Title of Invention	"HERBICIDAL COMPOSITIONS COMPRISING DIFLUOROMETHANE SULFONANILIDE AND ONE OR MORE HERBICIDES"
Abstract	Mixed herbicidal compositions for controlling weeds, preferably in paddy field are provided. The connpositions are characterized by comprising, as active ingredients, (a) an herbicidal difluoromethane sulfonanilide, (b) at least one herbicidal compound selected from the group consisting of known herbicides as defined in claim 1 and, optionally, (c) one or more compounds selected from the group consisting of safeners.

Title of Invention

"HERBICIDAL COMPOSITIONS COMPRISING DIFLUOROMETHANE SULFONANILIDE AND ONE OR MORE HERBICIDES"

Abstract

Mixed herbicidal compositions for controlling weeds, preferably in paddy field are provided. The connpositions are characterized by comprising, as active ingredients, (a) an herbicidal difluoromethane sulfonanilide, (b) at least one herbicidal compound selected from the group consisting of known herbicides as defined in claim 1 and, optionally, (c) one or more compounds selected from the group consisting of safeners.

Full Text	Mixed herbicidal compositions Technical Field The present invention relates to mixed herbicide compositions for controlling weeds, preferably for controlling weeds in crops of useful plants, for example cereal crops such as rice, wheat, barley, rye, oat, maize, millet and plantation crops, preferably paddy field crops, such as in fields for paddy rice. More particularly, the present invention relates to mixed herbicide compositions for paddy field comprising herbicidal difluoromethane sulfonanilide and known herbicidal compounds as active ingredients. Background Art Certain difluoromethane sulfonanilides are known to exhibit a good weed controlling effect on lowland weeds (WO 2005/096818, Japanese Patent Application Laying-open No. 2006-56870). However, contrary to our expectation, when using them actually, they may sometimes exhibit an insufficient herbicidal effect and pytotoxicity is also observed for paddy rice. For the actual application, it is actually difficult to provide a single active compound having the property to respond to different uses due to existence of many undertones affecting their hertiicidal effects. Particularly, the effects of active compounds are different depending on the type of the weeds to be controlled, the conditions of areas of weed emerging and the like. Further, the development of agents exhibiting useful effects in lower dose is strongly required in consideration of cost saving in agriculture production and environmental consequences. To satisfy such requirements, herbicides are often used with other active compounds mixed to improve the properties of the herbicides. However, even use of such mixed agents may often fail to exert favorable effects because of. for example, degradation of the active compounds, antagonism of their effects and the lil Summary of the Invention Now, the inventors have found that the compositions below exhibit very good and desirable effects in terms of weed control and, particularly, phytotoxicity of crops of useful plants such as of rice in paddy field. The present invention provides mixed herbicide compositions, preferably for paddy field, characterized by comprising, as active ingredients, wherein R^ represents a fluorine atom or a chlorine atom, R^ represents hydrogen, a fluorine atom or a chlorine atom, R^ represents hydrogen or a fluorine atom, R'* represents hydrogen or methyl, R^ represents hydrogen, R^ represents hydroxyl, a fluorine atom or a chlorine atom, or R^ and R® may be taken together with the carbon atom to which they are attached to form C=0, and X represents CH or N, provided that the following cases are excluded: (i) when R^, R^, R" and R^ represent hydrogen and R^ represents hydroxyl, and (ii) R^ R^ and R' represent hydrogen and R^ and R^ are taken together with the carbon atom to which they are attached to form C=0; and (b) one or more herbicidal compounds selected from the group consisting of pretilachlor, butachlor, alachlor, metolachlor, acetochlor, clomeprop, bromobutide, benfuresate, indanofan, pyrazolate, benzofenap, pyrazoxyfen, pyraclonil, oxazidomefone, bensulfuron-methyl, azimsulfuron, imazosulfuron, pyrazosulfuron-ethyl, cyclosulfamuron, ethoxysulfuron, halosulfuron-methyl, orthosulfamuron, cinosulfuron, metosulfuron-methyl, flucetosulfuron, TH547 (Code No.), NC620 (Code No.), penoxsulam, thiobencarb, pyributicarb, molinate, dimethametryn, simetryn, cafenstrole, quinclorac, anilofos, mefenacet, fentrazamide, pentoxazone, oxadiargyl, oxadiazon, benzobicyclon, mesotrione, AVH301{Code No.), cyhalofop-butyl, metamifop, bispyribac-sodium salt, pyriftalid, pyrimisulfan, pyriminobac-methyl, chlomethoxynil, oxyfluorfen, dithiopyr, MCPA, MCPB, 2,4-D, daimuron, cumyluron, quinoclamine and clomazone; and, optionally, (c) one or more compounds selected from the group consisting of dymron (daimuron), isoxadifen(-ethyl), flurazole, fenchlorazole-ethyl, fenclorim, doquintocet-mexyl, oxabetrinil, fluxofenim, mefenpyr-diethyl, furilazole, R-29148 (Code No.), benoxacor, dichlormid and dicyclonon as a safener. According to the above composition of the invention, surprisingly, the compositions exhibit substantially higher weed controlling effect (synergetic effect) than the sum of the effects derived from the single uses of each compound contained in the composition, resulting in allowing the used concentration of each drug to be substantially reduced. Also, the optimum time of weed controlling treatment may be extended for a long time, and, for example, in wet rice culture, good weed controlling effect may be obtained in any stages at onset of weed emergence shortly after implantation and over the growing period and thus their potency may be prolonged for a long time, resulting in the effident compositions having good residual efficacy and no damages against paddy rice obtained. In the composition of the invention, preferred spedfic examples of tine compound (a) of the formula (I) include those shown in Table A below. Table A Compound No. R^ R^ R^ R^ R^ R^ X 1 F H H CHs C=0 N 2 CI H H CH3 C=0 N 3 F F H H H OH CH 4 F CI H H H OH CM 5 F H F H H OH CH 6 F F H H H OH N 7 F H H CH3 H OH N 8 F H H H H F CH 9 CI H H H H F CH 10 F F H H H F CH 11 F H H H H CI CH 12 CI H H H H CI CH 13 F F H H H CI CH 14 CI H H CH3 H OH N These compounds can be used each independently or in combination with two or more of the compounds. At the same time, in the composition of the invention, the herbicidal compound (b) is as above described, and among others, preferred examples may include (b-1) clomeprop, (b-2) bromobutide, (b-3) benzofenap, (b-4) bensulfuron methyl, (b-5) ethoxysulfuron, (b-6) fentrazamide, (b-7) AVH301, (b-8) pyrimisulfan. Above mentioned herbicidal compounds (b) can be used each independently or in combination with two or more of the compounds (b) to make the mixed composition with the compound (a) of the formula (I). The compound (c) as a safener to use in combination with the compound (a) of the formula (I) (and compound (b)) according to the invention is as above described, and among others, preferred examples may include (c-1) dymron, (c-2) mefenpyr-diethyl and (c-3) isoxadifen(-ethyl). Above mentioned compounds (c) as a safener can be used each independently or in combination of two or more of the compounds (c) to make the mixed composition with the compound (a) of the formula (I) (and compound (b)). Above mentioned herbicidal compounds (b) and above mentioned compounds (c) as a safener are described in, for example, "The Pesticide Manual 13th Ed. (British Crop Protection Council, 2003)". The compound having the code number AVH 301 is a herbicide having the chemical name 2-{2-chloro-4-mesyl-3-[(tetrahydrofuran-2-ylmethoxy)-methyl]-ben2oyl)-cyclohexan-1,3-dione, also known under the common name "tefuryltrione". In the composition of the invention, the mixture ratio of the compound (a) of the formula (I) and the herbicidal compound (b) may vary over a relatively wide range depending on the type of the composition, the application term, the applied area, the application method and the like, and in general, at least one herbicidal compounds (b) may be used in the range of 0.01 to 200 parts by weight, preferably 0.05 to 100 parts by weight per one part by weight of the compound (a) of the fQ.rmula (I). Specifically, the preferred examples of mixture ratio of the herbicidal compound (b) per one part by weight of the compound (a) of the formula (I) may include the following ratio: domeprop (b-1): 0.5 to 50 parts by weight, preferably 1 to 15 parts by weight; bromobutide(b-2): 2 to 100 parts by weight, preferably 5 to 20 parts by weight; benzofenap (b-3): 1 to 100 parts by weight, preferably 5 to 20 parts by weight; bensulfuron methyl (b-4): 0.1 to 10 parts by weight, preferably 0.2 to 2 parts by weight; ethoxysulfuron (b-5): 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight; fentrazamide (b-6): 0.5 to 50 parts by weight, preferably 1 to 10 parts by weight; AVH301(b-7): 0.5 to 50 parts by weight, preferably 1 to 10 parts by weight; pyrimisulfan (b-8): 0.1 to 10 parts by weight, preferably 0.2 to 20 parts by weight. The mixture ratio of the compound (a) of the formula (I) and the compound (c) as a safener may vary over a relatively wide range depending on the type of the composition, the application term, the applied area, the application method and the like, and in general, at least one compound (c) as a safener may be used in the range of 0.05 to 200 parts by weight, preferably 0.1 to 100 parts by weight per one part by weight of the compound (a) of the formula (I). Specifically, the preferred examples of mixture ratio of the compound (c) as a safener per one part by weight of the compound (a) of the formula (I) may include the following ratio: Dymron (c-1): 1 to 100 parts by weight, preferably 2 to 50 parts by weight; mefenpyr-diethyl (c-2): 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight; isoxadifen(-ethyl) (c-3): 0.05 to 10 parts by weight, preferably 0.5 to 5 parts by weight. The composition of the invention exhibits a potent weed controlling effect against weeds, particularly lowland weeds. Thus the composition can be used as a mixed herbicide composition for controlling weeds, especially for selectively controlling weeds in crops of useful plants such as cereal crops or plantation crops, more preferably for controlling weeds in rice crops, including rice in paddy field, particularly a selective herbicide for paddy rice. The invention thus relates to the use of the compositions according to the invention for weed control. The