JP2009185021A - Release-controlled particle and solid herbicidal preparation containing the particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new particle and a preparation in which the release of a herbicidal active ingredient can be controlled. <P>SOLUTION: The particle includes penoxsulam as a herbicidal active ingredient, a hydrophobic substance which is solid at 25°C, calcium carbonate and an inert carrier. A solid herbicide preparation comprising the particle and a solid carrier is also provided. The particle may further comprise a herbicidal active ingredient other than penoxsulam and an auxiliary agent, and the solid herbicide preparation may be further comprise a herbicidal active ingredient other than penoxsulam and an auxiliary component. The solid herbicide preparation preferably has a granular form. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a granule in which the release of penox slam, which is a herbicidal active ingredient, is controlled, and a solid herbicidal formulation containing the granule.

  Penoxsulam (generic name) is a known compound having herbicidal activity, and its chemical name is 2- (2,2-difluoroethoxy) -N- (5,8-dimethoxy [1,2,4] triazolo [1 , 5-c] pyrimidin-2-yl) -6- (trifluoromethyl) benzenesulfonamide.

  Conventional herbicidal formulations for paddy fields include various forms such as granules, granule wettable powders, jumbo powders, powders, wettable powders, flowables, aqueous solvents, liquids, and emulsions. In general, granules in the form of granules are used. However, some herbicidal active ingredients may cause problems such as phytotoxicity to paddy rice and reduced residual effect on the target weeds, and control of herbicidal active ingredient release is desired. Yes.

Further, as a method for controlling the release of herbicidal active ingredients, 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), but remains in the formulation. There may be concerns about the effects of herbicidal active ingredients on subsequent cropping.
JP-A-2-288803 JP 2007-137868 A

  If penox slam, a herbicidal active ingredient, is used without controlled release, it may cause phytotoxicity to paddy rice. In addition, if the release of penox slam is suppressed too much, more herbicidal active ingredients remain in the preparation, and there is a concern that the effect on subsequent crops may be concerned.

  As a result of diligent research, the present inventors have found that penox slam, a herbicidal active ingredient, a solid hydrophobic substance, calcium carbonate, and a granular material containing an inert carrier can suppress the initial release of penox slam, It was found that almost all penox slam was released, and as a result, the phytotoxicity to paddy rice was reduced and the residual effect on weeds was improved. Moreover, since almost the whole amount of penox slam was finally released, it was found that there was almost no influence on the subsequent work. That is, the present invention relates to the following [1] to [10].

  [1] A granulated material containing penox slam as a herbicidal active ingredient, a hydrophobic substance that is solid at 25 ° C., calcium carbonate, and an inert carrier.

  [2] The granular material according to the above [1], wherein the inert carrier is a mineral carrier.

[3] The granular material according to the above [2], wherein the mineral carrier is silica or silicate. [4] The hydrophobic substance that is solid at 25 ° C. is one or more selected from wax, fatty acid, fatty acid ester and resin. The granular material according to any one selected from [1] to [3].

  [5] The granular material according to any one of [1] to [3], wherein the hydrophobic substance that is solid at 25 ° C. is paraffin wax.

  [6] The granular material according to any one of [1] to [5], further containing a herbicidal active ingredient other than penox slum.

  [7] A solid herbicidal preparation comprising the granular material according to any one of [1] to [6] and a solid carrier.

  [8] The solid herbicidal preparation according to the above [7], further comprising a herbicidal active ingredient other than penox slum.

  [9] The solid herbicidal preparation according to the above [7] or [8], further comprising an auxiliary component.

  [10] The solid herbicidal formulation according to any one of [7] to [9], wherein the solid herbicidal formulation is a granule.

  According to the present invention, the initial release of penox slam, which is a herbicidal active ingredient, is suppressed, and finally the entire amount of penox slam is released, resulting in reduced phytotoxicity to paddy rice and improved residual efficacy against weeds. The Moreover, since almost the whole amount of penox slam is finally released, there is almost no influence on the subsequent work.

  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, powdery penox slam, calcium carbonate and an inert carrier are added to a solid hydrophobic substance at 25 ° C. melted at a temperature above the melting point, preferably 10-30 ° C. above the melting point, and further necessary Depending on the above, an herbicidal active ingredient and an auxiliary agent other than penox slum are added, and the mixture is stirred with a stirrer (for example, a homomixer, a three-one motor, a kneader, a universal mixer, and a nauter) to uniformly disperse the penox slam.

  Alternatively, powdery penox slam, a hydrophobic substance that is solid at 25 ° C., calcium carbonate, and an inert carrier, and if necessary, other herbicidal active ingredients and adjuvants other than penox slum are added, and these are mixed in advance with a mixer (for example, NOW Mix evenly with a mixer or universal mixer). Next, while heating and melting at 25 ° C. at a temperature equal to or higher than the melting point of the solid hydrophobic substance, preferably 10-30 ° C. higher than the melting point, mixing and stirring may be performed with the above stirrer to uniformly disperse the penox slam. .

