JP2009184969A - Agrochemical granule - Google Patents

Abstract

[PROBLEMS] To provide an intermediate raw material having excellent storage stability, including an agrochemical active ingredient that is atomized while being sparingly soluble in water, and that the active ingredient of an agricultural chemical is easily eluted into an aqueous phase and is stable. The agrochemical granule which can exhibit the biological effect which can be used suitably for the flooding process is provided.
At least one surface activity selected from the group consisting of polyoxyalkylene allyl ethers, phosphates and sulfates of polyoxyalkylene allyl ethers, and phosphates and sulfates of polyoxyalkylene allyl ethers Contains a solid agrochemical active ingredient pulverized to a median diameter of 0.5 μm or less in the presence of an agent, and a solid agrochemical active ingredient having a water solubility of 0.5 ppm or less, and a condensate of lignin sulfonate and alkylnaphthalene sulfonate This is an agrochemical granule obtained by using a wet pulverized product and an inorganic mineral substance, mixing the wet pulverized product with an inorganic mineral substance, and extruding the mixture.
[Selection figure] None

Description

  The present invention relates to an agrochemical granule that is suitably used mainly for flooding treatment.

  Conventionally, in flooded sewage paddy fields, granules that can be easily sprayed as they are are widely used as herbicide formulation forms. The general application amount of the herbicide granule is 3 to 4 kg per 10 ares. However, from the viewpoint of reducing the burden of spraying work and reducing logistics costs, etc., a granule having a spraying amount of about 1 kg per 10 ares has become mainstream in recent years.

  Here, the reduction in the amount of sprayed granule means that the number of grains per unit area inevitably decreases. For this reason, in order to obtain a sufficient biological effect even if the application amount is reduced, it is necessary to release the active ingredient from the preparation granules more efficiently than the conventional preparation. In addition, about the granule using the solid agrochemical active ingredient with low water solubility, conventionally, various devices for performing discharge | release of an agrochemical active ingredient efficiently are made | formed.

  As a related prior art, micronized biocidal material containing 50 wt% or more of particles having a particle size of 0.5 μm or less, obtained by using a biocide dispersion containing a water-soluble or water-dispersible polymer as a dispersant. The drug substance is disclosed (for example, refer to Patent Document 1). Also, a method for producing an agrochemical formulation in which a solid agricultural chemical is supported on the surface of an oil-absorbing granular carrier using a slurry in which a solid agricultural chemical finely divided to 20 μm or less is dispersed in oil, and the presence of an alkyl naphthalene sulfonate A method for producing a granule for granulating a biocidal component for agricultural chemicals that is slightly water-soluble and wet-grinded under water is disclosed (for example, see Patent Documents 2 and 3).

  Furthermore, herbicidal granules for paddy fields obtained by extruding and granulating a mixture (slurry) such as oxadiazone and other herbicidal active ingredients which are sparingly soluble in water in a high-boiling solvent together with mineral fine powder Is disclosed (for example, see Patent Documents 4 and 5).

JP 61-63601 A Japanese Patent No. 2886572 Japanese Patent No. 2931603 JP-A-5-17303 JP-A-5-17304

  However, even if it is the manufacturing method of the granule disclosed in patent documents 1-5 etc., when formulating the solid agricultural chemical active ingredient (agrochemical raw material) whose water solubility is 0.5 ppm or less, it is sufficiently fine It is difficult to make it. This is considered to be due to the fact that the formed agrochemical substance becomes finer and more easily agglomerated among the formed particles. If the particle size of the pesticide raw material is too large, it will be difficult to achieve a sufficient biological effect. Therefore, it is necessary to make the pesticide raw material finer and finer in order to reduce the amount of application.

  However, when trying to wet pulverize a solid agrochemical base having a water solubility of 0.5 ppm or less until the median diameter is 0.5 μm or less, it becomes difficult to pulverize to a certain particle size or less, There was a case where the pulverization could not be performed due to a significant increase. In addition, when the wet pulverized material as an intermediate raw material is stored for a long period of time, there are cases in which the biological effect decreases due to the increase in particle size, the viscosity increases, or the handleability decreases due to the formation of a hard cake. For this reason, this wet pulverized product cannot always be said to have satisfactory performance for industrial use.

