JP5224527B2 - Agrochemical granular composition - Google Patents

Description

  The present invention relates to a pesticide granular composition containing a nereistoxin-based pesticide active ingredient that efficiently controls pests generated in paddy fields, fields and the like. More specifically, the present invention relates to an agrochemical granular composition in which nereistoxin-based agrochemical active ingredients are stably coated on a basic inorganic mineral granular material.

  Examples of nereistoxin pesticide active ingredients include thiocyclam oxalate (hereinafter TCHO), cartap hydrochloride, bensultap and the like. These act as contact poisons, food poisons, and are effective insecticides that are effective even when applied to the water surface. In addition to Lepidoptera and Coleopterous pests, it is effective against teatropod thrips, leafhoppers, rice scallop nematodes and the like, and has little risk of phytotoxicity (Non-patent Document 1).

  It is known that nereistoxin pesticide active ingredients are chemically unstable and unstable under alkaline conditions (Non-patent Document 2). Therefore, it has been recognized as a matter of course that the use of basic inorganic minerals such as calcium carbonate as the grain core of nereistoxin-based agrochemical active ingredient-containing granular compositions should be avoided. A granular composition using an inorganic mineral is not known.

  As a preparation aimed at improving the stability of the nereistoxin agrochemical active ingredient in the preparation, a preparation (Patent Document 1) coated with a waxy substance that is solid at room temperature has been known.

  In addition, among the nereistoxin pesticide active ingredients, there is the only report that bensultap was formulated stably under basic conditions. For example, a report on a benlustap solid preparation containing calcium carbonate as a bulking agent (Patent Document 2), and a report on the stabilization of bensultap in the preparation by containing a basic oxide such as calcium oxide, zinc oxide or magnesium oxide (Patent Document 3).

Edited by the Japanese Plant Protection Association, “Agricultural Chemicals Handbook (1998 Edition)” Japan Plant Protection Association December 15, 1998 123-125 C. D. S. Tomlin, “Pesticide Manual” 13th edition BCPC 2003 967-968 (C.D. S Tomlin, The Pesticide Manual, Thirteenth Edition, BCPC 2003 P.967-968) Edited by Mitsuru Sasaki et al., “Development of Japanese Agricultural Chemicals”, Japanese Pesticide Society, 2003 117-130 Japanese Patent No. 2696354 (column 6, line 2) JP-A-6-312902 (page 3) Japanese Patent No. 2706655 (column 10, line 32)

However, no examples of TCHO and cartap hydrochloride that have been stably formulated under basic conditions have been reported, and no stable formulation has yet been found for nereistoxin-based pesticide active ingredients in general.
Basic inorganic minerals that can be used as extenders, such as calcium carbonate, are safe and inexpensive, but are nereistoxin pesticides that are unstable under basic conditions. It could not be used to formulate active ingredients.

  As a result of investigations using various extenders, excipients, and stabilizers that can be used in granular compositions in the agricultural and horticultural field, the present inventors have found that nereistoxin-based agrochemical active ingredients can be used under alkaline conditions. In spite of the fact that it is known to be decomposed by the above, it has been found that nereistoxin-based agrochemical active ingredients can be stably coated on the cores of basic inorganic minerals such as calcium carbonate. In other words, basic inorganic minerals by coating a mixture of nereistoxin pesticidal active ingredient and stabilizer phosphoric acid on the nuclei of basic inorganic minerals such as calcium carbonate using a lipophilic liquid as an adhesive. It has been found that a stable granular composition can be obtained even when a granule nucleus is used as an extender.

