AU2009218765A1 - Diflufenican-containing herbicidal combinations - Google Patents

Description

WO 2009/106259 PCT/EP2009/001182 Description Diflufenican-containing herbicidal combinations 5 The invention relates to the technical field of plant protection compositions which can be used against harmful plants, e.g. in crop plants, and comprise, as active substances, a combination of diflufenican and an additional herbicide. The herbicidal active substance diflufenican is preferably used in postemergence 0 against some harmful plants in cereal crops, such as, for example, wheat and barley. The effectiveness of diflufenican against harmful plants in these cereal crops is, however, not always satisfactory. One possibility for improving the application profile of a herbicide can consist of the 5 combination of the active substance with one or more other active substances. However, with the combined use of several active substances, it is not infrequent for phenomena of physical and biological incompatibility to occur, e.g. lack of stability in a coformulation, decomposition of an active substance or opposite action of the active substances. In comparison, combinations of active substances with a 0 favorable profile of action, a high stability and an action strengthened as synergistically as possible are desired which allow a reduction in the amount expended in comparison with the individual application of the active substances to be combined. 5 Thus, the mixture of diflufenican and flupyrsulfuron-methyl is known from EP 1 053 679 B1. Mixtures of diflufenican and herbicides from the group consisting of thiocarbamates, such as prosulfocarb, pyributicarb and thiobencarb, are known from WO 2008/064787. O It is an object of the present invention to improve the application profile of the herbicidal active substance diflufenican.

WO 2009/106259 2 PCT/EP2009/001182 This object has been achieved by providing herbicide combinations comprising diflufenican and penoxsulam or pyroxsulam. A subject matter of the invention is accordingly herbicide combinations, which 5 comprise A) diflufenican (component A), and B) penoxsulam or pyroxsulam (component B). The active substances mentioned in this description with their common name are 10 known, for example, from The Pesticide Manual, 14th Ed., British Crop Protection Council, 2006, and the website http://www.alanwood.net/pesticides/. If, in the context of this description, the shortened form of the common name of an active substance is used, this comprises in each case all common derivatives, such 5 as the esters and salts, and isomers, in particular optical isomers; in particular the commercially available form or forms. If the common name describes an ester or a salt, this also in each case comprises all other common derivatives, such as other esters and salts, the free acids and neutral compounds, and isomers, in particular optical isomers; in particular the commercially available form or forms. The chemical 0 compound names given describe at least one of the compounds encompassed by the common name, frequently a preferred compound. The herbicide combinations according to the invention exhibit a herbicidally effective content of component A) and component B) and can comprise additional 5 constituents, e.g. agrochemical active substances from the group consisting of herbicides, insecticides, fungicides and safeners and/or additives and/or formulation auxiliaries conventional in plant protection, or can be used together with these. In a preferred embodiment, the herbicide combinations according to the invention o comprise component A) and component B) as sole herbicidal active substances. The herbicide combinations according to the invention exhibit synergistic effects.