  The molten mixture in which these penox slums are uniformly dispersed is cooled to a temperature exhibiting plasticity, and this is granulated by, for example, an extrusion granulator equipped with a screen having a hole having a diameter of 0.5 to 1.5 mm. A granular material is obtained. 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 volume 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 600 μm. If the volume median diameter of the granular material is smaller than this range, penox slam is released in a relatively short period of time, and there is a high possibility that phytotoxicity to paddy rice will be promoted. On the other hand, when the volume median diameter of the granular material is larger than this range, there is a high possibility that the release of penox slam is suppressed and it becomes difficult to obtain a sufficient herbicidal effect.

  Examples of the hydrophobic substance that is solid at 25 ° C. that can be used in the granular material of the present invention include plant waxes such as candelilla wax, wood wax, and rice wax, and animal waxes such as beeswax, lanolin, whale wax, and beef tallow. , Petroleum wax such as microcrystalline wax (isoparaffin, cycloparaffin), paraffin wax (normal paraffin), petrolactam, carnauba wax, oxidized wax, ester wax, urethane wax, polyolefin, polyethylene oxide, 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, Copolymer of vinyl acid, ethylene and vinyl chloride, polyacrylic acid ester, copolymer of acrylic acid ester and styrene, copolymer of acrylic acid ester and silicone, copolymer of acrylic acid ester and ethylene, polyurethane, styrene Water-insoluble thermoplastic resins such as acrylonitrile and butadiene copolymer, amino resin (urea resin and melamine resin, etc.), phenol resin (resole resin and novolac resin, etc.), resorcinol formaldehyde resin, xylene Examples thereof include thermosetting resins such as resins, furan resins, epoxy resins, polyisocyanate resins, unsaturated polyester resins, and acrylic resins, and two or more of these may be used in combination. Preferred as the hydrophobic substance that is solid at 25 ° C. is paraffin wax, microcrystalline 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 granular material of the present invention may further contain a herbicidal active ingredient other than penox slum. Specific examples of herbicidal active ingredients other than penox slam are as follows, but are not limited to these.

  Azimsulfuron, amidesulfuron, amidosulfuron, iodosulfuron-methyl, imazosulfuron, etamethsulfuron-methyl, ethoxysulfuron, oxasulfuron (Oxasulfuron), orthosulfamuron, chlorimuron-ethyl, chlorsulfuron, cyclosulfamuron, cinosulfuron, sulfosulfuron, sulfosulfuron- Methyl (sulfomethuron-methyl), thifensulfuron-methyl, triasulfuron, tritosulfuron, triflusulfuron-methyl, trifloxysulfuro (Trifloxysulfuron), tribenuron-methyl, nicosulfuron, halosulfuron-methyl, pyrazosulfuron-ethyl, foramsulfuron, Frazas Ruflon (flazasulfuron), primisulfuron-methyl, flucetosulfuron, flupirsulfuron-methyl (flupyrsulfuron), prosulfuron, bensulfuron-methyl, mesosulfuron- Methyl (mesosulfron-methyl), metsulfuron-methyl, rimsulfuron, 2-chloro-N- (4,6-dimethoxypyrimidin-2-ylcarbamoyl) -7-propylimidazo [1,2 -b] pyridazine-3-sulfonamide, 3-chloro-N- (4,6-dimethoxypyrimidine-2- Rucarbamoyl) -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-ylcarbamoyl) -1-methyl-4- (5-methyl-5,6-dihydro-1,4,2-dioxazin-3-yl ) -1H-pyrazole-5-sulfonamide, N- (4,6-dimethoxypyrimidin-2-ylcarbamoyl) -1-methyl-4- (6-methyl-5,6-dihydro-1,4,2- Dioxazin-3-yl) -1H-pyrazol-5-sulfonamide, 4- (5,6-dihydro-1,4,2-dioxazin-3-yl) -N- (4,6-dimethyl) Xypyrimidin-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-pyrazol-5-sulfonamide, 4- (5,6-dihydro-1,4,2-dioxazin-3-yl) -N- (4,6-Dimethoxypyrimidin-2-ylcarbamoyl) -1,3-dimethyl-1H-pyrazole-5-sulfonamide, bispyribac, pyrithiobac, pyriftalid, pyribenzoxim ), Pyrimisulfuron, pyriminobac-methyl, monosulfuron, monosulfuron-methyl and the like. These herbicidal active ingredients other than penox slam can be used alone or in admixture of two or more.

