JP4996230B2 - Granulated pesticide preparation with controlled dissolution and its application method - Google Patents

Description

  The present invention relates to a granular agrochemical formulation in which elution of an agrochemical active ingredient is controlled and its application method.

Conventionally, when using agrochemicals, it is desired to reduce the amount and frequency of use of agricultural chemicals and to shorten the period of use from the viewpoint of labor saving and environmental load reduction. In response to this demand, granular agrochemical formulations have been developed for the purpose of controlling the elution of agrochemical active ingredients and extending the elution period. For example, the following are known.
(1) Those using paraffin wax (see Patent Document 1).
(2) An alcohol type wax is used (see Patent Document 2).
(3) One using a divalent or higher valent inorganic metal salt (eg, salt of Al, Cr, Co, Cu, Fe, Mg, Zn, etc.) (see Patent Document 3).
(4) One using a water-soluble organic acid salt and an adsorbent carrier (see Patent Document 4).
(5) Those using carboxymethyl cellulose (see Patent Document 5).

  However, the granular pesticide preparations with controlled dissolution of (1) to (5) do not maintain long-lasting elution and cannot obtain sufficient biological effects, or the drug is retained in the granular pesticide preparations forever. In order to obtain the effect, there was a disadvantage that sufficient elution was not obtained.

In addition to the above, the following is known as a release control technique using an alginate.
(6) An example in which the release of the pesticidal active ingredient is suppressed by a granular pesticidal composition containing a water-insoluble alginate and bentonite (see Patent Document 6).
(7) An example in which the release of the pesticidal active ingredient is suppressed by a coated pesticidal granule obtained by coating a granular material containing an pesticidal active ingredient and an alginate with a resin (see Patent Document 7).
(8) An example in which elution of an agrochemical active ingredient is improved with a granular composition containing alginic acid or a salt thereof, acidic clay or activated clay, and an agrochemical active ingredient (see Patent Document 8).

  However, in the granular agrochemical composition using the water-insoluble alginate of (6) or the granule coated with a resin of the alginate containing the alginate of (7), the agrochemical active ingredient is gradually released, Although it is excellent in terms of the sustainability of the biological effect, for example, since almost no pesticidal active ingredient is released about one day after granule spraying, there are concerns about pest damage etc. for several days immediately after spraying. Moreover, the granular material using the alginic acid or its salt of (8) and acidic clay or activated clay may cause the pesticidal active ingredient to be adsorbed on the acidic clay or activated clay, and the effect of the pesticidal active ingredient may not be sufficiently exhibited. there were. Therefore, in any of the above-described inventions, it cannot be said that the elution control is sufficiently achieved.

On the other hand, as one method of applying agricultural chemicals, there is a planting hole treatment method in which a chemical is sprayed simultaneously with a seedling of a crop in a hole for planting the crop. When planting a plant, it can be sprayed with chemicals at the same time, so it is excellent in terms of labor saving, but there are problems in terms of phytotoxicity to young seedlings and long-term efficacy.
JP 63-35504 A Japanese Patent Laid-Open No. 11-292706 Japanese Patent Publication No. 6-76282 JP-A-8-175903 JP 2001-233706 A JP-A-7-228501 JP 2003-160407 A JP 2004-359567 A

  An object of the present invention is to provide a granular agrochemical formulation excellent in elution controllability that can be applied to various bactericidal active ingredients and / or insecticidal active ingredients. Another object of the present invention is to provide a granular pesticide preparation that has no phytotoxicity to young seedlings and has long-lasting medicinal effects even when used for planting holes.

  The present inventors have intensively studied to solve the above problems. As a result, a granular agrochemical formulation comprising a bactericidal active ingredient and / or an insecticidal active ingredient, a water-soluble alginate whose viscosity of an aqueous solution of 1% by weight is 100 to 1000 mPa · s, an anionic surfactant, and a carrier. Has found that the above-mentioned problems can be solved, and has reached the present invention.