  The present invention has been made in view of such problems of the prior art, and the problem is that the intermediate raw material has excellent storage stability and is hardly soluble in water. Provided is an agrochemical granule that can be suitably used for flooding treatment, including a finely divided atomized agrochemical active ingredient and capable of leaching into the aqueous phase and exhibiting a stable biological effect. There is.

  As a result of intensive investigations to achieve the above-mentioned problems, the present inventors formulated a solid agricultural chemical active ingredient that is sparingly soluble in water using a wet pulverized product obtained by pulverizing in the presence of a specific surfactant. As a result, the present inventors have found that the above-described problems can be achieved, and have completed the present invention.

  That is, according to the present invention, the following agricultural chemical granules are provided.

  [1] At least one surfactant selected from the group consisting of polyoxyalkylene allyl ether, phosphoric acid ester and sulfuric acid ester of polyoxyalkylene allyl ether, and phosphoric acid ester salt and sulfuric acid ester salt of polyoxyalkylene allyl ether In the presence of, a solid agrochemical active ingredient ground to a median diameter of 0.5 μm or less and having a water solubility of 0.5 ppm or less, and at least one of a condensate of lignin sulfonate and alkylnaphthalene sulfonate Using the wet pulverized product and the inorganic mineral material, mixing and extruding the wet pulverized product and the inorganic mineral material, spraying the wet pulverized product on the granules of the inorganic mineral material, or applying the wet pulverized product to the wet pulverized product. An agrochemical granule obtained by impregnating granules of the inorganic mineral.

  [2] The agrochemical granule according to [1], which is used for flooding treatment.

  The agrochemical granule of the present invention has an intermediate raw material that is excellent in storage stability and contains an agrochemical active ingredient that is atomized while being hardly soluble in water. Moreover, the agricultural chemical active ingredient is easily eluted into the aqueous phase and can exhibit a stable biological effect. For this reason, the agrochemical granule of this invention can be used suitably for a flooding process.

  BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention will be described below, but the present invention is not limited to the following embodiment, and is based on the ordinary knowledge of those skilled in the art without departing from the gist of the present invention. It should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention.

  One embodiment of the agrochemical granule of the present invention is from the group consisting of polyoxyalkylene allyl ether, polyoxyalkylene allyl phosphate phosphate and sulfate, and polyoxyalkylene allyl phosphate phosphate and sulfate. In the presence of at least one selected surfactant, it contains at least one of a lignin sulfonate and a condensate of an alkyl naphthalene sulfonate, and is pulverized to a median diameter of 0.5 μm or less. Wet pulverized product containing 0.5 ppm or less of solid agricultural chemical active ingredient and inorganic mineral material are mixed and extruded with wet pulverized product and inorganic mineral material. It is obtained by spraying or impregnating wet pulverized material with granules of inorganic mineral. The details will be described below.

  The pesticidal active ingredient (pesticidal active ingredient) used in the pesticidal granules of the present invention is solid at room temperature, and its water solubility is 0.5 ppm or less, preferably 0.1 ppm or less. Examples of the agrochemical active ingredient having such properties include various insecticides, fungicides, and herbicides. Specific examples of insecticides include propoxur, cypermethrin, bifenthrin, acrinatrin, etofenprox, tefluthrin, teflubenzuron, diflubenzuron, hexaflumuron, lufenuron, flufenoclson, chlorfluazuron, tebufenozide, chromafenozil, benzoepir, Examples include diafenthiuron and indoxacarb. Specific examples of the bactericides include diclocimet, trifloxystrovirlin, famoxadone, pencyclon, dithianone, cyazofamide and the like. Specific examples of herbicides include chromeprop, quizalofopethyl, fenmedifam, piributicalbu, benzophenap, prodiamine, pendimethalin, biphenox, pentoxazone, oxadichromemephone, and benzobicyclon. Two or more of these agrochemical active ingredients may be combined. In addition, it is preferable to mix | blend an agrochemical active ingredient so that it may become 10-60 mass% with respect to the whole wet pulverization thing obtained, and it is still more preferable to mix | blend so that it may become 35-50 mass%.