  In the granular material of the present invention, the ratio of the total weight of the herbicidal active ingredients to the weight of the hydrophobic substance that is 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 is less than 0.5 parts by weight at 25 ° C. with respect to 1 part by weight of the total amount of herbicidal active ingredients, the herbicidal active ingredients may be released in a relatively short period of time, which may promote phytotoxicity. Becomes higher. On the other hand, when the amount of the solid hydrophobic substance exceeds 30 parts by weight at 25 ° C. with respect to 1 part by weight of the total amount of herbicidal active ingredients, there is a high possibility that the release of active ingredients is suppressed and a sufficient herbicidal effect cannot be obtained.

  The production method of calcium carbonate contained in the granular material of the present invention is not particularly limited, and may be light calcium carbonate or heavy calcium carbonate, but is usually powdery. Examples of the calcium carbonate include NS # 3000 (trade name / Nitto Flour Industries), NS # 2700 (trade name / Nitto Flour Industries), NS # 2500 (trade name / Nitto Flour). Kogyo Co., Ltd.), NS # 2300 (Brand Name / Nitto Flour Industries), NS # 1000 (Brand Name / Nitto Flour Industries), NS # 600 (Brand Name / Nitto Flour Industries) NS # 400 (trade name / Nitto Flour Industries), NS # 200 (trade name / Nitto Flour Industries), NS # 100 (trade name / Nitto Flour Industries) ), SS # 80 (trade name / Nitto Flour Industries), SS # 30 (trade name / Nitto Flour Industries), NN # 500 (trade name / Nitto Flour Industries) NN # 200 (trade name / Nitto Flour Industries), NITOREX # 90 (trade name / Nitto Flour Industries), N TOREX # 80 (trade name / Nitto Flour Industries), NITREX # 75 (trade name / Nitto Flour Industries), NITREX # 70 (trade name / Nitto Flour Industries), P- LITE # 1000 (trade name / Nitto Flour Industries), P-LITE # 700 (trade name / Nitto Flour Industries), P-LITE # 500 (trade name / Nitto Flour Industries) ), S-Light # 1200 (trade name / Nitto Flour Industries), TS-70 (trade name / Nitto Flour Industries), MM # 400 (trade name / Nitto Flour Industries) ), MM # 100 (trade name / Nitto Flour Industries), Mama Carso (trade name / Nitto Flour Industries), Sedimentation 3S (trade name / Nitto Flour Industries), Calfin 1300 ( Product name / Adachi Lime Industry Co., Ltd.), Calfin 1000 (Product name / Adachi Lime Industry) Co., Ltd.), Calfin 600 (trade name / Adachi Lime Industry Co., Ltd.), Cal Choice 250 (trade name / Adachi Lime Industry Co., Ltd.), Tankar 330 (trade name / Adachi Lime Industry Co., Ltd.), Tankar 200 ( Product Name / Adachi Lime Industry Co., Ltd., Tankar 101 (Product Name / Adachi Lime Industry Co., Ltd.), Tankar 102 (Product Name / Adachi Lime Industry Co., Ltd.), Tankar 104 (Product Name / Adachi Lime Industry Co., Ltd.) )), Microcal 100 (trade name / Aokura Lime Industry Co., Ltd.), Microcal 150 (Product Name / Aokura Lime Industry Co., Ltd.), Microcal 250 (Product Name / Aokura Lime Industry Co., Ltd.), Microcal 350 (Product Name) / Aokura Lime Industry Co., Ltd.), Microcal 1525 (trade name / Aokura Lime Industry Co., Ltd.), Microcal 1535 (Product Name / Aokura Lime Industry Co., Ltd.), Callite-KT (Product Name / Shiraishi Naka) Central Research Laboratory), Super # 2300 (trade name / Maruo Calcium Co., Ltd.), Super # 2000 (trade name / Maruo Calcium Co., Ltd.), Super # 1700 (Product name / Maruo Calcium Co., Ltd.), Super # 1500 (Product name / Maruo Calcium Co., Ltd.), Super 4S (Product name / Maruo Calcium Co., Ltd.), Super SSS (Product name / Maruo Calcium Co., Ltd.), Super SS (Product name / Maruo Calcium Co., Ltd.), Super S (trade name / Maruo Calcium Co., Ltd.), general heavy coal (trade name / Maruo Calcium Co., Ltd.), selected heavy coal (trade name / Maruo Calcium Co., Ltd.) and R heavy coal (trade name / Maruo Calcium Co., Ltd.) Etc.).

  The content of calcium carbonate contained in the granular material of the present invention is usually 0.5 to 30% by weight, preferably 1 to 10% by weight, more preferably 1 to 5% by weight, based on the granular material. .