That is, the present invention can be summarized as follows.
(1) Bactericidal active ingredient and / or insecticidal active ingredient, a granular agrochemical formulation comprising a water-soluble alginate whose viscosity of a 1% by weight aqueous solution is 100 to 1000 mPa · s, an anionic surfactant and a carrier .
(2) A granular agrochemical formulation, wherein the water-soluble alginate is one or more compounds selected from water-soluble alkali metal alginate.
(3) A granular agrochemical formulation, wherein the amount of water-soluble alginate added in the formulation is 0.1% to 20% by weight.
(4) A method for applying a granular agrochemical formulation, wherein the granular agrochemical formulation according to any one of (1) to (3) is used for planting treatment.

  The granular agrochemical formulation of the present invention can control the elution rate of various bactericidal active ingredients or insecticidal active ingredients. As a result, it can be used as an excellent pesticide granule that exhibits its medicinal effects sufficiently and has no phytotoxicity to crops.

  Hereinafter, the present invention will be described in detail. The component which comprises the granular agrochemical formulation of this invention, the preparation method of a formulation, and the usage condition of a formulation are as follows.

<Constituents>
(1) Bactericidal active ingredient or insecticidal active ingredient The bactericidal active ingredient or insecticidal active ingredient that can be used in the present invention may be those generally used as active ingredients for agricultural chemicals such as bactericides and insecticides. Further, two or more kinds of bactericidal active ingredients or insecticidal active ingredients may be used in combination. Examples of such a bactericidal active ingredient or insecticidal active ingredient include the following.
For example, as a disinfectant, inorganic copper, organic copper, inorganic sulfur agent, organic sulfur agent, organic phosphorus, phthalide, benzimidazole, dicarboximide, acid amide, triazole, imidazole, methoxy Acrylate-based, strobilurin-based, anilinopyrimidine-based, dithiolane-based, quinoxaline-based, aminopyrimidine-based, phenylpyrrole-based, triazine-based, cyanoacetamide-based, guanidine-based fungicide, antibiotic-based fungicide, and natural product fungicide Can be mentioned.
Insecticides such as organophosphorus, carbamates such as carbosulfan, neonicotinoids such as acetamiprid, pyrethroids, chloronicotinyl, phenylpyrazole, nereistoxin and benzoylphenylurea, natural Examples include insecticides and acaricides.
The specific agrochemical active ingredients contained in these are, for example, “Agricultural Chemicals Handbook 2005 Edition” (Japan Plant Protection Association, issued on October 11, 2005), “SHIBUYA INDEX 11th Edition” (May 2006). May 25), “The Pesticide Manual Future Edition,” (published by British Crop Protection Council), and the like.
In addition, as the bactericidal active ingredient or insecticidal active ingredient used in the present invention, a publicly known or future developed bactericidal active ingredient or insecticidal active ingredient other than the above can also be applied.

(2) Water-soluble alginate The water-soluble alginate used in the present invention is an alginic acid extracted from dry alga and an industrially modified one. Industrially, seaweed can be obtained by washing with a calcium chloride solution and hydrochloric acid, extracting with a sodium carbonate solution, precipitating with a hydrochloric acid or calcium chloride solution and purifying, and then performing various chemical reactions. Specific examples include sodium alginate, potassium alginate, and ammonium alginate. From the viewpoint of elution control, a water-soluble alkali metal alginate is preferable.
The water-soluble alginate used in the present invention usually has a 1% by weight aqueous solution having a viscosity of 100 mPa · s to 1000 mPa · s, depending on the type of the pesticidal active ingredient to be controlled for elution. When an alginate having a viscosity of 1 wt% aqueous solution lower than 100 mPa · s is used, the sustainability of the elution amount is deteriorated, and when an alginate having a viscosity of 1 wt% aqueous solution higher than 1000 mPa · s is used. Although elution is sustained, the initial elution amount becomes low, and sufficient medicinal effects cannot be expected.
The use amount of the water-soluble alginate is 0.01 wt% to 50 wt%, preferably 0.05 wt% to 30 wt%, more preferably 0.1 wt% to as the content in the granular agrochemical composition. 20% by weight. When the alginate is less than 0.01% by weight, the elution persistence is poor and sufficient medicinal effects cannot be obtained. On the other hand, when the amount of the water-soluble alginate is more than 50% by weight, elution is sustained, but the initial elution amount becomes low, and sufficient medicinal effect cannot be expected.