That is, the present invention
(1) An agrochemical granular composition containing nereistoxin pesticide active ingredient as an agrochemical active ingredient, an inorganic mineral grain nucleus containing a basic inorganic mineral grain nucleus as an extender, an oleophilic liquid as an adhesive, and phosphoric acid as a stabilizer ,
(2) The pesticide granular composition according to the above (1), wherein the nereistoxin pesticide active ingredient is thiocyclam oxalate (hereinafter referred to as TCHO) or cartap hydrochloride,
(3) The agrochemical granular composition according to the above (1) or (2), wherein the lipophilic liquid is liquid paraffin,
(4) The agricultural chemical granular composition according to any one of (1) to (3), further comprising an anti-caking agent,
(5) 65-98% by weight of inorganic mineral grain core, 1.0-20.0% by weight of nereistoxin pesticide active ingredient, 0.5-10% by weight of lipophilic liquid, 0.05-0.5 phosphoric acid The agrochemical granular composition according to any one of the above (1) to (4), which contains, by weight, 0 to 2% by weight of an anti-caking agent,
(6) The agrochemical granule according to any one of (1) to (5) above, wherein the mineral mineral substance nucleus is coated with a nereistoxin-based pesticide active ingredient and phosphoric acid using a lipophilic liquid as an adhesive. Composition,
(7) Any one of the above (1) to (6) obtained by coating a composition obtained by mixing an inorganic mineral grain core and a lipophilic liquid with a nereistoxin pesticidal active ingredient and phosphoric acid mixed and coated The agrochemical granular composition as described in
(8) The agricultural chemical granular composition according to (6) or (7) above, wherein the anti-caking agent is used by mixing with nereistoxin agricultural chemical active ingredient and / or phosphoric acid,
(9) In any one of the above (1) to (8), which comprises mixing a lipophilic liquid into an inorganic mineral grain core and then adding, mixing and coating a nereistoxin pesticidal active ingredient and phosphoric acid A method for producing the described agrochemical granular composition,
(10) The method for producing a granular agricultural chemical composition according to the above (9), wherein the anti-caking agent is used by mixing with nereistoxin agricultural chemical active ingredient and / or phosphoric acid.

  The nereistoxin pesticide active ingredient in the pesticide granular composition uses lipophilic liquid in combination with lipophilic liquid and stabilizer, despite the use of basic inorganic mineral grain nuclei such as calcium carbonate as extenders It is stable for a long time.

  The nereistoxin pesticidal active ingredient used in the granular composition of the present invention includes TCHO, cartap hydrochloride, bensultap, etc., preferably TCHO, cartap hydrochloride. These nereistoxin-based agrochemical active ingredients can be synthesized by known methods (see Japanese Patent Application Laid-Open No. 51-136689, Japanese Patent Publication No. 45-18847, Non-Patent Document 3). These agrochemical active ingredients may be used alone or in combination of two or more in the agrochemical granular composition of the present invention. The content ratio of the nereistoxin-based pesticidal active ingredient in the pesticidal granular composition is usually about 1.0 to 20.0% by weight, preferably about 2.0 to 10.0% by weight.

  In addition to the nereistoxin agrochemical active ingredient, the following agrochemical active ingredients in the agrochemical granular composition of the present invention are within the range of not affecting the nereistoxin agrochemical active ingredient in terms of chemical stability. If it exists, one or more types can be used together. Specific examples include the following, but are not limited thereto. For example, pesticidal active ingredients include BPMC (2-sec-butylphenyl-N-methylcarbamate), MIPC (2-isopropylphenyl-N-methylcarbamate), NAC (1-naphthyl-N-methylcarbamate), nitenpyram (( E) -N- (6-Chloro-3-pyridylmethyl) -N-ethyl-N'-methyl-2-nitrovinylidenediamine), pyracrophos ((RS)-[O-1- (4-chlorophenyl) pyrazole- 4-yl] = O-ethyl = S-propyl = phosphorothioate), buprofezin (2-tert-butylimino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5- Thiadiazin-4-one), flucitrinate ((RS) -α-cyano-3-phenoxybenzyl = ( ) -2- (4-difluoromethoxyphenyl) -3-methylbutyrate), mesomil (S-methyl-N-[(methylcarbamoyl) oxy] thioacetimidate), etofenprox (2- (4-ethoxy) Phenyl) -2-methylpropyl = 3-phenoxybenzyl = ether), XMC (3,5-xylyl-N-methylcarbamate), dinotefuran ((RS) -1-methyl-2-nitro-3- (tetrahydro-3) -Furylmethyl) guanidine), acetamiprid ((E) -N-[(6-chloro-3-pyridyl) methyl] -N'-cyano-N-methylacetamidine), thiamethoxam (3- (2-chloro-1 , 3-thiazol-5-ylmethyl) -5-methyl-1,3,5-oxadiazinan-4-ylidene (nitro) amine, etc. Bactericidal active ingredients include IBP (O, O-diisopropyl-S-benzylthiophosphate), tricyclazole (5-methyl-1,2,4-triazolo [3,4-b] benzothiazole), and fusalide. (4,5,6,7-tetrachlorophthalide), validamycin, probenazole (3-allyloxy-1,2-benzisothiazole-1,1-dioxide), ferimzone ((Z) -2′-methylacetophenone = 4,6-dimethylpyrimidin-2-ylhydrazine), flutolanil (α, α, α-trifluoro-3′-isopropoxy-O-toluanilide), furametopyl ((RS) -5-chloro-N- (1, 3-dihydro-1,1,3-trimethylisobenzofuran-4-yl) -1,3-dimethylpyrazole-4-carb Boxamide, pencyclon (1- (4-chlorobenzyl) -1-cyclopentyl-3-phenylurea, dichromedin (6- (3,5-dichloro-4-methylphenyl) -3 (2H) -pyridazinone), kasugamycin monohydrochloride Examples include salt.

