Title of Invention	GRANULAR AGRICHEMICAL COMPOSITION
Abstract	Disclosed is a granular agrichemical composition produced by coating a mixture of a nereistoxin-type agrichemical active component and phosphoric acid as a stabilizing agent onto a granule core made of a basic inorganic mineral substance by using a lipophilic liquid as an adhesive agent. The granular agrichemical composition shows excellent stability of the nereistoxin-type agrichemical active component.

Title of Invention

GRANULAR AGRICHEMICAL COMPOSITION

Abstract

Disclosed is a granular agrichemical composition produced by coating a mixture of a nereistoxin-type agrichemical active component and phosphoric acid as a stabilizing agent onto a granule core made of a basic inorganic mineral substance by using a lipophilic liquid as an adhesive agent. The granular agrichemical composition shows excellent stability of the nereistoxin-type agrichemical active component.

Full Text	DESCRIPTION GRANULAR AGRICHEMICAL COMPOSITION Technical Field [0001] The present invention relates to a granular agricultural chemical composition containing a nereistoxin agricultural chemical active ingredient which can efficiently control harmful insects breeding in paddy fields and plowed fields. More particularly, it relates to a granular agricultural chemical composition which comprises basic inorganic mineral granules coated with a nereistoxin agricultural chemical active ingredient. Background Art [0002] The nereistoxin agricultural chemical active ingredients include, for example, thiocyclam oxalate (hereinafter referred to as "TCHO"), cartap hydrochloride, bensultap, etc. They are insecticides which act as contact toxicity or stomach poison, and also exhibit activity by submerged application, and furthermore they are expected to have residual activity. They are effective against Scirtothrips dorsalis Hood, leafhoppers and rice stem withering nematode as well as insects belonging to Lepidoptera and Coleoptera, and they are less in chemical injury (Non-Patent Document 1). [0003] It is known that the nereistoxin agricultural chemical active ingredients undergo hydrolysis under alkaline conditions and are unstable (Non-Patent Document 2). Therefore, it is naturally avoided to use basic inorganic minerals such as calcium carbonate as granular nuclei of granular composition containing a nereistoxin agricultural chemical active ingredient, and no granular compositions using basic inorganic minerals have been known. [0004] For improving the stability of nereistoxin agricultural chemical active ingredients in formulations, there have been known formulations coated with a waxy material which is solid at room temperature (Patent Document 1). [0005] It is reported that among nereistoxin agricultural chemical active ingredients, only bensultap has been formulated stably under basic conditions. For example, there are a report on solid besultap formulations using calcium carbonate as an extender (Patent Document 2) and a report that bensultap in formulations can be stabilized by containing a basic oxide such as calcium oxide, zinc oxide or magnesium oxide (Patent Document 3). [0006] Non-Patent Document 1: "Handbook of Agricultural Chemicals" (1998) edited by Japan Plant Quarantine Association on December 15, 1998, P. 123-125 Non-Patent Document 2: C.D.S. Tomlin, "The Pesticide Manual", Thirteenth Edition, BCPC 2003, P. 967-968 Non-Patent Document 3: M. Sasaki, et al, "Development of Agricultural Chemicals in Japan", Japan Agricultural Chemicals Society, 2003, P. 117-130 Patent Document 1: Patent No. 2696354 (column 6, line 2) Patent Document 2: JP-A-6-312902 (page 3) Patent Document 3: Patent No. 2706655 (column 10, line 32) Disclosure of Invention Problem to be Solved by the Invention [0007] However, it has not been reported that formulations of TCHO and cartap hydrochloride have been stably obtained under basic conditions, and stable formulations of overall nereistoxin agricultural chemical active ingredients have not yet been found. When a granular agricultural chemical composition is to be prepared, basic inorganic mineral materials such as calcium carbonate usable as an extender are high in safety and inexpensive, but they cannot be used for obtaining formulations of nereistoxin agricultural chemical active ingredients which are unstable under basic conditions. Means for Solving the Problem [0008] The inventors have conducted researches on various extenders, vehicles and stabilizers usable for granular composition in the fields of agriculture and horticulture, and as a result, have found that though it is known that nereistoxin agricultural chemical active ingredients decompose under alkaline conditions, the nereistoxin agricultural chemical active ingredients can be stably coated on basic inorganic mineral granular nuclei such as calcium carbonate. That is, it has been found that even when basic inorganic mineral granular nuclei are used as an extender, a stable granular composition can be obtained by coating a mixture of the nereistoxin agricultural chemical active ingredient and phosphoric acid as a stabilizer on basic inorganic mineral granular nuclei such as calcium carbonate using an oleophilic liquid as an adhesive. That is, the present invention relates to the following embodiments. [0009] (1) A granular agricultural chemical composition which comprises a nereistoxin agricultural chemical active ingredient as an agricultural chemical active ingredient, inorganic mineral granular nuclei containing basic inorganic mineral granular nuclei as an extender, an oleophilic liquid as an adhesive and phosphoric acid as a stabilizer. (2) A granular agricultural chemical composition described in the above (1), wherein the nereistoxin agricultural chemical active ingredient is thiocyclam oxalate (hereinafter referred to as "TCHO") or cartap hydrochloride. (3) A granular agricultural chemical composition described in the above (1) or (2), wherein the oleophilic liquid is liquid paraffin. (4) A granular agricultural chemical composition described in any one of the above (l)-(3) which additionally contains a solidification inhibitor. (5) A granular agricultural chemical composition described in any one of the above (l)-(4) which comprises 65-98% by weight of basic inorganic mineral granular nuclei, 1.0-20.0% by weight of a nereistoxin agricultural chemical active ingredient, 0.5-10% by weight of an oleophilic liquid,0.05-0.5% by weight of phosphoric acid and 0-2% by weight of a solidification inhibitor. (6) A granular agricultural chemical composition described in any one of the above (l)-(5), wherein the nereistoxin agricultural chemical active ingredient and phosphoric acid are coated on the inorganic mineral granular nuclei using the oleophilic liquid as an adhesive. (7) A granular agricultural chemical composition described in any one of the above (l)-(6) which is obtained by adding the nereistoxin agricultural chemical active ingredient and phosphoric acid to a composition comprising a mixture of inorganic mineral granular nuclei and the oleophilic liquid and mixing them to coat the nereistoxin agricultural chemical active ingredient. (8) A granular agricultural chemical composition described in any one of the above (6) or (7), wherein a solidification inhibitor is mixed with the nereistoxin agricultural chemical active ingredient and/or phosphoric acid. (9) A method for producing a granular agricultural chemical composition described in any one of the above (l)-(8) which comprises mixing the inorganic mineral granular nuclei with the oleophilic liquid, then adding the nereistoxin agricultural chemical active ingredient and phosphoric acid to the mixture and mixing them to coat the nereistoxin agricultural chemical active ingredient. (10) A method for producing a granular agricultural chemical composition described in the above (9), wherein a solidification inhibitor is mixed with the nereistoxin agricultural chemical active ingredient and/or phosphoric acid. Advantages of the Invention [0010] Although basic inorganic mineral granular nuclei such as calcium carbonate are used as extender, the nereistoxin agricultural chemical active ingredient in the granular agricultural chemical composition is stable for a long period of time by using an oleophilic liquid and phosphoric acid as a stabilizer in combination. Best Mode for Carrying Out the Invention [0011] The nereistoxin agricultural chemical active ingredients used in the granular composition of the present invention include, for example, TCHO, cartap hydrochloride, bensultap, etc., and preferred are TCHO and cartap hydrochloride. These nereistoxin agricultural chemical active ingredients can be prepared by known methods (JP-A-51-136689, JP-B-45- 18847, and the above Non-Patent Document 3). These agricultural chemical active ingredients may be used each alone or in combination of two or more in the granular agricultural chemical composition of the present invention. The content of the nereistoxin agricultural chemical active ingredients in the granular agricultural chemical composition is usually about 1.0-20.0% by weight, preferably about 2.0-10.0% by weight. [0012] In the granular agricultural chemical composition of the present invention, in addition to the nereistoxin agricultural chemical active ingredients, one or more of the following agricultural chemical active ingredients can also be used so long as they do not affect the chemical stability of the nereistoxin agricultural chemical active ingredients. Non-limiting examples of the other agricultural chemical active ingredients are as follows. As insecticidal active ingredients, mention may be made of, for example, BPMC (2-sec-butylphenyl-N-methyl carbamate), MIPC (2-isopropylphenyl-N-methyl carbamate), NAC (1-naphthyl-N-methyl carbamate), Nitenpyrum ((E)-N-(6-chloro-3-pyridylmethyl)-N-ethyl- N'-methyl-2-nitrovinylidenediamine), Pyraclofos ((RS)- [0-1-(4-chlorophenyl)pyrazole-4-yl]=O-ethyl=S- propyl=phosphorothioate) , Buprofezine (2-tert- butylimino-3-isopropyl-5-phenyl-3,4,5, 6-tetrahydro-2H- 1, 3, 5-thiadiazine-4-one), Flucythrinate ( (RS)- -cyano- 3-phenoxybenzyl=(S)-2-(4-difluoromethoxyphenyl)-3- methylbutyrate), Methomyl (S-methyl-N- [(methylcarbamoyl)oxy]thioacetoimidate), Ethofenprox (2-(4-ethoxyphenyl)-2-methylpropyl=3- phenoxybenzyl=ether), XMC (3,5-xylyl-N-methyl carbamate), Dinotefuran ((RS)-l-methyl-2-nitro-3- (tetrahydro-3-furylmethyl)guanidine), Acetamiprid ((E)- N-t 6-chloro-3-pyridyl]methyl)-N'-cyano-N- methylacetoamidine), Thiamethoxam (3-(2-chloro-l,3- thiazole-5-ylmethyl)-5-methyl-l,3,5-oxadiazinane-4- ylidene(nitro)amine, etc. As fungicidal active ingredients, mention may be made of, for example, IBP (0,0-diisopropyl-S-benzyl thiophopshate), Tricyclazole (5-methyl-l,2,4-triazolo[3,4,5]benzothiazole), Fusalide (4,5,6,7-tetrachlorophthalide), Validamycin, Probenazole (3-allyloxy-l,2-benzoisothiazole-l,1- dioxide) , Ferimzone ( (Z) -2' -naethylacetophenone=4, 6- dimethylpyrimidine-2-ylhydrazine), Flutolanil α,α,α- trifluoro-3'-isopropoxy-O-trianilide), Furametpyr ((RS)-5-chLoro-N-(1,3-dihydro-l, 1,3- trimethylisobenzofuran-4-yl)-1,3-dimethylpyrazole-4- carboxamide, Pencycuron (1-(4-chlorobenzyl)-1- cyclopentyl-3-phenylurea, Diclomezine (6-(3,5-dichloro- 4-methylphenyl)-3-(2H)-pyridazinone), Kasugamycin- hydrochloride, etc. [0013] Examples of the basic inorganic mineral granular nuclei contained in the inorganic mineral granular nuclei used as an extender in the present invention are calcium carbonate, talc, calcium oxide, etc., and calcium carbonate which is available in a large amount is preferred. The above basic inorganic mineral granular nuclei may be used each alone or in admixture of two or more. In the present invention, inorganic mineral granular nuclei which are not basic, such as sea sand, quartz and silica sand may be present in the basic inorganic mineral granular nuclei. The basic inorganic mineral granular nuclei contained in the inorganic mineral granular nuclei used in the present invention may be contained in an optional amount in the range of usually 5-100% by weight. [0014] Usually, in the case of granular agricultural chemical composition obtained by coating inorganic mineral granular nuclei with an agricultural chemical active ingredient, the proportion in weight of the agricultural chemical active ingredient coated on granular nuclei of smaller diameter to the weight of the granular nuclei is greater, and, on the other hand, the proportion in weight of the agricultural chemical active ingredient coated on granular nuclei of larger diameter to the weight of the granular nuclei is smaller. Thus, there is a difference in contents of these agricultural chemical active ingredients, and sometimes there occurs variation in the results of content analysis, which causes hindrance to control of quality. Therefore, particle size distribution of the inorganic mineral granular nuclei used in the present invention is usually 0.05-2.0 mm, preferably 0.06-1.7 mm. The amount of the inorganic mineral granular nuclei used is usually 65-98% by weight, preferably 75- 95% by weight in the composition. [0015] As the oleophilic liquids used as an adhesive in the granular agricultural chemical composition of the present invention, there may be used liquid paraffin (e.g., Moresco White 60, Moresco White 40, Moresco White 30 (trademarks) manufactured by Matsumura Sekiyu Kagaku Kenkyujo), petroleum fraction, animal and vegetable oils, etc., and the oleophilic liquids can be selected from those