AU2007234111B2 - Herbicidal compositions as dispersions comprising diflufenican and flurtamone - Google Patents

Abstract

The present invention relates to formulations in the form of aqueous dispersions comprising diflufenican and flurtamone and a mixture of anionic surfactants from the group of the naphthalenesulphonates or from the group of the condensates of naphthalenesulphonates with formaldehyde, nonionic surfactants from the group of the di- and tri-block copolymers of alkylene oxides, and polybasic organic acids, to which, if appropriate, thickeners, further agrochemical active substances and further customary adjuvants and additives may be added. In addition, the present invention relates to herbicidal compositions comprising, as components, diflufenican, flurtamone and flufenacet. The aqueous dispersions and herbicidal compositions are useful in the crop protection sector.

Description

WO 2007/112834 PCT/EP2007/002219 Description Herbicidal compositions as dispersions comprising diflufenican and flurtamone 5 The present invention relates to the field of formulations comprising plant protection agents. The invention relates in particular to - formulations in the form of aqueous dispersions which comprise at least the herbicidal active substances diflufenican and flurtamone and which are stable on storage after exchange of alkylphenol polyethoxylates in the formulations and 0 - herbicidal compositions which, in addition to the herbicidal active substances diflufenican and flurtamone, additionally comprise the active substance flufenacet. Herbicidal active substances are generally not used in their pure form. Depending on 5 the field of application and the type of application, and on physical, chemical and biological parameters, the active substances are used as a mixture with conventional auxiliaries and additives as active substance formulation. The combinations with additional active substances, in order to broaden the spectrum of activities and/or to protect crop plants (e.g., through safeners, antidotes), are also known. 0 Formulations of herbicidal active substances should generally exhibit high chemical and physical stability, good applicability and user friendliness, and a broad biological action with high selectivity. 5 Aqueous dispersions for herbicidal active substances are known, inter alia, from EP-A-0 514 768 (US 5 707 926) or EP-A-0 592 880 (US 5 376 621). The herbicidal active substances diflufenican and flurtamone are used alone and as a mixture (tank mix, coformulation), inter alia, as aqueous suspension concentrates 0 (SC), for example with the trade name Carat@ 350 SC. A disadvantage of the formulations underlying this or similar products is the fact that they comprise surfactants from the group consisting of the alkylphenol polyethoxylates (APE) WO 2007/112834 2 PCT/EP2007/002219 which, because of their delayed biodegradability, are classified as doubtful. On attempting to manufacture APE-free formulations for this active substance mixture, undesirable effects were produced, such as flocculation, agglomeration and/or crystal growth, resulting in satisfactory storage stability no longer being guaranteed. 5 Although the abovementioned mixtures of the herbicidal active substances diflufenican and flurtamone show a good herbicidal action, there always exists a broad scope for improvements. Thus, the users desire, with regard to the amounts which have to be expended, more flexible solutions with the same to increased 0 activity, for example in the combating of harmful grasses, such as wind grass and Poa species. The object of the present invention was, - to make available an aqueous formulation comprising plant protection agents, which comprises at least the active substances diflufenican and flurtamone, which is free from alkylphenol polyethoxylates and which exhibits a satisfactory 5 stability on storage, and - to discover a herbicidal composition which exhibits the abovementioned improvements to the herbicidal active substance mixture of diflufenican and flurtamone. 0 This object is achieved by - aqueous dispersions comprising diflufenican and flurtamone and a "surfactant/organic acid mixture" consisting of anionic surfactants from the group consisting of naphthalenesulfonates or from the group consisting of the condensation products of naphthalenesulfonates with formaldehyde, nonionic 5 surfactants from the group consisting of the di- and triblock copolymers of alkylene oxides and polybasic organic acids, to which also thickeners, additional agrochemical active substances, preferably flufenacet, and additional standard auxiliaries and additives can optionally be added, and - herbicidal compositions which, in addition to the herbicidal active substances 0 diflufenican and flurtamone, additionally comprise the active substance flufenacet.