  Specific examples of the basic inorganic mineral grain nuclei contained in the inorganic mineral grain nuclei used as the extender in the present invention include calcium carbonate, talc, calcium oxide, etc. Among them, calcium carbonate available in large quantities is desirable. . The above basic inorganic mineral grain nuclei may be used singly or in combination. In the present invention, non-basic inorganic mineral grain nuclei such as sea sand, quartz and quartz sand may be mixed in the basic inorganic mineral grain nuclei. The basic inorganic mineral grain nuclei contained in the inorganic mineral grain nuclei used in the present invention can usually take any value from 5 to 100% by weight.

  In general, an agrochemical granular composition obtained by coating an inorganic mineral grain core with an agrochemical active ingredient increases the ratio of the weight of the agrochemical active ingredient coated on a grain core with a small particle size to the grain core, and conversely, Large grain nuclei have a small proportion of the weight of the pesticidal active ingredient to the grain nuclei, resulting in a difference in the content of the pesticidal active ingredient between the two, which often causes variation in the analysis results and hinders quality control. Accordingly, the particle size distribution of the inorganic mineral grain nuclei used in the present invention is usually 0.05 to 2.0 mm, preferably 0.06 to 1.7 mm. The amount of the inorganic mineral grain nuclei used is usually 65 to 98% by weight, preferably 75 to 95% by weight in the composition.

In the pesticide granular composition of the present invention, as the lipophilic liquid used as an adhesive, liquid paraffin (eg, Moresco White 60, Moresco White 40, Moresco White 30: Trademark; Matsumura Petrochemical Laboratory), Petroleum fractions, animal and vegetable oils and the like can be mentioned. Usually, the viscosity can be selected from those of 68 mm / s ² (40 ° C.) or less, preferably 1.5 to 20 mm / s ² (40 ° C.), more preferably The thing of 1.75-13mm / s < ² > (40 degreeC) can be used. These can be used alone or in admixture of two or more, but are not limited thereto. The content of the lipophilic liquid in the granular agricultural chemical composition is usually about 0.5 to 10% by weight, preferably about 1.0 to 5.0% by weight.

In the agricultural chemical granular composition of the present invention, the phosphoric acid used as a stabilizer is preferably an industrial grade (75%) or more. The addition amount of phosphoric acid is usually in the range of 0.05 to 0.5% by weight, preferably 0.1 to 0.3% by weight in the composition. There is no specific method for adding phosphoric acid,
(1) Prepare a premix by mixing nereistoxin pesticide active ingredient and phosphoric acid,
(2) Add phosphoric acid after adhering nereistoxin pesticide active ingredient to inorganic mineral grain core,
(3) After adding an adhesive (lipophilic liquid) to the inorganic mineral grain core, add phosphoric acid alone before adhering the nereistoxin pesticide active ingredient,
(4) Add a mixture of phosphoric acid and the following anti-caking agent (white carbon etc.) at a ratio of 1: 1,
Such a method is preferable.

In the agrochemical granular composition of the present invention, in order to prevent caking during storage of the nereistoxin pesticide active ingredient, white carbon (eg, Sipernat22S: Trademark; Degussa), diatomaceous earth, magnesium stearate, Aluminum oxide, titanium dioxide, clay, vermiculite, pumice and the like can be used as necessary. In addition to the nereistoxin pesticide active ingredient, the powder as described above can be added to the powder coated on the grain core.
This anti-caking agent is usually used in an amount of 0 to 2% by weight, preferably 0.2 to 0.7% by weight, in the agricultural chemical granular composition.

  A surfactant can also be added to the granular agricultural chemical composition of the present invention. Specific examples of surfactants generally include nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants that are commonly used in agricultural chemical formulations. For example, nonionic interfaces such as polyoxyethylene alkyl aryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene phenyl ether polymer, polyoxyethylene alkylene aryl phenyl ether, polyoxyethylene polyoxypropylene block polymer, etc. Activators, anionic surfactants such as polyoxyethylene styryl phenyl ether sulfate, lignin sulfonate, alkylaryl sulfonate, alkylnaphthalene sulfonate, and cationic surfactants such as alkylbetaines and quaternary ammonium salts And amphoteric surfactants.

