JP2009203214A - Release-controlled granule and solid agrochemical preparation containing the granule - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new granule capable of controlling the release of an active agrochemical component and a solid agrochemical preparation. <P>SOLUTION: Provided are a granular material containing an active agrochemical component, a hydrophobic substance taking a solid state at 25°C and an oil-absorbing powder having an oil absorption of ≥200 ml/100 g, and a solid agrochemical preparation containing the granular material and a solid carrier. The active agrochemical component is preferably a sulfonylurea-based herbicidal component, the oil-absorbing powder is preferably calcium silicate or amorphous silica, and the form of the solid agrochemical preparation is preferably a granular form. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a granular material in which release of an agrochemical active ingredient is controlled, and a solid agricultural chemical preparation containing the granular material.

  Conventionally, as agrochemical formulations, there are various forms such as granules, wettable powders, jumbo powders, powders, wettable powders, flowables, aqueous solvents, liquids, and emulsions. The agent form is generally used in many cases. However, some pesticidal active ingredients may cause problems such as phytotoxicity to crops and short residual effects on target weeds and pests. It is rare.

Moreover, as a method for controlling the release of an agrochemical active ingredient, it is already known to use an agrochemical formulation whose release is controlled by blending paraffin wax (see, for example, Patent Documents 1 and 2). There may be concerns about the impact on the subsequent crops due to the remaining agrochemical active ingredients.
JP-A-2-288803 JP 2007-145792 A

  If agrochemical active ingredients are used without controlled release, phytotoxicity to crops may occur. In addition, if the release of the pesticidal active ingredient is excessively suppressed, more pesticidal active ingredient remains in the preparation, and there is a concern that the effect on the subsequent crop may be concerned.

  As a result of diligent research, the present inventor has achieved the initial release of the pesticidal active ingredient by using a pesticidal active ingredient, a solid hydrophobic substance at 25 ° C., and a granular material containing an oil absorbing powder having an oil absorption of 200 ml / 100 g or more. In addition to being able to control, it can eventually release almost all of the pesticidal active ingredient, which can reduce phytotoxicity to crops, improve the residual efficacy against weeds and pests, and reduce the impact on subsequent crops. I found it. That is, the present invention relates to the following [1] to [15].

  [1] A granular material containing an agrochemical active ingredient, a hydrophobic substance that is solid at 25 ° C., and an oil-absorbing powder having an oil absorption of 200 ml / 100 g or more.

  [2] The granular material according to the above [1], wherein the oil absorption amount of the oil absorbing powder is 400 ml / 100 g or more.

  [3] The granular material according to the above [1], wherein the oil absorption amount of the oil absorbing powder is 600 ml / 100 g or more.

  [4] The granular material according to any one of [1] to [3], wherein the oil-absorbing powder is calcium silicate or silica.

  [5] The granular material according to any one of [1] to [4], wherein the hydrophobic substance that is solid at 25 ° C is at least one selected from waxes, fatty acids, fatty acid esters, and resins.

  [6] The granular material according to any one of [1] to [4], wherein the hydrophobic substance that is solid at 25 ° C. is paraffin wax.

  [7] The granular material according to any one of [1] to [6], further including an auxiliary agent.

  [8] The granular material according to the above [7], wherein the auxiliary agent is a solid powder.

  [9] The granular material according to any one of [1] to [6] above, wherein an agrochemical active ingredient and an oil-absorbing powder having an oil absorption amount of 200 ml / 100 g or more are dispersed in a solid hydrophobic substance at 25 ° C.

  [10] The granular material according to [7] or [8] above, wherein an agrochemical active ingredient, an oil-absorbing powder having an oil absorption amount of 200 ml / 100 g or more, and an auxiliary agent are dispersed in a hydrophobic substance that is solid at 25 ° C.

[11] Agrochemical active ingredient is
Formula (1):

[Where,
G represents G1, G2, G3, G4, G5, G6, G7, G8, G9, G10 or CH ₃ (CH ₃ SO ₂ ) N;
L represents L1 or L2,
X and Y each independently represent a hydrogen atom, a halogen atom, a _C1-3 alkyl group or a _C1-3 alkoxy group.
Z represents CH or a nitrogen atom
L1 represents SO ₂ NH (C = O) N (R ¹ ), CH ₂ SO ₂ NH (C = O) N (R ¹ ) or NHSO ₂ NH (C = O) N (R ¹ )
L2 represents an oxygen atom, a sulfur atom, CH ₂ , CH (OH) or C═O,
R ¹ represents a hydrogen atom or a C _1-3 alkyl group,
G1, G2, G3, G4, G5, G6, G7, G8, G9 and G10 are

Represents
R ² represents a C _1-3 alkyl group, a C _1-3 alkoxy C _1-3 alkyl group, a phenyl group optionally substituted by A, or a pyridyl group optionally substituted by A;
A represents one or more substituents selected from a halogen atom, a _C1-3 alkyl group, a _C1-3 alkoxy group and a _C1-3 haloalkyl group;
R ³ is a hydrogen atom, a halogen atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _1-6 haloalkyl group, a C _2-6 haloalkenyl group, a C _2-6 halo. alkynyl group, C _{1 to 6} haloalkoxy group, C _{1 to 3} alkoxy C _{1 to 6} alkyl groups, C _{1 to 3} haloalkoxy C _{1 to 3} alkyl ^{_{groups, NO 2, CO 2 R 8}} , COR 9, CON (R _{^{10) 2, CONHR 10, NHCOR}} 9, SO 2 R 11, SO 2 N (R 10) 2, SO 2 NH (R 10), NHSO 2 (R 11), CH (CHFCH 3) (OCOCH 2 OCH 3) Represents a 2-methyl-2H-tetrazol-5-yl group or Q;
Q is

Represents
R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _1-6 haloalkyl group, C _2-6 haloalkenyl group, C _2-6 haloalkynyl group, C _1-3 alkoxy C _1-3 alkyl group, NHCOR ⁹ , CH ₂ NHSO ₂ R ¹¹ , C (R ¹² ) = NOR ¹³ or 4,6 Represents -dimethoxypyrimidin-2-yl group
When R ³ and R ⁴ are adjacent to each other, R ³ and R ⁴ may form a 5- or 6-membered ring with the carbon atoms to which they are bonded, and include an oxygen atom or a carbonyl group in the formed ring. Well,
R ⁸ is a hydrogen atom, C _1-6 alkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _1-6 haloalkyl group, C _3-6 cycloalkyl group, 3-oxetanyl group, 2-oxetanyl Group, or N = C (Ph) ₂
R ⁹ represents a hydrogen atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _1-6 haloalkyl group or a C _3-6 cycloalkyl group,
R ¹⁰ represents a C _1-6 alkyl group,
R ¹¹ represents a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group or a C _1-6 haloalkyl group,
R ¹² represents a hydrogen atom or a C _1-6 alkyl group,
R ¹³ represents a C _1-6 alkyl group,
Represents
R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a C _1-6 alkyl group. ] The granular material in any one of said [1]-[10] which is 1 or more types of herbicidal active ingredients chosen from the compound represented by these, and those salts.

  [12] A solid agricultural chemical preparation comprising the granular material according to any one of [1] to [11] and a solid carrier.

  [13] The solid agrochemical formulation according to the above [12], further comprising an agrochemical active ingredient.

  [14] The solid agricultural chemical preparation according to [12] or [13], further comprising an auxiliary component.

  [15] The solid agrochemical formulation according to any one of the above [12] to [14], wherein the solid agrochemical formulation is a granule.

  According to the present invention, it is possible to suppress the initial release of the pesticidal active ingredient, and finally to release almost the entire amount of the pesticidal active ingredient, to reduce the phytotoxicity to crops, and to improve the residual effect on weeds and pests. it can. Moreover, since almost the whole amount of the pesticidal active ingredient is finally released, almost no pesticidal active ingredient remains in the preparation, and the influence on the subsequent crop is reduced.

  Below, the granular material of this invention is demonstrated in detail.

  The granular material of the present invention can be produced, for example, by the following method. First, a powdery or liquid agrochemical active ingredient and an oil-absorbing powder are added to a solid hydrophobic substance at 25 ° C. melted at a temperature equal to or higher than the melting point, preferably 10 to 30 ° C. higher than the melting point, Add adjuncts as necessary, mix and stir with a stirrer (eg, homomixer, three-one motor, kneader, universal mixer, nauter, etc.) to mix agrochemical active ingredients and oil-absorbing powder into solid hydrophobic substances. Disperse uniformly.