(3) Anionic surfactant The anionic surfactant that can be used in the present invention is not particularly limited, and examples thereof include lignin sulfonate, alkylaryl sulfonate, dialkyl sulfosuccinate, polyoxyethylene alkylaryl phosphate, Examples include polyoxyethylene alkyl aryl ether sulfate, alkyl naphthalene sulfonate, polyoxyethylene styryl phenyl ether sulfate, and the like, but are not limited to these examples. These surfactants may be used alone or in combination of two or more. Moreover, the addition amount in a formulation is 0.01 to 20 weight% normally, Preferably it is 0.1 to 10 weight%.

(4) Carrier The carrier that can be used in the present invention is not particularly limited, and examples thereof include clay, talc, calcium carbonate, sodium carbonate, dikelite, sericite, quartzite, diatomaceous earth, pumice, zeolite, vermiculite, white carbon, rice bran, Examples include monosaccharides such as glucose, fructose, sucrose, maltose, lactose, starch, dextrin, disaccharides, polysaccharides, urea, potassium chloride, ammonium sulfate, sodium sulfate, bentonite, etc., but not limited to these examples Absent. These carriers may be used alone or in combination of two or more.

(5) Other components In addition to the above essential components, the granular agrochemical formulation of the present invention contains a surfactant other than an anionic surfactant, a binder, a solvent, an auxiliary agent, and the like as necessary. May be.
Examples of surfactants other than anionic surfactants include conventionally known nonionic surfactants, cationic surfactants, and amphoteric surfactants.
Examples of nonionic surfactants include polyoxyethylene alkyl aryl ether (eg, polyoxyethylene nonyl phenyl ether), polyoxyalkylene aryl phenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene Examples include sorbitan alkylate, polyoxyalkylene glycol, and polyoxyethylene phenyl ether polymer.
Examples of the cationic surfactant and the amphoteric surfactant include alkylamines, quaternary ammonium salts, alkylbetaines, amine oxides and the like.

Examples of the binder include the following.
Cellulose, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, starch, carboxymethyl starch, dextrin, pullulan, mannan, pectin, tragacanth gum, mannitol, sorbitol, guar gum, locust bean gum, gum arabic, xanthan gum, gelatin Casein, polyvinyl alcohol, polyethylene oxide, polyethylene glycol, ethylene / propylene block polymer, sodium polyacrylate, polyvinyl pyrrolidone, ethyl cellulose, corn fiber, chitin, chitosan and the like.
The binder may be used alone or in combination of two or more. The amount of the binder added to the agricultural chemical preparation is generally 0.1 to 20 parts by weight of the whole preparation, preferably 0.3 to 10 parts by weight, and more preferably 1 to 5 parts by weight.