WO 2007/112834 3 PCT/EP2007/002219 The present invention accordingly relates to aqueous dispersions which comprise a) the herbicidal active substances diflufenican and flurtamone, b) one or more anionic surfactants from the group consisting of the naphthalenesulfonates or from the group consisting of the condensation products of 5 naphthalenesulfonates with formaldehyde, c) one or more nonionic surfactants from the group consisting of the di- and triblock copolymers of alkylene oxides, d) one or more polybasic organic acids, e) optionally one or more thickeners, 10 f) optionally one or more agrochemical active substances other than component a), preferably the herbicidal active substance flufenacet, g) optionally one or more additional standard auxiliaries and additives, and water. 15 The dispersions according to the invention show an outstanding stability on storage. They are stable on storage at ambient temperature for at least 2 years and show, in this connection, no undesirable effects, such as, e.g., crystal growth. 20 In a preferred embodiment, these dispersions comprise a) 0.1 to 50% of diflufenican and 0.1 to 50% of flurtamone, b) 0.1 to 10% of one or more anionic surfactants from the group consisting of the naphthalenesulfonates or from the group consisting of the condensation products of naphthalenesulfonates with formaldehyde, 25 c) 0.1 to 20% of one or more nonionic surfactants from the group consisting of the di and triblock copolymers of alkylene oxides, d) 0.05 to 10% of one or more polybasic organic acids, e) 0 to 5% of one or more thickeners, f) 0 to 50% of one or more agrochemical active substances other than component a), 30 preferably 0.1 to 50% of flufenacet, g) 0 to 20% of one or more additional standard auxiliaries and additives, WO 2007/112834 4 PCT/EP2007/002219 and 20 to 70% of water. A particularly preferred embodiment is composed of dispersions according to the 5 invention in which are present a) 0.5 to 20% of diflufenican and 0.5 to 30% of flurtamone, b) 0.2 to 5% of one or more anionic surfactants from the group consisting of the naphthalenesulfonates or from the group consisting of the condensation products of naphthalenesulfonates with formaldehyde, 0 c) 0.5 to 14% of one or more nonionic surfactants from the group consisting of the di and triblock copolymers of alkylene oxides, d) 0.1 to 5% of one or more polybasic organic acids, e) 0.05 to 2.5% of one or more thickeners, f) 0 to 40% of one or more agrochemical active substances other than component a), 5 preferably 0.5 to 22% of flufenacet, g) 0 to 15% of one or more additional standard auxiliaries and additives, and 20 to 60% of water. 0 A very particularly preferred embodiment is composed of dispersions according to the invention in which are present a) 2 to 16% of diflufenican and 4 to 22% of flurtamone, b) 0.3 to 1.5% of one or more anionic surfactants from the group consisting of the naphthalenesulfonates or from the group consisting of the condensation products of 5 naphthalenesulfonates with formaldehyde, c) 1 to 10% of one or more nonionic surfactants from the group consisting of the di and triblock copolymers of alkylene oxides, d) 0.2 to 2% of one or more polybasic organic acids, e) 0.075 to 1.5% of one or more thickeners, 0 f) 4 to 22% of flufenacet, g) 0 to 15% of one or more additional standard auxiliaries and additives, and WO 2007/112834 5 PCT/EP2007/002219 30 to 55% of water. All percentage values are, here and throughout the description, percentages by weight (% by weight) and refer, unless otherwise defined, to the relative weight of the 5 respective component, based on the total weight of the formulation. The herbicidal active substances a) diflufenican (251) and flurtamone (392) are, as individual substances or as a mixture, e.g., known from "The Pesticide Manual", 13th edition (2003), The British Crop Protection Council (note: index number in 0 brackets). The proportion of these active substances in the dispersions according to the invention (component a)) can, for diflufenican, be 0.1 - 50% by weight, preferably 0.5 - 20% by weight, particularly preferably 2 - 16% by weight, and, for flurtamone, be 0.1 - 50% by weight, preferably 0.5 - 30% by weight, particularly preferably 4 - 22% 5 by weight. Examples of anionic surfactants b) from the group consisting of the naphthalenesulfonates are Galory@ MT 800 (sodium dibutylnaphthalenesulfonic acid) and Nekal@ BX (alkylnaphthalenesulfonate). Examples of anionic surfactants 0 b) from the group consisting of the condensation products of naphthalenesulfonates with formaldehyde are Galoryl@ DT 201 (naphthalenesulfonic acid hydroxy polymer with formaldehyde and methylphenol sodium salt), Galoryl@ DT 250 (condensation product of phenol- and naphthalenesulfonates) and Reserve@ C (condensation product of phenol- and naphthalenesulfonates). Preference is given to 5 naphthalenesulfonates 1,2-substituted by dibutyl or diisobutyl, such as, e.g., products such as Galoryl@ MT 800 (CFPI-Nufarm) and Nekal@ BX (BASF). The proportion of the anionic surfactants in the dispersions according to the invention (component b)) can be 0.1 - 10% by weight, preferably 0.2 - 5% by weight, particularly preferably 0.3 - 1.5% by weight. 0 Possible nonionic surfactants c) from the group consisting of the di- and triblock copolymers of alkylene oxides are, e.g., compounds synthesized on the basis of WO 2007/112834 6 PCT/EP2007/002219 ethylene and propylene oxide with average molar masses between 200 and 10 000 g/mol, preferably 1000 to 4000 g/mol, the proportion by weight of the polyethoxylated block varying between 10 and 80%, such as, e.g., Synperonic@ PE series (Uniqema), Pluronic@ PE series (BASF), VOP® 32 or Genapol@ PF series 5 (Clariant). Products such as Pluronic@ PE 10500 are preferred, for example. The proportion of the nonionic surfactants in the dispersions according to the invention (component c)) can be 0.1 - 20% by weight, preferably 0.5 - 14% by weight, particularly preferably 1 - 10% by weight. 0 Examples of polybasic organic acids d) are, e.g., citric acid, tartaric acid, succinic acid, maleic acid, fumaric acid, and the like. Citric acid is preferred. The proportion of the polybasic organic acids in the dispersions according to the invention (component d)) can be 0.05 - 10% by weight, preferably 0.1 - 5% by weight, particularly preferably 0.2 - 2% by weight. 5 Suitable thickeners e) optionally added are, for example: 1) modified natural silicates, such as chemically modified bentonites, hectorites, attapulgites, montmorillonites, smectites or other silicate minerals, such as Bentone@ (Elementis), Attagel@ (Engelhard), Agsorb@ (Oil-Dri Corporation) or 0 Hectorite@ (Akzo Nobel), 2) thickeners based on synthetic polymers, such as thickeners of the Thixin@ or Thixatrol@ series (Elementis) and also Rhodopol@ (Rhodia) and Kelzan@ S (Kelco Corp.), 3) synthetic silicates, such as silicates of the Sipernat@, Aerosil@ or Durosil@ series 5 (Degussa), of the CAB-0-SIL@ series (Cabot) or of the Van Gel series (R.T. Vanderbilt). Organic- and/or inorganic-based thickeners are preferred, such as, e.g., products such as Bentone@ EW (Elementis) and Rhodopol@ 23 (Rhodia). The proportion in the dispersions according to the invention of thickeners optionally 0 added (component e)) can be up to 5% by weight, preferably 0.05 - 2.5% by weight, particularly preferably 0.075 - 1.5% by weight.