invention also relates to a method for controlling weeds which comprises applying the components (a) and (b) and optionally (c), simultaneously or sequentially, to the plants, part of the weed plants or the area where they are growing. The composition of the invention can be used against various weeds, preferably weeds emerging in paddy field. The example of weeds may include those described below: Dicotyledon weeds of the genera: Polygonum, Rorippa, Rotala, Undemia, Bidens, Dopatnum, Eclipta, Elatine, Gratiola, Undemia, Ludwigia, Oenanthe, Ranunculus, Deinostema and the like. Monocotyledon weeds of the genera: Echinochloa, Panicum, Poa, Cyperus, Monochoria, Fimbristylis, Sagittaha, Eleochans, Scirpus, Alisma, AnBilema, BIyxa, Eriocaulon, Potamogeton and the like. Specifically the compositions of the invention may be used, for example, against the following representative lowland weeds. Plant name in Latin Dicotyledons plants: Rotala indica Koehne Lindemia procumbens Philcox Ludwigia prostrate Roxburgh Potamogeton distinctus A.Benn Elatine tn'andra Schk Oenanthe javanica Monocotyls plants: Echinochloa oryzicola Vasing Monochoha vaginalis Presl. Eleoctiahs acicularis L Eleociiaris Kuroguwai Oliwi Cyperus diffomiis L Cyperus serotinus Rottboel Sagittaha pygmaea Miq. Alisma canaliculatum A.Br.et Bouche Scirpus juncoldes Roxburgh However, use of the composition of the invention is not intended to be limited to uses against theses weeds, and can be used against other weeds as well. The composition of the invention may be formulated into general preparation forms in uses for control of lowland weeds. The examples of the formulations may include, for example, solution, emulsion, wettable powder, suspension, powder, soluble powder, granule, suspended dense emulsion, solid Gumbo), floating granule, microcapsule in polymeric materials and the like. These formulations may be prepared according to methods known per se. For example, the formulation according to the invention may be prepared by mixing the compound (a) of the formula (I) and the herbicidal compounds (b) and/or compounds (c) together with spreading agents such as liquid diluents and/or solid diluents, and, if desired, surfactants such as emulsifiers and/or dispersants and/or foam forming agents. When water is used as a spreading agent, organic solvents, for example, may be used as an auxiliary solvent. Liquid diluents may include, for example, organic solvents such as aromatic hydrocarbons (e.g. xylene, toluene, alkylnaphthalene etc.), chlorinated aromatic or chlorinated aliphatic hydrocariDons (e.g. chlorobenzens, ethylene chlorides, methylene chlorides etc.), aliphatic hydrocariDons (e.g. cyclohexanes or paraffins (e.g. mineral oil fractions, mineral and vegetable oils)), alcohols (e.g. butanol, glycol and ethers or esters thereof etc.), ketones (e.g. acetone, methylethylketone, methylisobutylketone, cyclohexanone etc.), strong polar solvents (e.g. dimethylformamide, dimethylsulfoxide etc.) and water. Solid diluents may include, for example, ammonium salts, crushed natural minerals (e.g. kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth etc.), crushed synthetic minerals (e.g. highly-dispersive silic acid, alumina, silicate etc.). Solid camers which can be used for powders may include, for example, crushed and fractionated rocks (e.g. calcite, martDJe, pumice stone, sepiolite, dolomite etc.), synthetic granules of inorganic or organic powders, fine particles of organic materials (e.g. sawdust, coconut shells, corncob, stalk of Indian weed etc.). Emulsifiers and/or foams may include nonionic or anionic emulsifiers (e.g. polyoxyethylene fatty add esters, polyoxyethylene fatty alcohol ethers (e.g. alkylarylpolyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates etc.)), albumin hydrolyzed products and the like. Suitable dispersants include, for example, lignin sulfite waste liquor, methylcellulose and the like. Adhesive agents may be used for the formulations (powder, granule, emulsion), such as carboxymethylcellulose, natural or synthetic polymers (e.g. acacia, polyvinyl alcohols, polyvinyl acetates etc.), natural phosphatides (e.g. cephalins or lecithins), synthetic phosphatides and the like. Further, mineral oils or vegetable oils may be also used as additives. Colorants may be used, such as inorganic pigments (e.g. ferric oxide, titanic oxide, Prussian blue etc.), organic pigments (e.g. alizarin dyes, azo dyes or metallophthalocyanine dyes etc.) as well as trace elements (e.g. salts of iron, manganese, boron, cupper, cobalt, molybdenum or zinc etc.). The formulation may contain the compound (a) of the formula (I) and the herbicidal compound (b) and, optionally, the compound (c) in the range of concentration from 0.1 to 95 % by weight, preferably 0.5 to 90% by weight in total. The composition of the invention may be used as it is or in the form of a dmg formulation to control weeds, or alternatively the compounds of the composition can be tank-mixed at the point of use, and it may contain other known active compounds, particularly active compounds to be generally used, particularly used for paddy field, such as bactericides, insecticides, plant regulators, plant nutritional agents, soil conditioners and the like. Additionally, the use the compositions together with external adjuvants is also possible and may improve the performance of the compositions. The extemal adjuvants can be added to the tank-mix or applied separately to the plants or the area where they are growing. The composition of the invention may be used as it is or in the form of a drug formulation, or altematively in the application form prepared by further dilution of said drug formulation, such as ready-to-use solution, emulsion, suspension, powder, wettable powder or granule. The formulafons in these fonns may be applied to the weed plants or the area were they are growing, preferably to the paddy field, according to general methods such as watering, spraying or atomizing, dusting, granule application and the like. The composition of the invention may be applied to the weed plants or the area where they are growing before, during or after emergence of the weed plants or the crop plants. The compositions preferably may be applied to the paddy rice field before, during or after rice planting. The amount of the composition to be applied may vary within the substantial range. The application amount may be, for example, within the range of 0.01 to 5 kg/ha, preferably 0.06 to 4.5 kg/ha, in total of the compound (a) of the formula (I), the herbicidal compound (b) and, optionally, the compound (c). The beneficial effects of the compound of the invention are more specifically illustrated by means of the following examples. However the present invention should not be limited only to these examples. Examples . Biological tests and examples of formulations [Active compounds] Ingredient (a) (a-1): compound No.1 (see Table A above.) (a-2): compound No.2 (same as above) (a-3): compound No.7 (same as above) (a-4): compound No. 14 (same as above) Ingredient (b): above described (b-1) to (b-8) [Preparation of test drugs] Carrier: 5 parts by weight of acetone Surfactant; one part by weight of benzyloxy polyglycol ether. Above described carrier and surfactant are mixed with one part by weight of the active compound ((a) ingredient and (b) ingredient) and the resulting preparation is then diluted with water to obtain given amount of the test drug (the formulation). Test example 1: Test of weed control by treatment for flooded paddy field (treatment at 1 leaf-stage) [Test method] In a greenhouse, seeds or tubers of Echinochloa, Scirpusjuncoides Roxburgii, l\/lonoclioria vaginalis PresI, annual broad-leaved weeds {Lindemia procumbens Phllcox, Lindemia dubia L Penn., Rotala indica Koehne, Elatine tiiandra Schk, Ammannia multiflora Roxb.), Cyperus serotinus Rottboel and Sagittaha pygnnaea Miq. were inoculated in a 500cm^ pot filled with paddy field soil. After 2 leaf-stage of rice were transplanted, water was poured to a depth of about 3 cm. At 1.0 leaf-stage of Echinochloa oryzicola Vasing, a prescribed, diluted solution of the formulation of each active compound and each herbicidal compound in the table was separately or simultaneously applied to the surface of water. After the treatment, the water depth of 3cm was maintained, and herbicidal effect was examined after 4 weeks. In the assessment of the herbicidal effect and the phytotoxicity, 100% refers to complete death and 0% refers to no effect or no phytotoxicity. [Results] The results are shown in Table 1. In this table, ECHSS refers to Echinochloa, SCPSS refers to Scirpusjuncoides Roxburgh, MOOVP refers to Monochoria vaginalis PresI, BBBBB refers to annual broad-leaved weeds, CYPSE refers to Cypems serotinus Rottboel, SAGPY refers to Sagittaria pygmaea Miq. and ORYSP refers to transplanted rice, respectively (in the table abbreviations of the plant species to be read vertically). Table 1: Test of weed control by treatment for flooded paddy field_(treatment at 1 leaf-stage) Active Amount of Herbicidal effect (%) Phyto- ingredients effective ingredients (g ai/ha) toxicity (%) E S M B C S 0 C C 0 B Y A R H P 0 B P G Y S S V B S P S S S P B E Y P (a-1) 50 95 87 47 45 93 90 0 30 93 85 25 25 90 70 0 (a-1)+(b-7) 50+200 100 100 100 100 100 100 0 (a-1)+(b-7) 30+200 100 100 100 100 100 100 0 (b-7) 200 95 95 90 90 90 90 0 (a-1)+(b-8) 50+50 100 100 100 100 100 98 15 (a-1)+(b-8) 30+50 100 100 100 100 100 98 15 (b-8) 50 95 95 95 95 95 90 15 (a-1)+(b-1) 50+350 100 100 100 100 95 95 10 (a-1)+(b-1) 30+350 100 100 100 100 95 95 10 (b-1) 350 20 90 100 100 50 90 10 (a-1)+(b-6) 50+300 100 100 100 100 100 95 0 (a-1)+(b-6) 30+300 100 100 100 95 100 95 0 (b-6) 300 95 95 95 85 95 50 0 (a-1)+(b-5) 50+20 100 100 100 100 100 100 10 (a-1)+(b-5) 30+20 100 100 100 100 100 100 10 (b-5) 20 30 95 95 95 60 90 10 (a-1)+(b-4) 50+50 100 100 100 95 95 95 0 (a-1)+(b-4) 30+50 100 95 95 95 95 95 0 (b-4) 50 50 90 90 90 85 90 0 (a-1)+(b-3) 50+800 100 100 100 100 100 100 0 (a-1)+(b-3) 30+800 100 100 100 100 100 100 0 (b-3) 800 80 70 80 100 20 70 0 (a-1)+(b-2) 50+750 100 100 100 85 100 95 0 (a-1)+(b-2) 30+750 100 100 100 85 100 95 0 (b-2) 750 100 90 80 50 70 70 0 (a-3) 50 90 60 40 35 90 90 0 30 90 60 20 20 90 70 0 (a-3)+(b-7) 50+200 100 100 100 100 100 100 0 (a-3)+(b-7) 30+200 100 100 100 100 100 100 0 (b-7) 200 95 95 90 90 90 90 0 (a-3)+(b-1) 50+350 100 100 100 100 95 95 0 (a-3)+(b-1) 30+350 95 100 100 100 95 95 0 (b-1) 350 20 90 100 100 50 90 0 ai: active ingredient Test example 2: Test of weed control by treatment for flooded paddy field (treatment at 3 leaf-stage) [Test