The granular composition of the pesticidal composition of the present invention is generally mixed with inorganic mineral grain nuclei and lipophilic liquid in a mixer, and then added with powder containing nereistoxin pesticidal active ingredient and phosphoric acid, and mixed well with a mixer. Obtained by coating. The powder containing nereistoxin pesticide active ingredient and phosphoric acid can be added in any order of addition.
In particular,
(1) A lipophilic liquid is mixed into an inorganic mineral grain core, then phosphoric acid is added, and then a powder containing a nereistoxin agrochemical active ingredient is added and mixed to obtain a coated granule.
(2) A powder containing phosphoric acid adsorbed to an anti-caking agent (such as white carbon) is added to a mixture of inorganic mineral grain nuclei and lipophilic liquid, followed by a powder containing a nereistoxin pesticide active ingredient Add and mix to get coated granules,
(3) Mixing the lipophilic liquid into the inorganic mineral grain core, then adding and mixing the powder containing the nereistoxin agrochemical active ingredient, and after coating, adding phosphoric acid to obtain the coated granule,
(4) Mixing lipophilic liquid with inorganic mineral grain cores, then adding and mixing powder containing nereistoxin pesticidal active ingredient, coating, and then phosphoric acid anti-caking agent (white carbon etc.) Add powder adsorbed on to obtain coated granules,
(5) A lipophilic liquid is mixed with an inorganic mineral grain core, and then a powder containing a nereistoxin agrochemical active ingredient and phosphoric acid is added and mixed to obtain a coated granule.
Any of these methods can obtain the agrochemical granular composition.

  The pesticide granular composition of the present invention exerts an insecticidal effect against pests that harm agricultural crops by directly spraying on the rice field and field soil.

  Next, the present invention will be described in detail using examples and test examples, but the present invention is not limited thereto. In the examples, all “parts” represent parts by weight.

Example 1
95.0 parts of TCHO and 5.0 parts of Sipernat 22S are mixed well and pulverized with a hammer mill to prepare a TCHO premix. Sipernat22S 50 parts and phosphoric acid 50 parts are mixed well to prepare a phosphoric acid premix. Grain core of basic inorganic mineral (mixed silica sand, particle size distribution: 0.5 to 1.7 mm, pH (10%): 9.5) 93.3 parts, Moresco White 60 1.5 parts with a concrete mixer After mixing well, 5.0 parts of TCHO premix and 0.2 part of phosphoric acid premix were added, mixed for 15 minutes, and sieved with a sieve having an opening of 0.5 to 1.7 mm. The TCHO 4% granular composition of the present invention I got a thing.

Example 2
95.0 parts of TCHO and 5.0 parts of Sipernat 22S are mixed well and pulverized with a hammer mill to prepare a TCHO premix. Sipernat22S 50 parts and phosphoric acid 50 parts are mixed well to prepare a phosphoric acid premix. Basic inorganic mineral grain core (mixed silica sand, particle size distribution: 0.5 to 1.7 mm, pH (10%): 9.5) 93.1 parts, Moresco White 60 1.5 parts with a concrete mixer After mixing well, 5.0 parts of TCHO premix and 0.4 part of phosphoric acid premix were added and mixed for 15 minutes, and sieved with a sieve having an opening of 0.5 to 1.7 mm. The TCHO 4% granular composition of the present invention I got a thing.

Example 3
95.0 parts of TCHO and 5.0 parts of Sipernat 22S are mixed well and pulverized with a hammer mill to prepare a TCHO premix. Sipernat22S 50 parts and phosphoric acid 50 parts are mixed well to prepare a phosphoric acid premix. Basic inorganic mineral grain core (mixed silica sand, particle size distribution: 0.5 to 1.7 mm, pH (10%): 9.5) 93.0 parts, Moresco White 60 1.4 parts with a concrete mixer After mixing well, 5.0 parts of TCHO premix and 0.6 parts of phosphoric acid premix are added and mixed for 15 minutes, and sieved with a sieve having an opening of 0.5 to 1.7 mm. The TCHO 4% granular composition of the present invention I got a thing.