which have a viscosity of usually 68 mm/s2 (40°C) or lower, preferably 1.5-20 mm/s2 (40°C) , more preferably 1.75-13 mm/s2 (40°C). These can be used each alone or in admixture of two or more, and the oleophilic liquids are not limited to the above examples. The content of the oleophilic liquids in the granular agricultural chemical composition is usually about 0.5-10% by weight, preferably about 1.0-5.0% by weight. [0016] The phosphoric acid used as a stabilizer in the granular agricultural chemical composition of the present invention is preferably higher than industrial grade (75%). The amount of phosphoric acid is usually 0.05-0.5% by weight, preferably 0.1-0.3% by weight in the composition. The method of addition of phosphoric acid is not particularly limited, and preferred are the following methods. (1) The nereistoxin agricultural chemical active ingredient is mixed with phosphoric acid to prepare a premix. (2) After the nereistoxin agricultural chemical active ingredient is adhered to the inorganic mineral granular nuclei, phosphoric acid is added. (3) After an adhesive (oleophilic liquid) is added to the inorganic mineral granular nuclei and before the nereistoxin agricultural chemical active ingredient is adhered, phosphoric acid is added alone. (4) A mixture of phosphoric acid and the following solidification inhibitor (such as white carbon) at 1:1 is added. [0017] In the granular agricultural chemical composition of the present invention, in order to inhibit solidification of the nereistoxin agricultural chemical active ingredient during storage of the composition, if necessary, there may be used white carbon (e.g., SIPERNAT 22S (trademark) manufactured by Degussa Co., Ltd.), diatomaceous earth, magnesium stearate, aluminum oxide, titanium dioxide, clay, vermiculite, pumice, etc. Not only the nereistoxin agricultural chemical active ingredient, but also the above powders may also be added to the powder to be coated on the granular nuclei. The solidification inhibitor is used in an amount of usually 0-2% by weight, preferably 0.2-0.7% by weight in the granular agricultural chemical composition. [0018] A surface active agent can also be added to the granular agricultural chemical composition of the present invention. The surface active agents include, for example, nonionic surface active agents, anionic surface active agents, cationic surface active agents and amphoteric surface active agents which are commonly used for agricultural chemical formulations. Specific examples of the surface active agents are nonionic surface active agents such as polyoxyethylenealkylaryl ethers, polyoxyethylenestyrylphenyl ether, polyoxyethylenealkyl esters, polyoxyethylenephenyl ether polymers, polyoxyethylenealkylenearylphenyl ethers, and polyoxyethylenepolyoxypropylene block polymers, anionic surface active agents such as polyoxyethylenestyrylphenyl ether sulfate, lignin sulfonic acid salts, alkylaryl sulfonates, and alkyl naphthalenesulfonates, cationic surface active agents such as alkyl betaine and quaternary ammonium salts, and amphoteric surface active agents. [0019] The granular agricultural chemical composition of the present invention is usually obtained by mixing well the inorganic mineral granular nuclei with the oleophilic liquid by a mixer, and thereafter adding phosphoric acid and a powder containing the nereistoxin agricultural chemical active ingredient, followed by mixing well by a mixer to coat the active ingredient. The powder containing the nereistoxin agricultural chemical active ingredient and phosphoric acid can be added in an optional order. Specifically, there are the following methods, and the granular agricultural chemical composition can be produced by any of these methods. (1) The inorganic mineral granular nuclei are mixed with oleophilic liquid, then phosphoric acid is added to the mixture, and thereafter a powder containing the nereistoxin agricultural chemical active ingredient is added, followed by mixing to obtain coated granules. (2) A powder obtained by adsorbing phosphoric acid to the solidification inhibitor (such as white carbon) is added to a mixture of inorganic mineral granular nuclei and oleophilic liquid, and then a powder containing nereistoxin agricultural chemical active ingredient is added, followed by mixing to obtain coated granules. (3) The inorganic mineral granular nuclei are mixed with oleophilic liquid, then a powder containing nereistoxin agricultural chemical active ingredient is added, followed by mixing to coat the active ingredient, and then phosphoric acid is added to obtain coated granules. (4) The inorganic mineral granular nuclei are mixed with oleophilic liquid, then a powder containing nereistoxin agricultural chemical active ingredient is added, followed by mixing to coat the active ingredient, and then a powder of solidification inhibitor (white carbon, etc.) to which phosphoric acid is adsorbed is added to obtain coated granules. (5) The inorganic mineral granular nuclei are mixed with oleophilic liquid, then a powder containing nereistoxin agricultural chemical active ingredient and phosphoric acid is added, followed by mixing to obtain coated granules. [0020] The granular agricultural chemical composition of the present invention exhibits insecticidal effect against harmful insects for farm products by direct application to paddy field or soil of plowed field. [0021] The present invention will be explained in detail below using the following examples and test examples, which should not be construed as limiting the invention. In examples, "part" is by weight. [0022] Example 1 95.0 parts of TCHO and 5.0 parts of Sipernat 22S were mixed well, and the mixture was pulverized by a hammer mill to prepare a TCHO premix. 50 parts of Sipernat 22S and 50 parts of phosphoric acid were mixed well to prepare a phosphoric acid premix. 93.3 parts of basic inorganic mineral granular nuclei (silica sand containing calcium carbonate grains, grain size distribution: 0.5-1.7 mm, pH (10%): 9.5) and 1.5 part of Moresco White 60 were mixed well by a concrete mixer, and to the mixture were added 5.0 parts of the TCHO premix and 0.2 part of the phosphoric acid premix, followed by mixing for 15 minutes. The mixture was screened by a sieve having an opening of 0.5-1.7 mm to obtain a granular composition containing 4% of TCHO of the present invention. [0023] Example 2 95.0 parts of TCHO and 5.0 parts of Sipernat 22S were mixed well, and the mixture was pulverized by a hammer mill to prepare a TCHO premix. 50 parts of Sipernat 22S and 50 parts of phosphoric acid were mixed well to prepare a phosphoric acid premix. 93.1 parts of basic inorganic mineral granular nuclei (silica sand containing calcium carbonate grains, grain size distribution: 0.5-1.7 mm, pH (10%): 9.5) and 1.5 part of Moresco White 60 were mixed well by a concrete mixer, and to the mixture were added 5.0 parts of the TCHO premix and 0.4 part of the phosphoric acid premix, followed by mixing for 15 minutes. The mixture was screened by a sieve having an opening of 0.5-1.7 mm to obtain a granular composition containing 4% of TCHO of the present invention. [0024] Example 3 95.0 parts of TCHO and 5.0 parts of Sipernat 22S were mixed well, and the mixture was pulverized by a hammer mill to prepare a TCHO premix. 50 parts of Sipernat 22S and 50 parts of phosphoric acid were mixed well to prepare a phosphoric acid premix. 93.0 parts of basic inorganic mineral granular nuclei (silica sand containing calcium carbonate grains, grain size distribution: 0.5-1.7 mm, pH (10%): 9.5) and 1.4 part of Moresco White 60 were mixed well by a concrete mixer, and to the mixture were added 5.0 parts of the TCHO premix and 0.6 part of the phosphoric acid premix, followed by mixing for 15 minutes. The mixture was screened by a sieve having an opening of 0.5-1.7 mm to obtain a granular composition containing 4% of TCHO of the present invention. [0025] Example 4 95.0 parts of TCHO and 5.0 parts of Sipernat 22S were mixed well, and the mixture was pulverized by a hammer mill to prepare a TCHO premix. 50 parts of Sipernat 22S and 50 parts of phosphoric acid were mixed well to prepare a phosphoric acid premix. 92.9 parts of basic inorganic mineral granular nuclei (silica sand containing calcium carbonate grains, grain size distribution: 0.5-1.7 mm, pH (10%): 9.5) and 1.3 part of Moresco White 60 were mixed well by a concrete mixer, and to the mixture were added 5.0 parts of the TCHO premix and 0.8 part of the phosphoric acid premix, followed by mixing for 15 minutes. The mixture was screened by a sieve having an opening of 0.5-1.7 mm to obtain a granular composition containing 4% of TCHO of the present invention. [0026] Example 5 95.0 parts of TCHO and 5.0 parts of Sipernat 22S were mixed well, and the mixture was pulverized by a hammer mill to prepare a TCHO premix. 50 parts of Sipernat 22S and 50 parts of phosphoric acid were mixed well to prepare a phosphoric acid premix. 92.7 parts of basic inorganic mineral granular nuclei (silica sand containing calcium carbonate grains, grain size distribution: 0.5-1.7 mm, pH (10%): 9.5) and 1.3 part of Moresco White 60 were mixed well by a concrete mixer, and to the mixture were added 5.0 parts of the TCHO premix and 1.0 part of the phosphoric acid premix, followed by mixing for 15 minutes. The mixture was screened by a sieve having an opening of 0.5-1.7 mm to obtain a granular composition containing 4% of TCHO of the present invention. [0027] Example 6 91.4 parts of TCHO, 6.7 parts of Sipernat 22S and 1.9 part of phosphoric acid were mixed well, and the mixture was pulverized by a hammer mill to prepare a TCHO premix. 88.3 parts of neutral inorganic mineral granular nuclei (silica sand occurring in Gifu Prefecture and manufactured by Takeori Kogyosho Co., Ltd., grain size distribution: 0.5-1.0 mm, pH (10%): 6.4) and 5.0 parts of calcium carbonate granular nuclei (calcium carbonate grains occurring in Hiroshima Prefecture and manufactured by Nitto Funka Kogyo Co., Ltd., grain size distribution: 0.5-1.0 mm, pH (10%): 9.7) were introduced into a concrete mixer and mixed well. Then, 1.5 part of Moresco White 60 was introduced, followed by further mixing. Finally, 5.2 parts of the TCHO premix was added to the mixture, followed by mixing for 15 minutes. The mixture was screened by a sieve having an opening of 0.5-1.7 mm to obtain a granular composition containing 4% of TCHO of the present invention. [0028] Example 7 91.4 parts of TCHO, 6.7 parts of Sipernat 22S and 1.9 part of phosphoric acid were mixed well, and the mixture was pulverized by a hammer mill to prepare a TCHO premix. 83.3 parts of neutral inorganic mineral granular nuclei (silica sand occurring in Gifu Prefecture and manufactured by Takeori Kogyosho Co., Ltd., grain size distribution: 0.5-1.0 mm, pH (10%): 6.4) and 10.0 parts of calcium carbonate granular nuclei (calcium carbonate grains occurring in Hiroshima Prefecture and manufactured by Nitto Funka Kogyo Co., Ltd., grain size distribution: 0.5-1.0 mm, pH (10%): 9.7) were introduced into a concrete mixer and mixed well. Then, 1.5 part of Moresco White 60 was introduced, followed by further mixing. Finally, 5.2 parts of the TCHO premix was added to the mixture, followed by mixing for 15 minutes. The mixture was screened by a sieve having an opening of 0.5-1.7 mm to obtain a granular composition containing 4% of TCHO of the present invention. [0029] Example 8 91.4 parts of TCHO, 6.7 parts of Sipernat 22S and 1.9 part of phosphoric acid were mixed well, and the mixture was pulverized by a hammer mill to prepare a TCHO premix. 73.3 parts of neutral inorganic mineral granular nuclei (silica sand occurring in Gifu Prefecture and manufactured by Takeori Kogyosho Co., Ltd., grain size distribution: 0.5-1.0 mm, pH (10%): 6.4) and 20.0 parts of calcium carbonate granular nuclei (calcium carbonate grains occurring in Hiroshima Prefecture and manufactured by Nitto Funka Kogyo Co., Ltd., grain size distribution: 0.5-1.0 mm, pH (10%): 9.7) were introduced into a concrete mixer and mixed well. Then, 1.5 part of Moresco White 60 was introduced, followed by further mixing. Finally, 5.2 parts of the TCHO premix was added to the mixture, followed by mixing for 15 minutes. The mixture was screened by a sieve having an opening of 0.5-1.7 mm to obtain a granular composition containing 4% of TCHO of the present invention. [0030] Example 9 91.4 parts of TCHO, 6.7 parts of Sipernat 22S and 1.9 part of phosphoric acid were mixed well, and the mixture was pulverized by a hammer mill to prepare a TCHO premix. 43.3 parts of neutral inorganic mineral granular nuclei (silica sand occurring in Gifu Prefecture and manufactured by Takeori Kogyosho Co., Ltd., grain size distribution: 0.5-1.0 mm, pH (10%): 6.4) and 50.0 parts of calcium carbonate granular nuclei (calcium carbonate grains occurring in Hiroshima Prefecture and manufactured by Nitto Funka Kogyo Co., Ltd., grain size distribution: 0.5-1.0 mm, pH (10%): 9.7) were introduced into a concrete mixer and mixed well. Then, 1.5 part of Moresco White 60 was introduced, followed by further mixing. Finally, 5.2 parts of the TCHO premix was added to the mixture, followed by mixing for 15 minutes. The mixture was screened by a sieve having an opening of 0.5-1.7 mm to obtain a granular composition containing 4% of TCHO of the present invention, [0031] Example 10 91.4 parts of TCHO, 6.7 parts of Sipernat 22S and 1.9 part of phosphoric acid were mixed well, and the mixture was pulverized by a hammer mill to prepare a TCHO premix. 