  Alternatively, a powdery or liquid agrochemical active ingredient, a hydrophobic substance solid at 25 ° C., and an oil-absorbing powder are further supplemented with auxiliary agents as necessary, and these are mixed in advance (for example, a Nauter mixer, a universal mixer). ) Etc. to mix evenly. Next, while being heated and melted at 25 ° C. above the melting point of the solid hydrophobic substance, preferably 10-30 ° C. higher than the melting point, the mixture is stirred with the above stirrer, etc. You may disperse | distribute uniformly in a solid hydrophobic substance.

  The molten mixture in which these agrochemical active ingredients and oil-absorbing powder are uniformly dispersed is cooled to a temperature exhibiting plasticity, and this is subjected to extrusion granulation equipped with a screen having a hole having a diameter of 0.5 to 1.5 mm, for example. Granulate with a machine to obtain a granular material. As the extrusion granulator, for example, “Agricultural Chemical Formulation Guide” p. An extrusion granulator such as a horizontal extrusion type, a pre-extrusion type, a vertical type or a roller extrusion type described in 131 (published by the Japan Plant Protection Association, edited by the Japanese Agricultural Chemical Society), can be used. Alternatively, without using these granulators, the molten mixture may be cooled as it is to form a lump or flake, and then pulverized into a granular material.

  If necessary, the obtained granular material is further cooled to near room temperature using a cool air machine or the like, pulverized using a pulverizer (eg, pin mill, hammer mill, rotor speed mill, sample mill), and sieved using a sieve. By doing so, a granular material having a desired median diameter can be obtained.

  The volume median diameter of the granular material is preferably in the range of 100 to 700 μm, more preferably 200 to 650 μm. When the volume median diameter of the granular material is smaller than this range, the pesticidal active ingredient is released in a relatively short period of time, and the phytotoxicity to the crop is promoted. On the other hand, when the volume median diameter of the granular material is larger than this range, the release of the pesticidal active ingredient is suppressed and it becomes difficult to obtain a sufficient pest control effect.

  Examples of the hydrophobic substance solid at 25 ° C. contained in the granular material of the present invention include plant waxes such as candelilla wax, wood wax, and rice wax, and animal systems such as beeswax, lanolin, whale wax, and beef tallow. Wax, microcrystal wax (isoparaffin, cycloparaffin), paraffin wax (normal paraffin), petrolactam, carnauba wax, oxidized wax, ester wax, urethane wax, polyolefin, oxidized polyethylene and other petroleum-based wax, palmitic acid, stearic acid , Fatty acid such as lanolin fatty acid, fatty acid ester such as methyl stearate, stearyl stearate, myristyl myristate, polyvinyl acetate, copolymer of vinyl acetate and ethylene, copolymer of vinyl acetate and vinyl versatate, vinegar Copolymer of vinyl, ethylene and vinyl chloride, polyacrylate, copolymer of acrylate and styrene, copolymer of acrylate and silicone, copolymer of acrylate and ethylene, polyurethane, styrene Water-insoluble thermoplastic resins such as butadiene copolymers, acrylonitrile and butadiene copolymers, and amino resins (such as urea resins and melamine resins), phenol resins (such as resole resins and novolac resins), resorcinol formaldehyde resins, xylene resins And thermosetting resins such as furan resin, epoxy resin, polyisocyanate resin, unsaturated polyester resin, and acrylic resin, and two or more of these may be used in combination. Preferred as the hydrophobic substance that is solid at 25 ° C. is microcrystalline wax, paraffin wax or a mixture thereof. The melting point of paraffin wax and microcrystalline wax is preferably 50 to 95 ° C, more preferably 60 to 80 ° C.

  The solid hydrophobic substance contained in the granular material of the invention can be used alone or in admixture of two or more. The total content of the solid hydrophobic substance is usually 20 to 40% by weight, preferably 25 to 35% by weight, based on the particulate matter.

  The agrochemical active ingredient contained in the granular material of the present invention is preferably a herbicidal active ingredient, and more preferably a herbicidal active ingredient selected from the compound represented by the above formula (1) or a salt thereof. Examples of the herbicidal active ingredient selected from the compound represented by the formula (1) or a salt thereof include acetolactate synthase (ALS) inhibitors such as a sulfonylurea herbicidal active ingredient and a pyrimidyloxybenzoic acid herbicidal active ingredient. Specific examples of common names are as follows, but the general names are not necessarily limited to these.

  As the herbicidal active ingredient selected from the compound represented by the formula (1) or a salt thereof, azimsulfuron, amidosulfuron, iodosulfuron-methyl, imazosulfuron, Ethametsulfuron-methyl, ethoxysulfuron, oxasulfuron, orthosulfamuron, chlorimuron-ethyl, chlorsulfuron, cyclo Sulfamuron, cyclosulfuron, sulfosulfuron, sulfomethuron-methyl, thifensulfuron-methyl, triasulfuron, tritosulfuron ), Triflusulfuron-methyl, trifloxysulfuron, tribenuron-methyl, nicosulfuron, halosulfuron-methyl, pyrazosulfuron- Ethyl (pyrazosulfuron-ethyl), foramsulfuron (foramsulfron), flazasulfuron (primasulfuron-methyl), flucetosulfuron (flucetosulfuron), flupirsulfuron-methyl (flupyrsulfuron), prosulfuron (Prosulfuron), bensulfuron-methyl, mesosulfron-methyl, metsulfuron-methyl, rimsulfuron, 2-chloro-N- (4,6-dimethoxy) Pyrimidin-2-ylcarbamoyl) -7-propylimida [1,2-b] pyridazine-3-sulfonamide, 3-chloro-N- (4,6-dimethoxypyrimidin-2-ylcarbamoyl) -1-methyl-4- (5-methyl-5,6-dihydro -1,4,2-dioxazin-3-yl) -1H-pyrazole-5-sulfonamide, 3-chloro-N- (4,6-dimethoxypyrimidin-2-ylcarbamoyl) -1-methyl-4- ( 6-methyl-5,6-dihydro-1,4,2-dioxazin-3-yl) -1H-pyrazole-5-sulfonamide, 3-chloro-4- (5,6-dihydro-1,4,2 -Dioxazin-3-yl) -N- (4,6-dimethoxypyrimidin-2-ylcarbamoyl) -1-methyl-1H-pyrazole-5-sulfonamide, N- (4,6-dimethoxypyrimidin-2-i Rucarbamoyl) -1-methyl-4- (5-methyl-5,6-dihydro-1,4,2-dioxazin-3-yl) -1H-pyrazole-5-sulfonamide, N- (4,6-dimethoxy Pyrimidin-2-ylcarbamoyl) -1-methyl-4- (6-methyl-5,6-dihydro-1,4,2-dioxazin-3-yl) -1H-pyra 5-sulfonamide, 4- (5,6-dihydro-1,4,2-dioxazin-3-yl) -N- (4,6-dimethoxypyrimidin-2-ylcarbamoyl) -1-methyl- 1H-pyrazole-5-sulfonamide, N- (4,6-dimethoxypyrimidin-2-ylcarbamoyl) -1,3-dimethyl-4- (5-methyl-5,6-dihydro-1,4,2- Dioxazin-3-yl) -1H-pyrazole-5-sulfonamide, 4- (5,6-dihydro-1,4,2-dioxazin-3-yl) -N- (4,6-dimethoxypyrimidine-2- Ylcarbamoyl) -1,3-dimethyl-1H-pyrazole-5-sulfonamide, bispyribac, pyrithiobac, pyriftalid, pyribenzoxim, pyrimisulfan, pyriminosulf-methyl ( Examples include pyriminobac-methyl, monosulfuron, and monosulfuron-methyl.