WO 2007/112834 7 PCT/EP2007/002219 Herbicides, fungicides, insecticides, plant growth regulators, safeners and the like are suitable as agrochemical active substances f) other than component a) optionally added. These active substances are, for example, known from "The Pesticide Manual", 13th edition (2003), The British Crop Protection Council (note: index 5 number in brackets). Preference is given to herbicides, such as flufenacet (369), loxynil (467), bromoxynil (95), bifenox (75), aclonifen (8), trifluralin (836), clodinafop-propargyl (156), oxadiazon (600), oxadiargyl (599), pyraflufen-ethyl (691), carbetamide (117), terbuthylazine (775), active substances based on phenylurea, such as isoproturon 0 (475), diuron (281), linuron (489), active substances based on phenoxyacetic or phenoxypropionic and phenoxybutyric acids, such as MCPA (499), mecoprop (503), mecoprop-P (504), 2,4-D (211), fluazifop-butyl (361), diclofop-methyl (238), fenoxaprop-P-ethyl (339), and also in each case the derivatives thereof in the form of acids or esters. The herbicidal active substances flufenacet and isoproturon are 5 particularly preferred and flufenacet is very particularly preferred. The proportion in the dispersions according to the invention of agrochemical active substances other than component a) (component f)) optionally added can be up to 50% by weight, preferably up to 40% by weight, particularly preferably up to 30% by weight. In the case of the herbicidal active substance flufenacet, the proportion can 0 be 0.1 - 50% by weight, preferably 0.5 - 22% by weight, particularly preferably 4 22% by weight. The additional standard auxiliaries and additives g) optionally added are, for example, antifoaming agents, antifreeze agents, structuring agents, preservatives, 5 antioxidants, colorants, aromatic principles, wetting agents, anti-drift agents, deposit builders, penetrating agents (adjuvants), fertilizers and additional surfactants other than the components b) and c). Suitable antifoaming agents are surface-active compounds based on silicone or 0 silane, such as the Tegopren@ products (Goldschmidt), the SE@ products (Wacker), and also the Bevaloid®, Rhodorsil@ and Silcolapse@ products (Rhodia, Dow Corning, Reliance, GE, Bayer). SE@ (Wacker), Rhodorsil@ and Silcolapse@ products WO 2007/112834 8 PCT/EP2007/002219 (Rhodia) are preferred and, e.g., products such as Silcolapse@ 5020 are particularly preferred. Suitable antifreeze agents are those from the group consisting of ureas, diols and polyols, such as ethylene glycol and propylene glycol, preferably propylene glycol. 5 Suitable preservatives are, e.g., products such as Acticide@ MBS (biocide, Thor Chemie). Suitable antioxidants, colorants, aromatic principles, wetting agents, anti-drift agents, deposit builders, penetrating agents (adjuvants) and fertilizers are known to a person skilled in the art. Additional surfactants other than the components b) and c) which 0 are suitable are, for example, emulsifiers and dispersants. Possible emulsifiers and dispersants are, e.g., nonionic emulsifiers and dispersants, e.g.: 1) polyalkoxylated, preferably polyethoxylated, saturated and unsaturated aliphatic 5 alcohols, - with 8 to 24 carbon atoms in the alkyl radical, which is derived from the corresponding fatty acids or from petrochemical products, and - with 1 to 100, preferably 2 to 50, ethylene oxide units (EO), the free hydroxyl group optionally being alkoxylated, and 0 - which, e.g., are available commercially as Genapol@ X and Genapol@ 0 series (Clariant), Crovol@ M series (Croda) or Lutensol@ series (BASF); 2) polyalkoxylated, preferably polyethoxylated, hydroxyfatty acids or glycerides comprising hydroxyfatty acids, such as, e.g., ricinine or castor oil, with a degree of ethoxylation of between 10 and 80, preferably 25 to 40, such as, e.g., 5 Emulsogen@ EL series (Clariant) or Agnique@ CSO series (Cognis); 3) polyalkoxylated, preferably polyethoxylated, sorbitan esters, such as, e.g., Atplus@ 309 F (Uniqema) or Alkamuls@ series (Rhodia). Preferred nonionic emulsifiers and dispersants are, e.g., polyethoxylated alcohols and polyethoxylated triglycerides comprising hydroxyfatty acids. 0 Ionic emulsifiers and dispersants are also possible, e.g.: 1) polyalkoxylated, preferably polyethoxylated, emulsifiers/dispersants which are WO 2007/112834 9 PCT/EP2007/002219 sonically modified, e.g. by conversion of the terminal free hydroxyl functional group of the polyethylene oxide block to give a sulfate or phosphate ester (e.g., as alkali metal and alkaline earth metal salts), such as, e.g., Genapol@ LRO or Dispersogen 3618 (Clariant), Emulphor@ (BASF) or Crafol@ AP (Cognis); 5 2) alkali metal and alkaline earth metal salts of alkylarylsulfonic acids with a linear or branched alkyl chain, such as phenylsulfonate CA or phenylsulfonate CAL (Clariant), Atlox@ 3377BM (ICI), Empiphos@ TM series (Huntsman); 3) polyelectrolytes, such as lignosulfonates, polystyrenesulfonate or sulfonated unsaturated or aromatic polymers (polystyrenes, polybutadienes or polyterpenes), 0 such as Tamol@ series (BASF), Morwet@ D425 (Witco), Kraftsperse@ series (Westvaco), Borresperse@ series (Borregard). Preferred ionic emulsifiers/dispersants are, e.g., salts of alkylarylsulfonic acids and lignosulfonates. 5 The proportion in the dispersions according to the invention of the additional standard auxiliaries and additives (component g)) optionally added can be up to 20% by weight, preferably up to 15% by weight. The proportion of the component water in the dispersions according to the invention 0 can be 20 - 70% by weight, preferably 20 - 60% by weight, particularly preferably 30 - 55% by weight. The abovementioned formulation auxiliaries of the components b), c), d), e) and g) are known to a person skilled in the art and/or are described, for example, in: 5 Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell, N.J.; H.v. Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, N.Y.; C. Marsden, "Solvents Guide", 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood, N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. o Pub[. Co. Inc., N.Y., 1964; Sch6nfeldt, "GrenzfIschenaktive Athylenoxidaddukte" [Surface-active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart, 1976; Winnacker-KOchler, "Chemische Technologie" [Chemical Technology], Volume 7, WO 2007/112834 10 PCT/EP2007/002219 4th edition, C. Hanser Verlag, Munich, 1986. The combination of the active substances diflufenican, flurtamone and flufenacet is novel per se and accordingly another subject matter of the invention is a herbicidal 5 composition comprising, as components, the active substances diflufenican, flurtamone and flufenacet. These active substances form the herbicidal composition and are used for this either alone and/or as partial or total mixture (tank mix, coformulation), simultaneously or sequentially. 