method] In a greenhouse, seeds or tubers of Echinochloa, Cyperus diiformis L, Scirpusjuncoides Roxburgh, l\/lonochoria vaginalis PresI, annual broad-leaved weeds {Lindemia procumbens Philcox, Lindernia dubia L Penn.,-Rotala indica Koehne, Elatine triandra Schk, Ammannia multiflora Roxb), Cyperus serotinus Rottboel and Sagittaria pygmaea Miq. were inoculated in a 500cm^ pot filled with paddy field soil. After 2 leaf-stage of rice were transplanted, water was poured to a depth of about 3 cm. At 3.0 leaf-stage of Echinochloa, a prescribed, diluted solution of the formulation of each active compound and each herbicidal compound in the table was separately or simultaneously applied to the surface of water. After the treatment, the water depth of 3cm was maintained, and herbicidal effect was examined after 4 weeks. In the assessment of the herbicidal effect and the phytotoxicity, 100% refers to complete death and 0% refers to no effect or no phytotoxicity. [Results] The results are shown in Table 2. In this table, ECHSS refers to Echinochloa, SCPSS refers to Scirpusjuncoides Roxburgh, MOOVP refers to Monochoria vaginalis PresI, BBBBB refers to annual broad-leaved weeds, CYPSE refers to Cypems serotinus Rottboel, SAGPY refers to Sagittaria pygmaea Miq. and ORYSP refers to transplanted rice, respectively (in the table abbreviations of the plant species to be read vertically). Table 2: Test of weed control by treatment for flooded paddy field (treatment at 3 leaf-stage) Active Amount of Herbicidal effect (%) Phyto- ingredients effective ingredients (9 ai/ha) toxicity (%) E S M B C S 0 C C 0 B Y A R H P 0 B P G Y S S V B S P S S S P B E Y P (a-1) 50 90 83 45 30 90 73 0 30 90 80 20 21 90 70 0 (a-1)+(b-7) 50+200 95 90 95 90 95 90 0 (a-1)+(b-7) 30+200 95 90 95 90 95 90 0 (b-7) 200 70 88 95 88 70 80 0 (a-1)+(b-8) 50+50 95 90 95 90 95 95 5 (a-1)+(b-8) 30+50 95 90 95 90 95 95 5 (b-8) 50 85 90 95 85 90 85 5 (a-1)+(b-1) 50+350 95 90 100 93 95 95 0 (a-1)+(b-1) 30+350 95 90 100 93 95 95 0 (b-1) 350 20 90 100 90 20 90 0 (a-1)+(b-6) 50+300 95 90 80 70 90 85 0 (a-1)+(b-6) 30+300 95 90 70 70 90 85 0 (b-6) 300 69 80 55 55 75 50 0 (a-1)+(b-5) 50+20 95 95 95 75 95 85 0 (a-1)+(b-5) 30+20 95 95 95 75 95 85 0 (b-5) 20 50 90 80 60 20 60 0 (a-1)+(b^) 50+50 95 90 95 90 95 90 0 (a-1)+(b-4) 30+50 95 90 95 90 95 90 0 (b-4) 50 20 85 90 90 80 80 0 (a-1)+(b-3) 50+800 95 85 80 95 90 95 0 (a-1)+(b-3) 30+800 95 80 65 95 90 95 0 (b-3) 800 10 0 50 70 0 60 0 (a-1)+(b-2) 50+750 95 90 90 50 95 90 0 (a-1)+(b-2) 30+750 95 90 90 50 95 90 0 (b-2) 750 45 80 70 30 90 40 0 (a-3) 50 90 60 13 8 90 70 0 30 90 60 10 3 90 70 0 (a-3)+(b-7) 50+200 95 90 95 90 90 95 0 (a-3)+(b-7) 30+200 95 90 95 90 90 95 0 (b-7) 200 70 88 95 80 70 80 0 (a-3)+(b-1) 50+350 95 95 100 90 90 95 0 (a-3)+(b-1) 30+350 95 95 100 90 90 95 0 (b-l) 350 20 90 100 90 20 90 0 ai: active ingredient Test example 3: Test of weed control by spray treatment (treatment at 1.5 to 3.0 leaf-stage) [Test method] In a greenhouse, seeds of rice (var.: Nipponbare and RD23) and weeds {Echinochloa oryzicola Vasing, Echinochloa cruss-galli, Leptochloa chinensis, Cypenjs diffonvis L, Cypems iria L, annual broad-leaved weeds {Monochoha vaginalis PresI, Lindemia procumbens Philcox, Lindemia dubia L. Penn., Rotala indica Koehne, Elatine thandra Schk, Ammannia multiflora Roxb. and the like)) were sown in a 500cm^ pot filled with paddy field soil and covered with soil. Water was added to the pot (a depth of 0 cm) to be a wet condition, and each test plant was grown in the greenhouse to 1.5 to 3.0 leaf-stage, after then a prescribed, diluted solution of the formulation of each active compound and each herbicidal compound in the table were separately or simultaneously sprayed over the pots with plants. At 3 days after the treatment, the water depth of 3 cm was maintained, and 4 weel [Results] The results are shown in Table 3. In this table, ECHOR refers to Echinochloa oryzicola Vasing, ECHCG refers to Echinochloa cmss-galli, LEFCH refers to Leptochloa chinensis, CYPDI refers to Cypems diffonnis L, CYPIR refers to Cypems iha L, MOOVP refers to Monochoha vaginalis PresI, BBBBB refers to annual broad-leaved weeds, ORYSW^ refers to submerged direct sown paddy (Nipponbare), ORYSW^ refers to submerged direct sown paddy (RD-23), respectively; (in the table abbreviations of the plant species to be read vertically). Table 3: Test of weed control by sprinkling treatment (treatment at 1.5 to 3.0 leaf-stage) Active Amount of Herbicidal effect (%) Phyto- ingredients effective ingredients (g ai/ha) toxicity (%) E E L C c M B 0 0 C c E Y Y 0 B R R H H F P p 0 B Y Y 0 C c D 1 V B S S R G H 1 R p B W 1 W *2 (a-1) 50 100 100 90 100 100 85 70 10 10 30 100 100 75 100 100 85 70 5 5 (a-3) 50 100 100 80 100 100 85 85 10 0 30 100 100 65 100 100 65 65 0 0 (a-2) 50 100 100 65 100 100 65 85 10 10 30 100 100 65 100 100 40 70 5 5 (a-4) 50 100 100 50 100 100 25 75 5 0 30 100 100 50 100 100 25 65 0 0 (b-5) 20 15 10 15 100 100 95 90 10 10 (a-1)+{b+5) 50+20 100 100 95 100 100 95 95 10 10 30+20 100 100 80 100 100 95 95 10 10 (a-3)+(b+5) 50+20 100 100 85 100 100 95 95 10 10 30+20 100 100 75 100 100 95 90 10 10 (a-2)+(b+5) 50+20 100 100 90 100 100 95 95 10 10 30+20 100 100 80 100 100 95 95 10 10 (a-4)+(b+5) 50+20 100 100 70 100 100 95 95 10 10 30+20 100 100 70 100 100 95 90 10 10 ai: active ingredient Formulation example 1 To the mixture of 0.5 parts by weight of the active compound (a-4), 3 parts by weight of the active compound (b-7), 33.5 parts by weight of bentonite (montmorillonite), 60 parts by weight of talc and 3 parts by weight of ligninsulfonate was added 25 parts by weight of water and the mixture is then well kneaded and made in granules of 10-40 mesh by an extrusion granulator, which are then dried at 40-50°C to obtain granules. Formulation example 2 96.5 parts by weight of clay mineral particles having particle size distribution of 0.2-2 mm are charged in a rotary mixer and the mixture is wetted uniformly by spraying 0.5 parts by weight of the active compound (a-4) and 3 parts by weight of frie active compound (b-6) in a liquid diluent under rotation and then dried at 40-50°C to obtain granules. Formulation example 3 The mixture of 0.5 parts by weight of the active compound (a-4) and 3.5 parts by weight of the active compound (b-1), 10 parts by weight of ethylene glycol, 3 parts by weight of polyoxyalkylene tristyryl phenyl ether, 10 parts by weight of xanthan gum, 0.5 parts by weight of 14% silicone oil emulsion and 72.5 parts by weight of water was stirred well and then crushed with a cmsher (DYNO-MILL, KDL type) to obtain an aqueous suspension. Formulation example 4 0.5 parts by weight of the active compound (a-4), 0.2 parts by weight of the active compound (b-5), 35 parts by weight of sodium ligninsulfonate, 19.3 parts by weight of bentonite and 45 parts by weight of calcined diatomaceous earth powder are well mixed, and after addition of water, the mixture is kneaded well, extruded with a screen of 0.3 mm and dried to obtain water-dispersible granules. Industrial availability The mixed herbicidal composition of the invention, preferably for paddy field, exhibits suitable controlling effect against various lowland weeds as well as has good residual effectiveness as shown in above examples. Claims 1. A mixed herbicidal compositbn characterized by comprising, as active ingredients, (a) a difluoromethane sulfonanilide represented by the fomiula: wherein R1 represents a fluorine atom or a chlorine atom, R1 represents hydrogen, a fluorine atom or a chlorine atom, R1 represents hydrogen or a fluorine atom, R' represents methyl, R1 represents hydrogen, R1 represents hydroxy!, a fluorine atom or a chlorine atom, or R1 and R1 may be taken together with the carixjn atom to which they are attached to form C=0, and X represents CH or N; and (b) one or more herbicidal compounds selected from the group consisting of pretilachlor, butachlor, alachlor, metolachlor, acetochlor, clomeprop, bromobutide, benfuresate, indanofan, pyrazolate, benzofenap, pyrazoxyfen, pyraclonil, oxaziclomefone, bensulfunon-methyl, azimsulfuron, imazosulluron, pyrazosulfliron-ethyl, cydosulfemuron, ethoxysulfliron, halosutfuron-methyl, orthosulfemuron, cinosulfuron, metosuHuron-methyl, flucetosulfuron, penoxsulam, thiobencarb, pyributicarb, molinate, dimethametryn, simetryn, cafenstrole, quinclorac, anilofbs, mefenacet, fentrazamide, pentoxazone, oxadiargyl, oxadiazon, t)enzobicyclon, mesotrione, tefuryltrione (Code No. AVH301), cyhalofop-butyl, metamifop, bispyribac-sodium salt, pyriftaiid, pyrimisulfan, pyriminobac-methyl, chlomethoxynil, oxyfluorfen, dithiopyr, MCPA, MCPB, 2,4-D, daimuron, cumyluron, quinodamine and clomazone. 2. The composition as claimed in daim 1, characterized by comprising additionally (c) one or more compounds selected from the group consisting of dymron (daimuron), isoxadifen(-ethyl), flurazole, fenchlorazole-ethyl, fendorim, doquintocet-mexyl, oxabetrinil, fluxofenim, mefenpyr-^iethyl, furilazole, benoxacor, dichlormid and dicydonon as a safener. 3. The composition as daimed in daim 1, characterized by comprising at least one hertjicidal compound (b) in the range of 0.01 to 200 parts by weight per one part by weight of the compound (a) of the formula (I). 4. The composition as daimed in daim 2, characterized by comprising one or more compounds (c) as a safener in the range of 0.05 to 200 parts by weight per one part by weight of the compound (a) of the formula (I). 5. The composition as daimed in daim 4, characterized by comprising at least one heriDiddal compound (b) in the range of 0.01 to 200 parts by weight per one part by weight of the compound (a) of the formula (I). 6. The composition as daimed in any of daims 1 to 5, characterized by comprising at least one herbiddal compound (b) selected from the group consisting of domeprop, bromobutide, benzofenap, bensulfuron methyl, ethoxysulfuron, fentrazamide, tetiiryltrione (AVH301) and pyrimisutfan. 7. A method for controlling weeds which comprises applying the components (a) and (b) and optionally (c) as defined in any of daims 1 to 6 simultaneously or sequentially, to the plants, part of the weed plants or the area where they are growing. 8. The method as daimed in daim 7, characterized by selectively controlling weeds in crops of useful plants. 9. The methcxl as claimed in claim 8, characterized in that the usefijl crop is a rice crop. 10. The method as claimed in claim 9, characterized in that the rice is paddy rice. 11. Use of the herbicidal composition as claimed in any of claims 1 to 6 for controlling weeds. 12. Use as claimed in claim 11 for selectively controlling weeds in rice crops.