  Other herbicidal active ingredients include esprocarb, benthiocarb, molinate, dimepiperate, pyributicarb, mefenacet, butachlor, pretilachlor, tenilchlor (Thenylchlor), bromobutide, etobenzanid, dymron, cumyluron, bentazone, bentazone salt, 2,4-D, 2,4-D salt, 2,4- D ester, MCP, MCP salt, MCP ester, MCPB, MCPB salt, MCPB ester, phenothiol (clopaprop), clomeprop, naproanilide, oxadiazon, pyrazolate ( pyrazolate, pyrazoxyfen, benzofenap, oxadiargyl, dimetamethrin, simetryn, piperophos, anilofos, butamiphos, butamiphos Dithiopyr, pyriminobac methyl, CNP, chlormethoxynil, cyhalofop butyl, bifenox, cafenstrole, pentoxazone, indanofan, Oxaziclomefone, fentrazamide, butenachlor, ACN, benzobicyclon, benfuresate, cinmethyline (cimm) ethylin, simazine, dichlobenil, diuron, chloro IPC (chlorpropham), atrazine, alachlor, isouron, chlorphtalim, cyanazin , Trifluralin, butamifos, propyzamide, promethryn, pendimethalin, metolachlor, metribchlor, linuron, lenurapil (Propanil), MCPA, ioxynil octanoate, ashram, quizalofop-ethyl, propaquizafop, quizalofop-tefuryl, sethoxydim, Chife Thulensulfuron-methyl, fenoxaprop-ethyl, phenmedipham, fluazifop-butyl, bentazone, SAP (bensulide), TCTP (chlorthal- dimethyl, tetorachlorothiophene, amiprophosmethyl, ametrin, isoxaben, orbencarb, carbutilate, dithiopyr, siduron, thiafluron, thiaza Napropamide, prodiaminine, benefin, methyl dymron, 2,4-PA, MCPPA, flazasulfuron, metsulfuron-methyl, imazaquin ) Imazapyr, flupropanate, tebuthiuron, bromacil, hexazinone, glyphosate ammonium salt (glyphosate-ammonium), glyphosate-iso-propylammonium salt, glyphosate-iso-propylammonium salt (Glyphosate-trimesium), glyphosate sodium salt (glyphosate-sodium), glyphosate-potassium, bialaphos, glufosinate-ammonium, MCC, pyraclonil, tefriltrione, tefuryltione Mesotrione, penoxsulam, aminopyralid, bencarbazone, pinoxaden, propoxycarbazone sodium salt (propoxycarbazone-s) odium), pyrasulfotole, pyroxasulfone, pyroxsulam, tembotrione, thiencarbazone-methyl, and topramezon.

  The agrochemical active ingredient contained in the granular material of the present invention can be used alone or in admixture of two or more. The total content of the pesticidal active ingredient is usually 1 to 30% by weight, preferably 2 to 25% by weight, based on the granular material.

  In the granular material of the present invention, the ratio of the total weight of the pesticidal active ingredient to the weight of the hydrophobic substance solid at 25 ° C. is preferably in the range of 1:30 to 1: 0.5, more preferably 1:20 to The range is 1: 1. If the amount of the solid hydrophobic substance at 25 ° C. is less than 0.5 parts by weight with respect to 1 part by weight of the pesticidal active ingredient, the pesticidal active ingredient may be released in a relatively short period of time, and phytotoxicity may be promoted. Get higher. On the other hand, if the amount of the solid hydrophobic substance exceeds 30 parts by weight at 25 ° C. with respect to 1 part by weight of the pesticidal active ingredient, the release of the active ingredient is suppressed and there is a high possibility that it is difficult to obtain a sufficient pest control effect. .

  The oil-absorbing powder contained in the granular material of the present invention needs to have an oil absorption amount of 200 ml / 100 g or more so that almost all of the agrochemical active ingredient is finally released and hardly remains in the preparation. However, it is preferably 400 ml / 100 g or more, more preferably 600 ml / 100 g or more. When the oil-absorbing powder is contained in the granular material of the present invention, the mechanism of finally releasing almost the total amount of the agrochemical active ingredient is not clear, but the oil-absorbing powder having a larger oil-absorbing amount has larger voids in the oil-absorbing powder. When it is dispersed in the granular material, the internal void leading to the outside of the granular material becomes large, the surrounding moisture easily enters the inside of the granular material through the void, and the agricultural chemical active ingredient dissolves in the moisture. This is presumed to be easily released to the outside in the form of an aqueous solution.

  The oil-absorbing powder is preferably calcium silicate or silica, and more preferably calcium silicate.

  Examples of the oil-absorbing calcium silicate include Florite R (trade name / Tokuyama Co., Ltd.), Florite RN (trade name / Tokuyama Co., Ltd.), and Toyohero TH (trade name / Toyo Denka Kogyo Co., Ltd.). Zonolite (trade name / Onoda Chemical), Microcell C (trade name / Celite Corporation), Microcell E (trade name / Celite Corporation), and the like.

  As the oil-absorbing silica, amorphous silica is preferable. For example, Carplex XR (trade name / Shionogi Pharmaceutical Co., Ltd.), Carplex # 80D (trade name / Shionogi Pharmaceutical Co., Ltd.), Carplex # 67 (Trade name / Shinogi Pharmaceutical Co., Ltd.), Carplex # 1120 (trade name / Shinogi Pharmaceutical Co., Ltd.), Fine Seal A (trade name / Tokuyama Soda Co., Ltd.), Fine Seal E-50 (trade name) / Tokuyama Soda Co., Ltd.), Fine Seal X-37 (trade name / Tokuyama Soda Co., Ltd.), Fine Seal K-41 (Product Name / Tokuyama Soda Co., Ltd.), Fine Seal P-8 (Product Name / Tokuyama) Soda Co., Ltd.), Toxeal U (trade name / Tokuyama Soda Co., Ltd.), Toxeal CU-N (trade name / Tokuyama Soda Co., Ltd.), Toxeal P (trade name / Tokuyama Soda Co., Ltd.), Toxeal NR ( Product name / Tokuyama Soda Co., Ltd.) Nip Seal NS (trade name / Nippon Silica Industry Co., Ltd.), Nip Seal NSK (trade name / Nippon Silica Industry Co., Ltd.), Nip Seal NA (trade name / Nippon Silica Industry Co., Ltd.), Syroid 244 (trade name / Fuji Devison) Chemical), Cyloid 65 (trade name / Fuji Devison Chemical), Cyroid 308 (trade name / Fuji Devison Chemical), Mizukacil P-705 (trade name / Mizusawa Chemical Co., Ltd.), Mizukacil P-802 (trade name / Mizusawa Chemical) Co., Ltd.), Mizukacil P-78 (trade name / Mizusawa Chemical Co., Ltd.) and Mizukasil P-832 (trade name / Mizusawa Chemical Co., Ltd.) and other hydrous silicas such as Carplex CS-5 (trade name / Shino) (Giyaku Pharmaceutical Co., Ltd.), Carplex CS-7 (trade name / Shionogi Pharmaceutical Co., Ltd.) and Carplex CS-701 (trade name / Shionogi Pharmaceutical) )) And the like, such as Aerosil 130 (trade name / Nippon Aerosil Co., Ltd.), Aerosil 200 (trade name / Nippon Aerosil Co., Ltd.), Aerosil 380 (trade name / Nippon Aerosil Co., Ltd.) and Anhydrosil MOX80 (trade name / Nippon Aerosil Co., Ltd.) and other anhydrous silica, for example, SIPERNATD17 (trade name / Nippon Aerosil Co., Ltd.), Nip Seal SS-10 (trade name / Nippon Silica Co., Ltd.), Nip Seal SS-20 ( Surface-treated silica using hydrous silica such as trade name / Nippon Silica Co., Ltd.) and Nipseal SS-30P (trade name / Nippon Silica Co., Ltd.), such as Aerosil R972 (trade name / Nippon Aerosil Co., Ltd.), Aerosil R202 (trade name / Japan Aerosil Co., Ltd.) and Aerosil R812 (trade name / Japan) And surface-treated silica made from anhydrous silica such as Aerosil Co., Ltd.

  These oil-absorbing powders can be used alone or in admixture of two or more. The total content of the oil-absorbing powder contained in the granular material of the present invention is usually 0.1 to 10.0% by weight, preferably 0.5 to 3.0% by weight, based on the granular material.

  The oil absorption amount of the oil-absorbing powder contained in the granular material of the present invention is a value obtained by a method defined in JIS: K5101-13-2.

  The granular material of the present invention can further contain an auxiliary agent. Examples of the auxiliary agent include a solid powder, a surfactant, a solvent, and the like, and a solid powder is preferable.

  The solid powder that can be contained in the granular material of the present invention is a solid powder having an oil absorption capacity of less than 200 ml / 100 g. For example, quartz, quartzite, calcite, gypsum, dolomite, chalk, kaolinite, pyrophyllite, sericite. , Minerals such as halosite, metahalosite, kibushi clay, glazed clay, porcelain stone, siegrite, allophane, shirasu, gira, talc, bentonite, activated clay, acid clay, pumice, attapulgite, zeolite and diatomite, for example Firing products of minerals such as calcined clay, perlite, shirasu balloon, vermiculite, attapulgus clay and calcined diatomaceous earth, such as magnesium carbonate, calcium carbonate, sodium carbonate, sodium bicarbonate, ammonium sulfate, sodium sulfate, magnesium sulfate, dihydrogen phosphate Ammonium, dihydrogen phosphate Inorganic salts such as monium and potassium chloride, saccharides such as glucose, fructose, sucrose and lactose, polysaccharides such as starch, powdered cellulose and dextrin, such as organic substances such as urea, urea derivatives, benzoic acid and benzoic acid salts, For example, plants such as wood flour, corn cobs, walnut shells and tobacco stems, fly ash and fertilizers can be mentioned.