0 This active substance mixture (3-component combination) is very highly suitable as herbicidal composition and solves the problems posed. In addition, it can be advantageous to add additional plant protection agents, alone or mixtures thereof, to this 3-component combination. Mention may in particular be made here of additional herbicides, safeners, plant growth regulators, insecticides, acaricides, nematicides, 5 fungicides and bactericides, and also substances which are effective as adjuvants. Examples of herbicides are, e.g., from the groups consisting of ALS inhibitors (acetolactate synthetase inhibitors, such as sulfonylureas), carbamates, thiocarbamates, haloacetanilides, phenylpyrazolines (such as pinoxaden), 0 substituted phenoxy-, naphthoxy- and phenoxyphenoxycarboxylic acid derivatives and also heteroaryloxyphenoxyalkanecarboxylic acid derivatives, such as quinolyloxy-, quinoxalyloxy-, pyridyloxy-, benzoxazolyloxy- and benzothiazolyloxyphenoxyalkanecarboxylic acid esters, cyclohexanedione derivatives, imidazolinones, phosphorus-comprising herbicides (e.g., of glufosinate 5 type or of glyphosate type), pyrimidinyloxypyridinecarboxylic acid derivatives, pyrimidyloxybenzoic acid derivatives, triazolopyrimidinesulfonamide derivatives and also S-(N-aryl-N-alkylcarbamoylmethyl)dithiophosphoric acid esters, ureas and also hydroxybenzonitriles. o Examples of safeners are, e.g., 4-dichloroacetyl-1-oxa-4-azaspiro[4.5]decane (AD-67), 1-dichloroacetyl-hexahydro-3,3,8a-trimethylpyrrolo[1,2-a]pyrimidin-6(2H)- WO 2007/112834 11 PCT/EP2007/002219 one (dicyclonone, BAS-145138), 4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4 benzoxazine (benoxacor), cloquintocet, (5-chloroquinolin-8-yloxy)acetic acid 1-methylhexyl ester (cloquintocet-mexyl), a-(cyanomethoxyimino)phenylacetonitrile (cyometrinil), 2,2-dichloro-N-(2-oxo-2-(2-propenylamino)ethyl)-N-(2-propenyl) 5 acetamide (DKA-24), 2,2-dichloro-N,N-di(2-propenyl)acetamide (dichlormid), N-(4-methylphenyl)-N'-(1-methyl-1 -phenylethyl)urea (Dymron), 4,6-dichloro-2-phenyl pyrimidine (fenclorim), 1-(2,4-dichlorophenyl)-5-trichloromethyl-1 H-1,2,4-triazole-3 carboxylic acid ethyl ester (fenchlorazole-ethyl), 2-chloro-4-(trifluoromethyl)thiazole 5-carboxylic acid phenylmethyl ester (flurazole), 4-chloro-N-((1,3-dioxolan 0 2-yl)methoxy)-a-trifluoroacetophenonoxime (fluxofenim), 3-dichloroacetyl 5-(2-furanyl)-2,2-dimethyloxazolidine (furilazole, MON-13900), ethyl 4,5-dihydro 5,5-diphenyl-3-isoxazolecarboxylate (isoxadifen-ethyl), diethyl 1-(2,4-dichlorophenyl)-4,5-dihydro-5-methyl-1 H-pyrazole-3,5-dicarboxylate (mefenpyr-diethyl), 2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191), 5 1,8-naphthalic acid anhydride, a-((1,3-dioxolan-2-yl)methoxyimino)phenylacetonitrile (oxabetrinil), 2,2-dichloro-N-((1,3-dioxolan-2-yl)methyl)-N-(2-propenyl)acetamide (PPG-1292), 3-dichloroacetyl-2,2-dimethyloxazolidine (R-28725), 3-dichloroacetyl 2,2,5-trimethyloxazolidine (R-29148), 1-(2-chlorophenyl)-5-phenyl-1 H-pyrazole 3-carboxylic acid methyl ester, 4-cyclopropylaminocarbonyl-N-(2-methoxybenzoyl) 0 benzenesulfonamide (cyprosulfamide), 4-isopropylaminocarbonyl-N (2-methoxybenzoyl)benzenesulfonamide and N-(2-methoxybenzoyl) 4-[(methylaminocarbonyl)amino]benzenesulfonamide. Examples of insecticides are, e.g., from the groups consisting of carbamates, 5 organophosphates, pyrethroids and chloronicotinyls (such as acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid, thiamethoxam). Examples of fungicides are, e.g., from the groups consisting of ergosterol 0 biosynthesis inhibitors (such as fenhexamid, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazol, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, WO 2007/112834 12 PCT/EP2007/002219 flusilazole, flutriafol, furconazole, furconazole-cis, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazol, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, voriconazole, imazalil, imazalil sulfate, 5 oxpoconazole, fenarimol, flurprimidol, nuarimol, pyrifenox, triforine, pefurazoate, prochloraz, triflumizole, viniconazole, aldimorph, dodemorph, dodemorph acetate, fenpropimorph, tridemorph, fenpropidin, spiroxamine, naftifine, pyributicarb, terbinafine) and respiratory chain inhibitors (e.g., complex 111, such as azoxystrobin, cyazofamid, dimoxystrobin, enestrobin, famoxadone, fenamidone, fluoxastrobin, 0 kresoxim-methyl, metominostrobin, orysastrobin, pyraclostrobin, picoxystrobin, trifloxystrobin). For application, the dispersions or herbicidal compositions according to the invention can be diluted in the normal way, e.g. using water. It can be advantageous to add, to 5 spray mixtures obtained, additional agrochemical active substances (e.g., tank mix components in the form of appropriate formulations) and/or auxiliaries and additives standard for application, e.g. self-emulsifying oils, such as vegetable oils or liquid paraffins, and/or fertilizers. The present invention also accordingly relates to those herbicidal compositions based on the dispersions according to the invention. 0 The dispersions or herbicidal compositions according to the invention exhibit an outstanding herbicidal activity against a broad spectrum of economically important harmful monocotyledonous and dicotyledonous plants. Even perennial weeds which sprout from rhizomes, root stocks or other perennial organs and which are difficult to 5 combat are successfully included. In this connection, the compositions can be applied, e.g., in the presowing, preemergence or postemergence method. Specifically, mention may be made, by way of example, of some representatives of the mono- and dicotyledonous weed flora which can be controlled by the dispersions or herbicidal compositions according to the invention, without the designation 0 resulting in a limitation to certain species. In the case of the monocotyledonous weed species, Apera spica-venti, Avena spp., WO 2007/112834 13 PCT/EP2007/002219 Alopecurus spp., Brachiaria spp., Digitaria spp., Lolium spp., Echinochloa spp., Panicum spp., Phalaris spp., Poa spp., Setaria spp. and also Bromus spp., such as Bromus catharticus, Bromus secalinus, Bromus erectus, Bromus tectorum and Bromus japonicus, and Cyperus species from the group of the annuals and, in the 5 case of the perennial species, Agropyron, Cynodon, Imperata and also Sorghum and even perennial Cyperus species, e.g., are successfully included. With dicotyledonous weed species, the spectrum of activity applies to species such as, e.g., Abutilon spp., Amaranthus spp., Chenopodium spp., Chrysanthemum spp., o Galium spp., such as Galium aparine, lpomoea spp., Kochia spp., Lamium spp., Matricaria spp., Pharbitis spp., Polygonum spp., Sida spp., Sinapis spp., Solanum spp., Stellaria spp., Veronica spp. and Viola spp., Xanthium spp., in the case of the annuals, and Convolvulus, Cirsium, Rumex and Artemisia with the perennial weeds. 5 Harmful plants occurring under the specific cultivation conditions in rice, such as, e.g., Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus, are likewise combated in an outstanding fashion by the dispersions or herbicidal compositions according to the invention. 0 If the dispersions or herbicidal compositions according to the invention are applied to the soil surface before germination, then either the emergence of the weed seedlings is completely prevented or the weeds grow until they have reached the cotyledon stage but then their growth ceases and finally, after 3 to 4 weeks have elapsed, they completely die. 5 On application of the dispersions or herbicidal compositions according to the invention to the green parts of the plants in the postemergence method, a drastic halt in growth likewise occurs very quickly after the treatment and the weed plants stay in the growth stage present at the time of application or completely die after a certain 0 time, so that in this way competition by weeds, which is harmful for the crop plants, is eliminated very early and with lasting effect.