  The inert carrier contained in the granular material of the present invention is an inert carrier other than calcium carbonate. The inert carrier is usually in the form of a powder, preferably a powdered mineral, and more preferably a powdered clay mineral (silica or silicate). Examples of the inert carrier include quartz, quartzite, calcite, foamite, dolomite, chalk, kaolinite, pyrophyllite, sericite, halosite, metahalosite, Kibushi clay, Sasame clay, pottery stone , Sieglite, Allophane, Shirasu, Kira, Talc, Bentonite, Activated clay, Acid clay, Pumice, Attapulgite, Zeolite and Diatomite etc., such as calcined clay, perlite, shirasu balloon, vermiculite, attapulgus clay and calcined diatomite Mineral fired products such as magnesium carbonate, sodium carbonate, sodium bicarbonate, ammonium sulfate, sodium sulfate, magnesium sulfate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and potassium chloride, such as glucose, fructose, sucrose And lactose Sugars such as polysaccharides such as starch, powdered cellulose and dextrin, organic materials such as urea, urea derivatives, benzoic acid and benzoic acid salts, plants such as wood flour, corn cobs, walnut shells and tobacco stems, Examples include fly ash, white carbon, and fertilizer.

  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 bentonite include H fine powder (trade name / Keiwa Furnace Co., Ltd.), Hana HB (trade name / Keiwa Furnace Co., Ltd.), Silica TM-4. (Brand name / Keiwa Furnace Co., Ltd.), SP-7F (Brand name / Keiwa Furnace Co., Ltd.), NeoCarrier K (Brand name / Asada Flour Milling Co., Ltd.), Fubasami K Clay ( Product name / manufactured by Fubasami Clay Co., Ltd.) and Special Snow F clay (trade name / manufactured by Showa Mining Co., Ltd.).

  Specific examples of the white carbon include, for example, Carplex # 80D (trade name / Shinogi Pharmaceutical Co., Ltd.), Carplex # 67 (trade name / Shinogi Pharmaceutical Co., Ltd.), Carplex # 1120 (trade name / Shionogi Seiyaku Co., Ltd.), Carplex #XR (trade name / Shinogi Seiyaku Co., Ltd.), Fine Seal A (trade name / Tokuyama Soda Co., Ltd.), Fine Seal E-50 (trade name / Tokuyama Soda) Fine Seal X-37 (trade name / Tokuyama Soda Co., Ltd.), Fine Seal K-41 (trade name / Tokuyama Soda Co., Ltd.), Fine Seal P-8 (trade 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 (trade name / Tokuyama Soda Co., Ltd.), Nip 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.), Syloid 244 (trade name / Fuji Devison Chemical), Cyroid 65 (trade name / Fuji Devison Chemical), Cyroid 308 (trade name / Fuji Devison Chemical), Mizukasil P-705 (trade name / Mizusawa Chemical Co., Ltd.), Mizukasil P-802 (trade name / Mizusawa) Chemical Co., Ltd.), Mizukasil 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 / Shionogi Pharmaceutical Co., Ltd.), Carplex CS-7 (trade name / Shinogi Pharmaceutical Co., Ltd.), Carplex CS-701 (trade name / Shinogi Pharmaceutical Co., Ltd.), etc. A fired product of hydrous silica 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 Aerosil MOX80 (Product) Silica, such as FLORITE R (trade name / Tokuyama Soda Co., Ltd.), FLORITE RN (trade name / Tokuyama Soda Co., Ltd.), Toyohero TH (trade name / Toyo) Hydrous calcium silicates such as Denka Kogyo Co., Ltd., Zonolite (trade name / Onoda Chemical) and Microcell E (trade name / Johns Manville), for example, SIPERNAT D17 (trade name / Nippon Aerosil Co., Ltd.), Nipsea SS- 10 (trade name / Nihon Silica Co., Ltd.), Nip Seal SS-20 (trade name / Nihon Silica Co., Ltd.) ) And nip seal SS-30P (trade name / Nippon Silica Co., Ltd.) and other surface-treated silicas such as Aerosil R972 (trade name / Nippon Aerosil Co.), Aerosil R202 (trade name / Nippon Aerosil) And surface-treated silica made from anhydrous silica such as Aerosil R812 (trade name / Nippon Aerosil Co., Ltd.).

The content of the inert carrier contained in the granular material of the present invention is usually 20 to 90 with respect to the granular material.
% By weight, preferably 40-70% by weight.

  Examples of the auxiliary agent that can be contained in the granular material of the present invention include a surfactant and a solvent. Details of the surfactant will be described later.

  Next, the solid herbicidal preparation of the present invention will be described in more detail.