Full Text

Mixed herbicidal compositions Technical Field
The present invention relates to mixed herbicide compositions for controlling weeds, preferably for controlling weeds in crops of useful plants, for example cereal crops such as rice, wheat, barley, rye, oat, maize, millet and plantation crops, preferably paddy field crops, such as in fields for paddy rice. More particularly, the present invention relates to mixed herbicide compositions for paddy field comprising herbicidal difluoromethane sulfonanilide and known herbicidal compounds as active ingredients.
Background Art
Certain difluoromethane sulfonanilides are known to exhibit a good weed controlling effect on lowland weeds (WO 2005/096818, Japanese Patent Application Laying-open No. 2006-56870). However, contrary to our expectation, when using them actually, they may sometimes exhibit an insufficient herbicidal effect and pytotoxicity is also observed for paddy rice. For the actual application, it is actually difficult to provide a single active compound having the property to respond to different uses due to existence of many undertones affecting their hertiicidal effects. Particularly, the effects of active compounds are different depending on the type of the weeds to be controlled, the conditions of areas of weed emerging and the like. Further, the development of agents exhibiting useful effects in lower dose is strongly required in consideration of cost saving in agriculture production and environmental consequences.
To satisfy such requirements, herbicides are often used with other active compounds mixed to improve the properties of the herbicides.
However, even use of such mixed agents may often fail to exert favorable effects because of.