WO 2009/106259 3 PCT/EP2009/001182 The synergistic effects can, e.g., be observed on applying the components A and B together; however, they can also frequently be detected when applied displaced in time (splitting). The application of the individual herbicides or of the herbicide combinations in several portions (sequence application) is also possible, e.g. 5 applications in preemergence, followed by postemergence applications or early postemergence applications, followed by applications in middle or late postemergence. In this connection, the joint or the contemporaneous application of the active substances of the herbicidal compositions according to the invention is preferred. 0 The synergistic effects allow a reduction in the amounts of the individual active substances expended, an increased strength with the same amount expended, the control of species hitherto not included (gaps), an extension of the application period and/or a reduction in the number of individual applications necessary and, as a 5 consequence for the user, economically and ecologically more advantageous weed control systems. The herbicide combinations according to the invention comprise the combinations of diflufenican with penoxsulam and diflufenican with pyroxsulam. 0 The amount of the components A and B and the salts thereof expended can vary within wide limits, for example in each case between 5 and 500 g AS/ha. Insofar as the abbreviation AS/ha is used in this description, this term means "active substance per hectare", based on 100% active substance. A relatively broad spectrum of 5 annual and perennial weeds, including grass weeds, and Cyperaceae is combated in the pre- and postemergence method when the components A and B are applied with amounts expended of 5 to 500 AS/ha. The amounts expended are generally lower with herbicidal compositions according to the invention, e.g. in the range from 50 to 500 g AS/ha, preferably from 50 to 250 g AS/ha, for component A and in the ) range from 5 to 250 g AS/ha, preferably from 5 to 100 g AS/ha, for component B. The ratios generally used of the amounts expended of the components A:B are WO 2009/106259 4 PCT/EP2009/001182 given below and describe the ratio by weight of the components A:B to one another. The ratio by weight of the components A and B to one another is in this connection generally from 2:1 to 100:1, preferably 2:1 to 20:1. 5 For the use of the active substances of the herbicide combinations according to the invention in crop plants, it may be advisable, depending on the crop plant, starting from particular amounts expended, to apply a safener in order to reduce or prevent possible damage to the crop plant. Such safeners are known to a person skilled in the art. Safeners which are particularly highly suitable are fenchlorazole-ethyl (S1), 0 mefenpyr-diethyl (S2), isoxadifen-ethyl (S3), cyprosulfamide (S4), cloquintocet-mexyl (S5), fenclorim (S6), dichlormid (S7), benoxacor (S8), furilazole (S9), oxabetrinil (S10), fluxofenim (S11), flurazole (S12) and naphthalic anhydride (S13). The invention also comprises those herbicide combinations which, in addition to the 5 components A and B, also comprise one or more additional agrochemical active substances from the group consisting of insecticides, fungicides and safeners. The preferred conditions explained above are valid for such combinations. Particularly suitable are those herbicide combinations comprising a safener such as mefenpyr diethyl (S2), isoxadifen-ethyl (S3), cyprosulfamide (S4) and cloquintocet-mexyl (55). 0 Accordingly, in addition to the combinations of diflufenican and penoxsulam or diflufenican and pyroxsulam according to the invention which have already been mentioned, the combinations of diflufenican, penoxsulam and mefenpyr-diethyl, 5 diflufenican, penoxsulam and isoxadifen-ethyl, diflufenican, penoxsulam and cyprosulfamide, diflufenican, penoxsulam and cloquintocet-mexyl, diflufenican, pyroxsulam and mefenpyr-diethyl, diflufenican, pyroxsulam and isoxadifen-ethyl, 0 diflufenican, pyroxsulam and cyprosulfamide, and diflufenican, pyroxsulam and cloquintocet-mexyl, are also particularly preferred.

WO 2009/106259 5 PCTIEP2009/001182 The herbicide combinations 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 5 from rhizomes, rootstocks or other perennial organs and which are difficult to combat are successfully included by the active substances. In this connection, it is immaterial whether the substances are applied in the presowing, preemergence or postemergence method. 0 If the herbicide combinations 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 active substances 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 time, so that in this way competition by 0 weeds, which is harmful for the crop plants, is eliminated very early and with lasting effect. The herbicide combinations according to the invention are distinguished by a rapidly commencing and long lasting herbicidal action. The resistance to rain of the active 5 substances in the combinations according to the invention is generally good. A particular advantage is crucially that the dosages of components A and B which are used in the combinations 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 0 substantial reduction in the amount of the active substances which has to be expended is made possible by the active substance combination according to the invention.

WO 2009/106259 6 PCT/EP2009/001182 In a preferred embodiment, superadditive (= synergistic) effects occur when components A and B are used jointly. The action in the combinations is in this connection stronger than the sum to be expected of the actions of the individual 5 herbicides used. The synergistic effects allow a reduction in the amount expended, the combating of a broader spectrum of weeds, including grass weeds, a faster onset of the herbicidal action, a longer lasting action, better control of the harmful plants, with only one or a few applications, and a broadening of the possible application period. The amount of harmful ingredients, such as nitrogen or oleic acid, 10 and their introduction into the soil are sometimes reduced by the use of the herbicide combinations. 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 5 and accordingly to safeguard and/or to increase the yields in terms of quality and quantity. The technical standard is, with regard to the properties described, clearly exceeded by these new combinations. Although the herbicide combinations according to the invention exhibit an outstanding herbicidal activity with regard to harmful mono- and dicotyledonous 0 plants, the crop plants are only insignificantly damaged or completely undamaged. In addition, the herbicide combinations according to the invention sometimes exhibit outstanding growth-regulatory properties in the crop plants. They intervene in a regulatory manner in the plants' metabolism and can accordingly be used for the 5 selective influencing of plant contents and for making harvesting easier, such as, e.g., by controlling desiccation and stunted growth. Furthermore, they are also suitable for the general control and inhibition of 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 crop losses by lodging 0 can be reduced or completely prevented through this.