18.3 parts of neutral inorganic mineral granular nuclei (silica sand occurring in Gifu Prefecture and manufactured by Takeori Kogyosho Co., Ltd., grain size distribution: 0.5-1.0 mm, pH (10%): 6.4) and 75.0 parts of calcium carbonate granular nuclei (calcium carbonate grains occurring in Hiroshima Prefecture and manufactured by Nitto Funka Kogyo Co., Ltd., grain size distribution: 0.5-1.0 mm, pH (10%): 9.7) were introduced into a concrete mixer and mixed well. Then, 1.5 part of Moresco White 60 was introduced, followed by further mixing. Finally, 5.2 parts of the TCHO premix was added to the mixture, followed by mixing for 15 minutes. The mixture was screened by a sieve having an opening of 0.5-1.7 mm to obtain a granular composition containing 4% of TCHO of the present invention. [0032] Example 11 91.4 parts of TCHO, 6.7 parts of Sipernat 22S and 1.9 part of phosphoric acid were mixed well, and the mixture was pulverized by a hammer mill to prepare a TCHO premix. 93.3 parts of calcium carbonate granular nuclei (calcium carbonate grains occurring in Hiroshima Prefecture and manufactured by Nitto Funka Kogyo Co., Ltd., grain size distribution: 0.5-1.0 mm, pH (10%): 9.7) was introduced into a concrete mixer and mixed well. Then, 1.5 part of Moresco White 60 was introduced, followed by further mixing. Finally, 5.2 parts of the TCHO premix was added to the mixture, followed by mixing for 15 minutes. The mixture was screened by a sieve having an opening of 0.5-1.7 mm to obtain a granular composition containing 4% of TCHO of the present invention. [0033] Example 12 83.3 parts of cartap hydrochloride, 10.8 parts of Sipernat 22S and 5.9 parts of phosphoric acid were mixed well, and the mixture was pulverized by a hammer mill to prepare a cartap hydrochloride premix. 93.0 parts of calcium carbonate granular nuclei (calcium carbonate grains occurring in Hiroshima Prefecture and manufactured by Nitto Funka Kogyo Co., Ltd., grain size distribution: 0.5-1.0 mm, pH (10%): 9.7) and 1.9 part of Moresco White 60 were mixed well by a concrete mixer, and then 5.1 parts of the cartap hydrochloride premix was added to the mixture, followed by mixing for 15 minutes. The mixture was screened by a sieve having an opening of 0.5-1.7 mm to obtain a granular composition containing 4% of cartap hydrochloride of the present invention. [0034] Comparative Example 1 95.0 parts of TCHO and 5.0 parts of Sipernat 22S were mixed well, and the mixture was pulverized by a hammer mill to prepare a TCHO premix. 93.5 parts of basic inorganic mineral granular nuclei (silica sand containing calcium carbonate grains, grain size distribution: 0.5-1.7 mm, pH (10%): 9.5) and 1.5 part of Moresco White 60 were mixed well by a concrete mixer, and then 5.0 parts of the TCHO premix was added to the mixture, followed by mixing for 15 minutes. The mixture was screened by a sieve having an opening of 0.5-1.7 mm to obtain a comparative granular composition containing 4% of TCHO. [0035] Comparative Example 2 91.4 parts of TCHO, 6.7 parts of Sipernat 22S and 1.9 part of phosphoric acid were mixed well, and the mixture was pulverized by a hammer mill to prepare a TCHO premix. 93.3 parts of calcium carbonate granular nuclei (calcium carbonate grains occurring in Hiroshima Prefecture and manufactured by Nitto Funka Kogyo Co., Ltd., grain size distribution: 0.5-1.0 mm, pH (10%): 9.7) and 1.5 part of PEG-400 were mixed well by a concrete mixer, and then 5.2 parts of the TCHO premix was added to the mixture, followed by mixing for 15 minutes. The mixture was screened by a sieve having an opening of 0.5-1.7 mm to obtain a comparative granular composition containing 4% of TCHO. [0036] Comparative Example 3 93.1 parts of TCHO and 6.9 parts of Sipernat 22S were mixed well, and the mixture was pulverized by a hammer mill to prepare a TCHO premix. 93.5 parts of calcium carbonate granular nuclei (calcium carbonate grains occurring in Hiroshima Prefecture and manufactured by Nitto Funka Kogyo Co., Ltd., grain size distribution: 0.5-1.0 mm, pH (10%): 9.7) and 1.5 part of PEG-400 were mixed well by a concrete mixer. Then, 5.0 parts of the TCHO premix was added to the mixture, followed by mixing for 15 minutes. The mixture was screened by a sieve having an opening of 0.5-1.7 mm to obtain a comparative granular composition containing 4% of TCHO. [0037] Comparative Example 4 83.3 parts of cartap hydrochloride, 10.8 parts of Sipernat 22S and 5.9 parts of phosphoric acid were mixed well, and the mixture was pulverized by a hammer mill to prepare a cartap hydrochloride premix. 93.0 parts of calcium carbonate granular nuclei (calcium carbonate grains occurring in Hiroshima Prefecture and manufactured by Nitto Funka Kogyo Co., Ltd., grain size distribution: 0.5-1.0 mm, pH (10%): 9.7) and 1.9 part of PEG-400 were mixed well by a concrete mixer, and then 5.1 parts of the cartap hydrochloride premix was added to the mixture, followed by mixing for 15 minutes. The mixture was screened by a sieve having an opening of 0.5-1.7 mm to obtain a comparative granular composition containing 4% of cartap hydrochloride. [0038] Comparative Example 5 94.4 parts of cartap hydrochloride and 5.6 parts of Sipernat 22S were mixed well, and the mixture was pulverized by a hammer mill to prepare a cartap hydrochloride premix. 94.0 parts of calcium carbonate granular nuclei (calcium carbonate grains occurring in Hiroshima Prefecture and manufactured by Nitto Funka Kogyo Co., Ltd., grain size distribution: 0.5-1.0 mm, pH (10%): 9.7) and 1.5 part of Moresco White 60 were mixed well by a concrete mixer, and then 4.5 parts of the cartap hydrochloride premix was added to the mixture, followed by mixing for 15 minutes. The mixture was screened by a sieve having an opening of 0.5-1.7 mm to obtain a comparative granular composition containing 4% of cartap hydrochloride. [0039] Comparative Example 6 (TCHO was used in Patent Document 3) 4.7 parts of TCHO, 8.0 parts of dextrin, 5.0 parts of Newcalgen BX-C, 25 parts of magnesium oxide and 57.3 parts of clay were mixed well, and then 12 parts of water was added, followed by kneading intimately. The kneaded product was granulated by an extrusion granulator (screen diameter: 1.0 mm) to obtain a wet product. This was dried, subjected to dressing of grains, and screened by a sieve of 0.5-1.7 mm to obtain a comparative granular product containing 4% of TCHO. [0040] Comparative Example 7 (cartap hydrochloride was used in Patent Document 3) 4.2 parts of cartap hydrochloride, 8.0 parts of dextrin, 5.0 parts of Newcalgen BX-C, 25 parts of magnesium oxide and 57.8 parts of clay were mixed well, and then 12 parts of water was added, followed by kneading intimately. The kneaded product was granulated by an extrusion granulator (screen diameter: 1.0 mm) to obtain a wet product. This was dried, then subjected to dressing of grains, and screened by a sieve of 0.5-1.7 mm to obtain a comparative granular product containing 4% of cartap hydrochloride. [0041] Comparative Example 8 (TCHO was used in Patent Document 2) 4.7 parts of TCHO, 3.2 parts of Cellogen 7A, 0.54 part of Newcalgen BX-C and 91.5 parts of calcium carbonate powder were mixed well, and then 12 parts of water was added, followed by kneading intimately. The kneaded product was granulated by an extrusion granulator (screen diameter: 1.0 mm) to obtain a wet product. This was dried, then subjected to dressing of grains, and screened by a sieve of 0.5-1.7 mm to obtain a comparative granular product containing 4% of TCHO. [0042] Comparative Example 9 (Cartap hydrochloride was used in Patent Document 2) 4.2 parts of cartap hydrochloride, 3.2 parts of Cellogen 7A, 0.54 part of Newcalgen BX-C and 92.0 parts of calcium carbonate powder were mixed well, and then 12 parts of water was added, followed by kneading intimately. The kneaded product was granulated by an extrusion granulator (screen diameter: 1.0 mm) to obtain a wet product. This was dried, then subjected to dressing of grains, and screened by a sieve of 0.5- 1.7 mm to obtain a comparative granular product containing 4% of cartap hydrochloride. [0043] Test example (Stability test) Stability of the granular agricultural chemical compositions obtained in the above Examples and Comparative Examples was compared in the following manner. 50 g of the granular agricultural chemical composition was put in an aluminum bag, and the bag was sealed. The bag was stored in a thermostat of 54°C, and storage stabilities of the active ingredient after 2 weeks and 4 weeks were examined. The test results are shown (Tables 1-3). The abbreviation "A.I." in the Table means "active ingredient", and the term "Cartap" means "cartap hydrochloride". [0044] [0045] As is clear from the results of Tables 1 and 2, TCHO in the granular agricultural chemical compositions of the present invention was stable although basic inorganic mineral granular nuclei were used as extenders. Even when the content of calcium carbonate as inorganic mineral granular nuclei was high, the agricultural chemical active ingredient in the granular compositions was stable. As is clear from Table 3, when phosphoric acid was not contained (Comparative Example 1), stability of TCHO was damaged. Furthermore, when PEG-400 which was water-soluble liquid was used as an adhesive in place of the oleophilic liquid (liquid paraffin) (Comparative Examples 2 and 3), decomposition of the agricultural chemical active ingredient was conspicuous regardless of whether phosphoric acid was added or not. The above-mentioned tendency seen in the case of TCHO was similarly seen in the case of cartap hydrochloride (Example 12 and Comparative Examples 4 and 5). When TCHO and cartap hydrochloride were applied to the patent relating to stabilization of bensultap (Comparative Examples 6-9), both the agricultural chemical active ingredients were conspicuously decomposed. Thus, it can be seen that even when basic inorganic minerals are used or known formulations in which bensultap is stable are used, TCHO and cartap hydrochloride which are the same nereistoxins cannot be Industrial Applicability [0046] A granular agricultural chemical composition excellent in stability of nereistoxin agricultural chemical active ingredients which uses basic inorganic mineral granular nuclei as an extender can be obtained by coating a mixture of the nereistoxin agricultural chemical active ingredient and phosphoric acid as a stabilizer on basic inorganic mineral granular nuclei such as calcium carbonate using an oleophilic liquid as an adhesive. CLAIMS 1. A granular agricultural chemical composition which comprises a nereistoxin agricultural chemical active ingredient as an agricultural chemical active ingredient, inorganic mineral granular nuclei containing basic inorganic mineral granular nuclei as an extender, an oleophilic liquid as an adhesive and phosphoric acid as a stabilizer. 2. A granular agricultural chemical composition according to claim 1, wherein the nereistoxin agricultural chemical active ingredient is thiocyclam oxalate (hereinafter referred to as "TCHO") or cartap hydrochloride. 3. A granular agricultural chemical composition according to claim 1 or 2, wherein the oleophilic liquid is liquid paraffin. 4. A granular agricultural chemical composition according to any one of claims 1-3 which additionally contains a solidification inhibitor. 5. A granular agricultural chemical composition according to any one of claims 1-4 which comprises 65- 98% by weight of inorganic mineral granular nuclei, 1.0-20.0% by weight of a nereistoxin agricultural chemical active ingredient, 0.5-10% by weight of an oleophilic liquid, 0.05-0.5% by weight of phosphoric acid and 0-2% by weight of a solidification inhibitor. 6. A granular agricultural chemical composition according to claims 1-5, wherein the nereistoxin agricultural chemical active ingredient and phosphoric acid are coated on the inorganic mineral granular nuclei using the oleophilic liquid as an adhesive. 7. A granular agricultural chemical composition according to any one of claims 1-6 which is obtained by adding the nereistoxin agricultural chemical active ingredient and phosphoric acid to a composition comprising a mixture of inorganic mineral granular nuclei and the oleophilic liquid and mixing them to coat the nereistoxin agricultural chemical active ingredient. 8. A granular agricultural chemical composition according to claim 6 or 7, wherein a solidification inhibitor is mixed with the nereistoxin agricultural chemical active ingredient and/or phosphoric acid. 9. A method for producing a granular agricultural chemical composition according to any one of claims 1-8 which comprises mixing an inorganic mineral granular nuclei with an oleophilic liquid, then adding a nereistoxin agricultural chemical active ingredient and phosphoric acid to the mixture and mixing them to coat the nereistoxin agricultural chemical active ingredient. 10. A method for producing a granular agricultural chemical composition according to claim 9, wherein a solidification inhibitor is mixed with the nereistoxin agricultural chemical active ingredient and/or phosphoric acid. /) Disclosed is a granular agrichemical composition produced by coating a mixture of a nereistoxin-type agrichemical active component and phosphoric acid as a stabilizing agent onto a granule core made of a basic inorganic mineral substance by using a lipophilic liquid as an adhesive agent. The granular agrichemical composition shows excellent stability of the nereistoxin-type agrichemical active component.