for example, degradation of the active compounds, antagonism of their effects and the lil Summary of the Invention
Now, the inventors have found that the compositions below exhibit very good and desirable effects in terms of weed control and, particularly, phytotoxicity of crops of useful plants such as of rice in paddy field.
The present invention provides mixed herbicide compositions, preferably for paddy field, characterized by comprising, as active ingredients,

wherein
R^ represents a fluorine atom or a chlorine atom, R^ represents hydrogen, a fluorine atom or
a chlorine atom, R^ represents hydrogen or a fluorine atom, R'* represents hydrogen or
methyl, R^ represents hydrogen, R^ represents hydroxyl, a fluorine atom or a chlorine atom,
or R^ and R® may be taken together with the carbon atom to which they are attached to form
C=0, and X represents CH or N,
provided that the following cases are excluded:
(i) when R^, R^, R" and R^ represent hydrogen and R^ represents hydroxyl,
and
(ii) R^ R^ and R' represent hydrogen and R^ and R^ are taken together with
the carbon atom to which they are attached to form C=0; and

(b) one or more herbicidal compounds selected from the group consisting of pretilachlor, butachlor, alachlor, metolachlor, acetochlor, clomeprop, bromobutide, benfuresate, indanofan, pyrazolate, benzofenap, pyrazoxyfen, pyraclonil, oxazidomefone, bensulfuron-methyl, azimsulfuron, imazosulfuron, pyrazosulfuron-ethyl, cyclosulfamuron, ethoxysulfuron, halosulfuron-methyl, orthosulfamuron, cinosulfuron, metosulfuron-methyl, flucetosulfuron, TH547 (Code No.), NC620 (Code No.), penoxsulam, thiobencarb, pyributicarb, molinate, dimethametryn, simetryn, cafenstrole, quinclorac, anilofos, mefenacet, fentrazamide, pentoxazone, oxadiargyl, oxadiazon, benzobicyclon, mesotrione, AVH301{Code No.), cyhalofop-butyl, metamifop, bispyribac-sodium salt, pyriftalid, pyrimisulfan, pyriminobac-methyl, chlomethoxynil, oxyfluorfen, dithiopyr, MCPA, MCPB, 2,4-D, daimuron, cumyluron, quinoclamine and clomazone; and, optionally,
(c) one or more compounds selected from the group consisting of dymron (daimuron), isoxadifen(-ethyl), flurazole, fenchlorazole-ethyl, fenclorim, doquintocet-mexyl, oxabetrinil, fluxofenim, mefenpyr-diethyl, furilazole, R-29148 (Code No.), benoxacor, dichlormid and dicyclonon as a safener.
According to the above composition of the invention, surprisingly, the compositions exhibit substantially higher weed controlling effect (synergetic effect) than the sum of the effects derived from the single uses of each compound contained in the composition, resulting in allowing the used concentration of each drug to be substantially reduced. Also, the optimum time of weed controlling treatment may be extended for a long time, and, for example, in wet rice culture, good weed controlling effect may be obtained in any stages at onset of weed emergence shortly after implantation and over the growing period and thus their potency may be prolonged for a long time, resulting in the effident compositions having good residual efficacy and no damages against paddy rice obtained.
In the composition of the invention, preferred spedfic examples of tine compound (a) of the formula (I) include those shown in Table A below.

Table A

Compound No. R^ R^ R^ R^ R^ R*^ X
1 F H H CHs C=0 N
2 CI H H CH3 C=0 N
3 F F H H H OH CH
4 F CI H H H OH CM
5 F H F H H OH CH
6 F F H H H OH N
7 F H H CH3 H OH N
8 F H H H H F CH
9 CI H H H H F CH
10 F F H H H F CH
11 F H H H H CI CH
12 CI H H H H CI CH
13 F F H H H CI CH
14 CI H H CH3 H OH N
These compounds can be used each independently or in combination with two or more of the compounds.
At the same time, in the composition of the invention, the herbicidal compound (b) is as above described, and among others, preferred examples may include (b-1) clomeprop, (b-2) bromobutide, (b-3) benzofenap, (b-4) bensulfuron methyl, (b-5) ethoxysulfuron, (b-6) fentrazamide, (b-7) AVH301, (b-8) pyrimisulfan.
Above mentioned herbicidal compounds (b) can be used each independently or in combination with two or more of the compounds (b) to make the mixed composition with the compound (a) of the formula (I).
The compound (c) as a safener to use in combination with the compound (a) of the formula (I) (and compound (b)) according to the invention is as above described, and among others, preferred examples may include (c-1) dymron, (c-2) mefenpyr-diethyl and (c-3) isoxadifen(-ethyl).

Above mentioned compounds (c) as a safener can be used each independently or in combination of two or more of the compounds (c) to make the mixed composition with the compound (a) of the formula (I) (and compound (b)).
Above mentioned herbicidal compounds (b) and above mentioned compounds (c) as a
safener are described in, for example, "The Pesticide Manual 13th Ed. (British Crop
Protection Council, 2003)".
The compound having the code number AVH 301 is a herbicide having the chemical name
2-{2-chloro-4-mesyl-3-[(tetrahydrofuran-2-ylmethoxy)-methyl]-ben2oyl)-cyclohexan-1,3-dione,
also known under the common name "tefuryltrione".
In the composition of the invention, the mixture ratio of the compound (a) of the formula (I) and the herbicidal compound (b) may vary over a relatively wide range depending on the type of the composition, the application term, the applied area, the application method and the like, and in general, at least one herbicidal compounds (b) may be used in the range of 0.01 to 200 parts by weight, preferably 0.05 to 100 parts by weight per one part by weight of the compound (a) of the fQ.rmula (I). Specifically, the preferred examples of mixture ratio of the herbicidal compound (b) per one part by weight of the compound (a) of the formula (I) may include the following ratio:
domeprop (b-1): 0.5 to 50 parts by weight, preferably 1 to 15 parts by weight; bromobutide(b-2): 2 to 100 parts by weight, preferably 5 to 20 parts by weight; benzofenap (b-3): 1 to 100 parts by weight, preferably 5 to 20 parts by weight; bensulfuron methyl (b-4): 0.1 to 10 parts by weight, preferably 0.2 to 2 parts by weight; ethoxysulfuron (b-5): 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight; fentrazamide (b-6): 0.5 to 50 parts by weight, preferably 1 to 10 parts by weight; AVH301(b-7): 0.5 to 50 parts by weight, preferably 1 to 10 parts by weight; pyrimisulfan (b-8): 0.1 to 10 parts by weight, preferably 0.2 to 20 parts by weight.
The mixture ratio of the compound (a) of the formula (I) and the compound (c) as a safener

may vary over a relatively wide range depending on the type of the composition, the application term, the applied area, the application method and the like, and in general, at least one compound (c) as a safener may be used in the range of 0.05 to 200 parts by weight, preferably 0.1 to 100 parts by weight per one part by weight of the compound (a) of the formula (I). Specifically, the preferred examples of mixture ratio of the compound (c) as a safener per one part by weight of the compound (a) of the formula (I) may include the following ratio:
Dymron (c-1): 1 to 100 parts by weight, preferably 2 to 50 parts by weight; mefenpyr-diethyl (c-2): 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight; isoxadifen(-ethyl) (c-3): 0.05 to 10 parts by weight, preferably 0.5 to 5 parts by weight.
The composition of the invention exhibits a potent weed controlling effect against weeds, particularly lowland weeds. Thus the composition can be used as a mixed herbicide composition for controlling weeds, especially for selectively controlling weeds in crops of useful plants such as cereal crops or plantation crops, more preferably for controlling weeds in rice crops, including rice in paddy field, particularly a selective herbicide for paddy rice. The invention thus relates to the use of the compositions according to the invention for weed control. The invention also relates to a method for controlling weeds which comprises applying the components (a) and (b) and optionally (c), simultaneously or sequentially, to the plants, part of the weed plants or the area where they are growing.
The composition of the invention can be used against various weeds, preferably weeds emerging in paddy field. The example of weeds may include those described below:
Dicotyledon weeds of the genera: Polygonum, Rorippa, Rotala, Undemia, Bidens, Dopatnum, Eclipta, Elatine, Gratiola, Undemia, Ludwigia, Oenanthe, Ranunculus, Deinostema and the like.
Monocotyledon weeds of the genera: Echinochloa, Panicum, Poa, Cyperus, Monochoria,

