mass or more.