  The surfactant used for producing the agrochemical granule of the present invention is polyoxyalkylene allyl ether, polyoxyalkylene allyl ether phosphate, polyoxyalkylene allyl sulfate, polyoxyalkylene allyl ether phosphorus An acid ester salt or a sulfate ester salt of polyoxyalkylene allyl ether. Of these, polyoxyalkylene allyl ether, polyoxyalkylene allyl ether phosphate ester salt, or polyoxyalkylene allyl ether sulfate ester salt is preferable. The molecular weight of these surfactants, the number of aromatic rings in the hydrophobic group, and the like are not particularly limited, and it is also preferable to use a combination of two or more of these surfactants. When the above-mentioned pesticidal active ingredient is wet-ground in the presence of these surfactants, it can be atomized in a stable state to a median diameter of 0.5 μm or less.

  The wet pulverized product includes at least one selected from the group consisting of polyoxyalkylene allyl ether, polyoxyalkylene allyl ether phosphate and sulfate, and polyoxyalkylene allyl phosphate phosphate and sulfate. A surfactant is contained. The blending ratio of these surfactants is preferably 0.2 to 20% by mass, and more preferably 0.5 to 10% by mass with respect to the whole wet pulverized product. When the pesticidal active ingredient is wet pulverized under the condition in which a surfactant is contained so as to be within this numerical range, it can be atomized in a more stable state to a median diameter of 0.5 μm or less.

  Among the above surfactants, the lignin sulfonate and the alkyl naphthalene sulfonate condensate are preferably blended in an amount of 1.0 to 10% by mass based on the whole wet pulverized product obtained. It is still more preferable to mix | blend 0.0-5.0 mass%. These surfactants are at least one selected from the group consisting of polyoxyalkylene allyl ether, polyoxyalkylene allyl phosphate phosphate and sulfate, and polyoxyalkylene allyl phosphate phosphate and sulfate. The surfactant may be added at the same time, or a predetermined amount may be added to the pulverized liquid pulverized to the target particle size.

  The blending ratio of the other surfactant is preferably 0.1 to 20% by mass, and more preferably 0.2 to 5% by mass with respect to the entire suspension. In addition, it is also preferable to add these surfactants to the wet pulverized material obtained by the wet pulverization treatment.

  Anti-foaming agents such as unmodified or modified silicone emulsions; antifreezing agents such as propylene glycol, ethylene glycol and glycerin; hydrochloric acid, sulfuric acid, acetic acid, citric acid, sodium hydroxide, PH regulators such as potassium hydroxide; Cellulosic or biological bio gums such as carboxymethylcellulose; Thickeners such as polyvinyl alcohol; Antibacterial agents such as BIT, parabens, sorbic acid and their salts, etc. as necessary Can be added.

  If the prepared suspension is wet pulverized, and the pesticidal active ingredient contained in the suspension is pulverized and atomized, the pesticidal active ingredient having a median diameter of 0.5 μm or less, preferably 0.2 to 0.3 μm A wet pulverized product containing can be obtained. The specific method of the wet pulverization treatment is not particularly limited as long as it is a method that is employed in normal formulations of agricultural chemicals. For example, a wet pulverization method using a bead mill is preferably employed. In addition, you may perform a wet grinding process, monitoring the particle size of an agrochemical active ingredient sequentially.

  Using the wet pulverized product and the inorganic mineral obtained by the above-mentioned wet pulverization treatment, (1) mixing the wet pulverized product and the inorganic mineral material to form an extrudate, and (2) granulating the inorganic pulverized material with the wet pulverized product. The pesticidal granule of the present invention can be obtained by spraying onto a formulation or (3) impregnating a wet pulverized product with an inorganic mineral granule. The inorganic mineral substance may be any material that can be used for producing general agricultural chemical granules. Specific examples of the inorganic mineral material include calcium carbonate, talc, kaolin clay, bentonite, potassium chloride and the like. Two or more of these inorganic mineral materials may be combined.

  In addition, if necessary, the above-mentioned preparation can be carried out by adding auxiliary components such as water, other active ingredients for agricultural chemicals, and binders to the wet pulverized product. Furthermore, it is also preferable to screen the obtained agricultural chemical granules and perform a treatment such as drying as necessary.