Example 4
95.0 parts of TCHO and 5.0 parts of Sipernat 22S are mixed well and pulverized with a hammer mill to prepare a TCHO premix. Sipernat22S 50 parts and phosphoric acid 50 parts are mixed well to prepare a phosphoric acid premix. Basic inorganic mineral grain nuclei (mixed silica sand, particle size distribution: 0.5 to 1.7 mm, pH (10%): 9.5) 92.9 parts, Moresco White 60 1.3 parts with a concrete mixer After mixing well, 5.0 parts of TCHO premix and 0.8 part of phosphoric acid premix were added, mixed for 15 minutes, and sieved with a sieve having an opening of 0.5 to 1.7 mm. The TCHO 4% granular composition of the present invention I got a thing.

Example 5
95.0 parts of TCHO and 5.0 parts of Sipernat 22S are mixed well and pulverized with a hammer mill to prepare a TCHO premix. Sipernat22S 50 parts and phosphoric acid 50 parts are mixed well to prepare a phosphoric acid premix. Basic inorganic mineral grain core (mixed silica sand, particle size distribution: 0.5 to 1.7 mm, pH (10%): 9.5) 92.7 parts, Moresco White 60 1.3 parts with a concrete mixer After mixing well, 5.0 parts of TCHO premix and 1.0 part of phosphoric acid premix were added, mixed for 15 minutes, and sieved with a sieve having an opening of 0.5 to 1.7 mm. The TCHO 4% granular composition of the present invention I got a thing.

Example 6
91.4 parts of TCHO, 6.7 parts of Sipernat 22S, and 1.9 parts of phosphoric acid are mixed well, and ground with a hammer mill to prepare a TCHO premix. Neutral inorganic mineral grain nuclei (Gifu-produced quartz sand, Takeori Sakai, particle size distribution: 0.5 to 1.0 mm, pH (10%): 6.4) 88.3 parts, calcium carbonate grain nuclei (Nitto powdered Industrially produced Hiroshima granule, particle size distribution: 0.5 to 1.0 mm, pH (10%): 9.7) After 5.0 parts were put into a concrete mixer and mixed well, Moresco White 60 1.5 Add parts and mix further. Finally, 5.2 parts of TCHO premix was added and mixed for 15 minutes, and sieved with a sieve having an opening of 0.5 to 1.7 mm to obtain a TCHO 4% granular composition of the present invention.

Example 7
91.4 parts of TCHO, 6.7 parts of Sipernat 22S, and 1.9 parts of phosphoric acid are mixed well, and ground with a hammer mill to prepare a TCHO premix. Neutral inorganic mineral grain nuclei (Gifu silica sand, manufactured by Takeori Sakai, particle size distribution: 0.5 to 1.0 mm, pH (10%): 6.4) 83.3 parts, calcium carbonate grain nuclei (Nitto powdered Industrial-made Hiroshima grain, particle size distribution: 0.5 to 1.0 mm, pH (10%): 9.7) After 10.0 parts were put into a concrete mixer and mixed well, Moresco White 60 1.5 Add parts and mix further. Finally, 5.2 parts of TCHO premix was added and mixed for 15 minutes, and sieved with a sieve having an opening of 0.5 to 1.7 mm to obtain a TCHO 4% granular composition of the present invention.

Example 8
91.4 parts of TCHO, 6.7 parts of Sipernat 22S, and 1.9 parts of phosphoric acid are mixed well, and ground with a hammer mill to prepare a TCHO premix. Neutral inorganic mineral grain nuclei (Gifu-produced silica sand, Takeori Sakai, particle size distribution: 0.5 to 1.0 mm, pH (10%): 6.4) 73.3 parts, calcium carbonate grain nuclei (Nitto powdered Industrial-made Hiroshima granule, particle size distribution: 0.5 to 1.0 mm, pH (10%): 9.7) After 20.0 parts were put into a concrete mixer and mixed well, Moresco White 60 1.5 Add parts and mix further. Finally, 5.2 parts of TCHO premix was added and mixed for 15 minutes, and sieved with a sieve having an opening of 0.5 to 1.7 mm to obtain a TCHO 4% granular composition of the present invention.