  Specific examples of the bentonite include, for example, Kunigel VA (trade name / Kunimine Industry Co., Ltd.), Kunigel V2 (trade name / Kunimine Industry Co., Ltd.), Hotaka Bentonite (trade name / Toyojun Yoko Co., Ltd.) ), Myogi bentonite (trade name / manufactured by Toyoshiro Yoko Co., Ltd.), Haruna bentonite (brand name / manufactured by Toyoshun Yoko Co., Ltd.), bentonite super clay (brand name / manufactured by Toyoshun Yoko Co., Ltd.) and granular bentonite Examples thereof include sodium bentonite (trade name / manufactured by Toyoshun Yoko Co., Ltd.) and calcium bentonite such as Kunibond (trade name / manufactured by Kunimine Kogyo Co., Ltd.).

  Specific examples of natural minerals other than the bentonite include H fine powder (trade name / Keiwa Furnace Co., Ltd.), Neocarrier K (trade name / Asada Milling Co., Ltd.), Fusami K clay (trade name) / Fusami Clay Co., Ltd.) and Tokuyuki F Clay (trade name / Showa KDE Co., Ltd.), Reika HB Fine Powder (trade name / Keiwa Furnace Co., Ltd.), Reika H Fine Powder (Product Name / Keiwa Furnace Co., Ltd.), SP-F (Brand name / Keiwa Furnace Co., Ltd.), SP-7F (Brand name / Keiwa Furnace Co., Ltd.), Showa DL clay (Brand name) / Showa KDE Co., Ltd.), SW clay (trade name / Showa Chemical Co., Ltd.), Miyagi wettable powder clay (trade name / Sanyo Kikou Co., Ltd.) Miyagi wettable powder clay A (Product) Name / manufactured by Sanyo Kikou Kogyo Co., Ltd.).

  Specific examples of the calcium carbonate include Microcal 250 (trade name / Aokura Lime Industry Co., Ltd.), Microcal 100 (trade name / Aokura Industry Co., Ltd.), NS # 100 (trade name / Nitto Flour Industry) NS # 200 (trade name / manufactured by Nitto Flour Chemical Co., Ltd.), NS # 3000 (trade name / manufactured by Nitto Flour Chemical Co., Ltd.) and Super SS (trade name / Maruo Calcium Co., Ltd.) )) And the like.

  These solid powders can be used alone or in admixture of two or more. The total content of the solid powder contained in the granular material of the present invention is usually 40 to 80% by weight, preferably 45 to 70% by weight, based on the granular material.

  Next, the solid agricultural chemical formulation of the present invention will be described in more detail.

  Examples of the dosage form of the solid agricultural chemical preparation of the present invention include, for example, wettable powder, water soluble powder, water dispersible granule, water soluble granule, Examples thereof include dustable powder, granule, and tablet.

  When the solid agricultural chemical preparation of the present invention is a granule, granulators such as an extrusion granulator, a pressure granulator, a fluidized bed granulator, a stirring granulator, and a rolling granulator Can be manufactured. For example, in the case of extrusion granulation, an agrochemical active ingredient (which may be the same as or different from the agrochemical active ingredient contained in the granule) or an auxiliary component is added to the granular material and solid carrier of the present invention as necessary. An extrusion type equipped with a screen having a hole having a diameter of 0.5 to 1.5 mm after adding a liquid auxiliary component and an appropriate amount of water to the mixture obtained by uniformly mixing them and kneading into a paste. After granulation using a granulator, it can be produced by drying.

  The content of the granular material contained in the solid agricultural chemical formulation of the present invention is usually 1 to 20% by weight, preferably 2 to 15% by weight, based on the solid agricultural chemical formulation.

  From the viewpoint of reducing phytotoxicity to crops (particularly paddy rice), the water dissolution rate after 1 day of the pesticidal active ingredient contained in the granular material from the solid agricultural chemical formulation of the present invention is preferably 65% or less.

  The solid agrochemical formulation of the present invention can contain an agrochemical active ingredient that is not contained in the granular material. As the agrochemical active ingredient, a herbicidal active ingredient is preferable, and specific examples of the agrochemical active ingredient contained in the granular material described above can be given.

  Agrochemical active ingredients that are not contained in the particulate matter can be used alone or in admixture of two or more. The total content of the pesticidal active ingredient is usually 0.1 to 20% by weight based on the solid agrochemical formulation.

  Examples of auxiliary components that can be used in the solid agricultural chemical formulation of the present invention include surfactants, binders, solvents, absorbents, grinding aids, pH adjusters, decomposition inhibitors, colorants, and preservatives. Can be mentioned.

  The solid carrier contained in the solid agrochemical formulation of the present invention can be contained in the oil-absorbing powder having an oil absorption amount of 200 ml / 100 g or more contained in the above-mentioned granular material of the present invention and the above-mentioned granular material of the present invention. A solid powder can be mentioned.

  The solid carriers can be used alone or in admixture of two or more. The total content of the solid carrier is usually 20 to 70% by weight based on the solid agricultural chemical preparation.

  Examples of the surfactant that can be contained in the granular material and solid agricultural chemical preparation of the present invention include the following (A), (B), (C), (D), and (E).

(A) Nonionic surfactant:
(A-1) Polyethylene glycol type surfactant: For example, polyoxyethylene alkyl (C _12-18 ) ether, ethylene oxide adduct of alkyl naphthol, polyoxyethylene (mono or di) alkyl (C _8-12 ) phenyl Ether, formalin condensate of polyoxyethylene (mono or di) alkyl ( _C8-12 ) phenyl ether, polyoxyethylene (mono, di or tri) phenyl phenyl ether, polyoxyethylene (mono, di or tri) benzyl phenyl Ether, polyoxypropylene (mono, di or tri) benzyl phenyl ether, polyoxyethylene (mono, di or tri) styryl phenyl ether, polyoxypropylene (mono, di or tri) styryl phenyl ether, polyoxyethylene Emissions (mono-, di- or tri-) styryl phenyl ether polymer, polyoxyethylene polyoxypropylene block polymers, alkyl _{(C 12 to 18)} polyoxyethylene polyoxypropylene block polymer ethers, alkyl _{(C 8 to 12)} phenyl polyoxyethylene Ethylene polyoxypropylene block polymer ether, polyoxyethylene bisphenyl ether, polyoxyethylene resin acid ester, polyoxyethylene fatty acid (C _12-18 ) monoester, polyoxyethylene fatty acid (C _12-18 ) diester, polyoxyethylene sorbitan fatty acid (C _{12 to 18)} ester, glycerol fatty acid ester ethylene oxide adducts, castor oil ethylene oxide adduct, hydrogenated castor oil ethylene oxide adduct , Alkyl _{(C 12 to 18)} amine ethylene oxide adduct and a fatty acid _{(C 12 to 18)} amide ethylene oxide adducts.

(A-2) Polyhydric alcohol type surfactant: For example, glycerol fatty acid ester, polyglycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol fatty acid (C _12-18 ) ester, sorbitan fatty acid (C _12-18 ) ester, Examples thereof include sugar fatty acid esters, polyhydric alcohol alkyl ethers, and fatty acid alkanolamides.

  (A-3) Acetylene-based surfactant: Examples thereof include acetylene glycol, acetylene alcohol, ethylene oxide adduct of acetylene glycol, ethylene oxide adduct of acetylene alcohol, and the like.

  (A-4) Other surfactants: Examples include alkyl glycosides.

(B) Anionic surfactant:
(B-1) Carboxylic acid type surfactant: For example, polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, maleic acid or maleic anhydride and olefin (for example, isobutylene and diisobutylene) Polymer, Copolymer of acrylic acid and itaconic acid, Copolymer of methacrylic acid and itaconic acid, Copolymer of maleic acid or maleic anhydride and styrene, Copolymer of acrylic acid and methacrylic acid, Acrylic acid Copolymer of acrylic acid and methyl ester of acrylic acid, copolymer of acrylic acid and vinyl acetate, copolymer of acrylic acid and maleic acid or maleic anhydride, N-methyl-fatty acid ( _C12-18 ) sarcosinate, resin _Examples thereof include carboxylic acids such as acids and fatty acids (C _12-18 ), and salts of these carboxylic acids.