Full Text

DESCRIPTION
GRANULAR AGRICHEMICAL COMPOSITION
Technical Field
[0001]
The present invention relates to a granular
agricultural chemical composition containing a
nereistoxin agricultural chemical active ingredient
which can efficiently control harmful insects breeding
in paddy fields and plowed fields. More particularly,
it relates to a granular agricultural chemical
composition which comprises basic inorganic mineral
granules coated with a nereistoxin agricultural
chemical active ingredient.
Background Art
[0002]
The nereistoxin agricultural chemical active
ingredients include, for example, thiocyclam oxalate
(hereinafter referred to as "TCHO"), cartap
hydrochloride, bensultap, etc. They are insecticides
which act as contact toxicity or stomach poison, and
also exhibit activity by submerged application, and
furthermore they are expected to have residual
activity. They are effective against Scirtothrips
dorsalis Hood, leafhoppers and rice stem withering
nematode as well as insects belonging to Lepidoptera

and Coleoptera, and they are less in chemical injury
(Non-Patent Document 1).
[0003]
It is known that the nereistoxin agricultural
chemical active ingredients undergo hydrolysis under
alkaline conditions and are unstable (Non-Patent
Document 2). Therefore, it is naturally avoided to use
basic inorganic minerals such as calcium carbonate as
granular nuclei of granular composition containing a
nereistoxin agricultural chemical active ingredient,
and no granular compositions using basic inorganic
minerals have been known.
[0004]
For improving the stability of nereistoxin
agricultural chemical active ingredients in
formulations, there have been known formulations coated
with a waxy material which is solid at room temperature
(Patent Document 1).
[0005]
It is reported that among nereistoxin
agricultural chemical active ingredients, only
bensultap has been formulated stably under basic
conditions. For example, there are a report on solid
besultap formulations using calcium carbonate as an
extender (Patent Document 2) and a report that
bensultap in formulations can be stabilized by
containing a basic oxide such as calcium oxide, zinc
oxide or magnesium oxide (Patent Document 3).