WO 2009/106259 7 PCT/EP2009/001182 Because of their herbicidal and plant-growth-regulatory properties, the herbicide combinations according to the invention can be used for combating harmful plants in genetically modified crop plants or crop plants obtained by mutation selection. These crop plants are generally distinguished by particular advantageous properties, such 5 as resistance to herbicides or 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, e.g., transgenic plants with increased starch content or modified quality of the starch or 0 those with a different fatty acid composition of the harvested crops are known. Conventional routes for the production of novel plants which exhibit modified properties in comparison with plants occurring hitherto consist, for example, of classical breeding methods and the generation of mutants (see, e.g., US 5 162 602; US 4 761 373 and US 4 443 971). Alternatively, novel plants with modified 5 properties can be generated using genetic engineering methods (see, e.g., EP-A-0 221 044 and EP-A-0 131 624). The following have, for example, been described in several cases: - genetically engineered modifications to crop plants for the purpose of modifying the starch synthesized in the plants (e.g., WO 92/11376, WO 0 92/14827 and WO 91/19806), - transgenic crop plants which exhibit resistance to other herbicides, for example to sulfonylureas (EP-A-0 257 993, US-A-5 013 659), - transgenic crop plants with the capability of producing Bacillus thuringiensis toxins (Bt toxins) which render the plants resistant to particular pests 5 (EP-A-0 142 924 and EP-A-0 193 259), - transgenic crop plants with a modified fatty acid composition (WO 91/13972). Numerous techniques in molecular biology by which novel transgenic plants with modified properties can be produced are known in principle; see, e.g., Sambrook et 0 al., 1989, Molecular Cloning, A Laboratory Manual, 2nd edition, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker, "Gene und Klone" [Genes and Clones], VCH Weinheim, 2nd edition, 1996; or Christou, "Trends in Plant WO 2009/106259 8 PCT/EP2009/001182 Science", 1 (1996), 423-431. For such genetic engineering manipulations, nucleic acid molecules can be introduced into plasmids, which allow a mutagenesis or a sequence alteration by 5 recombination of DNA sequences. Using the abovementioned standard methods, it is possible, e.g., to carry out base substitutions, to remove part sequences or to add natural or synthetic sequences. The DNA fragments can be provided with adaptors or linkers to link the fragments to one another. 10 The production of plant cells with a reduced activity of a gene product can be achieved, for example, by the expression of at least one corresponding antisense RNA, a sense RNA for obtaining a cosuppression effect, or the expression of at least one suitably constructed ribozyme which specifically cleaves transcripts of the abovementioned gene product. 5 To this end, it is possible, on the one hand, to use DNA molecules which encompass all of the coding sequence of a gene product, including any flanking sequences which may be present, but also DNA molecules which only encompass portions of the coding sequence, it being necessary for these portions to be long enough to .0 cause an antisense effect in the cells. The use is also possible of DNA sequences which have a high degree of homology with the coding sequences of a gene product, but are not completely identical. When expressing nucleic acid molecules in plants, the protein synthesized may be 5 localized in any compartment whatever of the plant cell. However, to achieve localization in a particular compartment, the coding region can, e.g., be linked to DNA sequences which guarantee localization in a particular compartment. Such sequences are known to a person skilled in the art (see, for example, Braun et al., EMBO J., 11 (1992), 3219-3227; Wolter et al., Proc. Nati. Acad. Sci. USA, 85 0 (1988), 846-850; Sonnewald et al., Plant J., 1 (1991), 95-106). The transgenic plant cells can be regenerated using known techniques to give intact WO 2009/106259 9 PCT/EP2009/001182 plants. In principle, the transgenic plants can be plants of any plant species whatever, i.e. both monocotyledonous and dicotyledonous plants. Thus, transgenic plants can be obtained which exhibit modified properties owing to the overexpression, suppression or