WO 2007/112834 14 PCT/EP2007/002219 The dispersions or herbicidal compositions according to the invention are distinguished by a rapidly commencing and longlasting herbicidal action. The resistance to rain of the active substances in the combinations according to the invention is generally good. A particular advantage is crucially that the dosages of 5 herbicidal compounds which are used in the herbicidal compositions and which are effective can be adjusted to such a low value that their soil action is optimally low. Accordingly, not only is their use finally possible in sensitive crops but groundwater contamination is virtually avoided. A substantial reduction in the amount of the active substances which has to be expended is made possible by the active substance 0 combination according to the invention. The properties and advantages mentioned are of use in the practical combating of weeds in order to keep agricultural crops free from undesirable competing plants and accordingly to safeguard and/or to increase the yields in terms of quality and 5 quantity. The technical standard is, with regard to the properties described, clearly exceeded by these new dispersions or compositions. Although the dispersions or herbicidal compositions according to the invention exhibit an outstanding herbicidal activity with regard to mono- and dicotyledonous 0 weeds, crop plants of economically important crops, e.g. dicotyledonous crops, such as soya, cotton, rape, sugar beet, or gramineous crops, such as wheat, barley, rye, oats, millet, rice or corn, are only insignificantly damaged or completely undamaged. The dispersions or the components of the herbicidal composition according to the invention, for these reasons, are very well suited to the selective combating of 5 undesirable plant growth in agriculturally useful plants or in ornamental plants. In addition, the dispersions according to the invention or the components of the herbicidal composition exhibit outstanding growth-regulatory properties in crop plants. They intervene in a regulatory manner in the plants' metabolism and can 0 accordingly be used for the selective influencing of plant contents and for making it easier to harvest, such as, e.g., by controlling desiccation and stunted growth. Furthermore, they are also suitable for the general control and inhibition of WO 2007/112834 15 PCT/EP2007/002219 undesirable vegetative growth, without in this connection killing the plants. Inhibition of vegetative growth plays a major role in many mono- and dicotyledonous crops since lodging can be reduced or completely prevented through this. 5 Because of their herbicidal and plant-growth-regulatory properties, the dispersions or the components of the herbicidal composition according to the invention can also be used for combating harmful plants in crops of known genetically modified plants or genetically modified plants still to be developed. The transgenic plants are generally distinguished by particular advantageous properties, for example by resistance to 0 certain pesticides, mainly certain herbicides, resistance to plant diseases or causative agents of plant diseases, such as certain insects or microorganisms, such as fungi, bacteria or viruses. Other particular properties relate, e.g., to the harvested crops with regard to amount, quality, storability, composition and special ingredients. Thus, transgenic plants with increased starch content or modified quality of the 5 starch or those with a different fatty acid composition of the harvested crops are known. Preference is given to the use of the dispersions or herbicidal compositions according to the invention in economically important transgenic crops of useful and 0 ornamental plants, e.g. of gramineous crops, such as wheat, barley, rye, oats, millet, rice and corn, or also crops of sugar beet, cotton, soya, rape, potato, tomato, peas and other kinds of vegetable. Preferably, the dispersions or compositions according to the invention can be used as herbicides in crops of useful plants which are resistant to the phytotoxic effects of the herbicides or which have been made 5 resistant by genetic engineering. When the dispersions or herbicidal compositions according to the invention are used in transgenic crops, effects often occur, in addition to the effects with regard to harmful plants to be observed in other crops, which are specific for the application in 0 the respective transgenic crop, for example a modified or specially broadened weed spectrum which can be combated, modified amounts to be expended which can be used for the application, preferably good ability to be combined with the herbicides to WO 2007/112834 16 PCT/EP2007/002219 which the transgenic crop is resistant, and influencing of growth and yield of the transgenic crop plants. Another subject matter of the present invention is furthermore a process for 5 combating undesirable plant growth, preferably in crop plants, such as cereals (e.g., wheat, barley, rye, oats, rice, corn, millet), sugar beet, sugar cane, rape, cotton and soya, particularly preferably in monocotyledonous crops, such as cereals, e.g. wheat, barley, rye, oats, hybrids thereof, such as triticale, rice, corn and millet, one or more dispersions or the components of the herbicidal composition according to the 0 invention being applied to the harmful plants, plant parts, plant seeds or the area on which the plants are growing, e.g. the area under cultivation. The crop plants can also be modified by genetic engineering or obtained by mutation selection and are preferably tolerant to acetolactate synthase (ALS) inhibitors. 5 The dispersions according to the invention can be prepared according to processes known to a person skilled in the art; for example according to Houben-Weil, by wet milling by means of bead mills (see: Winnacker-KOchler, "Chemische Technologie" [Chemical Technology], Volume 7, 4th edition, C. Hanser Verlag, Munich, 1986; 0 Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying Handbook", 3rd Ed., G. Goodwin Ltd., London, 1979). A uniform particle distribution of the relevant active substances is optionally advantageous in this connection, in order additionally to further prevent crystal growth and flocculation. 5 Examples of aqueous dispersions according to the invention are found in the following table.