[0006]
Non-Patent Document 1: "Handbook of
Agricultural Chemicals" (1998) edited by Japan Plant
Quarantine Association on December 15, 1998, P. 123-125
Non-Patent Document 2: C.D.S. Tomlin, "The
Pesticide Manual", Thirteenth Edition, BCPC 2003, P.
967-968
Non-Patent Document 3: M. Sasaki, et al,
"Development of Agricultural Chemicals in Japan", Japan
Agricultural Chemicals Society, 2003, P. 117-130
Patent Document 1: Patent No. 2696354 (column
6, line 2)
Patent Document 2: JP-A-6-312902 (page 3)
Patent Document 3: Patent No. 2706655 (column
10, line 32)
Disclosure of Invention
Problem to be Solved by the Invention
[0007]
However, it has not been reported that
formulations of TCHO and cartap hydrochloride have been
stably obtained under basic conditions, and stable
formulations of overall nereistoxin agricultural
chemical active ingredients have not yet been found.
When a granular agricultural chemical
composition is to be prepared, basic inorganic mineral
materials such as calcium carbonate usable as an
extender are high in safety and inexpensive, but they

cannot be used for obtaining formulations of
nereistoxin agricultural chemical active ingredients
which are unstable under basic conditions.
Means for Solving the Problem
[0008]
The inventors have conducted researches on
various extenders, vehicles and stabilizers usable for
granular composition in the fields of agriculture and
horticulture, and as a result, have found that though
it is known that nereistoxin agricultural chemical
active ingredients decompose under alkaline conditions,
the nereistoxin agricultural chemical active
ingredients can be stably coated on basic inorganic
mineral granular nuclei such as calcium carbonate.
That is, it has been found that even when basic
inorganic mineral granular nuclei are used as an
extender, a stable granular composition can be obtained
by coating a mixture of the nereistoxin agricultural
chemical active ingredient and phosphoric acid as a
stabilizer on basic inorganic mineral granular nuclei
such as calcium carbonate using an oleophilic liquid as
an adhesive.
That is, the present invention relates to the
following embodiments.
[0009]
(1) A granular agricultural chemical
composition which comprises a nereistoxin agricultural

chemical active ingredient as an agricultural chemical
active ingredient, inorganic mineral granular nuclei
containing basic inorganic mineral granular nuclei as
an extender, an oleophilic liquid as an adhesive and
phosphoric acid as a stabilizer.
(2) A granular agricultural chemical
composition described in the above (1), wherein the
nereistoxin agricultural chemical active ingredient is
thiocyclam oxalate (hereinafter referred to as "TCHO")
or cartap hydrochloride.
(3) A granular agricultural chemical
composition described in the above (1) or (2), wherein
the oleophilic liquid is liquid paraffin.
(4) A granular agricultural chemical
composition described in any one of the above (l)-(3)
which additionally contains a solidification inhibitor.
(5) A granular agricultural chemical
composition described in any one of the above (l)-(4)
which comprises 65-98% by weight of basic inorganic
mineral granular nuclei, 1.0-20.0% by weight of a
nereistoxin agricultural chemical active ingredient,
0.5-10% by weight of an oleophilic liquid,0.05-0.5% by
weight of phosphoric acid and 0-2% by weight of a
solidification inhibitor.
(6) A granular agricultural chemical
composition described in any one of the above (l)-(5),
wherein the nereistoxin agricultural chemical active
ingredient and phosphoric acid are coated on the

inorganic mineral granular nuclei using the oleophilic
liquid as an adhesive.
(7) A granular agricultural chemical
composition described in any one of the above (l)-(6)
which is obtained by adding the nereistoxin
agricultural chemical active ingredient and phosphoric
acid to a composition comprising a mixture of inorganic
mineral granular nuclei and the oleophilic liquid and
mixing them to coat the nereistoxin agricultural
chemical active ingredient.
(8) A granular agricultural chemical
composition described in any one of the above (6) or
(7), wherein a solidification inhibitor is mixed with
the nereistoxin agricultural chemical active ingredient
and/or phosphoric acid.
(9) A method for producing a granular
agricultural chemical composition described in any one
of the above (l)-(8) which comprises mixing the
inorganic mineral granular nuclei with the oleophilic
liquid, then adding the nereistoxin agricultural
chemical active ingredient and phosphoric acid to the
mixture and mixing them to coat the nereistoxin
agricultural chemical active ingredient.
(10) A method for producing a granular
agricultural chemical composition described in the
above (9), wherein a solidification inhibitor is mixed
with the nereistoxin agricultural chemical active
ingredient and/or phosphoric acid.

Advantages of the Invention
[0010]
Although basic inorganic mineral granular
nuclei such as calcium carbonate are used as extender,
the nereistoxin agricultural chemical active ingredient
in the granular agricultural chemical composition is
stable for a long period of time by using an oleophilic
liquid and phosphoric acid as a stabilizer in
combination.
Best Mode for Carrying Out the Invention
[0011]
The nereistoxin agricultural chemical active
ingredients used in the granular composition of the
present invention include, for example, TCHO, cartap
hydrochloride, bensultap, etc., and preferred are TCHO
and cartap hydrochloride. These nereistoxin
agricultural chemical active ingredients can be
prepared by known methods (JP-A-51-136689, JP-B-45-
18847, and the above Non-Patent Document 3). These
agricultural chemical active ingredients may be used
each alone or in combination of two or more in the
granular agricultural chemical composition of the
present invention. The content of the nereistoxin
agricultural chemical active ingredients in the
granular agricultural chemical composition is usually
about 1.0-20.0% by weight, preferably about 2.0-10.0%

by weight.
[0012]
In the granular agricultural chemical
composition of the present invention, in addition to
the nereistoxin agricultural chemical active
ingredients, one or more of the following agricultural
chemical active ingredients can also be used so long as
they do not affect the chemical stability of the
nereistoxin agricultural chemical active ingredients.
Non-limiting examples of the other agricultural
chemical active ingredients are as follows. As
insecticidal active ingredients, mention may be made
of, for example, BPMC (2-sec-butylphenyl-N-methyl
carbamate), MIPC (2-isopropylphenyl-N-methyl
carbamate), NAC (1-naphthyl-N-methyl carbamate),
Nitenpyrum ((E)-N-(6-chloro-3-pyridylmethyl)-N-ethyl-
N'-methyl-2-nitrovinylidenediamine), Pyraclofos ((RS)-
[0-1-(4-chlorophenyl)pyrazole-4-yl]=O-ethyl=S-
propyl=phosphorothioate) , Buprofezine (2-tert-
butylimino-3-isopropyl-5-phenyl-3,4,5, 6-tetrahydro-2H-
1, 3, 5-thiadiazine-4-one), Flucythrinate ( (RS)- -cyano-
3-phenoxybenzyl=(S)-2-(4-difluoromethoxyphenyl)-3-
methylbutyrate), Methomyl (S-methyl-N-
[(methylcarbamoyl)oxy]thioacetoimidate), Ethofenprox
(2-(4-ethoxyphenyl)-2-methylpropyl=3-
phenoxybenzyl=ether), XMC (3,5-xylyl-N-methyl
carbamate), Dinotefuran ((RS)-l-methyl-2-nitro-3-
(tetrahydro-3-furylmethyl)guanidine), Acetamiprid ((E)-

N-t 6-chloro-3-pyridyl]methyl)-N'-cyano-N-
methylacetoamidine), Thiamethoxam (3-(2-chloro-l,3-
thiazole-5-ylmethyl)-5-methyl-l,3,5-oxadiazinane-4-
ylidene(nitro)amine, etc. As fungicidal active
ingredients, mention may be made of, for example, IBP
(0,0-diisopropyl-S-benzyl thiophopshate), Tricyclazole
(5-methyl-l,2,4-triazolo[3,4,5]benzothiazole), Fusalide
(4,5,6,7-tetrachlorophthalide), Validamycin,
Probenazole (3-allyloxy-l,2-benzoisothiazole-l,1-
dioxide) , Ferimzone ( (Z) -2' -naethylacetophenone=4, 6-
dimethylpyrimidine-2-ylhydrazine), Flutolanil α,α,α-
trifluoro-3'-isopropoxy-O-trianilide), Furametpyr
((RS)-5-chLoro-N-(1,3-dihydro-l, 1,3-
trimethylisobenzofuran-4-yl)-1,3-dimethylpyrazole-4-
carboxamide, Pencycuron (1-(4-chlorobenzyl)-1-
cyclopentyl-3-phenylurea, Diclomezine (6-(3,5-dichloro-
4-methylphenyl)-3-(2H)-pyridazinone), Kasugamycin-
hydrochloride, etc.
[0013]
Examples of the basic inorganic mineral
granular nuclei contained in the inorganic mineral
granular nuclei used as an extender in the present
invention are calcium carbonate, talc, calcium oxide,
etc., and calcium carbonate which is available in a
large amount is preferred. The above basic inorganic
mineral granular nuclei may be used each alone or in
admixture of two or more. In the present invention,
inorganic mineral granular nuclei which are not basic,

such as sea sand, quartz and silica sand may be present
in the basic inorganic mineral granular nuclei. The
basic inorganic mineral granular nuclei contained in
the inorganic mineral granular nuclei used in the
present invention may be contained in an optional
amount in the range of usually 5-100% by weight.
[0014]
Usually, in the case of granular agricultural
chemical composition obtained by coating inorganic
mineral granular nuclei with an agricultural chemical
active ingredient, the proportion in weight of the
agricultural chemical active ingredient coated on
granular nuclei of smaller diameter to the weight of
the granular nuclei is greater, and, on the other hand,
the proportion in weight of the agricultural chemical
active ingredient coated on granular nuclei of larger
diameter to the weight of the granular nuclei is
smaller. Thus, there is a difference in contents of
these agricultural chemical active ingredients, and
sometimes there occurs variation in the results of
content analysis, which causes hindrance to control of
quality. Therefore, particle size distribution of the
inorganic mineral granular nuclei used in the present
invention is usually 0.05-2.0 mm, preferably 0.06-1.7
mm. The amount of the inorganic mineral granular
nuclei used is usually 65-98% by weight, preferably 75-
95% by weight in the composition.
[0015]

As the oleophilic liquids used as an adhesive
in the granular agricultural chemical composition of
the present invention, there may be used liquid
paraffin (e.g., Moresco White 60, Moresco White 40,
Moresco White 30 (trademarks) manufactured by Matsumura
Sekiyu Kagaku Kenkyujo), petroleum fraction, animal and
vegetable oils, etc., and the oleophilic liquids can be
selected from those which have a viscosity of usually
68 mm/s2 (40°C) or lower, preferably 1.5-20 mm/s2 (40°C) ,
more preferably 1.75-13 mm/s2 (40°C). These can be used
each alone or in admixture of two or more, and the
oleophilic liquids are not limited to the above
examples. The content of the oleophilic liquids in the
granular agricultural chemical composition is usually
about 0.5-10% by weight, preferably about 1.0-5.0% by
weight.
[0016]
The phosphoric acid used as a stabilizer in
the granular agricultural chemical composition of the
present invention is preferably higher than industrial
grade (75%). The amount of phosphoric acid is usually
0.05-0.5% by weight, preferably 0.1-0.3% by weight in
the composition. The method of addition of phosphoric
acid is not particularly limited, and preferred are the
following methods.
(1) The nereistoxin agricultural chemical
active ingredient is mixed with phosphoric acid to
prepare a premix.