inhibition of homologous (= natural) genes or gene 5 sequences or expression of heterologous (= foreign) genes or gene sequences. Another subject matter of the present invention is furthermore a process for combating undesirable plant growth (e.g. harmful plants), preferably in crop plants, such as cereals (e.g. wheat, barley, rye, oats, hybrids thereof, such as triticale, rice, 10 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 herbicides of the type A with one or more herbicides of the type B and, if appropriate, one or more herbicides of the type C or a safener being applied together or separately, e.g. in 5 preemergence, postemergence or in pre- and postemergence, to the plants, e.g. 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 .0 selection and are preferably tolerant to acetolactate synthase (ALS) inhibitors. Another subject matter of the invention is the use of the herbicide combinations according to the invention for combating harmful plants, preferably in crop plants. 5 The herbicide combinations according to the invention can also be used non selectively in combating undesirable plant growth, e.g. in plantation crops, on roadsides, yards, industrial plants or railroad installations. The herbicide combinations according to the invention can exist both as mixed 0 formulations of the components A and B and, if appropriate, with additional agrochemical active substances, additives and/or conventional formulation auxiliaries, which are then used in the conventional way diluted with water, or WO 2009/106259 10 PCT/EP2009/001182 prepared as "tank mixes" by joint diluting of the separately formulated or partially separately formulated components with water. The components A and B or the combinations thereof can be formulated in different 5 ways, depending on which biological and/or chemical/physical parameters are specified. The following are possible, for example, as general formulation possibilities: wettable powders (WP), water-soluble concentrates, emulisifiable concentrates (EC), aqueous solutions (SL), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions or emulsions, suspension 0 concentrates (SC), oil- or water-based dispersions, suspoemulsions, dustable powders (DP), seed dressings, granules for soil application or broadcasting, water dispersible granules (WG), ULV formulations, microcapsules or waxes. The individual formulation types are known in principle and are described, for 5 example, in: Winnacker-Kachler, "Chemische Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag, Munich, 4th edition, 1986; van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying Handbook", 3rd Ed., 1979, G. Goodwin Ltd., London. O The formulation auxiliaries necessary, such as inert materials, surfactants, solvents and additional additives, are likewise known and are described, for example, in: 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.; Marsden, "Solvents Guide", 2nd Ed., Interscience, N.Y., 5 1950; McCutcheon's, "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood, N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Pubi. Co. Inc., N.Y., 1964; Schbnfeldt, "Grenzflachenaktive Athylenoxidaddukte" [Surface-active Ethylene Oxide Adducts], Wiss. Verlagsgesellschaft, Stuttgart, 1976; Winnacker-KOchler, "Chemische Technologie" [Chemical Technology], Volume 7, C. ) Hauser Verlag Munich, 4th Ed., 1986. Based on these formulations, combinations with other agrochemical active substances, such as fungicides or insecticides, and also safeners, fertilizers and/or WO 2009/106259 11 PCT/EP2009/001182 growth regulators can also be prepared, e.g. in the form of a ready-for-use formulation or as tank mix. Wettable powders are preparations which can be uniformly dispersed in water and 5 which, in addition to the active substance, also comprise ionic or nonionic surfactants (wetting agents, dispersants), e.g. polyoxyethylated alkylphenols, polyethoxylated fatty alcohols or fatty amines, alkanesulfonates or alkylbenzene sulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyltaurinate, in addition to a 10 diluent or inert substance. Emulsifiable concentrates are prepared by dissolving the active substance in an organic solvent, e.g. butanol, cyclohexanone, dimethylformamide, xylene or also higher-boiling aromatic compounds or hydrocarbons, with addition of one or more 5 ionic or nonionic surfactants (emulsifiers). Use