  Examples of the solvent that can be used in the present invention include Solvesso 150 (trade name, manufactured by Exxon Chemical Co., Ltd.), Hysol E, Hysol F (trade name, manufactured by Nippon Petrochemical Co., Ltd.), Cactus Solvent P100, Cactus Solvent P150, Cactus Alkylbenzene solvents such as Solvent P187, Cactus Solvent P200 (trade name, manufactured by Japan Energy Co., Ltd.), Alkene 56N, Alkene 60NH, Alkene L (trade name, manufactured by Nippon Petrochemical Co., Ltd.), Cactus Solvent 220, Cactus Solvent P240 ( Trade name of Japan Energy Co., Ltd., Solvesso 200 (trade name of Exxon Corporation), purified methylnaphthalene (manufactured by Sumikin Kako Co., Ltd.), diisopropylnaphthalene (trade name “KMC-113”, Kureha Chemical Industry Co., Ltd.) ), Etc., isoparaffin (trade name “Isosol 300” manufactured by Nippon Petrochemical Co., Ltd.), paraffinic solvents such as liquid paraffin and n-paraffin, naphthesol (manufactured by Nippon Petrochemical Co., Ltd.), Exsol (Exxon Corporation) Naphthenic solvents such as company name), ether solvents such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol mono-n-butyl ether, 3-methyl-3-methoxybutanol, 3-methyl-3- Alcohol solvents such as methoxybutyl acetate and 3-methyl-1,3-butanediol, alkylpyrrolidone solvents such as N-methylpyrrolidone, n-octylpyrrolidone and n-dodecylpyrrolidone, DuPont DBE Pon Co., Ltd. product name), ditridecyl phthalate, diisobutyl adipate, diisodecyl adipate, didecyl phthalate, dialkyl phthalate (C10 to C12), trinormal alkyl trimellitic acid (C8 to C10), trimellitic acid trimethyl 2-ethylhexyl, trialkyl trimellitic acid (C9), tribasic acid ester of trimellitic acid, polybasic acid ester solvent such as dioleyl adipate, isobutyl oleate, methyl palm fatty acid, methyl laurate, methyl palm fatty acid, isopropyl palmitate Aromatic hydrocarbons based on fatty acid esters such as isotridecyl stearate, 2-ethylhexyl stearate, methyl oleate, octyl oleate, lauryl oleate, decyl oleate, and diallylethane Solvent, Hysol SAS-296 (trade name, manufactured by Nippon Petrochemical Co., Ltd.), aromatic hydrocarbon solvent based on triallyldiethane, Hysol SAS-LH (trade name, manufactured by Nippon Petrochemical Co., Ltd.) Solvents such as, vegetable oil fatty acid esters such as rice bran oil fatty acid methyl ester, soybean oil fatty acid methyl ester, vegetable oils such as rapeseed oil, soybean oil, castor oil, cottonseed oil, corn oil, etc. In addition, one of these may be used, or two or more may be used in combination.

  Adjuvants that can be used in the present invention include stabilizers such as antioxidants, UV inhibitors, and crystal precipitation inhibitors, sorbic acid, potassium sorbate, p-chloro-m-xylenol, p-butyl oxyoxybenzoate, and the like. Anti-fungal agents, citric acid, phosphoric acid, calcium carbonate, magnesium carbonate and other pH adjusters

<Preparation method of granular agrochemical formulation>
In obtaining the granular agrochemical formulation of the present invention, various granulation methods may be used to obtain a granular material, and as such methods, extrusion granulation method, rolling granulation method, rolling fluid granulation method And fluidized bed granulation method, compression granulation method, stirring and mixing granulation method, coating granulation method and tableting method. When obtaining a columnar granulated product, the extrusion granulation method is preferred, and when obtaining a spherical granulated product, the rolling granulation method and the stirring and mixing granulation method are preferred.

In the extrusion granulation method, first, agrochemical active ingredients, water-soluble alginate, anionic surfactant, carrier with or without a binder, and if necessary, a surfactant other than an anionic surfactant. Add agents, solvents, and adjuvants and mix evenly using a juice mixer, hammer mill, Redige mixer or ribbon mixer. Water and / or an aqueous solution or dispersion of a binder is added to this mixture and kneaded using a double-arm kneader or a ribbon mixer.
Next, the kneaded product is granulated using an extrusion granulator such as a basket type granulator or a screw type granulator. The extrusion hole diameter (screen diameter) during granulation is usually in the range of 0.3 to 5 mm, preferably 0.5 to 2 mm. The obtained granulated material is sized using a Malmerizer and the like, then dried using a fluidized bed dryer or a bed dryer, and then sieved to obtain the granular material used in the present invention.