Example 9
91.4 parts of TCHO, 6.7 parts of Sipernat 22S, and 1.9 parts of phosphoric acid are mixed well, and ground with a hammer mill to prepare a TCHO premix. Neutral inorganic mineral grain nuclei (Silver sand from Gifu, Takeori Sakai, particle size distribution: 0.5 to 1.0 mm, pH (10%): 6.4) 43.3 parts, calcium carbonate grain nuclei (Nitto powdered Industrial-made Hiroshima grain, particle size distribution: 0.5 to 1.0 mm, pH (10%): 9.7) After 50.0 parts were put into a concrete mixer and mixed well, Moresco White 60 1.5 Add parts and mix further. Finally, 5.2 parts of TCHO premix was added and mixed for 15 minutes, and sieved with a sieve having an opening of 0.5 to 1.7 mm to obtain a TCHO 4% granular composition of the present invention.

Example 10
91.4 parts of TCHO, 6.7 parts of Sipernat 22S, and 1.9 parts of phosphoric acid are mixed well, and ground with a hammer mill to prepare a TCHO premix. Neutral inorganic mineral grain nuclei (Gifu-produced silica sand, Takeori Sakai, particle size distribution: 0.5 to 1.0 mm, pH (10%): 6.4) 18.3 parts, calcium carbonate grain nuclei (Nitto powdered Industrially produced Hiroshima grain, particle size distribution: 0.5 to 1.0 mm, pH (10%): 9.7) After 75.0 parts were put into a concrete mixer and mixed well, Moresco White 60 1.5 Add parts and mix further. Finally, 5.2 parts of TCHO premix was added and mixed for 15 minutes, and sieved with a sieve having an opening of 0.5 to 1.7 mm to obtain a TCHO 4% granular composition of the present invention.

Example 11
91.4 parts of TCHO, 6.7 parts of Sipernat 22S, and 1.9 parts of phosphoric acid are mixed well, and ground with a hammer mill to prepare a TCHO premix. After putting 93.3 parts into a concrete mixer and mixing well, calcium carbonate grain nuclei (Nitto Flour & Chemicals Hiroshima grain, particle size distribution: 0.5 to 1.0 mm, pH (10%): 9.7) Add 1.5 parts of Moresco White 60 and mix further. Finally, 5.2 parts of TCHO premix was added and mixed for 15 minutes, and sieved with a sieve having an opening of 0.5 to 1.7 mm to obtain a TCHO 4% granular composition of the present invention.

Example 12
Cartap hydrochloride 83.3 parts, Sipernat 22S 10.8 parts, phosphoric acid 5.9 parts are mixed well and ground with a hammer mill to prepare a cartap hydrochloride premix. Calcium carbonate granule core (Nippon Flour & Chemical Industries Hiroshima grain, particle size distribution: 0.5 to 1.0 mm, pH (10%): 9.7) 93.0 parts, Moresco White 60 1.9 parts After mixing well with a concrete mixer, 5.1 parts of cartap hydrochloride premix is added, mixed for 15 minutes, and sieved with a sieve having an opening of 0.5 to 1.7 mm, and the composition of cartap hydrochloride 4% granular composition of the present invention I got a thing.

Comparative Example 1
95.0 parts of TCHO and 5.0 parts of Sipernat 22S are mixed well and pulverized with a hammer mill to prepare a TCHO premix. Basic inorganic mineral grain core (mixed silica sand, particle size distribution: 0.5 to 1.7 mm, pH (10%): 9.5) 93.5 parts, Moresco White 60 1.5 parts with a concrete mixer After mixing well, 5.0 parts of TCHO premix was added, mixed for 15 minutes, and sieved with a sieve having an aperture of 0.5 to 1.7 mm to obtain a TCHO 4% granular composition for comparison.

Comparative Example 2
91.4 parts of TCHO, 6.7 parts of Sipernat 22S, and 1.9 parts of phosphoric acid are mixed well, and ground with a hammer mill to prepare a TCHO premix. Calcium carbonate kernel (Nitto Flour & Chemicals, Hiroshima-made granule, particle size distribution: 0.5 to 1.0 mm, pH (10%): 9.7) 93.3 parts, PEG-400 1.5 parts concrete After thoroughly mixing with a mixer, 5.2 parts of TCHO premix was added, mixed for 15 minutes, and sieved with a sieve having an opening of 0.5 to 1.7 mm to obtain a TCHO 4% granular composition for comparison.

Comparative Example 3
93.1 parts of TCHO and 6.9 parts of Sipernat 22S are mixed well and ground with a hammer mill to prepare a TCHO premix. Calcium carbonate granule (Nitto Fluka Kogyo Hiroshima grain, particle size distribution: 0.5-1.0 mm, pH (10%): 9.7) 93.5 parts, PEG-400 1.5 parts concrete After thoroughly mixing with a mixer, 5.0 parts of TCHO premix was added, mixed for 15 minutes, and sieved with a sieve having an aperture of 0.5 to 1.7 mm to obtain a TCHO 4% granular composition for comparison.