may be made, as emulsifiers, for example, of: calcium alkylarylsulfonates, such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensation products, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty 0 acid esters or polyoxyethylene sorbitol esters. Dustable powders are obtained by milling the active substance with finely divided solid materials, e.g. talc, natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth. 5 Suspension concentrates (SC) can be water- or oil-based. They can be prepared, for example, by wet milling using commercial bead mills and, if appropriate, addition of additional surfactants, such as those, e.g., which have already been mentioned above for the other formulation types. 0 Emulsions, e.g. oil-in-water emulsions (EW), can be prepared, for example, by means of stirrers, colloid mills and/or static mixers using aqueous organic solvents and, if appropriate, additional surfactants, such as those, e.g., which have already WO 2009/106259 12 PCTIEP2009/001182 been listed above for the other formulation types. Granules can be prepared either by spraying the active substance onto adsorptive granulated inert material or by applying active substance concentrates to the surface 5 of carriers, such as sand or kaolinite, or of granulated inert material using binders, e.g. polyvinyl alcohol, sodium polyacrylate or else mineral oils. Suitable active substances can also be granulated in the standard way for the preparation of fertilizer granules, if desired as a mixture with fertilizers. Water-dispersible granules are generally prepared according to the standard 10 methods, such as spray drying, fluidized-bed granulation, disk granulation, mixing with high-speed mixers and extrusion without solid inert material. For the preparation of disk granules, fluidized-bed granules, extruder granules and spray granules, see, e.g., methods in "Spray Drying Handbook" 3rd Ed., 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and Engineering, 1967, pages 147 ff; 5 "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57. For further details on the formulating of plant protection compositions, see, e.g., G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 0 1961, pages 81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103. The agrochemical formulations generally comprise from 0.1 to 99 percent by weight, in particular from 2 to 95% by weight, of active substances of the components A 5 and/or B, the following concentrations being normal according to the type of formulation: in wettable powders, the active substance concentration is, e.g., from approximately 10 to 95% by weight, the balance for 100% by weight consisting of standard formulation constituents. With emulsifiable concentrates, the active substance concentration can be, e.g., from 5 to 80% by weight. Formulations in the 0 form of dust for the most part comprise from 5 to 20% by weight of active substance, sprayable solutions from approximately 0.2 to 25% by weight of active substance. With granules, such as dispersible granules, the active substance content partly WO 20091106259 13 PCT/EP2009/001182 depends on whether the active compound is present in the liquid or solid form and on which granulation auxiliaries and fillers are being used. With water-dispersible granules, the content is generally between 10 and 90% by weight. In addition, the active substance formulations mentioned comprise, if appropriate, 5 the stickers, wetting agents, dispersing agents, emulsifying agents, preservatives, antifreeze agents, solvents, fillers, colorants, carriers, antifoaming agents, evaporation inhibitors, pH regulators or viscosity regulators which are standard in each case. 10 The herbicidal action of the herbicide combinations according to the invention can be improved, e.g., by surface-active substances, preferably by wetting agents from the series of the fatty alcohol polyglycol ethers. The fatty alcohol polyglycol ethers preferably comprise 10-18 carbon atoms in the fatty alcohol radical and 2-20 ethylene oxide units in the polyglycol ether part. The fatty alcohol polyglycol ethers 15 can be present in nonionic form or in ionic form, e.g. in the form of fatty alcohol polyglycol ether sulfates which are used, e.g., as alkali metal salts (e.g., sodium and calcium salts) or ammonium salts or also as alkaline earth metal salts, such as magnesium salts, such as sodium C 1 2