(B-2) Sulfate ester type surfactant: For example, alkyl (C _12-18 ) sulfate ester, polyoxyethylene alkyl (C _12-18 ) ether sulfate ester, polyoxyethylene (mono or di) alkyl (C _{8 -12} ) phenyl ether sulfate, polyoxyethylene (mono or di) alkyl ( _C8-12 ) phenyl ether polymer sulfate, polyoxyethylene (mono, di or tri) phenyl phenyl ether sulfate, polyoxyethylene (Mono, di or tri) benzyl phenyl ether sulfate, polyoxyethylene (mono, di or tri) styryl phenyl ether sulfate, polyoxyethylene (mono, di or tri) styryl phenyl ether polymer sulfate, polyoxy Sulfate esters Ji Ren polyoxypropylene block polymers, sulfated oils, sulfated fatty acid esters, salts of sulfuric esters, and their sulfates, such as sulfated fatty acids and sulfated olefins.

(B-3) Sulfonic acid type surfactant: For example, paraffin ( _C12-22 ) sulfonic acid, alkyl ( _C8-12 ) benzenesulfonic acid, alkyl ( _C8-12 ) benzenesulfonic acid formalin condensate, Formalin condensate of cresol sulfonic acid, α-olefin (C _14-16 ) sulfonic acid, dialkyl (C _8-12 ) sulfosuccinic acid, lignin sulfonic acid, polyoxyethylene (mono or di) alkyl (C _8-12 ) phenyl Ether sulfonic acid, polyoxyethylene alkyl (C _12-18 ) ether sulfosuccinic acid half ester, naphthalene sulfonic acid, (mono or di) alkyl (C _1-6 ) naphthalene sulfonic acid, formalin condensate of naphthalene sulfonic acid, (mono or di) alkyl _{(C 1 to 6)} naphthalenesulfonic Formalin condensates of phosphate, formalin condensate of creosote oil sulfonic acid, alkyl (C _{8 to 12)} ether disulfonic acid, Igepon T (trade name), a copolymer of polystyrene sulfonic acid and styrene sulfonic acid and methacrylic acid And the sulfonic acid salts thereof.

(B-4) Phosphate ester type surfactants: for example, alkyl (C _8-12 ) phosphate ester, polyoxyethylene alkyl (C _12-18 ) ether phosphate ester, polyoxyethylene (mono or di) alkyl (C _{8 -12} ) phenyl ether phosphate ester, polyoxyethylene (mono, di or tri) alkyl ( _C8-12 ) phenyl ether polymer phosphate ester, polyoxyethylene (mono, di or tri) phenyl phenyl ether phosphate ester, poly Oxyethylene (mono, di or tri) benzyl phenyl ether phosphate ester, polyoxyethylene (mono, di or tri) styryl phenyl ether phosphate ester, polyoxyethylene (mono, di or tri) styryl phenyl ether polymer phosphate ester, Polyoxy Examples thereof include phosphate esters of ethylene polyoxypropylene block polymers, phosphate esters such as phosphatidylcholine, phosphatidylethanolimine, and condensed phosphoric acid (such as tripolyphosphoric acid), and salts of these phosphate esters.

  Examples of the salt in the above (B-1) to (B-4) include alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.), ammonium and various amines (for example, alkylamine, cyclohexane). Alkylamine and alkanolamine).

(C) Cationic surfactant:
Examples thereof include alkylamines, alkyl quaternary ammonium salts, alkylamine ethylene oxide adducts, and alkyl quaternary ammonium salt ethylene oxide adducts.

(D) Amphoteric surfactant:
Examples thereof include betaine type surfactants and amino acid type surfactants.

(E) Other surfactants:
For example, silicone surfactants and fluorine surfactants can be used.

  These surfactants can be used alone or in admixture of two or more. Moreover, the total content of the surfactant contained in the granular material of the present invention is usually in the range of 0 to 20% by weight with respect to the granular material. The total content of the surfactant contained in the solid agrochemical formulation of the present invention (excluding the surfactant contained in the granular material) is usually 2 to 15% by weight based on the solid agrochemical formulation. It is a range.

  Examples of binders that can be used in the solid agricultural chemical formulation of the present invention include dextrin (roasted dextrin, enzyme-modified dextrin, etc.), acid-decomposed starch, oxidized starch, pregelatinized starch, etherified starch (carboxymethyl starch, hydroxy). Alkyl starch and cationic starch), esterified starch (acetate starch and phosphate starch, etc.), processed starch such as crosslinked starch and grafted starch, such as sodium alginate, gum arabic, gelatin, tragacanth gum, locust bean gum and casein Natural substances such as carboxymethylcellulose sodium salt, cellulose derivatives such as hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, ethylcellulose and acetylcellulose And, for example, polyvinyl methyl ether, polyethylene glycol, polypropylene glycol, polyethylene polypropylene block copolymers, polyvinyl alcohol, partially saponified vinyl acetate and vinyl ether copolymers, polyvinyl pyrrolidone, polyvinyl pyrrolidone and vinyl acetate copolymers and polyacrylamide And other polymers.

  These binders can be used alone or in admixture of two or more. Moreover, the total content of the binder contained in the solid agricultural chemical formulation of the present invention is usually in the range of 1 to 10% by weight with respect to the solid agricultural chemical formulation.

  The granular material and solid agricultural chemical preparation of the present invention can be applied to paddy fields, upland fields, rice seedling boxes, cell trays for horticultural crops, and the like, but are particularly suitable for application to paddy fields. The application amount when applying the granular material or solid agricultural chemical formulation of the present invention varies depending on the type of the agricultural chemical active ingredient, etc., but in the case of paddy field or field, it is usually 0.1-20 kg per 10 ares, preferably 0. 2 to 5 kg, usually 10 to 200 g, preferably 10 to 100 g per seedling box in the case of application of rice (especially paddy rice) seedling boxes, usually per cell tray in the case of application of horticultural crop cell trays 1 to 2000 g, preferably 5 to 1000 g.

EXAMPLES Next, an Example is given and this invention is demonstrated still in detail. However, the present invention is not limited only to these examples and test examples. In the following, “Compound A” is 3-chloro-N- (4,6-dimethoxypyrimidin-2-ylcarbamoyl) -1-methyl-4- (5-methyl-5,6-dihydro-1,4 , 2-Dioxazin-3-yl) -1H-pyrazole-5-sulfonamide. The purity of Compound A used in Examples 1 to 5 and Comparative Examples 1 to 4 was 98.6%, and 3-chloro-N- (4,6-dimethoxypyrimidin-2-ylcarbamoyl)-was used as an impurity. Contains 1.0% 1-methyl-4- (6-methyl-5,6-dihydro-1,4,2-dioxazin-3-yl) -1H-pyrazole-5-sulfonamide. Further, the purity of Compound A used in Examples 6 to 11 was 91.3%, and 3-chloro-N- (4,6-dimethoxypyrimidin-2-ylcarbamoyl) -1-methyl-4- was used as an impurity. Contains 3.9% (6-methyl-5,6-dihydro-1,4,2-dioxazin-3-yl) -1H-pyrazole-5-sulfonamide. The following parts all mean parts by weight.
[Example 1]
21.3 parts of Compound A finely pulverized to about 5 microns, 2.0 parts of Microcell E (trade name / calcium silicate, Celite Corporation, oil absorption 460 ml / 100 g), H fine powder (trade name / silicon dioxide, Kei 46.7 parts of Japanese furnace material and 30 parts of petroleum-based paraffin wax (melting point 70-80 ° C, penetration 5-7 (25 ° C), average molecular weight 500-600) are melted at about 100 ° C. While mixing and stirring with a three-one motor, Compound A was uniformly dispersed. These compounds were cooled to room temperature and pulverized to obtain the granular material of the present invention.

  Along with 4.7 parts of this granular material having a volume median diameter of 513 μm, 1.0 part of dioctylsulfosuccinate Na salt, 3.1 parts of polyacrylic acid Na, 5 parts of dextrin, 10 parts of bentonite and 76.2 parts of clay Mix, knead by adding an appropriate amount of granulated water, extrude and granulate with a screen having a hole with a diameter of 1.0 mm, dry at 50 ° C. for 2 hours, adjust the size, and then screen with a 710 to 1,400 μm sieve. By screening, a granule of the present invention containing Compound A was obtained.