(2) After the nereistoxin agricultural
chemical active ingredient is adhered to the inorganic
mineral granular nuclei, phosphoric acid is added.
(3) After an adhesive (oleophilic liquid) is
added to the inorganic mineral granular nuclei and
before the nereistoxin agricultural chemical active
ingredient is adhered, phosphoric acid is added alone.
(4) A mixture of phosphoric acid and the
following solidification inhibitor (such as white
carbon) at 1:1 is added.
[0017]
In the granular agricultural chemical
composition of the present invention, in order to
inhibit solidification of the nereistoxin agricultural
chemical active ingredient during storage of the
composition, if necessary, there may be used white
carbon (e.g., SIPERNAT 22S (trademark) manufactured by
Degussa Co., Ltd.), diatomaceous earth, magnesium
stearate, aluminum oxide, titanium dioxide, clay,
vermiculite, pumice, etc. Not only the nereistoxin
agricultural chemical active ingredient, but also the
above powders may also be added to the powder to be
coated on the granular nuclei.
The solidification inhibitor is used in an
amount of usually 0-2% by weight, preferably 0.2-0.7%
by weight in the granular agricultural chemical
composition.
[0018]

A surface active agent can also be added to
the granular agricultural chemical composition of the
present invention. The surface active agents include,
for example, nonionic surface active agents, anionic
surface active agents, cationic surface active agents
and amphoteric surface active agents which are commonly
used for agricultural chemical formulations. Specific
examples of the surface active agents are nonionic
surface active agents such as polyoxyethylenealkylaryl
ethers, polyoxyethylenestyrylphenyl ether,
polyoxyethylenealkyl esters, polyoxyethylenephenyl
ether polymers, polyoxyethylenealkylenearylphenyl
ethers, and polyoxyethylenepolyoxypropylene block
polymers, anionic surface active agents such as
polyoxyethylenestyrylphenyl ether sulfate, lignin
sulfonic acid salts, alkylaryl sulfonates, and alkyl
naphthalenesulfonates, cationic surface active agents
such as alkyl betaine and quaternary ammonium salts,
and amphoteric surface active agents.
[0019]
The granular agricultural chemical
composition of the present invention is usually
obtained by mixing well the inorganic mineral granular
nuclei with the oleophilic liquid by a mixer, and
thereafter adding phosphoric acid and a powder
containing the nereistoxin agricultural chemical active
ingredient, followed by mixing well by a mixer to coat
the active ingredient. The powder containing the

nereistoxin agricultural chemical active ingredient and
phosphoric acid can be added in an optional order.
Specifically, there are the following
methods, and the granular agricultural chemical
composition can be produced by any of these methods.
(1) The inorganic mineral granular nuclei
are mixed with oleophilic liquid, then phosphoric acid
is added to the mixture, and thereafter a powder
containing the nereistoxin agricultural chemical active
ingredient is added, followed by mixing to obtain
coated granules.
(2) A powder obtained by adsorbing
phosphoric acid to the solidification inhibitor (such
as white carbon) is added to a mixture of inorganic
mineral granular nuclei and oleophilic liquid, and then
a powder containing nereistoxin agricultural chemical
active ingredient is added, followed by mixing to
obtain coated granules.
(3) The inorganic mineral granular nuclei
are mixed with oleophilic liquid, then a powder
containing nereistoxin agricultural chemical active
ingredient is added, followed by mixing to coat the
active ingredient, and then phosphoric acid is added to
obtain coated granules.
(4) The inorganic mineral granular nuclei
are mixed with oleophilic liquid, then a powder
containing nereistoxin agricultural chemical active
ingredient is added, followed by mixing to coat the

active ingredient, and then a powder of solidification
inhibitor (white carbon, etc.) to which phosphoric acid
is adsorbed is added to obtain coated granules.
(5) The inorganic mineral granular nuclei are
mixed with oleophilic liquid, then a powder containing
nereistoxin agricultural chemical active ingredient and
phosphoric acid is added, followed by mixing to obtain
coated granules.
[0020]
The granular agricultural chemical
composition of the present invention exhibits
insecticidal effect against harmful insects for farm
products by direct application to paddy field or soil
of plowed field.
[0021]
The present invention will be explained in
detail below using the following examples and test
examples, which should not be construed as limiting the
invention. In examples, "part" is by weight.
[0022]
Example 1
95.0 parts of TCHO and 5.0 parts of Sipernat
22S were mixed well, and the mixture was pulverized by
a hammer mill to prepare a TCHO premix. 50 parts of
Sipernat 22S and 50 parts of phosphoric acid were mixed
well to prepare a phosphoric acid premix. 93.3 parts
of basic inorganic mineral granular nuclei (silica sand
containing calcium carbonate grains, grain size

distribution: 0.5-1.7 mm, pH (10%): 9.5) and 1.5 part
of Moresco White 60 were mixed well by a concrete
mixer, and to the mixture were added 5.0 parts of the
TCHO premix and 0.2 part of the phosphoric acid premix,
followed by mixing for 15 minutes. The mixture was
screened by a sieve having an opening of 0.5-1.7 mm to
obtain a granular composition containing 4% of TCHO of
the present invention.
[0023]
Example 2
95.0 parts of TCHO and 5.0 parts of Sipernat
22S were mixed well, and the mixture was pulverized by
a hammer mill to prepare a TCHO premix. 50 parts of
Sipernat 22S and 50 parts of phosphoric acid were mixed
well to prepare a phosphoric acid premix. 93.1 parts
of basic inorganic mineral granular nuclei (silica sand
containing calcium carbonate grains, grain size
distribution: 0.5-1.7 mm, pH (10%): 9.5) and 1.5 part
of Moresco White 60 were mixed well by a concrete
mixer, and to the mixture were added 5.0 parts of the
TCHO premix and 0.4 part of the phosphoric acid premix,
followed by mixing for 15 minutes. The mixture was
screened by a sieve having an opening of 0.5-1.7 mm to
obtain a granular composition containing 4% of TCHO of
the present invention.
[0024]
Example 3
95.0 parts of TCHO and 5.0 parts of Sipernat

22S were mixed well, and the mixture was pulverized by
a hammer mill to prepare a TCHO premix. 50 parts of
Sipernat 22S and 50 parts of phosphoric acid were mixed
well to prepare a phosphoric acid premix. 93.0 parts
of basic inorganic mineral granular nuclei (silica sand
containing calcium carbonate grains, grain size
distribution: 0.5-1.7 mm, pH (10%): 9.5) and 1.4 part
of Moresco White 60 were mixed well by a concrete
mixer, and to the mixture were added 5.0 parts of the
TCHO premix and 0.6 part of the phosphoric acid premix,
followed by mixing for 15 minutes. The mixture was
screened by a sieve having an opening of 0.5-1.7 mm to
obtain a granular composition containing 4% of TCHO of
the present invention.
[0025]
Example 4
95.0 parts of TCHO and 5.0 parts of Sipernat
22S were mixed well, and the mixture was pulverized by
a hammer mill to prepare a TCHO premix. 50 parts of
Sipernat 22S and 50 parts of phosphoric acid were mixed
well to prepare a phosphoric acid premix. 92.9 parts
of basic inorganic mineral granular nuclei (silica sand
containing calcium carbonate grains, grain size
distribution: 0.5-1.7 mm, pH (10%): 9.5) and 1.3 part
of Moresco White 60 were mixed well by a concrete
mixer, and to the mixture were added 5.0 parts of the
TCHO premix and 0.8 part of the phosphoric acid premix,
followed by mixing for 15 minutes. The mixture was

screened by a sieve having an opening of 0.5-1.7 mm to
obtain a granular composition containing 4% of TCHO of
the present invention.
[0026]
Example 5
95.0 parts of TCHO and 5.0 parts of Sipernat
22S were mixed well, and the mixture was pulverized by
a hammer mill to prepare a TCHO premix. 50 parts of
Sipernat 22S and 50 parts of phosphoric acid were mixed
well to prepare a phosphoric acid premix. 92.7 parts
of basic inorganic mineral granular nuclei (silica sand
containing calcium carbonate grains, grain size
distribution: 0.5-1.7 mm, pH (10%): 9.5) and 1.3 part
of Moresco White 60 were mixed well by a concrete
mixer, and to the mixture were added 5.0 parts of the
TCHO premix and 1.0 part of the phosphoric acid premix,
followed by mixing for 15 minutes. The mixture was
screened by a sieve having an opening of 0.5-1.7 mm to
obtain a granular composition containing 4% of TCHO of
the present invention.
[0027]
Example 6
91.4 parts of TCHO, 6.7 parts of Sipernat 22S
and 1.9 part of phosphoric acid were mixed well, and
the mixture was pulverized by a hammer mill to prepare
a TCHO premix. 88.3 parts of neutral inorganic mineral
granular nuclei (silica sand occurring in Gifu
Prefecture and manufactured by Takeori Kogyosho Co.,