/C

14 -fatty alcohol diglycol ether sulfate (Genapol* LRO, Clariant GmbH); see, e.g., EP-A-0 476 555, EP-A-0 048 436, ?0 EP-A-0 336 151 or US-A-4 400 196, and also Proc. EWRS Symp., "Factors Affecting Herbicidal Activity and Selectivity", 227 - 232 (1988). Nonionic fatty alcohol polyglycol ethers are, for example, (C10-C 8 )-, preferably (C 10

-C

14 )-, fatty alcohol polyglycol ethers comprising 2 - 20, preferably 3 - 15, ethylene oxide units (e.g. isotridecyl alcohol polyglycol ether), e.g. from the Genapol* X series, such as .5 Genapol X-030, Genapol® X-060, Genapol* X-080 or Genapol' X-1 50 (all from Clariant GmbH). The present invention furthermore comprises the combination of components A and B with the abovementioned wetting agents from the series of the fatty alcohol 0 polyglycol ethers which preferably comprise 10 - 18 carbon atoms in the fatty alcohol radical and 2 - 20 ethylene oxide units in the polyglycol ether part and which can be present in nonionic or ionic form (e.g., as fatty alcohol polyglycol ether sulfates).

WO 2009/106259 14 PCT/EP2009/001182 Preference is given to sodium C12/C 14 -fatty alcohol diglycol ether sulfate (Genapol* LRO, Clariant GmbH) and to isotridecyl alcohol polyglycol ethers with 3 - 15 ethylene oxide units, e.g. from the Genapol' X series, such as Genapol* X-030, Genapol* X-060, Genapol* X-080 and Genapol® X-150 (ail from Clariant GmbH). Furthermore, 5 it is known that fatty alcohol polyglycol ethers, such as nonionic or ionic fatty alcohol polyglycol ethers (e.g., fatty alcohol polyglycol ether sulfates), are also suitable as penetrants and activity enhancers for a series of other herbicides, inter alia also for herbicides from the series of the imidazolinones (see, e.g., EP-A-0 502 014). [0 Furthermore, it is known that fatty alcohol polyglycol ethers, such as nonionic or ionic fatty alcohol polyglycol ethers (e.g., fatty alcohol polyglycol ether sulfates), are also suitable as penetrants and activity enhancers for a series of other herbicides, inter alia also for herbicides from the series of the imidazolinones (see, e.g., EP-A-0 502 014). 5 The herbicidal action of the herbicide combinations according to the invention can also be enhanced by the use of vegetable oils. The term "vegetable oils" is to be understood as meaning oils from oleaginous plant species, such as soybean oil, rapeseed oil, corn oil, sunflower oil, cottonseed oil, linseed oil, coconut oil, palm oil, 0 thistle oil or castor oil, in particular rapeseed oil, and also the transesterification products thereof, e.g. alkyl esters, such as rapeseed oil methyl ester or rapeseed oil ethyl ester. The vegetable oils are preferably esters of C 1 0

-C

22 -fatty acids, preferably C 12

-C

20 5 fatty acids. The C 1 0-C2 2 -fatty acid esters are, for example, esters of unsaturated or saturated C 1 0-C2 2 -fatty acids, in particular with an even number of carbon atoms, e.g. erucic acid, lauric acid, palmitic acid and in particular C 1 -fatty acids, such as stearic acid, oleic acid, linoleic acid or linolenic acid. 0 Examples of C 10

-C

22 -fatty acid esters are esters obtained by reacting glycerol or glycol with the C1 0

-C

22 -fatty acids, such as those, e.g., present in oils from oleaginous plant species, or C-C2 0 -alkyl C 1 0 -C2 2 -fatty acid esters, such as those, WO 2009/106259 15 PCT/EP2009/001182 e.g., which can be obtained by transesterification of the abovementioned glycerol or glycol C10-C 22 -fatty acid esters with C,-C 20 -alcohols (e.g., methanol, ethanol, propanol or butanol). The transesterification can be carried out according to known methods, such as those, e.g., described in Rdmpp Chemie Lexikon, 9th edition, 5 Volume 2, page 1343, Thieme Verlag, Stuttgart. Preference is given, as C 1