  The agrochemical granule of the present invention obtained by the above-described operation contains an agrochemical active ingredient hardly soluble in water in a state of being atomized. For this reason, it is expected that the pesticidal active ingredient is easily eluted into the aqueous phase and exhibits a stable biological effect, and is particularly suitable as a granule for flooding treatment.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. Hereinafter, “parts” and “%” are based on mass unless otherwise specified.

(Reference Example 1)
Benzobicyclone base 50 parts, Surfactant: Polyoxyalkylene allyl phenyl ether phosphate potassium salt (trade name “New Calgen FS-3K”, Takemoto Yushi Co., Ltd.) 3 parts, Modified silicone emulsion (trade name “ Purified water is added to 0.1 part of Antihome E-20 "(manufactured by Kao Corporation), 5 parts of propylene glycol, and 4 parts of sodium lignin sulfonate (trade name" New Calgen RX-B ", Takemoto Yushi Co., Ltd.) A total of 100 parts of suspension was prepared. While measuring the median diameter of the benzobicyclon drug substance using a laser particle size measuring device (trade name “MT-3300EX”, manufactured by Nikkiso Co., Ltd.) And a wet pulverized product (Reference Example 1) was obtained. The median diameter of the benzobicyclon base contained in the obtained wet pulverized product was 0.49 μm.

(Reference Example 2)
Reference Example 1 except that “Polyoxyalkylene allyl phenyl ether phosphate potassium salt” was changed to “Polyoxyalkylene allyl phenyl ether sulfate ammonium (trade name“ New Calgen FS-7PG ”, Takemoto Yushi Co., Ltd.). In the same manner, a wet pulverized product (Reference Example 2) was obtained. The median diameter of the benzobicyclon base contained in the obtained wet pulverized product was 0.30 μm.

(Reference Example 3)
The same as Reference Example 1 except that “Polyoxyalkylene allyl phenyl ether phosphate potassium salt” was changed to “Polyoxyalkylene allyl phenyl ether (trade name“ New Calgen FS-1 ”, Takemoto Yushi Co., Ltd.). Thus, a wet pulverized product (Reference Example 3) was obtained. The median diameter of the benzobicyclone base contained in the obtained wet pulverized product was 0.29 μm.

(Reference Example 4)
A wet pulverized product (Reference Example 4) was obtained in the same manner as in Reference Example 1 except that “sodium lignin sulfonate” was changed to sodium alkylnaphthalene sulfonate (trade name “Demol MS”, manufactured by Kao Corporation). The median diameter of the benzobicyclon base contained in the obtained wet pulverized product was 0.30 μm.

(Comparative Reference Example 1)
Except for changing “Polyoxyalkylene allyl phenyl ether phosphate potassium salt” to “sodium alkylnaphthalene sulfonate (trade name“ New Calgen BX-C ”, manufactured by Takemoto Yushi Co., Ltd.), the same as in Reference Example 1 Thus, a wet pulverized product (Comparative Reference Example 1) was obtained. Note that the viscosity suddenly increased during the pulverization process, making it impossible to continue the pulverization. For this reason, the median diameter of the benzobicyclon base material remained at 0.61 μm.

(Comparative Reference Example 2)
"Polyoxyalkylene allyl phenyl ether phosphate potassium salt" is converted to "Polyacrylic acid salt (trade name" Agrisol G-200 ", manufactured by Kao Corporation)" and "Sodium lignin sulfonate" is "Alkylene maleic acid copolymer" A wet pulverized product (Comparative Reference Example 2) was obtained in the same manner as in Reference Example 1 except that the product name was changed to “trade name“ Demol EP Powder ”manufactured by Kao Corporation.” Note that the viscosity suddenly increased during the pulverization process, making it impossible to continue the pulverization. For this reason, the median diameter of the benzobicyclon base material remained at 0.58 μm.

  [Storage Stability Test]: The wet pulverized products of Reference Examples 1 to 4 and Comparative Reference Examples 1 to 3 were each placed in a glass screw mouth vial and left at 54 ° C. for 7 days. On the other hand, the same was left at 4 ° C. for 7 days. After standing, the median diameter of each wet pulverized product was measured, and the particle size increase ratio (= “median diameter after standing at 54 ° C. for 7 days” / “median diameter after standing at 4 ° C. for 7 days”) was calculated. . The calculation results are shown in Table 1.