Ltd., grain size distribution: 0.5-1.0 mm, pH (10%):
6.4) and 5.0 parts of calcium carbonate granular nuclei
(calcium carbonate grains occurring in Hiroshima
Prefecture and manufactured by Nitto Funka Kogyo Co.,
Ltd., grain size distribution: 0.5-1.0 mm, pH (10%):
9.7) were introduced into a concrete mixer and mixed
well. Then, 1.5 part of Moresco White 60 was
introduced, followed by further mixing. Finally, 5.2
parts of the TCHO premix was added to the mixture,
followed by mixing for 15 minutes. The mixture was
screened by a sieve having an opening of 0.5-1.7 mm to
obtain a granular composition containing 4% of TCHO of
the present invention.
[0028]
Example 7
91.4 parts of TCHO, 6.7 parts of Sipernat 22S
and 1.9 part of phosphoric acid were mixed well, and
the mixture was pulverized by a hammer mill to prepare
a TCHO premix. 83.3 parts of neutral inorganic mineral
granular nuclei (silica sand occurring in Gifu
Prefecture and manufactured by Takeori Kogyosho Co.,
Ltd., grain size distribution: 0.5-1.0 mm, pH (10%):
6.4) and 10.0 parts of calcium carbonate granular
nuclei (calcium carbonate grains occurring in Hiroshima
Prefecture and manufactured by Nitto Funka Kogyo Co.,
Ltd., grain size distribution: 0.5-1.0 mm, pH (10%):
9.7) were introduced into a concrete mixer and mixed
well. Then, 1.5 part of Moresco White 60 was

introduced, followed by further mixing. Finally, 5.2
parts of the TCHO premix was added to the mixture,
followed by mixing for 15 minutes. The mixture was
screened by a sieve having an opening of 0.5-1.7 mm to
obtain a granular composition containing 4% of TCHO of
the present invention.
[0029]
Example 8
91.4 parts of TCHO, 6.7 parts of Sipernat 22S
and 1.9 part of phosphoric acid were mixed well, and
the mixture was pulverized by a hammer mill to prepare
a TCHO premix. 73.3 parts of neutral inorganic mineral
granular nuclei (silica sand occurring in Gifu
Prefecture and manufactured by Takeori Kogyosho Co.,
Ltd., grain size distribution: 0.5-1.0 mm, pH (10%):
6.4) and 20.0 parts of calcium carbonate granular
nuclei (calcium carbonate grains occurring in Hiroshima
Prefecture and manufactured by Nitto Funka Kogyo Co.,
Ltd., grain size distribution: 0.5-1.0 mm, pH (10%):
9.7) were introduced into a concrete mixer and mixed
well. Then, 1.5 part of Moresco White 60 was
introduced, followed by further mixing. Finally, 5.2
parts of the TCHO premix was added to the mixture,
followed by mixing for 15 minutes. The mixture was
screened by a sieve having an opening of 0.5-1.7 mm to
obtain a granular composition containing 4% of TCHO of
the present invention.
[0030]

Example 9
91.4 parts of TCHO, 6.7 parts of Sipernat 22S
and 1.9 part of phosphoric acid were mixed well, and
the mixture was pulverized by a hammer mill to prepare
a TCHO premix. 43.3 parts of neutral inorganic mineral
granular nuclei (silica sand occurring in Gifu
Prefecture and manufactured by Takeori Kogyosho Co.,
Ltd., grain size distribution: 0.5-1.0 mm, pH (10%):
6.4) and 50.0 parts of calcium carbonate granular
nuclei (calcium carbonate grains occurring in Hiroshima
Prefecture and manufactured by Nitto Funka Kogyo Co.,
Ltd., grain size distribution: 0.5-1.0 mm, pH (10%):
9.7) were introduced into a concrete mixer and mixed
well. Then, 1.5 part of Moresco White 60 was
introduced, followed by further mixing. Finally, 5.2
parts of the TCHO premix was added to the mixture,
followed by mixing for 15 minutes. The mixture was
screened by a sieve having an opening of 0.5-1.7 mm to
obtain a granular composition containing 4% of TCHO of
the present invention,
[0031]
Example 10
91.4 parts of TCHO, 6.7 parts of Sipernat 22S
and 1.9 part of phosphoric acid were mixed well, and
the mixture was pulverized by a hammer mill to prepare
a TCHO premix. 18.3 parts of neutral inorganic mineral
granular nuclei (silica sand occurring in Gifu
Prefecture and manufactured by Takeori Kogyosho Co.,

Ltd., grain size distribution: 0.5-1.0 mm, pH (10%):
6.4) and 75.0 parts of calcium carbonate granular
nuclei (calcium carbonate grains occurring in Hiroshima
Prefecture and manufactured by Nitto Funka Kogyo Co.,
Ltd., grain size distribution: 0.5-1.0 mm, pH (10%):
9.7) were introduced into a concrete mixer and mixed
well. Then, 1.5 part of Moresco White 60 was
introduced, followed by further mixing. Finally, 5.2
parts of the TCHO premix was added to the mixture,
followed by mixing for 15 minutes. The mixture was
screened by a sieve having an opening of 0.5-1.7 mm to
obtain a granular composition containing 4% of TCHO of
the present invention.
[0032]
Example 11
91.4 parts of TCHO, 6.7 parts of Sipernat 22S
and 1.9 part of phosphoric acid were mixed well, and
the mixture was pulverized by a hammer mill to prepare
a TCHO premix. 93.3 parts of calcium carbonate
granular nuclei (calcium carbonate grains occurring in
Hiroshima Prefecture and manufactured by Nitto Funka
Kogyo Co., Ltd., grain size distribution: 0.5-1.0 mm,
pH (10%): 9.7) was introduced into a concrete mixer and
mixed well. Then, 1.5 part of Moresco White 60 was
introduced, followed by further mixing. Finally, 5.2
parts of the TCHO premix was added to the mixture,
followed by mixing for 15 minutes. The mixture was
screened by a sieve having an opening of 0.5-1.7 mm to

obtain a granular composition containing 4% of TCHO of
the present invention.
[0033]
Example 12
83.3 parts of cartap hydrochloride, 10.8
parts of Sipernat 22S and 5.9 parts of phosphoric acid
were mixed well, and the mixture was pulverized by a
hammer mill to prepare a cartap hydrochloride premix.
93.0 parts of calcium carbonate granular nuclei
(calcium carbonate grains occurring in Hiroshima
Prefecture and manufactured by Nitto Funka Kogyo Co.,
Ltd., grain size distribution: 0.5-1.0 mm, pH (10%):
9.7) and 1.9 part of Moresco White 60 were mixed well
by a concrete mixer, and then 5.1 parts of the cartap
hydrochloride premix was added to the mixture, followed
by mixing for 15 minutes. The mixture was screened by
a sieve having an opening of 0.5-1.7 mm to obtain a
granular composition containing 4% of cartap
hydrochloride of the present invention.
[0034]
Comparative Example 1
95.0 parts of TCHO and 5.0 parts of Sipernat
22S were mixed well, and the mixture was pulverized by
a hammer mill to prepare a TCHO premix. 93.5 parts of
basic inorganic mineral granular nuclei (silica sand
containing calcium carbonate grains, grain size
distribution: 0.5-1.7 mm, pH (10%): 9.5) and 1.5 part
of Moresco White 60 were mixed well by a concrete

mixer, and then 5.0 parts of the TCHO premix was added
to the mixture, followed by mixing for 15 minutes. The
mixture was screened by a sieve having an opening of
0.5-1.7 mm to obtain a comparative granular composition
containing 4% of TCHO.
[0035]
Comparative Example 2
91.4 parts of TCHO, 6.7 parts of Sipernat 22S
and 1.9 part of phosphoric acid were mixed well, and
the mixture was pulverized by a hammer mill to prepare
a TCHO premix. 93.3 parts of calcium carbonate
granular nuclei (calcium carbonate grains occurring in
Hiroshima Prefecture and manufactured by Nitto Funka
Kogyo Co., Ltd., grain size distribution: 0.5-1.0 mm,
pH (10%): 9.7) and 1.5 part of PEG-400 were mixed well
by a concrete mixer, and then 5.2 parts of the TCHO
premix was added to the mixture, followed by mixing for
15 minutes. The mixture was screened by a sieve having
an opening of 0.5-1.7 mm to obtain a comparative
granular composition containing 4% of TCHO.
[0036]
Comparative Example 3
93.1 parts of TCHO and 6.9 parts of Sipernat
22S were mixed well, and the mixture was pulverized by
a hammer mill to prepare a TCHO premix. 93.5 parts of
calcium carbonate granular nuclei (calcium carbonate
grains occurring in Hiroshima Prefecture and
manufactured by Nitto Funka Kogyo Co., Ltd., grain size

distribution: 0.5-1.0 mm, pH (10%): 9.7) and 1.5 part
of PEG-400 were mixed well by a concrete mixer. Then,
5.0 parts of the TCHO premix was added to the mixture,
followed by mixing for 15 minutes. The mixture was
screened by a sieve having an opening of 0.5-1.7 mm to
obtain a comparative granular composition containing 4%
of TCHO.
[0037]
Comparative Example 4
83.3 parts of cartap hydrochloride, 10.8
parts of Sipernat 22S and 5.9 parts of phosphoric acid
were mixed well, and the mixture was pulverized by a
hammer mill to prepare a cartap hydrochloride premix.
93.0 parts of calcium carbonate granular nuclei
(calcium carbonate grains occurring in Hiroshima
Prefecture and manufactured by Nitto Funka Kogyo Co.,
Ltd., grain size distribution: 0.5-1.0 mm, pH (10%):
9.7) and 1.9 part of PEG-400 were mixed well by a
concrete mixer, and then 5.1 parts of the cartap
hydrochloride premix was added to the mixture, followed
by mixing for 15 minutes. The mixture was screened by
a sieve having an opening of 0.5-1.7 mm to obtain a
comparative granular composition containing 4% of
cartap hydrochloride.
[0038]
Comparative Example 5
94.4 parts of cartap hydrochloride and 5.6
parts of Sipernat 22S were mixed well, and the mixture

was pulverized by a hammer mill to prepare a cartap
hydrochloride premix. 94.0 parts of calcium carbonate
granular nuclei (calcium carbonate grains occurring in
Hiroshima Prefecture and manufactured by Nitto Funka
Kogyo Co., Ltd., grain size distribution: 0.5-1.0 mm,
pH (10%): 9.7) and 1.5 part of Moresco White 60 were
mixed well by a concrete mixer, and then 4.5 parts of
the cartap hydrochloride premix was added to the
mixture, followed by mixing for 15 minutes. The
mixture was screened by a sieve having an opening of
0.5-1.7 mm to obtain a comparative granular composition
containing 4% of cartap hydrochloride.
[0039]
Comparative Example 6 (TCHO was used in Patent Document
3)
4.7 parts of TCHO, 8.0 parts of dextrin, 5.0
parts of Newcalgen BX-C, 25 parts of magnesium oxide
and 57.3 parts of clay were mixed well, and then 12
parts of water was added, followed by kneading
intimately. The kneaded product was granulated by an
extrusion granulator (screen diameter: 1.0 mm) to
obtain a wet product. This was dried, subjected to
dressing of grains, and screened by a sieve of 0.5-1.7
mm to obtain a comparative granular product containing
4% of TCHO.
[0040]
Comparative Example 7 (cartap hydrochloride was used in
Patent Document 3)