  In the stirring and mixing granulation method, first, an agrochemical active ingredient, a water-soluble alginic acid, an anionic surfactant, and a carrier, with or without a binder, and if necessary, other than an anionic surfactant. Surfactant, solvent and auxiliary agent are added and mixed uniformly using a juice mixer, hammer mill, Redige mixer or ribbon mixer. This mixture is stirred and rolled in a granulation vessel of a stirring and mixing granulator by rotating a stirring blade. The aqueous mixture or aqueous dispersion of water and / or a binder is dropped or sprayed onto the rolling mixture, and the particles are grown to an appropriate size and granulated. The granulated material used in the present invention can be obtained by taking out this granulated material, drying it using a fluidized bed dryer or bed dryer, and then sieving it.

  The granular material obtained by the rolling granulation method or the rolling fluidized bed granulation method is spherical, and the diameter or maximum diameter of the granular material used in the present invention is usually 0.1 to 20 mm, preferably 0.5. The thing in the range of -10 mm is preferable.

  In the tableting method, a predetermined amount of the granular material obtained by the extrusion granulation method may be directly compressed and compressed using a tableting machine, and may be shaped and granulated. Also, the agrochemical active ingredient, water-soluble alginate Add an anionic surfactant, carrier, and if necessary, a binder, a surfactant other than the anionic surfactant, a solvent, and an auxiliary agent, and mix them. It is good also as a granulation by shaping and granulating by pressure-compression. The form of the granular material in this case is determined by the shape of the mortar and punch of the tableting machine, and they are obtained in various shapes and sizes such as a circular plate shape, an oval plate shape, a square plate shape, and an oval shape. Any of these can be used in the present invention. The diameter or maximum diameter of the granular material obtained by these tableting methods is usually in the range of 0.1 to 30 mm, preferably 0.5 to 20 mm.

<Usage of granular agrochemical formulation>
The granular pesticide preparation prepared as described above can be applied by the same method as that for ordinary granular pesticides. For example, direct spraying by hand, human-powered granulator, electric granulator, back type power granulator, traveling power granulator, tractor mounted granulator, rice transplanter mounted granulator, Examples of methods include a seedling box granulator, a side-row application medicine machine, and the like, preferably a planting hole treatment.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.
In the following examples and comparative examples, “part” means “part by weight”.
The viscosity was measured using a B-type viscometer, rotor No. The measurement was performed under conditions of 2, 12 rpm and a temperature of 20 ° C.

  2.0 parts of acetamiprid, 5.0 parts of sodium alginate with a 1% by weight aqueous solution viscosity of 550 mPa · s, 0.5 parts of sodium lauryl sulfate, 89.5 parts of clay and 3.0 parts of dextrin were added to a hammer mill (atomizer, And pulverized and mixed. 13.0 parts of water was added to this pulverized mixture and kneaded with a double-arm kneader (manufactured by Fuji Powder Co., Ltd.). Next, this kneaded material was granulated with an extrusion granulator (NYG-200, manufactured by Nippon Pharmaceutical Co., Ltd.) equipped with a basket type screen having a pore diameter of 1.0 mm. The granulated product was dried with a fluidized bed dryer (Fuji Paudal Co., Ltd.) and then sieved with a 500 to 1400 μm sieve to obtain the granular agrochemical formulation of the present invention.

  After 3.0 parts of carbosulfane is absorbed into 3.0 parts of white carbon, 5.0 parts of sodium alginate whose viscosity of a 1% by weight aqueous solution is 550 mPa · s, 0.5 parts of sodium lauryl sulfate, dextrin 3.0 And 85.5 parts of clay were pulverized and mixed with a hammer mill. 15.0 parts of water was added to this pulverized mixture, kneaded by a double arm kneader, and granulated by an extrusion granulator equipped with a basket type screen having a pore diameter of 1.2 mm. The granulated product was dried with a fluidized bed dryer and then sieved with a 1400-500 μm sieve to obtain the granular agrochemical formulation of the present invention.