WO 2007/112834 17 PCT/EP2007/002219 The terms used in the following examples have the following meaning: diflufenican = common name (BSI, draft E-ISO, (m) draft F-ISO); IUPAC name: 2',4'-difluoro-2-(a,a,a-trifluoro-m 5 tolyloxy)nicotinanilide (Bayer CropScience) flurtamone = common name (BSI, ANSI, draft E-ISO); IUPAC name: (RS)-5-methylamino-2-phenyl-4-(a,a,a-trifluoro-m tolyl)furan-3(2H)-one (Bayer CropScience) Nekal@ BX = alkylnaphthalenesulfonic acid sodium salt (BASF) 0 Pluronic@ PE 10500 = propylene oxide/ethylene oxide (PO/EO) block polymer (BASF) citric acid = polybasic organic acid Bentone@ EW modified sheet silicate (Elementis) Rhodopol@ 23 = xanthan derivate (Rhodia) 5 flufenacet = common name (BSI, pa ISO); IUPAC name: 4'-fluoro-N isopropyl-2-(5-trifluoromethyl- 1,3,4-thiad iazol-2 yloxy)acetanilide (Bayer CropScience) Silcolapse@ 5020 = silicone antifoaming agent (Rhodia) propylene glycol = antifreeze agent 0 Acticide@ MBS = preservative (biocide, Thor Chemie) Preparation of an aqueous dispersion: For the preparation of the examples mentioned in table 1, water is first placed in a vessel. Diflufenican and flurtamone and also the additional constituents of the 5 formulation are subsequently added with stirring. The sequence of the addition of the additional components is generally unimportant. A wet milling, for example by means of a bead mill, is optionally carried out subsequently.