  Examples of the dosage form of the solid herbicidal 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 herbicidal 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, a herbicidal active ingredient and auxiliary ingredients other than penox slam are further added to the granular material containing penox slam produced by the above method and a solid carrier as necessary, and these are mixed uniformly. After adding a liquid auxiliary component or an appropriate amount of water to the obtained mixture and kneading it into a paste, granulation is performed using an extrusion granulator equipped with a screen having a hole having a diameter of 0.5 to 1.5 mm. After that, it can be dried.

  The content of penox slam used in the solid herbicidal preparation of the present invention is not particularly limited, but is preferably in the range of 0.01 to 1% by weight with respect to the solid herbicidal preparation.

  The elution rate of penox slam from the solid herbicidal preparation of the present invention in water at 30 ° C after 1 day is preferably 70% or less from the viewpoint of reducing phytotoxicity to paddy rice.

  Specific examples of herbicidal active ingredients other than penox slam that can be contained in solid herbicidal preparations together with the granular material and solid carrier of the present invention are as follows, but are not limited to these. is not.

  Pyrazosulfuron ethyl, halosulfuron methyl, bensulfuron methyl, imazosulfuron, azimsulfuron, cinosulfuron, cyclosulfamuron, ethoxy Ethoxysulfuron, esprocarb, benthiocarb, molinate, dimepiperate, pyributicarb, mefenacet, butachlor, pretilachlor, enylchlor , Bromobutide, etobenzanid, dymron, cumyluron, bentazone, salt of bentazone, 2,4-D, 2,4-D Salt, 2,4-D ester, MCP, MCP salt, MCP ester, MCPB, MCPB salt, MCPB ester, phenothiol (MCPA-thioethyl), clomeprop, naproanilide, oxadiazone (Oxadiazon), pyrazolate, pyrazoxifene, benzofenap, oxadiargyl, dimethametryn, simethrin, piperophos, anilofos, butomis , Bensulide, dithiopyr, pyriminobac methyl, CNP, chlormethoxynil, cyhalofop butyl, bifenox, cafenstrole, pentoxy Pentoxazone, indanofan, oxaziclomefone, fentolazamide, butenachlor, ACN, benzobicyclon, benfuresate, cinmethylin, simazine, simazine Benzyl (dichlobenil), diuron, chloro IPC (chlorpropham), atrazine, alachlor, isouron, chlorphtalim, cyanazin, trifluralin, butamifos ), Propyzamide, promethrin, pendimethalin, metolachlor, metribuzin, linuron, lenacil, propanil (pr) opanil, MCPA, ioxynil octanoate, asuram, quizalofop-ethyl, propaquizafop, quizalofop-tefuryl, sethoxydim, chi Fensulfuron-methyl, fenoxaprop-ethyl, phenmedipham, fluazifop-butyl, bentazone, SAP (bensulide), TCTP (chlorthal- dimethyl, tetorachlorothiophene, amiprophosmethyl, ametryn, isoxaben, orbencarb, karbutilate, dithiopyr, siduron, thiazafluron, Napropamide Amine (prodiamine), Besfin (benefin), methyl dymron, 2,4-PA, MCPPA, flazasulfuron, metsulfuron-methyl, imazaquin, imazapyr , Tetrapionate (flupropanate), tebuthiuron, bromacil, hexazinone, glyphosate-ammonium, glyphosate-iso-propylammonium, glyphosate-mesium salt ), Glyphosate-sodium, glyphosate-potassium, bialaphos, glufosinate-ammonium and MCC, pyraclonil, tefuryltirone, mesotho Mesotrione, aminopyralid, bencarbazone, pinoxaden, propoxycarbazone sodium salt (propoxycarbazone-sodium), pyrasulfotole, pyroxasulfone, pyroxsulam, Examples thereof include tembotrione, thiencarbazone-methyl, and topramezon.

  These herbicidal active ingredients other than penox slam can be used alone or in admixture of two or more. Moreover, although these content is not specifically limited, It is the range of 0.01 to 20 weight% normally with respect to a solid type herbicidal formulation.

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

  Examples of the solid carrier used in the solid herbicidal preparation of the present invention include calcium carbonate and an inert carrier that can be contained in the above-described granular material. The solid carriers can be used alone or in admixture of two or more. The content of the solid carrier is not particularly limited, but is usually in the range of 40 to 95% by weight with respect to the solid herbicidal preparation.