[Example 2]
Compound A21.3 parts finely pulverized to about 5 microns, Florite R (trade name / calcium silicate, manufactured by Tokuyama Corporation, oil absorption 695 ml / 100 g), H fine powder (trade name / silicon dioxide, 46.7 parts of Keiwa Furnace Co., Ltd.) and 30 parts of petroleum-based paraffin wax (melting point 70-80 ° C., penetration 5-7 (25 ° C.), average molecular weight 500-600) at about 100 ° C. While melting, compound A was uniformly dispersed by mixing and stirring with a three-one motor. These compounds were cooled to room temperature and pulverized to obtain the granular material of the present invention.

  Along with 4.7 parts of this granular material having a volume median diameter of 560 μm, 1.0 part of dioctylsulfosuccinate sodium salt, 3.1 parts of polyacrylic acid, 5 parts of dextrin, 10 parts of bentonite and 76.2 parts of clay Mix, knead by adding an appropriate amount of granulated water, extrude and granulate with a screen having a hole with a diameter of 1.0 mm, dry at 50 ° C. for 2 hours, adjust the size, and then screen with a 710 to 1,400 μm sieve. By screening, a granule of the present invention containing Compound A was obtained.

Example 3
21.3 parts of Compound A finely pulverized to about 5 microns, Carplex XR (trade name / white carbon, Shionogi & Co., Ltd., oil absorption 277 ml / 100 g), H fine powder (trade name / silicon dioxide) 46.7 parts made by Keiwa Furnace Co., Ltd.) and 30 parts petroleum paraffin wax (melting point 70-80 ° C, penetration 5-7 (25 ° C), average molecular weight 500-600), about 100 ° C While being melted, the mixture A was mixed and stirred with a three-one motor to uniformly disperse Compound A. These compounds were cooled to room temperature and pulverized to obtain the granular material of the present invention.

  Along with 4.7 parts of this granular material having a volume median diameter of 378 μm, 1.0 part of dioctylsulfosuccinate sodium salt, 3.1 parts of polyacrylic acid Na, 5 parts of dextrin, 10 parts of bentonite and 76.2 parts of clay Mix, knead by adding an appropriate amount of granulated water, extrude and granulate with a screen having a hole with a diameter of 1.0 mm, dry at 50 ° C. for 2 hours, adjust the size, and then screen with a 710 to 1,400 μm sieve. By screening, a granule of the present invention containing Compound A was obtained.

Example 4
21.3 parts of pyrazosulfuron ethyl finely pulverized to about 5 microns, 2.0 parts of Microcell E (trade name / calcium silicate, Celite Corporation, oil absorption 460 ml / 100 g), H fine powder (trade name / dioxide) About 100 parts of 46.7 parts of silicon (manufactured by Keiwa Furnace Co., Ltd.) and 30 parts of petroleum paraffin wax (melting point 70 to 80 ° C., penetration 5 to 7 (25 ° C.), average molecular weight 500 to 600) While melting at 0 ° C., the mixture was stirred with a three-one motor to uniformly disperse pyrazosulfuron ethyl. These compounds were cooled to room temperature and pulverized to obtain the granular material of the present invention.

  Along with 4.7 parts of this granular material having a volume median diameter of 649 μm, 1.0 part of dioctylsulfosuccinate sodium salt, 3.1 parts of polyacrylic acid Na, 5 parts of dextrin, 10 parts of bentonite, 76.2 parts of clay Mix, knead by adding an appropriate amount of granulated water, extrude and granulate with a screen having a hole with a diameter of 1.0 mm, dry at 50 ° C. for 2 hours, adjust the size, and then screen with a 710 to 1,400 μm sieve. The granule of the present invention containing pyrazosulfuron ethyl was obtained by sieving.

Example 5
21.3 parts of pyrazosulfuron ethyl finely pulverized to about 5 microns, 1.5 parts of Florite R (trade name / calcium silicate, manufactured by Tokuyama Corporation, oil absorption 695 ml / 100 g), fine H powder (trade name / About 47.2 parts of silicon dioxide (manufactured by Keiwa Furnace Co., Ltd.) and 30 parts of petroleum paraffin wax (melting point: 70-80 ° C., penetration: 5-7 (25 ° C.), average molecular weight: 500-600) While melting at 100 ° C., the mixture was stirred with a three-one motor to uniformly disperse pyrazosulfuron ethyl. These compounds were cooled to room temperature and pulverized to obtain the granular material of the present invention.

  Along with 4.7 parts of this granular material having a volume median diameter of 586 μm, 1.0 part of dioctylsulfosuccinate sodium salt, 3.1 parts of polyacrylic acid Na, 5 parts of dextrin, 10 parts of bentonite and 76.2 parts of clay Mix, knead by adding an appropriate amount of granulated water, extrude and granulate with a screen having a hole with a diameter of 1.0 mm, dry at 50 ° C. for 2 hours, adjust the size, and then screen with a 710 to 1,400 μm sieve. The granule of the present invention containing pyrazosulfuron ethyl was obtained by sieving.

[Comparative Example 1]
21.3 parts of compound A finely pulverized to about 5 microns, 48.7 parts of H fine powder (trade name / silicon dioxide, manufactured by Keiwa Furnace Co., Ltd.) and petroleum paraffin wax (melting point: 70 to 80 ° C., penetration) While melting at about 100 ° C., 30 parts of 5 to 7 (25 ° C., average molecular weight 500 to 600) were mixed and stirred with a three-one motor to uniformly disperse Compound A. These compounds were cooled to room temperature and pulverized to obtain granular materials.

  Along with 4.7 parts of this granular material having a volume median diameter of 410 μm, 1.0 part of dioctylsulfosuccinate Na salt, 3.1 parts of polyacrylic acid Na, 5 parts of dextrin, 10 parts of bentonite, 76.2 parts of clay Mix, knead by adding an appropriate amount of granulated water, extrude and granulate with a screen having a hole with a diameter of 1.0 mm, dry at 50 ° C. for 2 hours, adjust the size, and then screen with a 710 to 1,400 μm sieve. Sieve and granule containing compound A was obtained.

[Comparative Example 2]
Compound A21.3 parts finely pulverized to about 5 microns, Radiolite # 200 (trade name / calcined diatomaceous earth, Showa Chemical Industries, Ltd., oil absorption 135 ml / 100 g), H fine powder (trade name / About 46.7 parts of silicon dioxide (manufactured by Keiwa Furnace Co., Ltd.) and 30 parts of petroleum paraffin wax (melting point 70 to 80 ° C., penetration 5 to 7 (25 ° C.), average molecular weight 500 to 600) While melting at 100 ° C., the mixture A was mixed and stirred with a three-one motor to uniformly disperse Compound A. These compounds were cooled to room temperature and pulverized to obtain granular materials.

  Along with 4.7 parts of this granular material having a volume median diameter of 400 μm, 1.0 part of dioctylsulfosuccinate Na salt, 3.1 parts of polyacrylic acid Na, 5 parts of dextrin, 10 parts of bentonite and 76.2 parts of clay Mix, knead by adding an appropriate amount of granulated water, extrude and granulate with a screen having a hole with a diameter of 1.0 mm, dry at 50 ° C. for 2 hours, adjust the size, and then screen with a 710 to 1,400 μm sieve. Sieve and granule containing compound A was obtained.

[Comparative Example 3]
21.3 parts of compound A finely pulverized to about 5 microns, 2.0 parts of Galeon Earth V2 (trade name / activated clay, Mizusawa Chemical Industries, Ltd., oil absorption 77 ml / 100 g), H fine powder (trade name / About 46.7 parts of silicon dioxide (manufactured by Keiwa Furnace Co., Ltd.) and 30 parts of petroleum paraffin wax (melting point 70 to 80 ° C., penetration 5 to 7 (25 ° C.), average molecular weight 500 to 600) While melting at 100 ° C., the mixture A was mixed and stirred with a three-one motor to uniformly disperse Compound A. These compounds were cooled to room temperature and pulverized to obtain granular materials.

  Along with 4.7 parts of this granular material having a volume median diameter of 379 μm, 1.0 part of dioctylsulfosuccinate sodium salt, 3.1 parts of polyacrylic acid Na, 5 parts of dextrin, 10 parts of bentonite and 76.2 parts of clay Mix, knead by adding an appropriate amount of granulated water, extrude and granulate with a screen having a hole with a diameter of 1.0 mm, dry at 50 ° C. for 2 hours, adjust the size, and then screen with a 710 to 1,400 μm sieve. Sieve and granule containing compound A was obtained.