WO 2007/112834 18 PCT/EP2007/002219 Table 1 (figures follow in percentage by weight) Component Example No. 1 2 3 4 5 6 7 a Diflufenican 10.7 10.5 10.3 15.7 8 4 12 a Flurtamone 10.7 10.5 14.8 11 20 8 12 b Nekal@ BX 0.5 0.7 0.8 0.6 0.4 0.6 1 Pluronic@ PE c 10500 5 6 6.3 7 7 7 6 d Citric acid 0.5 0.6 0.7 0.7 0.4 0.6 1 e Bentone@ EW 0.1 0.1 0.1 0.2 0.1 0.1 0.1 e Rhodopol@ 23 0.1 0.2 0.1 0.1 0.2 0.2 0.1 f Flufenacet 10.7 15.3 10.3 11 8 22 12 g Silcolapse@ 5020 1 0.8 1.2 1 1.5 1 1 g Propylene glycol 8 7 7.5 6 10 9 8 g Acticide@ MBS 0.2 0.1 0.2 0.2 0.2 0.2 0.2 Water 52.5 48.2 47.7 46.5 44.2 47.3 46.6 Total: 100 100 100 100 100 100 100 Stability of the aqueous dispersion: The dispersions according to the invention of examples 1 to 7 exhibit an excellent 5 stability on storage. They are stable at ambient temperature for at least 2 years and at 50*C for at least 3 months without visible change. Herbicidal action: 0 1. The herbicidal action of the dispersions according to the invention with regard to all important harmful plants achieves at least the level of the APE-comprising dispersions or herbicidal compositions comprising diflufenican and flurtamone known from the state of the art (as individual substances and in a mixture with one another and/or additional agrochemical active substances). 5 2. The action of the herbicidal compositions according to the invention comprising the active substances diflufenican, flurtamone and flufenacet as 19 components (3-component combination) corresponds to the requirements and accordingly solves the problem posed (inter alia, provision of more flexible solutions, with regard to the amounts which have to be expended, with the same to increased activity). 5 In field trials, it was established, inter alia, that, by the use of the 3-component combination, the amounts of application products necessary in the combating of harmful grasses, such as wind grass and Poa species, could be reduced by up to 40%, in comparison with the 2-component combination (diflufenican and 10 flurtamone active substance mixture). In addition, with the same amount expended, a greater activity of the 3-component combination compared with the 2-component combination was established. Comprises/comprising and grammatical variations thereof when used in this 15 specification are to be taken to specify the presence of stated features, integers, steps or components or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.