4.2 parts of cartap hydrochloride, 8.0 parts
of dextrin, 5.0 parts of Newcalgen BX-C, 25 parts of
magnesium oxide and 57.8 parts of clay were mixed well,
and then 12 parts of water was added, followed by
kneading intimately. The kneaded product was
granulated by an extrusion granulator (screen diameter:
1.0 mm) to obtain a wet product. This was dried, then
subjected to dressing of grains, and screened by a
sieve of 0.5-1.7 mm to obtain a comparative granular
product containing 4% of cartap hydrochloride.
[0041]
Comparative Example 8 (TCHO was used in Patent Document
2)
4.7 parts of TCHO, 3.2 parts of Cellogen 7A,
0.54 part of Newcalgen BX-C and 91.5 parts of calcium
carbonate powder were mixed well, and then 12 parts of
water was added, followed by kneading intimately. The
kneaded product was granulated by an extrusion
granulator (screen diameter: 1.0 mm) to obtain a wet
product. This was dried, then subjected to dressing of
grains, and screened by a sieve of 0.5-1.7 mm to obtain
a comparative granular product containing 4% of TCHO.
[0042]
Comparative Example 9 (Cartap hydrochloride was used in
Patent Document 2)
4.2 parts of cartap hydrochloride, 3.2 parts
of Cellogen 7A, 0.54 part of Newcalgen BX-C and 92.0
parts of calcium carbonate powder were mixed well, and

then 12 parts of water was added, followed by kneading
intimately. The kneaded product was granulated by an
extrusion granulator (screen diameter: 1.0 mm) to
obtain a wet product. This was dried, then subjected
to dressing of grains, and screened by a sieve of 0.5-
1.7 mm to obtain a comparative granular product
containing 4% of cartap hydrochloride.
[0043]
Test example (Stability test)
Stability of the granular agricultural
chemical compositions obtained in the above Examples
and Comparative Examples was compared in the following
manner.
50 g of the granular agricultural chemical
composition was put in an aluminum bag, and the bag was
sealed. The bag was stored in a thermostat of 54°C, and
storage stabilities of the active ingredient after 2
weeks and 4 weeks were examined. The test results are
shown (Tables 1-3). The abbreviation "A.I." in the
Table means "active ingredient", and the term "Cartap"
means "cartap hydrochloride".
[0044]

[0045]
As is clear from the results of Tables 1 and
2, TCHO in the granular agricultural chemical
compositions of the present invention was stable
although basic inorganic mineral granular nuclei were
used as extenders. Even when the content of calcium
carbonate as inorganic mineral granular nuclei was
high, the agricultural chemical active ingredient in
the granular compositions was stable. As is clear from
Table 3, when phosphoric acid was not contained
(Comparative Example 1), stability of TCHO was damaged.
Furthermore, when PEG-400 which was water-soluble
liquid was used as an adhesive in place of the
oleophilic liquid (liquid paraffin) (Comparative
Examples 2 and 3), decomposition of the agricultural
chemical active ingredient was conspicuous regardless
of whether phosphoric acid was added or not. The
above-mentioned tendency seen in the case of TCHO was
similarly seen in the case of cartap hydrochloride
(Example 12 and Comparative Examples 4 and 5). When
TCHO and cartap hydrochloride were applied to the
patent relating to stabilization of bensultap
(Comparative Examples 6-9), both the agricultural
chemical active ingredients were conspicuously
decomposed. Thus, it can be seen that even when basic
inorganic minerals are used or known formulations in
which bensultap is stable are used, TCHO and cartap
hydrochloride which are the same nereistoxins cannot be

Industrial Applicability
[0046]
A granular agricultural chemical composition
excellent in stability of nereistoxin agricultural
chemical active ingredients which uses basic inorganic
mineral granular nuclei as an extender can be obtained
by coating a mixture of the nereistoxin agricultural
chemical active ingredient and phosphoric acid as a
stabilizer on basic inorganic mineral granular nuclei
such as calcium carbonate using an oleophilic liquid as
an adhesive.

CLAIMS
1. A granular agricultural chemical composition
which comprises a nereistoxin agricultural chemical
active ingredient as an agricultural chemical active
ingredient, inorganic mineral granular nuclei
containing basic inorganic mineral granular nuclei as
an extender, an oleophilic liquid as an adhesive and
phosphoric acid as a stabilizer.
2. A granular agricultural chemical composition
according to claim 1, wherein the nereistoxin
agricultural chemical active ingredient is thiocyclam
oxalate (hereinafter referred to as "TCHO") or cartap
hydrochloride.
3. A granular agricultural chemical composition
according to claim 1 or 2, wherein the oleophilic
liquid is liquid paraffin.
4. A granular agricultural chemical composition
according to any one of claims 1-3 which additionally
contains a solidification inhibitor.
5. A granular agricultural chemical composition
according to any one of claims 1-4 which comprises 65-
98% by weight of inorganic mineral granular nuclei,
1.0-20.0% by weight of a nereistoxin agricultural
chemical active ingredient, 0.5-10% by weight of an
oleophilic liquid, 0.05-0.5% by weight of phosphoric
acid and 0-2% by weight of a solidification inhibitor.
6. A granular agricultural chemical composition
according to claims 1-5, wherein the nereistoxin

agricultural chemical active ingredient and phosphoric
acid are coated on the inorganic mineral granular
nuclei using the oleophilic liquid as an adhesive.
7. A granular agricultural chemical composition
according to any one of claims 1-6 which is obtained by
adding the nereistoxin agricultural chemical active
ingredient and phosphoric acid to a composition
comprising a mixture of inorganic mineral granular
nuclei and the oleophilic liquid and mixing them to
coat the nereistoxin agricultural chemical active
ingredient.
8. A granular agricultural chemical composition
according to claim 6 or 7, wherein a solidification
inhibitor is mixed with the nereistoxin agricultural
chemical active ingredient and/or phosphoric acid.
9. A method for producing a granular
agricultural chemical composition according to any one
of claims 1-8 which comprises mixing an inorganic
mineral granular nuclei with an oleophilic liquid, then
adding a nereistoxin agricultural chemical active
ingredient and phosphoric acid to the mixture and
mixing them to coat the nereistoxin agricultural
chemical active ingredient.
10. A method for producing a granular
agricultural chemical composition according to claim 9,
wherein a solidification inhibitor is mixed with the
nereistoxin agricultural chemical active ingredient
and/or phosphoric acid. /)

Disclosed is a granular agrichemical
composition produced by coating a mixture of a
nereistoxin-type agrichemical active component and phosphoric acid as a stabilizing agent onto a granule core made of a basic inorganic mineral substance by using a lipophilic liquid as an adhesive agent. The granular agrichemical composition shows excellent stability of the nereistoxin-type agrichemical active
component.

Documents:

1888-KOLNP-2009-(10-10-2014)-ABSTRACT.pdf

1888-KOLNP-2009-(10-10-2014)-ANNEXURE TO FORM 3.pdf

1888-KOLNP-2009-(10-10-2014)-CLAIMS.pdf

1888-KOLNP-2009-(10-10-2014)-CORRESPONDENCE.pdf

1888-KOLNP-2009-(10-10-2014)-FORM-1.pdf

1888-KOLNP-2009-(10-10-2014)-OTHERS.pdf

1888-KOLNP-2009-(10-10-2014)-PETITION UNDER RULE 137.pdf

1888-kolnp-2009-abstract.pdf

1888-kolnp-2009-claims.pdf

1888-KOLNP-2009-CORRESPONDENCE-1.1.pdf

1888-kolnp-2009-correspondence.pdf

1888-kolnp-2009-description (complete).pdf

1888-kolnp-2009-form 1.pdf

1888-KOLNP-2009-FORM 18.pdf

1888-kolnp-2009-form 2.pdf

1888-KOLNP-2009-FORM 3.1.pdf

1888-kolnp-2009-form 3.pdf

1888-kolnp-2009-form 5.pdf

1888-kolnp-2009-international publication.pdf

1888-kolnp-2009-international search report.pdf

1888-kolnp-2009-others pct form.pdf

1888-KOLNP-2009-PA.pdf

1888-kolnp-2009-pct priority document notification.pdf

1888-kolnp-2009-specification.pdf

1888-kolnp-2009-translated copy of priority document.pdf

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Patent Number

264357

Indian Patent Application Number

1888/KOLNP/2009

PG Journal Number

52/2014

Publication Date

26-Dec-2014

Grant Date

23-Dec-2014

Date of Filing

21-May-2009

Name of Patentee

NIPPON KAYAKU KABUSHIKI KAISHA

Applicant Address

11-2, FUJIMI 1-CHOME, CHIYODA-KU, TOKYO

Inventors:

#	Inventor's Name	Inventor's Address
1	KOUKI TANIGAKIUCHI	C/O AGROCHEMICALS LABORATORIES, NIPPON KAYAKU KABUSHIKI KAISHA OF 6, SUNAYAMA, KAMISU-SHI, IBARAKI
2	KANZI YOSHIZAWA	C/O AGROCHEMICALS LABORATORIES, NIPPON KAYAKU KABUSHIKI KAISHA OF 6, SUNAYAMA, KAMISU-SHI, IBARAKI
3	MIKIO SEKIGUCHI	C/O AGROCHEMICALS LABORATORIES, NIPPON KAYAKU KABUSHIKI KAISHA OF 6, SUNAYAMA, KAMISU-SHI, IBARAKI

PCT International Classification Number

A01N 43/32,A01P 7/04

PCT International Application Number

PCT/JP2007/073162

PCT International Filing date

2007-11-30

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2006-327704	2006-12-05	Japan