Fimbristylis, Sagittaha, Eleochans, Scirpus, Alisma, AnBilema, BIyxa, Eriocaulon, Potamogeton and the like.
Specifically the compositions of the invention may be used, for example, against the following representative lowland weeds.
Plant name in Latin Dicotyledons plants: Rotala indica Koehne Lindemia procumbens Philcox Ludwigia prostrate Roxburgh Potamogeton distinctus A.Benn Elatine tn'andra Schk Oenanthe javanica Monocotyls plants: Echinochloa oryzicola Vasing Monochoha vaginalis Presl. Eleoctiahs acicularis L Eleociiaris Kuroguwai Oliwi Cyperus diffomiis L Cyperus serotinus Rottboel Sagittaha pygmaea Miq. Alisma canaliculatum A.Br.et Bouche Scirpus juncoldes Roxburgh
However, use of the composition of the invention is not intended to be limited to uses against theses weeds, and can be used against other weeds as well.
The composition of the invention may be formulated into general preparation forms in uses for control of lowland weeds. The examples of the formulations may include, for example,

solution, emulsion, wettable powder, suspension, powder, soluble powder, granule, suspended dense emulsion, solid Gumbo), floating granule, microcapsule in polymeric materials and the like.
These formulations may be prepared according to methods known per se. For example, the formulation according to the invention may be prepared by mixing the compound (a) of the formula (I) and the herbicidal compounds (b) and/or compounds (c) together with spreading agents such as liquid diluents and/or solid diluents, and, if desired, surfactants such as emulsifiers and/or dispersants and/or foam forming agents.
When water is used as a spreading agent, organic solvents, for example, may be used as an auxiliary solvent. Liquid diluents may include, for example, organic solvents such as aromatic hydrocarbons (e.g. xylene, toluene, alkylnaphthalene etc.), chlorinated aromatic or chlorinated aliphatic hydrocariDons (e.g. chlorobenzens, ethylene chlorides, methylene chlorides etc.), aliphatic hydrocariDons (e.g. cyclohexanes or paraffins (e.g. mineral oil fractions, mineral and vegetable oils)), alcohols (e.g. butanol, glycol and ethers or esters thereof etc.), ketones (e.g. acetone, methylethylketone, methylisobutylketone, cyclohexanone etc.), strong polar solvents (e.g. dimethylformamide, dimethylsulfoxide etc.) and water.
Solid diluents may include, for example, ammonium salts, crushed natural minerals (e.g. kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth etc.), crushed synthetic minerals (e.g. highly-dispersive silic acid, alumina, silicate etc.). Solid camers which can be used for powders may include, for example, crushed and fractionated rocks (e.g. calcite, martDJe, pumice stone, sepiolite, dolomite etc.), synthetic granules of inorganic or organic powders, fine particles of organic materials (e.g. sawdust, coconut shells, corncob, stalk of Indian weed etc.).
Emulsifiers and/or foams may include nonionic or anionic emulsifiers (e.g. polyoxyethylene fatty add esters, polyoxyethylene fatty alcohol ethers (e.g. alkylarylpolyglycol ethers, alkyl

sulfonates, alkyl sulfates, aryl sulfonates etc.)), albumin hydrolyzed products and the like.
Suitable dispersants include, for example, lignin sulfite waste liquor, methylcellulose and the
like.
Adhesive agents may be used for the formulations (powder, granule, emulsion), such as
carboxymethylcellulose, natural or synthetic polymers (e.g. acacia, polyvinyl alcohols,
polyvinyl acetates etc.), natural phosphatides (e.g. cephalins or lecithins), synthetic
phosphatides and the like. Further, mineral oils or vegetable oils may be also used as
additives.
Colorants may be used, such as inorganic pigments (e.g. ferric oxide, titanic oxide, Prussian
blue etc.), organic pigments (e.g. alizarin dyes, azo dyes or metallophthalocyanine dyes etc.)
as well as trace elements (e.g. salts of iron, manganese, boron, cupper, cobalt, molybdenum
or zinc etc.).
The formulation may contain the compound (a) of the formula (I) and the herbicidal compound (b) and, optionally, the compound (c) in the range of concentration from 0.1 to 95 % by weight, preferably 0.5 to 90% by weight in total.
The composition of the invention may be used as it is or in the form of a dmg formulation to control weeds, or alternatively the compounds of the composition can be tank-mixed at the point of use, and it may contain other known active compounds, particularly active compounds to be generally used, particularly used for paddy field, such as bactericides, insecticides, plant regulators, plant nutritional agents, soil conditioners and the like. Additionally, the use the compositions together with external adjuvants is also possible and may improve the performance of the compositions. The extemal adjuvants can be added to the tank-mix or applied separately to the plants or the area where they are growing.
The composition of the invention may be used as it is or in the form of a drug formulation, or altematively in the application form prepared by further dilution of said drug formulation, such as ready-to-use solution, emulsion, suspension, powder, wettable powder or granule. The

formulafons in these fonns may be applied to the weed plants or the area were they are growing, preferably to the paddy field, according to general methods such as watering, spraying or atomizing, dusting, granule application and the like.
The composition of the invention may be applied to the weed plants or the area where they are growing before, during or after emergence of the weed plants or the crop plants. The compositions preferably may be applied to the paddy rice field before, during or after rice planting. The amount of the composition to be applied may vary within the substantial range. The application amount may be, for example, within the range of 0.01 to 5 kg/ha, preferably 0.06 to 4.5 kg/ha, in total of the compound (a) of the formula (I), the herbicidal compound (b) and, optionally, the compound (c).
The beneficial effects of the compound of the invention are more specifically illustrated by means of the following examples. However the present invention should not be limited only to these examples.
Examples .
Biological tests and examples of formulations
[Active compounds] Ingredient (a)
(a-1): compound No.1 (see Table A above.)
(a-2): compound No.2 (same as above)
(a-3): compound No.7 (same as above)
(a-4): compound No. 14 (same as above) Ingredient (b): above described (b-1) to (b-8)
[Preparation of test drugs]
Carrier: 5 parts by weight of acetone

Surfactant; one part by weight of benzyloxy polyglycol ether.
Above described carrier and surfactant are mixed with one part by weight of the active compound ((a) ingredient and (b) ingredient) and the resulting preparation is then diluted with water to obtain given amount of the test drug (the formulation).
Test example 1: Test of weed control by treatment for flooded paddy field (treatment at 1 leaf-stage)
[Test method]
In a greenhouse, seeds or tubers of Echinochloa, Scirpusjuncoides Roxburgii, l\/lonoclioria vaginalis PresI, annual broad-leaved weeds {Lindemia procumbens Phllcox, Lindemia dubia L Penn., Rotala indica Koehne, Elatine tiiandra Schk, Ammannia multiflora Roxb.), Cyperus serotinus Rottboel and Sagittaha pygnnaea Miq. were inoculated in a 500cm^ pot filled with paddy field soil. After 2 leaf-stage of rice were transplanted, water was poured to a depth of about 3 cm. At 1.0 leaf-stage of Echinochloa oryzicola Vasing, a prescribed, diluted solution of the formulation of each active compound and each herbicidal compound in the table was separately or simultaneously applied to the surface of water. After the treatment, the water depth of 3cm was maintained, and herbicidal effect was examined after 4 weeks. In the assessment of the herbicidal effect and the phytotoxicity, 100% refers to complete death and 0% refers to no effect or no phytotoxicity.
[Results]
The results are shown in Table 1. In this table, ECHSS refers to Echinochloa, SCPSS refers to Scirpusjuncoides Roxburgh, MOOVP refers to Monochoria vaginalis PresI, BBBBB refers to annual broad-leaved weeds, CYPSE refers to Cypems serotinus Rottboel, SAGPY refers to Sagittaria pygmaea Miq. and ORYSP refers to transplanted rice, respectively (in the table abbreviations of the plant species to be read vertically).