Comparative Example 4
Cartap hydrochloride 83.3 parts, Sipernat 22S 10.8 parts, phosphoric acid 5.9 parts are mixed well and ground with a hammer mill to prepare a cartap hydrochloride premix. Calcium carbonate grain core (Hiroshima grain made by Nitto Flour Chemical Co., Ltd., particle size distribution: 0.5 to 1.0 mm, pH (10%): 9.7) 93.0 parts, PEG-400 1.9 parts concrete After mixing well with a mixer, 5.1 parts of Cartap hydrochloride premix is added, mixed for 15 minutes, sieved with a sieve having an aperture of 0.5 to 1.7 mm, and a Cartap hydrochloride 4% granular composition for comparison Got.

Comparative Example 5
94.4 parts of Cartap hydrochloride and 5.6 parts of Sipernat 22S are mixed well and pulverized with a hammer mill to prepare Cartap hydrochloride premix. Calcium carbonate granule (Hiroshima grain made by Nitto Flour Chemical Co., Ltd., particle size distribution: 0.5-1.0 mm, pH (10%): 9.7) 94.0 parts, Moresco White 60 1.5 parts After mixing well with a concrete mixer, add 4.5 parts of Cartap Hydrochloride Premix, mix for 15 minutes, sieve through a sieve with an opening of 0.5 to 1.7 mm, and a 4% granular composition of Cartap Hydrochloride for comparison I got a thing.

Comparative Example 6 (Patent Document 3 applied to TCHO)
After thoroughly mixing 4.7 parts of TCHO, 8.0 parts of dextrin, 5.0 parts of Neukalgen BX-C, 25 parts of magnesium oxide and 57.3 parts of clay, 12 parts of water was added and kneaded well. Is granulated with an extrusion granulator (screen diameter 1.0 mm) to obtain a wet-formed product. This was dried, sized and sieved with a 0.5 to 1.7 mm sieve to obtain a TCHO 4% granule for comparison.

Comparative example 7 (patent document 3 applied to cartap hydrochloride)
Cartap hydrochloride 4.2 parts, Dextrin 8.0 parts, Neukalgen BX-C 5.0 parts, Magnesium oxide 25 parts, Clay 57.8 parts were mixed well, but 12 parts of water was added and kneaded well. The kneaded product is granulated with an extrusion granulator (screen diameter 1.0 mm) to obtain a wet-formed product. This was dried and then sized and sieved with a sieve of 0.5 to 1.7 mm to obtain a cartap hydrochloride 4% granule for comparison.

Comparative Example 8 (patent document 2 applied to TCHO)
After thoroughly mixing 4.7 parts of TCHO, 3.2 parts of serogen 7A, 0.54 parts of Neukalgen BX-C, 91.5 parts of calcium carbonate powder, 12 parts of water was added and kneaded well, and the kneaded product was extruded. Granulate with a granulator (screen diameter 1.0 mm) to obtain a wet-formed product. This was dried, sized and sieved with a 0.5 to 1.7 mm sieve to obtain a TCHO 4% granule for comparison.

Comparative Example 9 (patent document 2 applied to cartap hydrochloride)
Cartap hydrochloride 4.2 parts, Cellogen 7A 3.2 parts, Neucargen BX-C 0.54 parts, Calcium carbonate powder 92.0 parts were mixed well, then 12 parts of water was added and kneaded well. Is granulated with an extrusion granulator (screen diameter 1.0 mm) to obtain a wet-formed product. This was dried and then sized and sieved with a sieve of 0.5 to 1.7 mm to obtain a cartap hydrochloride 4% granule for comparison.

Test example (stability test)
Stability comparison was performed as follows using the agrochemical granular composition obtained in each Example and Comparative Example.
50 g of the agricultural chemical granular composition was put in an aluminum bag, sealed, stored in a 54 ° C. incubator, and the storage stability of the active ingredient after 2 weeks and 4 weeks was examined. The test results are shown below (Table 1-3). In the table, A. I. Means active ingredient and Cartap means cartap hydrochloride.