(Example 1)
Inorganic mineral granules (trade name “Ishikawa Light 3”, manufactured by Ishikawa Light Industry Co., Ltd.) and sodium dodecylbenzenesulfonate (trade name “Neoperex G-15”, manufactured by Kao Corporation) at a dry mass content of 5% And the wet pulverized product of Reference Example 5 were sprayed so that the active ingredient (benzobicyclon raw material) content was 2%, and then a fluidized-bed dryer (trade name “STREA-1 type”, manufactured by Fuji Sangyo Co., Ltd.) ) To obtain 2% benzobicyclone granules.

(Example 2)
4 parts of “wet pulverized product of Reference Example 1”, 3 parts of sodium dodecylbenzenesulfonate (trade name “Neopelex G-15”, manufactured by Kao Corporation), bentonite (trade name “Kunigel V1”, manufactured by Kunimine Industries) 5 parts, soluble starch (trade name “soluble starch”, manufactured by Wako Pure Chemical Industries, Ltd.) 5 parts, clay (trade name “Fusami clay”, manufactured by Fubasami clay) are adjusted to 2% benzobicyclone, and added appropriately. After stirring and mixing with a blender (trade name “Satake Laboratory Kneader KC-6” Satake Seisakusho), extrusion granulation was performed with an extrusion granulator (trade name “Kikusui RG-5M” Kikusui Seisakusho) with a pore size of 1.2 mm. . The obtained granulated product was dried with a shelf dryer at 70 ° C. to obtain a granulated product of Example 2.

(Example 3)
A benzobicyclone 2% granule was obtained in the same manner as in Example 2 except that “wet pulverized product of Reference Example 1” was changed to “wet pulverized product of Reference Example 2”.

(Comparative Example 1)
2% benzobicyclon granules in the same manner as in Example 1 except that “wet pulverized product of Reference Example 1” was changed to “jet mill pulverized product of benzobicyclon base (median diameter: 4.5 μm)”. The agent was obtained.

(Comparative Example 2)
A benzobicyclone 2% granule was obtained in the same manner as in Example 2 except that “wet pulverized product of Reference Example 1” was changed to “Comparative Reference Example 1”.
(Comparative Example 3)
A benzobicyclone 2% granule was obtained in the same manner as in Example 2 except that “wet pulverized product of Reference Example 1” was changed to “Comparative Reference Example 2”.

  [Efficacy simulation test] A filter paper (manufactured by ADVANTEC, No. 50) cut according to the shape of the bottom surface was laid on the bottom of a stainless steel bat having an outer size of 173 × 230 × 78 mm. 1 L of 3 degree hard water was put into the vat, and 30 mg each of the benzobicyclone 2% granules obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were uniformly sprayed. Water was collected from the vat after 24 hours, 72 hours, and 168 hours, and the concentration (ppm) of benzobicyclone in water was measured and calculated. Table 2 shows the measurement and calculation results. In order for the biological effect of the agrochemical granule for flooding treatment to be stably exhibited, it is important that the contained active ingredient is eluted from the preparation grain into the aqueous phase and spreads uniformly throughout the field. In this efficacy simulation test, the efficacy of the agricultural chemical granules is simulated by measuring the concentration of the active ingredients eluted from the agricultural chemical granules in the simulated flooded environment over time. ing.

  The agrochemical granule of the present invention is expected to exhibit a stable biological effect in which an agrochemical active ingredient is easily eluted into an aqueous phase, and is particularly suitable as an agrochemical granule for flooding treatment. .

Claims (2)

In the presence of at least one surfactant selected from the group consisting of polyoxyalkylene allyl ethers, polyoxyalkylene allyl ether phosphates and sulfates, and polyoxyalkylene allyl ether phosphates and sulfates And wet pulverization containing at least one of a solid agricultural chemical active ingredient pulverized to a median diameter of 0.5 μm or less and a water solubility of 0.5 ppm or less, and a condensate of lignin sulfonate and alkylnaphthalene sulfonate. Materials and inorganic minerals,
Agrochemical particles obtained by mixing and extruding the wet pulverized product and the inorganic mineral material, spraying the wet pulverized product on the inorganic mineral granule, or impregnating the wet pulverized product with the inorganic mineral granule. Agent.   The agrochemical granule according to claim 1, which is used for flooding treatment.