Table 1: Test of weed control by treatment for flooded paddy field_(treatment at 1 leaf-stage)

Active Amount of Herbicidal effect (%) Phyto-
ingredients effective ingredients (g ai/ha) toxicity (%)

E S M B C S 0
C C 0 B Y A R
H P 0 B P G Y
S S V B S P S
S S P B E Y P
(a-1) 50 95 87 47 45 93 90 0
30 93 85 25 25 90 70 0
(a-1)+(b-7) 50+200 100 100 100 100 100 100 0
(a-1)+(b-7) 30+200 100 100 100 100 100 100 0
(b-7) 200 95 95 90 90 90 90 0
(a-1)+(b-8) 50+50 100 100 100 100 100 98 15
(a-1)+(b-8) 30+50 100 100 100 100 100 98 15
(b-8) 50 95 95 95 95 95 90 15
(a-1)+(b-1) 50+350 100 100 100 100 95 95 10
(a-1)+(b-1) 30+350 100 100 100 100 95 95 10
(b-1) 350 20 90 100 100 50 90 10
(a-1)+(b-6) 50+300 100 100 100 100 100 95 0
(a-1)+(b-6) 30+300 100 100 100 95 100 95 0
(b-6) 300 95 95 95 85 95 50 0
(a-1)+(b-5) 50+20 100 100 100 100 100 100 10
(a-1)+(b-5) 30+20 100 100 100 100 100 100 10
(b-5) 20 30 95 95 95 60 90 10
(a-1)+(b-4) 50+50 100 100 100 95 95 95 0
(a-1)+(b-4) 30+50 100 95 95 95 95 95 0
(b-4) 50 50 90 90 90 85 90 0
(a-1)+(b-3) 50+800 100 100 100 100 100 100 0
(a-1)+(b-3) 30+800 100 100 100 100 100 100 0
(b-3) 800 80 70 80 100 20 70 0
(a-1)+(b-2) 50+750 100 100 100 85 100 95 0
(a-1)+(b-2) 30+750 100 100 100 85 100 95 0
(b-2) 750 100 90 80 50 70 70 0
(a-3) 50 90 60 40 35 90 90 0
30 90 60 20 20 90 70 0
(a-3)+(b-7) 50+200 100 100 100 100 100 100 0
(a-3)+(b-7) 30+200 100 100 100 100 100 100 0
(b-7) 200 95 95 90 90 90 90 0
(a-3)+(b-1) 50+350 100 100 100 100 95 95 0
(a-3)+(b-1) 30+350 95 100 100 100 95 95 0
(b-1) 350 20 90 100 100 50 90 0
ai: active ingredient
Test example 2: Test of weed control by treatment for flooded paddy field (treatment at 3

leaf-stage) [Test method]
In a greenhouse, seeds or tubers of Echinochloa, Cyperus diiformis L, Scirpusjuncoides Roxburgh, l\/lonochoria vaginalis PresI, annual broad-leaved weeds {Lindemia procumbens Philcox, Lindernia dubia L Penn.,-Rotala indica Koehne, Elatine triandra Schk, Ammannia multiflora Roxb), Cyperus serotinus Rottboel and Sagittaria pygmaea Miq. were inoculated in a 500cm^ pot filled with paddy field soil. After 2 leaf-stage of rice were transplanted, water was poured to a depth of about 3 cm. At 3.0 leaf-stage of Echinochloa, a prescribed, diluted solution of the formulation of each active compound and each herbicidal compound in the table was separately or simultaneously applied to the surface of water. After the treatment, the water depth of 3cm was maintained, and herbicidal effect was examined after 4 weeks. In the assessment of the herbicidal effect and the phytotoxicity, 100% refers to complete death and 0% refers to no effect or no phytotoxicity.
[Results]
The results are shown in Table 2. In this table, ECHSS refers to Echinochloa, SCPSS refers to Scirpusjuncoides Roxburgh, MOOVP refers to Monochoria vaginalis PresI, BBBBB refers to annual broad-leaved weeds, CYPSE refers to Cypems serotinus Rottboel, SAGPY refers to Sagittaria pygmaea Miq. and ORYSP refers to transplanted rice, respectively (in the table abbreviations of the plant species to be read vertically).

Table 2: Test of weed control by treatment for flooded paddy field (treatment at 3 leaf-stage)

Active Amount of Herbicidal effect (%) Phyto-
ingredients effective ingredients (9 ai/ha) toxicity (%)

E S M B C S 0
C C 0 B Y A R
H P 0 B P G Y
S S V B S P S
S S P B E Y P
(a-1) 50 90 83 45 30 90 73 0
30 90 80 20 21 90 70 0
(a-1)+(b-7) 50+200 95 90 95 90 95 90 0
(a-1)+(b-7) 30+200 95 90 95 90 95 90 0
(b-7) 200 70 88 95 88 70 80 0
(a-1)+(b-8) 50+50 95 90 95 90 95 95 5
(a-1)+(b-8) 30+50 95 90 95 90 95 95 5
(b-8) 50 85 90 95 85 90 85 5
(a-1)+(b-1) 50+350 95 90 100 93 95 95 0
(a-1)+(b-1) 30+350 95 90 100 93 95 95 0
(b-1) 350 20 90 100 90 20 90 0
(a-1)+(b-6) 50+300 95 90 80 70 90 85 0
(a-1)+(b-6) 30+300 95 90 70 70 90 85 0
(b-6) 300 69 80 55 55 75 50 0
(a-1)+(b-5) 50+20 95 95 95 75 95 85 0
(a-1)+(b-5) 30+20 95 95 95 75 95 85 0
(b-5) 20 50 90 80 60 20 60 0
(a-1)+(b^) 50+50 95 90 95 90 95 90 0
(a-1)+(b-4) 30+50 95 90 95 90 95 90 0
(b-4) 50 20 85 90 90 80 80 0
(a-1)+(b-3) 50+800 95 85 80 95 90 95 0
(a-1)+(b-3) 30+800 95 80 65 95 90 95 0
(b-3) 800 10 0 50 70 0 60 0
(a-1)+(b-2) 50+750 95 90 90 50 95 90 0
(a-1)+(b-2) 30+750 95 90 90 50 95 90 0
(b-2) 750 45 80 70 30 90 40 0
(a-3) 50 90 60 13 8 90 70 0
30 90 60 10 3 90 70 0
(a-3)+(b-7) 50+200 95 90 95 90 90 95 0
(a-3)+(b-7) 30+200 95 90 95 90 90 95 0
(b-7) 200 70 88 95 80 70 80 0
(a-3)+(b-1) 50+350 95 95 100 90 90 95 0
(a-3)+(b-1) 30+350 95 95 100 90 90 95 0
(b-l) 350 20 90 100 90 20 90 0
ai: active ingredient

Test example 3: Test of weed control by spray treatment (treatment at 1.5 to 3.0 leaf-stage)
[Test method]
In a greenhouse, seeds of rice (var.: Nipponbare and RD23) and weeds {Echinochloa oryzicola Vasing, Echinochloa cruss-galli, Leptochloa chinensis, Cypenjs diffonvis L, Cypems iria L, annual broad-leaved weeds {Monochoha vaginalis PresI, Lindemia procumbens Philcox, Lindemia dubia L. Penn., Rotala indica Koehne, Elatine thandra Schk, Ammannia multiflora Roxb. and the like)) were sown in a 500cm^ pot filled with paddy field soil and covered with soil. Water was added to the pot (a depth of 0 cm) to be a wet condition, and each test plant was grown in the greenhouse to 1.5 to 3.0 leaf-stage, after then a prescribed, diluted solution of the formulation of each active compound and each herbicidal compound in the table were separately or simultaneously sprayed over the pots with plants. At 3 days after the treatment, the water depth of 3 cm was maintained, and 4 weel [Results]
The results are shown in Table 3. In this table, ECHOR refers to Echinochloa oryzicola
Vasing, ECHCG refers to Echinochloa cmss-galli, LEFCH refers to Leptochloa chinensis,
CYPDI refers to Cypems diffonnis L, CYPIR refers to Cypems iha L, MOOVP refers to
Monochoha vaginalis PresI, BBBBB refers to annual broad-leaved weeds, ORYSW*^ refers
to submerged direct sown paddy (Nipponbare), ORYSW*^ refers to submerged direct sown
paddy (RD-23), respectively;
(in the table abbreviations of the plant species to be read vertically).