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

(A) Nonionic surfactant:
(A-1) Polyethylene glycol surfactants: for example, polyoxyethylene alkyl _(C 12 _{~ 18)} ether, ethylene oxide adducts of alkyl naphthol, polyoxyethylene (mono or di) alkyl _{(C 8 ~ 12)} phenyl ether, polyoxyethylene (mono or di) alkyl (C 8 _{~ 12)} formalin condensates of 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, polyoxy Styrene (mono-, di- or tri-) styryl phenyl ether polymer, polyoxyethylene polyoxypropylene block polymers, alkyl _(C 12 _{~ 18)} polyoxyethylene polyoxypropylene block polymer ethers, alkyl _{(C 8 ~ 12)} phenyl polyoxyethylene polyoxypropylene block polymer ether, polyoxyethylene bisphenyl ether, polyoxyethylene resin acid esters, polyoxyethylene fatty acid _(C 12 _{~ 18)} monoesters, polyoxyethylene fatty acid _(C 12 _{~ 18)} diesters, polyoxyethylene sorbitan fatty acid (C _{12 ~ 18)} esters, glycerol fatty acid ester ethylene oxide adducts, castor oil ethylene oxide adduct, hydrogenated castor oil ethylene oxide Side adduct, alkyl _(C 12 _{~ 18)} amine ethylene oxide adduct and a fatty acid _(C 12 _{~ 18)} amide ethylene oxide adducts.

(A-2) a polyhydric alcohol type surfactants: For example, glycerol fatty acid esters, polyglycerol fatty acid esters, pentaerythritol fatty acid esters, sorbitol fatty acid _(C 12 _{~ 18)} esters, sorbitan fatty acid _(C 12 _{~ 18)} esters, sucrose 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 methyl ester, a copolymer of acrylic acid and vinyl acetate, a copolymer of acrylic acid and maleic acid or maleic anhydride, N- methyl - fatty (C _{12 ~ 18)} sarcosinate, resin carboxylic acids such as acid and fatty acid _(C 12 _{~ 18),} and salts of these carboxylic acids.

(B-2) sulfate surfactants: for example, alkyl _(C 12 _{~ 18)} sulfates, polyoxyethylene alkyl _(C 12 _{~ 18)} ether sulfuric acid ester, polyoxyethylene (mono or di) alkyl _{(C 8} ~ ₁₂₎ phenyl ether sulfuric acid ester, polyoxyethylene (mono or di) alkyl (C 8 _{~ 12)} sulfuric acid ester of a polymer of phenyl ether, polyoxyethylene (mono-, di- or tri-) phenyl phenyl ether sulfuric acid ester, 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, Examples thereof include sulfates of a xylene polyoxypropylene block polymer, sulfated oils, sulfated fatty acid esters, sulfated fatty acids such as sulfated fatty acids and sulfated olefins, and salts of these sulfates.

(B-3) a sulfonic acid type surfactants: For example, paraffin _(C 12 _{~ 22)} sulfonic acid, alkyl _{(C 8 ~ 12)} benzenesulfonic acid, alkyl _{(C 8 ~ 12)} formalin condensates of benzenesulfonic acid, formalin condensate of cresol sulfonic acid, alpha-olefins _(C 14 _{~ 16)} sulfonic acid, dialkyl _{(C 8 ~ 12)} sulfosuccinate, lignin sulfonate, polyoxyethylene (mono or di) alkyl _{(C 8 ~ 12)} phenyl ether sulfonate, polyoxyethylene alkyl _(C 12 _{~ 18)} ether sulfosuccinic acid half ester, naphthalene sulfonic acid, (mono or di) alkyl _(C 1 _{~ 6)} naphthalenesulfonic acid formalin condensate of naphthalenesulfonic acid, (mono or di) alkyl _(C 1 _{~ 6)} Na Formalin condensates of Tarensuruhon acid, formalin condensates of creosote oil sulfonic acid, alkyl (C 8 _{~ 12)} ether disulfonic acid, Igepon T (trade name), a copolymer of polystyrene sulfonic acid and styrene sulfonic acid and methacrylic acid Sulfonic acids such as products, and salts of these sulfonic acids.

(B-4) phosphoric acid ester type surfactants: For example, alkyl _{(C 8 ~ 12)} phosphates, polyoxyethylene alkyl _(C 12 _{~ 18)} ether phosphate esters, polyoxyethylene (mono or di) alkyl _{(C 8} ~ ₁₂₎ phenyl ether phosphate ester, a polyoxyethylene (mono-, di- or tri-) phosphate esters of alkyl (C 8 _{~ 12)} phenyl ether polymer, 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, Poly Alkoxy polyoxypropylene block phosphate ester of the polymer, phosphatidylcholine, phosphoric acid esters, such as phosphatidylethanolamine imine and condensation phosphoric acid (e.g., tripolyphosphate, etc.), 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 0.1 to 10% by weight with respect to the granular material. The total content of the surfactant contained in the solid herbicidal preparation of the present invention (excluding the surfactant contained in the granular material) is usually 0.1 to 20 wt. % Range.