[Comparative Example 4]
21.3 parts of pyrazosulfuron ethyl finely pulverized to about 5 microns, 48.7 parts of H fine powder (trade name / silicon dioxide, manufactured by Keiwa Furnace Co., Ltd.) and petroleum-based paraffin wax (melting point: 70 to 80 ° C. Further, 30 parts of a penetration of 5 to 7 (25 ° C., average molecular weight of 500 to 600) were mixed and stirred with a three-one motor while being melted at about 100 ° C. to uniformly disperse pyrazosulfuron ethyl. These compounds were cooled to room temperature and pulverized to obtain granular materials.

  Along with 4.7 parts of this granular material having a volume median diameter of 648 μm, 1.0 part of dioctylsulfosuccinate sodium salt, 3.1 parts of polyacrylic acid Na, 5 parts of dextrin, 10 parts of bentonite and 76.2 parts of clay Mix, knead by adding an appropriate amount of granulated water, extrude and granulate with a screen having a hole with a diameter of 1.0 mm, dry at 50 ° C. for 2 hours, adjust the size, and then screen with a 710 to 1,400 μm sieve. Sieve and granule containing pyrazosulfuron ethyl was obtained.

[Test Example 1] Underwater dissolution test of Compound A or pyrazosulfuron-ethyl-containing granules 300 mg each of granules prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were placed in a beaker containing 1 liter of 10 degree hard water. After a lapse of 24 hours, a part of the solution was collected from the center of the beaker, and the amount of compound A or pyrazosulfuron ethyl eluted in water by HPLC (high performance liquid chromatograph) was quantified. The initial water dissolution rate was calculated by the formula.

Initial water dissolution rate (%) = (X / Y) x 100
X: Component amount eluted in water after 24 hours Y: Component content in granules After 30 days, the granules and water in the beaker were filtered, and the residue on the filter paper was extracted with tetrahydrofuran. Compound A or pyrazosulfuron ethyl was quantified by (high performance liquid chromatograph), and the residual rate was calculated by the following formula.

Residual rate (%) = (X / Y) × 100
X: Component amount remaining in the granular material of the present invention after 30 days Y: Component content in granules

The results of the compound A-containing granule are shown in Table 1.

Table 1 ――――――――――――――――――――――――――
Initial water dissolution rate (%) Residual rate (%)
――――――――――――――――――――――――――
Example 1 55 2.5
Example 2 56 1.4
Example 3 57 3.4
Comparative Example 1 52 9.2
Comparative Example 2 53 6.8
Comparative Example 3 51 7.1
――――――――――――――――――――――――――

The results of the pyrazosulfuron ethyl-containing granules are shown in Table 2.

Table 2 ――――――――――――――――――――――――――
Initial water dissolution rate (%) Residual rate (%)
――――――――――――――――――――――――――
Example 4 32 5.6
Example 5 32 1.8
Comparative Example 4 26 26.1
――――――――――――――――――――――――――

Example 6
Compound A 21.9 parts finely pulverized to about 5 microns, Florite R (trade name / calcium silicate, manufactured by Tokuyama Corporation, oil absorption 695 ml / 100 g), H fine powder (trade name / silicon dioxide, 47.3 parts of Keiwa Furnace Co., Ltd.) and 30 parts of petroleum paraffin wax (melting point 70-80 ° C, penetration 5-7 (25 ° C), average molecular weight 500-600) at about 100 ° C While melting, the mixture A was mixed and stirred to disperse Compound A uniformly. These compounds were cooled to room temperature and pulverized to obtain the granular material of the present invention.

  Along with 5.0 parts of this granular material having a volume median diameter of 425 μm, 1.3 parts of dioctylsulfosuccinate Na salt, 3.1 parts of polyacrylic acid Na, 5 parts of dextrin, 10 parts of bentonite and 75.6 parts of clay After mixing, an appropriate amount of granulated water was added and kneaded. Extrusion granulation was performed with a screen having a hole having a diameter of 1.0 mm, and fluidized bed drying was performed at a blowing temperature of 55 ° C. for 10 minutes. After the dried product was sized, it was sieved with a 710 to 1,700 μm sieve to obtain a granule of the present invention containing Compound A.

Example 7
21.9 parts of compound A finely pulverized to about 5 microns, 0.75 parts of Florite R (trade name / calcium silicate, manufactured by Tokuyama Co., Ltd., oil absorption 695 ml / 100 g), Miyagi wettable powder clay (trade name) / Waxite powder (manufactured by Sanyo Kikou Co., Ltd.) 47.3 parts and petroleum-based paraffin wax (melting point 70-80 ° C, penetration 5-7 (25 ° C), average molecular weight 500-600) about 30 parts, While melting at 100 ° C., the mixture A was mixed and stirred to uniformly disperse Compound A. These compounds were cooled to room temperature and pulverized to obtain the granular material of the present invention.

  Along with 5.0 parts of this granular material having a volume median diameter of 399 μm, 1.3 parts of dioctylsulfosuccinate Na salt, 3.1 parts of polyacrylic acid Na, 5 parts of dextrin, 10 parts of bentonite, 75.6 parts of clay After mixing, an appropriate amount of granulated water was added and kneaded. Extrusion granulation was performed with a screen having a hole having a diameter of 1.0 mm, and fluidized-bed drying was performed at a blowing temperature of 55 ° C. for 10 minutes. After the dried product was sized, it was sieved with a 710 to 1,700 μm sieve to obtain a granule of the present invention containing Compound A.

Example 8
Compound A 21.9 parts finely pulverized to about 5 microns, Florite R (trade name / calcium silicate, manufactured by Tokuyama Corporation, oil absorption 695 ml / 100 g), Showa DL clay (trade name /, Showa KDE (made by KDE Co., Ltd.) 47.3 parts and petroleum paraffin wax (melting point 70-80 ° C, penetration 5-7 (25 ° C), average molecular weight 500-600) 30 parts while melting at about 100 ° C The mixture was stirred and dispersed to uniformly disperse Compound A. These compounds were cooled to room temperature and pulverized to obtain the granular material of the present invention.

  Along with 5.0 parts of this granular material having a volume median diameter of 418 μm, 1.3 parts of dioctylsulfosuccinate Na salt, 3.1 parts of polyacrylic acid Na, 5 parts of dextrin, 10 parts of bentonite and 75.6 parts of clay After mixing, an appropriate amount of granulated water was added and kneaded. Extrusion granulation was performed with a screen having a hole having a diameter of 1.0 mm, and fluidized-bed drying was performed at a blowing temperature of 55 ° C. for 10 minutes. After the dried product was sized, it was sieved with a 710 to 1,700 μm sieve to obtain a granule of the present invention containing Compound A.

Example 9
Compound A 21.9 parts finely pulverized to about 5 microns, Florite R (trade name / calcium silicate, manufactured by Tokuyama Corporation, oil absorption 695 ml / 100 g), Showa SW clay (trade name /, Showa (Chemical Co., Ltd.) 47.3 parts and petroleum-based paraffin wax (melting point 70-80 ° C., penetration 5-7 (25 ° C.), average molecular weight 500-600) while melting at about 100 ° C. The mixture was stirred and dispersed to uniformly disperse Compound A. These compounds were cooled to room temperature and pulverized to obtain the granular material of the present invention.

  Along with 5.0 parts of this granular material having a volume median diameter of 380 μm, 1.3 parts of dioctylsulfosuccinate Na salt, 3.1 parts of polyacrylic acid Na, 5 parts of dextrin, 10 parts of bentonite and 75.6 parts of clay After mixing, an appropriate amount of granulated water was added and kneaded. Extrusion granulation was performed with a screen having a hole having a diameter of 1.0 mm, and fluidized-bed drying was performed at a blowing temperature of 55 ° C. for 10 minutes. After the dried product was sized, it was sieved with a 710 to 1,700 μm sieve to obtain a granule of the present invention containing Compound A.

Example 10
21.9 parts of Compound A finely pulverized to about 5 microns, 0.75 parts of Florite R (trade name / calcium silicate, manufactured by Tokuyama Corporation, oil absorption 695 ml / 100 g), Hana H (trade name / crystalline) About 100 parts of 47.3 parts of quartz (manufactured by Keiwa Furnace Co., Ltd.) and 30 parts of petroleum-based paraffin wax (melting point 70-80 ° C., penetration 5-7 (25 ° C.), average molecular weight 500-600) While melting at 0 ° C., the mixture A was mixed and stirred to disperse Compound A uniformly. These compounds were cooled to room temperature and pulverized to obtain the granular material of the present invention.