Table 3: Test of weed control by sprinkling treatment (treatment at 1.5 to 3.0 leaf-stage)

Active Amount of Herbicidal effect (%) Phyto-
ingredients effective ingredients (g ai/ha) toxicity (%)

E E L C c M B 0 0
C c E Y Y 0 B R R
H H F P p 0 B Y Y
0 C c D 1 V B S S
R G H 1 R p B W
*1 W
*2
(a-1) 50 100 100 90 100 100 85 70 10 10
30 100 100 75 100 100 85 70 5 5
(a-3) 50 100 100 80 100 100 85 85 10 0
30 100 100 65 100 100 65 65 0 0
(a-2) 50 100 100 65 100 100 65 85 10 10
30 100 100 65 100 100 40 70 5 5
(a-4) 50 100 100 50 100 100 25 75 5 0
30 100 100 50 100 100 25 65 0 0
(b-5) 20 15 10 15 100 100 95 90 10 10
(a-1)+{b+5) 50+20 100 100 95 100 100 95 95 10 10
30+20 100 100 80 100 100 95 95 10 10
(a-3)+(b+5) 50+20 100 100 85 100 100 95 95 10 10
30+20 100 100 75 100 100 95 90 10 10
(a-2)+(b+5) 50+20 100 100 90 100 100 95 95 10 10
30+20 100 100 80 100 100 95 95 10 10
(a-4)+(b+5) 50+20 100 100 70 100 100 95 95 10 10
30+20 100 100 70 100 100 95 90 10 10
ai: active ingredient
Formulation example 1
To the mixture of 0.5 parts by weight of the active compound (a-4), 3 parts by weight of the active compound (b-7), 33.5 parts by weight of bentonite (montmorillonite), 60 parts by weight of talc and 3 parts by weight of ligninsulfonate was added 25 parts by weight of water and the mixture is then well kneaded and made in granules of 10-40 mesh by an extrusion granulator, which are then dried at 40-50°C to obtain granules.
Formulation example 2
96.5 parts by weight of clay mineral particles having particle size distribution of 0.2-2 mm are
charged in a rotary mixer and the mixture is wetted uniformly by spraying 0.5 parts by weight

of the active compound (a-4) and 3 parts by weight of frie active compound (b-6) in a liquid diluent under rotation and then dried at 40-50°C to obtain granules.
Formulation example 3
The mixture of 0.5 parts by weight of the active compound (a-4) and 3.5 parts by weight of the active compound (b-1), 10 parts by weight of ethylene glycol, 3 parts by weight of polyoxyalkylene tristyryl phenyl ether, 10 parts by weight of xanthan gum, 0.5 parts by weight of 14% silicone oil emulsion and 72.5 parts by weight of water was stirred well and then crushed with a cmsher (DYNO-MILL, KDL type) to obtain an aqueous suspension.
Formulation example 4
0.5 parts by weight of the active compound (a-4), 0.2 parts by weight of the active compound (b-5), 35 parts by weight of sodium ligninsulfonate, 19.3 parts by weight of bentonite and 45 parts by weight of calcined diatomaceous earth powder are well mixed, and after addition of water, the mixture is kneaded well, extruded with a screen of 0.3 mm and dried to obtain water-dispersible granules.
Industrial availability
The mixed herbicidal composition of the invention, preferably for paddy field, exhibits suitable controlling effect against various lowland weeds as well as has good residual effectiveness as shown in above examples.

Claims
1. A mixed herbicidal compositbn characterized by comprising, as active ingredients,
(a) a difluoromethane sulfonanilide represented by the fomiula:

wherein
R1 represents a fluorine atom or a chlorine atom, R1 represents hydrogen, a
fluorine atom or a chlorine atom, R1 represents hydrogen or a fluorine atom, R' represents methyl, R1 represents hydrogen, R1 represents hydroxy!, a fluorine atom or a chlorine atom, or R1 and R1 may be taken together with the carixjn atom to which they are attached to form C=0, and X represents CH or N;
and
(b) one or more herbicidal compounds selected from the group consisting of
pretilachlor, butachlor, alachlor, metolachlor, acetochlor, clomeprop, bromobutide,
benfuresate, indanofan, pyrazolate, benzofenap, pyrazoxyfen, pyraclonil, oxaziclomefone,
bensulfunon-methyl, azimsulfuron, imazosulluron, pyrazosulfliron-ethyl, cydosulfemuron,
ethoxysulfliron, halosutfuron-methyl, orthosulfemuron, cinosulfuron, metosuHuron-methyl,
flucetosulfuron, penoxsulam, thiobencarb, pyributicarb, molinate, dimethametryn, simetryn,
cafenstrole, quinclorac, anilofbs, mefenacet, fentrazamide, pentoxazone, oxadiargyl,
oxadiazon, t)enzobicyclon, mesotrione, tefuryltrione (Code No. AVH301), cyhalofop-butyl,
metamifop, bispyribac-sodium salt, pyriftaiid, pyrimisulfan, pyriminobac-methyl,
chlomethoxynil, oxyfluorfen, dithiopyr, MCPA, MCPB, 2,4-D, daimuron, cumyluron,
quinodamine and clomazone.

2. The composition as claimed in daim 1, characterized by comprising additionally (c) one or more compounds selected from the group consisting of dymron (daimuron), isoxadifen(-ethyl), flurazole, fenchlorazole-ethyl, fendorim, doquintocet-mexyl, oxabetrinil, fluxofenim, mefenpyr-^iethyl, furilazole, benoxacor, dichlormid and dicydonon as a safener.
3. The composition as daimed in daim 1, characterized by comprising at least one hertjicidal compound (b) in the range of 0.01 to 200 parts by weight per one part by weight of the compound (a) of the formula (I).
4. The composition as daimed in daim 2, characterized by comprising one or more compounds (c) as a safener in the range of 0.05 to 200 parts by weight per one part by weight of the compound (a) of the formula (I).
5. The composition as daimed in daim 4, characterized by comprising at least one heriDiddal compound (b) in the range of 0.01 to 200 parts by weight per one part by weight of the compound (a) of the formula (I).
6. The composition as daimed in any of daims 1 to 5, characterized by comprising at least one herbiddal compound (b) selected from the group consisting of domeprop, bromobutide, benzofenap, bensulfuron methyl, ethoxysulfuron, fentrazamide, tetiiryltrione (AVH301) and pyrimisutfan.
7. A method for controlling weeds which comprises applying the components (a) and (b) and optionally (c) as defined in any of daims 1 to 6 simultaneously or sequentially, to the plants, part of the weed plants or the area where they are growing.
8. The method as daimed in daim 7, characterized by selectively controlling weeds in crops of useful plants.

9. The methcxl as claimed in claim 8, characterized in that the usefijl crop is a rice
crop.
10. The method as claimed in claim 9, characterized in that the rice is paddy rice.
11. Use of the herbicidal composition as claimed in any of claims 1 to 6 for controlling
weeds.
12. Use as claimed in claim 11 for selectively controlling weeds in rice crops.

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Patent Number

279949

Indian Patent Application Number

4804/CHENP/2009

PG Journal Number

06/2017

Publication Date

10-Feb-2017

Grant Date

06-Feb-2017

Date of Filing

14-Aug-2009

Name of Patentee

Bayer Intellectual Property GmbH

Applicant Address

Alfred-Nobel-Strasse 10, 40789 Monheim am Rhein, Germany

Inventors:

#	Inventor's Name	Inventor's Address
1	ENDO, KEIJI	4233-4, AMI, AMI-MACHI, INASHIKI-GUN, IBARAKI 300-0331
2	SHIRAKURA, SHINICHI	2-6-3, EKIHIGASHI-DORI, OYAMA-SHI, TOCHIGI 323-0022
3	NAKAMURA, SHIN	4-4-8, JOTO, OYAMA-SHI, TOCHIGI 323-0807

PCT International Classification Number

A01N 43/88

PCT International Application Number

PCT/EP08/00870

PCT International Filing date

2008-02-05

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2007-37531	2007-02-19	Japan