As shown in Table 1 below, formulation no. 1-11 were prepared. Formulation No. 1 is a preparation obtained in Example 1, and preparation No. Nos. 2 to 9 are preparations prepared according to Example 1. In Example 1, the preparations were prepared by the same production method by changing the types and blending amounts of the respective components to other ones. Similarly, formulation no. 10 is the formulation obtained in Example 2, 11 is the variation.
Comparative formulation No. 2 shown in Table 2. 1 to 11 were prepared according to Examples 1 and 2, but comparative preparation No. Nos. 1 and 2 are examples in which the viscosity of a 1% by weight aqueous solution of a water-soluble alginate is outside the range of 100 to 1000 mPa · s. 3, 6, and 8 are examples in which an anionic surfactant is not blended. Nos. 4 and 10 are examples in which an alginate is not blended. Nos. 5 and 9 are examples in which an anionic surfactant and an alginate are not blended. 7 and 11 are examples in which water-insoluble alginate is blended.

Next, the usefulness of the granular agrochemical formulation of the present invention will be shown by test examples.
Test Example 1 Dissolution test
To a 1 L glass petri dish having a bottom diameter of about 11 cm, 500 ml of 3 degree hard water is added (the height of the water surface is about 6 cm). Thereafter, 1 g of a granular pesticide preparation prepared according to the examples is added and left in a constant temperature room at 20 ° C. When the granular pesticide preparation was introduced, the granular pesticide preparation was present almost uniformly on the bottom of the beaker. After a predetermined time (24, 48, 72, 96, 120 hours), sample 3ml each from 5 locations 3cm in height from the bottom of the beaker, mix all, and then analyze the concentration of the pesticidal active ingredient by high performance liquid chromatography. (HPLC), gas chromatography (GC) or other method to quantify (when a degradation product is produced, the degradation product is also quantified and converted into agrochemical active ingredient concentration) and calculated from the following formula . The results are shown in Tables 3-4.

Test Example 2 Insecticidal effect test on thrips Using a plastic pot with a diameter of 30 cm, 1 g of drug per plant was treated in the planting hole when cucumber seedlings were planted. On 2, 7, 14, and 30 days after planting, cucumber leaves were cut out and placed in plastic cups, and 10 thrips adults were inoculated. Three days after inoculation, the death rate was calculated from the following formula. The results are shown in Tables 5-6.

As is apparent from the results in Tables 3 and 4, formulation No. The elution rate of 1 to 11 is 4 to 15% after 24 hours and 31 to 95% after 120 hours. On the other hand, comparative preparation No. 1, 3, 5, 7 to 9 and 11 are 1 to 2% after 24 hours, and the amount of elution is small. 2, 4, 6, and 10 became 100% elution after 72 hours.
In addition, from the results of Tables 5 and 6, formulation No. The mortality rate of 1 to 11 was as high as 90 to 100% until 2 to 30 days later, whereas the amount of elution after 24 hours was small. Nos. 1, 3, 5, 7-9 and 11 show comparative preparations No. 2 having a low mortality rate of 2 to 60% after 2 days and an elution amount of 100% after 72 hours. 2, 4, 6, and 10 had a low mortality rate of 40 to 60% after 30 days, and a significant difference was observed.

Claims (4)

  A granular agrochemical formulation comprising a bactericidal active ingredient and / or an insecticidal active ingredient, a water-soluble alginate whose viscosity of an aqueous solution of 1% by weight is 100 to 1000 mPa · s, an anionic surfactant and a carrier.   The granular agrochemical formulation according to claim 1, wherein the water-soluble alginate is one or more compounds selected from alkali metal alginate.   The granular agrochemical formulation according to claim 1 or 2, wherein the amount of the water-soluble alginate added in the formulation is 0.1% to 20% by weight.   A method for applying a granular agrochemical formulation, comprising using the granular agrochemical formulation according to any one of claims 1, 2, or 3 for planting treatment.