  Along with 5.0 parts of this granular material having a volume median diameter of 423 μm, 1.3 parts of dioctylsulfosuccinate Na salt, 3.1 parts of polyacrylic acid Na, 5 parts of dextrin, 10 parts of bentonite and 75.6 parts of clay After mixing, an appropriate amount of granulated water was added and kneaded. Extrusion granulation was performed with a screen having a hole having a diameter of 1.0 mm, and fluidized-bed drying was performed at a blowing temperature of 55 ° C. for 10 minutes. After the dried product was sized, it was sieved with a 710 to 1,700 μm sieve to obtain a granule of the present invention containing Compound A.

Example 11
Compound A 21.9 parts finely pulverized to about 5 microns, Fluorite R (trade name / calcium silicate, manufactured by Tokuyama Co., Ltd., oil absorption 695 ml / 100 g), SP-7F (trade name / silica, 47.3 parts of Keiwa Furnace Co., Ltd.) and 30 parts of petroleum-based paraffin wax (melting point 70-80 ° C, penetration 5-7 (25 ° C), average molecular weight 500-600) at about 100 ° C While melting, the mixture A was mixed and stirred to disperse Compound A uniformly. These compounds were cooled to room temperature and pulverized to obtain the granular material of the present invention.

  Along with 5.0 parts of this granular material having a volume median diameter of 420 μm, 1.3 parts of dioctylsulfosuccinate Na salt, 3.1 parts of polyacrylic acid Na, 5 parts of dextrin, 10 parts of bentonite and 75.6 parts of clay After mixing, an appropriate amount of granulated water was added and kneaded. Extrusion granulation was performed with a screen having a hole having a diameter of 1.0 mm, and fluidized bed drying was performed at a blowing temperature of 55 ° C. for 10 minutes. After the dried product was sized, it was sieved with a 710 to 1,700 μm sieve to obtain a granule of the present invention containing Compound A.

[Test Example 2] Underwater dissolution test of Compound A-containing granules 2
300 mg of each granule produced in Examples 6 to 11 was put into a beaker containing 1 liter of 10 degree hard water, and after 24 hours, a part of the solution was collected from the center of the beaker, and HPLC (high speed The component amount of Compound A eluted in water was quantified by liquid chromatography, and the initial water elution rate was calculated by the following formula.

Initial water dissolution rate (%) = (X / Y) x 100
X: Component amount eluted in water after 24 hours Y: Component content in granules After 14 days, the granules and water in the beaker were filtered, and the residue on the filter paper was extracted with tetrahydrofuran. Compound A was quantified by (high performance liquid chromatograph), and the residual ratio was calculated by the following formula.

Residual rate (%) = (X / Y) × 100
X: component amount remaining in the granular material of the present invention after 14 days Y: component content in granules

The results of the compound A-containing granule are shown in Table 3.

Table 3 ――――――――――――――――――――――――
Initial water dissolution rate (%) Residual rate (%)
――――――――――――――――――――――――
Example 6 57 3.6
Example 7 57 3.9
Example 8 62 5.7
Example 9 63 5.4
Example 10 57 2.3
Example 11 60 2.2
――――――――――――――――――――――――

  The granular material and solid agricultural chemical preparation of the present invention can be used for controlling pests such as weeds and pests.

Claims (15)

  A granular material containing an agrochemical active ingredient, a hydrophobic substance that is solid at 25 ° C., and an oil-absorbing powder having an oil absorption of 200 ml / 100 g or more.   The granular material according to claim 1, wherein the oil absorption amount of the oil absorbing powder is 400 ml / 100 g or more.   The granular material according to claim 1, wherein the oil absorption amount of the oil absorbing powder is 600 ml / 100 g or more.   The granular material according to any one of claims 1 to 3, wherein the oil-absorbing powder is calcium silicate or silica.   The granular material according to any one of claims 1 to 4, wherein the hydrophobic substance that is solid at 25 ° C is at least one selected from waxes, fatty acids, fatty acid esters, and resins.   The granular material according to any one of claims 1 to 4, wherein the hydrophobic substance that is solid at 25 ° C is paraffin wax.   Furthermore, the granular material of any one of Claims 1-6 containing an adjuvant.   The granular material according to claim 7, wherein the auxiliary agent is a solid powder.   The granular material according to any one of claims 1 to 6, wherein an agrochemical active ingredient and an oil-absorbing powder having an oil absorption amount of 200 ml / 100 g or more are dispersed in a solid hydrophobic substance at 25 ° C.   The granular material according to claim 7 or 8, wherein an agrochemical active ingredient, an oil-absorbing powder having an oil absorption amount of 200 ml / 100 g or more, and an auxiliary agent are dispersed in a hydrophobic substance that is solid at 25 ° C. Agrochemical active ingredients
Formula (1):

[Where,
G represents G1, G2, G3, G4, G5, G6, G7, G8, G9, G10 or CH ₃ (CH ₃ SO ₂ ) N;
L represents L1 or L2,
X and Y each independently represent a hydrogen atom, a halogen atom, a _C1-3 alkyl group or a _C1-3 alkoxy group.
Z represents CH or a nitrogen atom
L1 represents SO ₂ NH (C = O) N (R ¹ ), CH ₂ SO ₂ NH (C = O) N (R ¹ ) or NHSO ₂ NH (C = O) N (R ¹ )
L2 represents an oxygen atom, a sulfur atom, CH ₂ , CH (OH) or C═O,
R ¹ represents a hydrogen atom or a C _1-3 alkyl group,
G1, G2, G3, G4, G5, G6, G7, G8, G9 and G10 are

Represents
R ² represents a C _1-3 alkyl group, a C _1-3 alkoxy C _1-3 alkyl group, a phenyl group optionally substituted by A, or a pyridyl group optionally substituted by A;
A represents one or more substituents selected from a halogen atom, a _C1-3 alkyl group, a _C1-3 alkoxy group and a _C1-3 haloalkyl group;
R ³ is a hydrogen atom, a halogen atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _1-6 haloalkyl group, a C _2-6 haloalkenyl group, a C _2-6 halo. alkynyl group, C _{1 to 6} haloalkoxy group, C _{1 to 3} alkoxy C _{1 to 6} alkyl groups, C _{1 to 3} haloalkoxy C _{1 to 3} alkyl ^{_{groups, NO 2, CO 2 R 8}} , COR 9, CON (R _{^{10) 2, CONHR 10, NHCOR}} 9, SO 2 R 11, SO 2 N (R 10) 2, SO 2 NH (R 10), NHSO 2 (R 11), CH (CHFCH 3) (OCOCH 2 OCH 3) Represents a 2-methyl-2H-tetrazol-5-yl group or Q;
Q is

Represents
R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _1-6 haloalkyl group, C _2-6 haloalkenyl group, C _2-6 haloalkynyl group, C _1-3 alkoxy C _1-3 alkyl group, NHCOR ⁹ , CH ₂ NHSO ₂ R ¹¹ , C (R ¹² ) = NOR ¹³ or 4,6 Represents -dimethoxypyrimidin-2-yl group
When R ³ and R ⁴ are adjacent to each other, R ³ and R ⁴ may form a 5- or 6-membered ring with the carbon atoms to which they are bonded, and include an oxygen atom or a carbonyl group in the formed ring. Well,
R ⁸ is a hydrogen atom, C _1-6 alkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _1-6 haloalkyl group, C _3-6 cycloalkyl group, 3-oxetanyl group, 2-oxetanyl Group, or N = C (Ph) ₂
R ⁹ represents a hydrogen atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _1-6 haloalkyl group or a C _3-6 cycloalkyl group,
R ¹⁰ represents a C _1-6 alkyl group,
R ¹¹ represents a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group or a C _1-6 haloalkyl group,
R ¹² represents a hydrogen atom or a C _1-6 alkyl group,
R ¹³ represents a C _1-6 alkyl group,
Represents
R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a C _1-6 alkyl group. The granular material according to any one of claims 1 to 10, which is one or more herbicidal active ingredients selected from compounds represented by the formula (I) and salts thereof.   The solid agricultural chemical formulation containing the granule of any one of Claims 1-11, and a solid support | carrier.   The solid agricultural chemical formulation according to claim 12, further comprising an agricultural chemical active ingredient.   The solid agricultural chemical formulation according to claim 12 or 13, further comprising an auxiliary component.   The solid agricultural chemical formulation according to any one of claims 12 to 14, wherein the solid agricultural chemical formulation is a granule.