  As is clear from the results of Tables 1 and 2, the agrochemical granular composition of the present invention has stable TCHO in the granular composition despite using the basic inorganic mineral grain core as an extender. It was. Even when the content of calcium carbonate as the inorganic mineral grain nucleus was high, the pesticidal active ingredient in the granular composition was stable. As is clear from the results in Table 3, the stability of TCHO was impaired when phosphoric acid was not included (Comparative Example 1). In addition, when PEG-400, which is a water-soluble liquid, is used as an adhesive instead of a lipophilic liquid (liquid paraffin) (Comparative Examples 2 and 3), the degradation of the agrochemical active ingredient is performed regardless of whether or not phosphoric acid is added. Was authoritative. The above-mentioned tendency observed with TCHO could be similarly observed with cartap hydrochloride (Example 12 and Comparative Examples 4 and 5). When the patent concerning the stabilization of bensultap was applied to TCHO and cartap hydrochloride (Comparative Examples 6 to 9), the degradation of both agrochemical active ingredients was remarkable. Therefore, even if a known pharmaceutical formulation in which bensultap is stable even if a basic inorganic mineral is used, it cannot be simply applied to TCHO and cartap hydrochloride, which are the same nereistoxin pesticide active ingredients. I understand.

  By coating a mixture of nereistoxin pesticidal active ingredient and stabilizer phosphoric acid using lipophilic liquid as an adhesive to basic inorganic mineral grain nuclei such as calcium carbonate, basic inorganic mineral grain nuclei Is used as a bulking agent to obtain an agricultural chemical granular composition excellent in the stability of the nereistoxin-based agricultural chemical active ingredient.

Claims (10)

At least one nereistoxin pesticide active ingredient selected from the group consisting of thiocyclam oxalate, cartap hydrochloride and bensultap as an agrochemical active ingredient, and an inorganic mineral grain nucleus containing a basic inorganic mineral grain nucleus as an extender An agrochemical granular composition containing , as an adhesive, at least one lipophilic liquid selected from the group consisting of liquid paraffin, petroleum fractions and animal and vegetable oils and phosphoric acid as a stabilizer.   The granular agricultural chemical composition according to claim 1, wherein the nereistoxin-based agricultural chemical active ingredient is thiocyclam oxalate (hereinafter referred to as TCHO) or cartap hydrochloride.   The pesticidal granular composition according to claim 1 or 2, wherein the lipophilic liquid is liquid paraffin. Furthermore, it contains at least one type of anti-caking agent selected from the group consisting of amorphous silicon dioxide, diatomaceous earth, magnesium stearate, aluminum oxide, titanium dioxide, clay and vermiculite. The pesticide granular composition according to Item. 65 to 98% by weight of inorganic mineral grain core, 1.0 to 20.0% by weight of nereistoxin pesticide active ingredient, 0.5 to 10% by weight of lipophilic liquid, 0.05 to 0.5% by weight of phosphoric acid, The agrochemical granular composition of Claim 4 containing 0 to 2 weight% of anti-caking agents.   The granular composition of an agrochemical according to any one of claims 1 to 5, wherein an inorganic mineral grain core is coated with a nereistoxin-based agrochemical active ingredient and phosphoric acid using a lipophilic liquid as an adhesive. .   7. A composition obtained by mixing an inorganic mineral grain core and a lipophilic liquid, and adding and mixing a nereistoxin-based pesticidal active ingredient and phosphoric acid, and coating the resultant composition according to any one of claims 1 to 6. Pesticide granular composition. At least one anti-caking agent selected from the group consisting of amorphous silicon dioxide, diatomaceous earth, magnesium stearate, aluminum oxide, titanium dioxide, clay and vermiculite is mixed with nereistoxin pesticide active ingredient and / or phosphoric acid. The agrochemical granular composition according to claim 6 or 7, which is used as a composition. At least one lipophilic liquid selected from the group consisting of liquid paraffin, petroleum fraction and animal and vegetable oil as an adhesive is mixed with an inorganic mineral grain nucleus including a basic inorganic mineral grain nucleus as a bulking agent , A method comprising adding, mixing and coating at least one nereistoxin pesticidal active ingredient selected from the group consisting of thiocyclam oxalate, cartap hydrochloride and bensultap as an agrochemical active ingredient, and phosphoric acid. The manufacturing method of the agrochemical granular composition as described in any one of Claim 1 thru | or 8. At least one anti-caking agent selected from the group consisting of amorphous silicon dioxide, diatomaceous earth, magnesium stearate, aluminum oxide, titanium dioxide, clay and vermiculite is mixed with nereistoxin pesticide active ingredient and / or phosphoric acid. The manufacturing method of the agrochemical granular composition of Claim 9 used.