Claims (22)

1. An aqueous dispersions which comprises: a) the herbicidal active substances diflufenican and flurtamone, 5 b) one or more anionic surfactants from the group consisting of the naphthalenesulfonates or from the group consisting of the condensation products of naphthalenesulfonates with formaldehyde, c) one or more nonionic surfactants from the group consisting of the di and triblock copolymers of alkylene oxides, 10 d) one or more polybasic organic acids, and water.

2. The dispersion as claimed in claim 1, which additionally comprises: 15 e) one or more thickeners.

3. The dispersion as claimed in claim 1 or claim 2, which additionally comprises: f) one or more agrochemical active substance(s) other than 20 component a).

4. The dispersion as claimed in claim 3, wherein the one or more agrochemical active substances is the herbicidal active substance flufenacet. 25

5. The dispersion as claimed in any one of claims 1 to 4, which additionally comprises: g) one or more further conventional auxiliary substances and additives.

6. The dispersion as claimed in any one of claims 1 to 4, comprising: 30 a) 0.1 to 50% of diflufenican and 0.1 to 50% of flurtamone, b) 0.1 to 10% of one or more anionic surfactants from the group consisting of the naphthalenesulfonates or from the group consisting of the condensation products of naphthalenesulfonates with formaldehyde, 21 c) 0.1 to 20% of one or more nonionic surfactants from the group consisting of di- and triblock copolymers of alkylene oxides, d) 0.05 to 10% of one or more polybasic organic acids, e) 0 to 5% of one or more thickeners, 5 f) 0 to 50% of one or more agrochemical substances other than component a), g) 0 to 20% of one or more additional standard auxiliaries and additives, and 10 20 to 70% of water.

7. The dispersion as claimed in claim 6, wherein the 0 to 50% of one or more agrochemical active substance(s) is 0.1 to 50% flufenacet. 15

8. The dispersion as claimed in any one of claims 1 to 7, which comprises: a) 0.5 to 20% of diflufenican and from 0.5 to 30% of flurtamone, b) 0.2 to 5% of one or more anionic surfactants from the group consisting of the naphthalenesulfonates or from the group consisting of the condensation products of naphthalenesulfonates with 20 formaldehyde, c) 0.5 to 14% of one or more nonionic surfactants from the group consisting of di- and triblock copolymers of alkylene oxides, d) 0.1 to 5% of one or more polybasic organic acids, e) 0.05 to 2.5% of one or more thickeners, 25 f) 0 to 40% of one or more agrochemical active substances other than component a) preferably 0.5 to 22% of flufenacet, g) 0 to 15% of one or more additional standard auxiliaries and additives, and 30 20 to 60% water.

9. The dispersion as claimed in claim 8, wherein the 0 to 40% of one or more agrochemical active substance(s) is 0.5 to 22% of flufanacet. 22

10. The dispersion as claimed in any one of claims 1 to 9, which comprises a) 2 to 16% of diflufenican and 4 to 22% of flurtamone, b) 0.3 to 1.5% of one or more anionic surfactants from the group consisting of the naphthalenesulfonates or from the group consisting 5 of the condensation products of naphthalenesulfonates with formaldehyde, c) 1 to 10% of one or more nonionic surfactants from the group consisting of di- and tri-block copolymers of alkylene oxides, d) 0.2 to 2% of one or more polybasic organic acids, 10 e) 0.075 to 1.5% of one or more thickeners, f) 4 to 22% of flufenacet, g) 0 to 15% of one or more additional standard auxiliaries and additives, and 15 30 to 55% of water.

11. A process for the preparation of an aqueous dispersion as claimed in any one of claims 1 to 10, which process comprises the mixing of the components and optionally the milling thereof. 20

12. The use of an aqueous dispersion as claimed in any one of claims 1 to 7, in the preparation of a herbicidal composition.

13. The use according to claim 12, wherein the herbicidal composition is a 25 suspension or suspoemulsion.

14. A process for combating undesirable plant growth, which process comprises the application of an effective amount of an aqueous dispersion as claimed in any one of claims 1 to 10 to the plants, plant parts, seed or the area on 30 which plants are growing.

15. The use of an aqueous dispersion as claimed in any one of claims 1 to 10 in combating undesirable plant growth. 23

16. A liquid herbicidal composition which can be obtained by diluting an aqueous dispersion as claimed in any one of claims 1 to 10.

17. The liquid herbicidal composition as claimed in claim 16, the herbicidal 5 composition being selected from the group consisting of an emulsion, suspension, suspoemulsion and solution.

18. A liquid herbicidal composition which comprises: a) diflufenican and flurtamone, 10 b) one or more anionic surfactants from the group consisting of the naphthalenesulfonates or from the group consisting of the condensation products of naphthalenesulfonates with formaldehyde, c) one or more nonionic surfactants from the group consisting of di and triblock copolymers of alkylene oxides, 15 d) one or more polybasic organic acids, and water.

19. The liquid herbicidal composition as claimed in claim 18, which additionally comprises: 20 e) one or more thickeners, f) one or more agrochemical active substances other than component a) g) one or more additional standard auxiliaries and additives. 25

20. The liquid herbicidal liquid as claimed in claim 19, where the one or more active substance(s) is/are flufenacet.

21. A process for combating undesirable plant growth, which process comprises the application of an effective amount of a herbicidal composition as 30 claimed in any one of claims 16 to 19 to the plants, plant parts, seed or the area on which plants are growing. 24

22. The use of a herbicidal composition as claimed in any one of claims 16 to 19 in combating undesirable plant growth. 5 BAYER CROPSCIENCE AG WATERMARK PATENT AND TRADE MARKS ATTORNEYS 10 P30892AU00