  Examples of binders that can be used in the solid herbicidal preparation of the present invention include dextrin (roasted dextrin and enzyme-modified dextrin, etc.), acid-decomposed starch, oxidized starch, pregelatinized starch, etherified starch (carboxymethyl starch, hydroxyalkyl starch). And cationic starch, etc.), esterified starch (acetate starch and phosphate starch, etc.), processed starch such as crosslinked starch and grafted starch, natural substances such as sodium alginate, gum arabic, gelatin, tragacanth gum, locust bean gum and casein Cellulose derivatives such as carboxymethylcellulose sodium salt, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, ethylcellulose and acetylcellulose; For example, polyvinyl methyl ether, polyethylene glycol, polypropylene glycol, polyethylene polypropylene block copolymer, polyvinyl alcohol, partially saponified vinyl acetate and vinyl ether copolymer, polyvinyl pyrrolidone, polyvinyl pyrrolidone and vinyl acetate copolymer, and polyacrylamide. Other polymers are mentioned.

  These binders can be used alone or in admixture of two or more. Moreover, the total content of the binder contained in the solid herbicidal preparation of the present invention is usually in the range of 1 to 20% by weight with respect to the solid herbicidal preparation.

Next, specific examples and test examples of the present invention will be described. However, the present invention is not limited only to these examples and test examples. The following parts all mean parts by weight. The herbicidal active ingredients used in the following examples, comparative examples and test examples are as follows.
(1) 2- (2,2-difluoroethoxy) -N- (5,8-dimethoxy [1,2,4] triazolo [1,5-c] pyrimidin-2-yl) -6- (trifluoromethyl ) Benzenesulfonamide (generic name: penox slam; hereinafter abbreviated as compound A)
(2) N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-ethoxycarbonyl-1-methylpyrazol-5-sulfonamide (generic name: pyrazosulfuron ethyl; hereinafter, compound B) Abbreviated.)
(3) S-benzyl = 1,2-dimethylpropyl (ethyl) thiocarbamate (generic name: Esprocarb; hereinafter abbreviated as compound C)

[Reference Example 1]
4.3 parts of Compound B finely pulverized to about 5 microns, 65.7 parts of H fine powder (trade name / silicon dioxide, manufactured by Keiwa Furnace Co., Ltd.) and 30 parts of petroleum-based paraffin wax (melting point 69-72 ° C.) Was melted and kneaded using a kneader at about 100 ° C. Thereafter, the mixture was cooled to about 75 ° C., extruded and granulated with a screen having a hole having a diameter of 1.2 mm, and pulverized with a pin mill to obtain a granular material having a volume median diameter of 144 μm.
[Example 1]
10 parts of Compound A finely pulverized to about 5 microns, 2.0 parts of calcium carbonate NS # 200 (trade name, volume median diameter 3.4 μm, manufactured by Nitto Flour Chemical Co., Ltd.), 58.0 parts of H fine powder and 30 parts of petroleum paraffin wax (melting point: 69 to 72 ° C.) was melted and kneaded at about 100 ° C. using a kneader. Then, it cooled to about 75 degreeC, extrusion granulated with the screen which has a hole of diameter 1.2mm, and this was grind | pulverized with the pin mill, and the granular material of this invention was obtained.

3.0 parts of the obtained granular material having a volume median diameter of 347 μm, 5.0 parts of the granular material obtained in Reference Example 1, 7.2 parts of white carbon, 1.5 parts of dioctylsulfosuccinate sodium salt, polyacrylic The mixture was mixed with 3.1 parts of an acid sodium salt, 5 parts of dextrin, 30 parts of bentonite and 33.1 parts of pyrophyllite, and further 12.1 parts of compound C was added and mixed. Furthermore, an appropriate amount of granulated water was added and kneaded, extruded and granulated with a screen having a hole with a diameter of 1.0 mm, dried at 50 ° C. for 2 hours, sized, then sieved, and then 710 to 1, A granule of the present invention containing compounds A, B and compound C having a particle size of 400 μm was obtained.
[Example 2]
In the production of the granular material of Example 1, 2.0 parts of calcium carbonate NS # 200 and 58.0 parts of H fine powder were replaced with 2.5 parts of calcium carbonate NS # 200 and 57.5 parts of H fine powder, A granule of the present invention containing compounds A, B and C was obtained in the same manner as in Example 1 except that the granular material having a diameter of 347 μm was replaced with a granular material having a volume median diameter of 368 μm.
Example 3
In the production of the granular material of Example 1, 2.0 parts of calcium carbonate NS # 200 was added to 2.0 parts of calcium carbonate NS # 3000 (trade name, volume median diameter 1.9 μm, manufactured by Nitto Flour Industry Co., Ltd.) 2.0. The particles of the present invention containing compounds A, B, and C were prepared in the same manner as in Example 1 except that the granular material having a volume median diameter of 347 μm was replaced with the granular material having a volume median diameter of 356 μm. An agent was obtained.
Example 4
Compound A 10 parts finely pulverized to about 5 microns, calcium carbonate NS # 200 (trade name, volume median diameter 3.4 μm, manufactured by Nitto Flour Chemical Co., Ltd.), silica TM-4 57.5 And 30 parts of petroleum-based paraffin wax (melting point: 69 to 72 ° C.) were melted and kneaded using a kneader at about 100 ° C. Then, it cooled to about 75 degreeC, extrusion granulated with the screen which has a hole of diameter 1.2mm, and this was grind | pulverized with the pin mill, and the granular material of this invention was obtained.

3.0 parts of the obtained granular material having a volume median diameter of 506 μm, 5.0 parts of the granular material obtained in Reference Example 1, 1.5 parts of dioctylsulfosuccinate sodium salt, 3.1 parts of polyacrylic acid sodium salt , 5 parts of dextrin, 5 parts of bentonite and 77.4 parts of pyrophyllite. Furthermore, an appropriate amount of granulated water was added and kneaded, extruded and granulated with a screen having a hole with a diameter of 1.0 mm, dried at 50 ° C. for 2 hours, sized, then sieved, and then 710 to 1, A granule of the present invention containing compounds A and B having a particle size of 400 μm was obtained.
Example 5
In the production of the granular material of Example 4, 57.5 parts of silica TM-4 was replaced with 57.5 parts of SP-7F, and the granular material with a volume median diameter of 506 μm was replaced with a granular material with a volume median diameter of 467 μm. Except for this, the same operation as in Example 4 was carried out to obtain granules of the present invention containing compounds A and B.

[Comparative Example 1]
In the production of the granular material of Example 1, 2.0 parts of calcium carbonate NS # 200, 58.0 parts of H fine powder were replaced with 60.0 parts of H fine powder, and the same operation as in Example 1 was performed. Granules containing Compound A, B and Compound C were obtained.
[Comparative Example 2]
In the production of the granular material of Example 4, 2.5 parts of calcium carbonate NS # 200 and 57.5 parts of silica TM-4 were replaced with 60.0 parts of H fine powder, and granular materials having a volume median diameter of 506 μm were contained in the volume. Granules containing compounds A and B were obtained in the same manner as in Example 4 except that the granule having a unit diameter of 266 μm was used.

[Test Example 1] Underwater dissolution test of Compound A 300 mg each of granules prepared in Examples 1 to 3 and Comparative Example 1 were put into a beaker containing 10 liters of hard water at a water temperature of 30 ° C. and 24 hours later. A part of the solution was collected from the center of the sample, and the amount of compound A eluted in water by HPLC (high performance liquid chromatograph) was quantified, and the elution rate in water was calculated by the following formula.

Elution rate in water (%) = (X / Y) x 100
X: Compound A content eluted in water Y: Compound A content in granules After 30 days at a water temperature of 20 ° C., the granules and water inside the beaker were filtered, and the residue on the filter paper was removed with tetrahydrofuran. Compound A was quantified by HPLC (high performance liquid chromatograph) in the extracted extract, and the residual ratio was calculated by the following formula. The results are shown in Table 1.

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

Table 1
――――――――――――――――――――――――――――――
Calcium carbonate content Elution rate in water Residual rate
(% By weight of granular material) (%) (%)
――――――――――――――――――――――――――――――
Example 1 2.0 54 1.8
Example 2 2.5 59 3.6
Example 3 2.0 57 1.9
Example 4 2.5 47 4.8
Example 5 2.5 50 1.3
Comparative Example 1-55 16.4
Comparative Example 2-49 26.6
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  According to the present invention, it is possible to control the release of herbicidal active ingredients, reduce the phytotoxicity to paddy rice, and improve the residual effect on weeds.

Claims (10)

  Granules containing penox slam, a herbicidal active ingredient, a hydrophobic substance that is solid at 25 ° C., calcium carbonate and an inert carrier.   The granular material according to claim 1, wherein the inert carrier is a mineral carrier.   The granular material according to claim 2, wherein the mineral carrier is silica or silicate.   The granular material according to any one of claims 1 to 3, 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 3, wherein the hydrophobic substance that is solid at 25 ° C is paraffin wax.   The granular material according to any one of claims 1 to 5, further comprising a herbicidal active ingredient other than penox slum.   A solid herbicidal preparation comprising the granular material according to any one of claims 1 to 6 and a solid carrier.   The solid herbicidal preparation according to claim 7, further comprising a herbicidal active ingredient other than penox slum.   The solid herbicidal preparation according to claim 7 or 8, further comprising an auxiliary component. The solid herbicidal preparation according to any one of claims 7 to 9, wherein the solid herbicidal preparation is a granule.