-C

20 -alkyl C 10

-C

22 -fatty acid esters, to methyl esters, ethyl esters, propyl esters, butyl esters, 2-ethylhexyl esters and dodecyl esters. Preference is given, as glycol and glycerol C1o-C 22 -fatty acid esters, to the uniform or 10 mixed glycol esters and glycerol esters of C1O-C 22 -fatty acids, in particular those fatty acids with an even number of carbon atoms, e.g. erucic acid, lauric acid, palmitic acid and in particular C 1 -fatty acids, such as stearic acid, oleic acid, linoleic acid or linolenic acid. 15 The vegetable oils can be present in the herbicide combinations according to the invention, e.g., in the form of commercially available oil-comprising formulation additives, in particular those based on rapeseed oil, such as Hasten® (Victorian Chemical Company, Australia, subsequently referred to as Hasten, main constituent: rapeseed oil ethyl ester), Actirob"B (Novance, France, subsequently referred to as ?0 ActirobB, main constituent: rapeseed oil methyl ester), Rako-Binol* (Bayer AG, Germany, subsequently referred to as Rako-Binoi, main constituent: rapeseed oil), Renol* (Stefes, Germany, subsequently referred to as Renol, vegetable oil constituent: rapeseed oil methyl ester) or Stefes Mero* (Stefes, Germany, subsequently referred to as Mero, main constituent: rapeseed oil methyl ester). !5 In a further embodiment, the present invention comprises combinations of components A and B with the abovementioned vegetable oils, such as rapeseed oil, preferably in the form of commercially available oil-comprising formulation additives, in particular those based on rapeseed oil, such as Hasten* (Victorian Chemical o Company, Australia, subsequently referred to as Hasten, main constituent: rapeseed oil ethyl ester), Actirob*B (Novance, France, subsequently referred to as ActirobB, main constituent: rapeseed oil methyl ester), Rako-Binol* (Bayer AG, Germany, WO 20091106259 16 PCT/EP2009/001182 subsequently referred to as Rako-Binol, main constituent: rapeseed oil), Renol* (Stefes, Germany, subsequently referred to as Renol, vegetable oil constituent: rapeseed oil methyl ester) or Stefes Mero* (Stefes, Germany, subsequently referred to as Mero, main constituent: rapeseed oil methyl ester). 5 For use, the formulations existing in commercially available form are, if appropriate, diluted in the standard way, e.g. using water for wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Compositions in the form of dusts, soil granules, granules for broadcasting and sprayable solutions are [0 normally not diluted further with additional inert materials before use. The active substances can be applied to the plants, plant parts, plant seeds or the area under cultivation (arable land), preferably to the green plants and plant parts and, if appropriate, additionally to the arable land. One possibility of use is the joint 5 application of the active substances in the form of tank mixes, where the concentrated formulations, which are optimally formulated, of the individual active substances are mixed together in a tank with water and the spray mixture obtained is applied. 0 A joint herbicidal formulation of the herbicide combinations according to the invention of components A and B has the advantage of being able to be applied more easily because the amounts of the components have already been adjusted to the correct ratio to one another. Moreover, the auxiliaries in the formulation can be optimally matched to one another. 5 A. Formulation examples of general type a) A dustable powder is obtained by mixing 10 parts by weight of an active substance/active substance mixture and 90 parts by weight of talc as inert 0 material and comminuting in a hammer mill. b) A wettable powder readily dispersible in water is obtained by mixing 25 parts WO 20091106259 17 PCT/EP2009/001182 by weight of active substance/active substance mixture, 64 parts by weight of kaolin-comprising quartz as inert material, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurinate as wetting and dispersing agent and milling in a pin mill. 5 c) A dispersion concentrate readily dispersible in water is obtained by mixing 20 parts by weight of an active substance/active substance mixture with 6 parts by weight of alkylphenol polyglycol ether (Triton® X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic 10 mineral oil (boiling range, e.g., approximately 255 to 277 0 C) and milling in a friction ball mill to a fineness of less than 5 microns. d) An emulsifiable concentrate is obtained from 15 parts by weight of an active substance/active substance mixture, 75 parts by weight of cyclohexanone as 15 solvent and 10 parts by weight of oxyethylated nonylphenol as emulsifier. e) A water-dispersible granule is obtained by mixing 75 parts by weight of an active substance/active substance mixture, 10 parts by weight of calcium lignosulfonate, 20 5 parts by weight of sodium lauryl sulfate, 3 parts by weight of polyvinyl alcohol and 7 parts by weight of kaolin milling on a pin mill and granulating the powder in a fluidized bed by spraying on water as granulation liquid. !5 f) A water-dispersible granule is also obtained by homogenizing and precomminuting 25 parts by weight of an active substance/active substance mixture, 5 parts by weight of sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, 0 2 parts by weight of sodium oleoylmethyltaurinate, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and WO 2009/106259 18 PCT/EP2009/001182 50 parts by weight of water on a colloid mill, subsequently milling on a bead mill and atomizing and drying the suspension thus obtained in a spray tower using a single-substance nozzle. 5 B. Biological examples Herbicidal action The seeds or rhizome pieces of typical harmful plants present in the soi were grown 10 under natural field conditions. Treatment with the herbicide combinations according to the invention or with the individual components A and B used was carried out after the emergence of the harmful and crop plants, generally at the 2- to 4-leaf stage. Application of the active substances or active substance combinations formulated as WG, WP or EC was carried out in postemergence. After 2 to 8 weeks, visual 5 evaluation was carried out in comparison with an untreated comparative group. It proved to be the case, in this connection, that the herbicide combinations according to the invention exhibit a synergistic herbicidal action against economically important harmful mono- and dicotyledonous plants, i.e., that the herbicide combinations according to the invention for the most part exhibit a higher, sometimes markedly .0 higher, herbicidal action than is corresponded to by the sum of the actions of the individual herbicides. In addition, the herbicidal actions of the herbicide combinations according to the invention lie above the expected values according to Colby. On the other hand, the crop plants were undamaged or only damaged to an insignificant extend by the treatment. 5 If the observed activity values of the mixtures already exceed the formal sum of the values for the trials with individual applications, then they likewise exceed the expected value according to Colby, which is calculated according to the following formula (cf. S. R. Colby in Weeds, 15 (1967), pp. 20 to 22): 0 WO 20091106259 19 PCTIEP2009/001182 E = A+B - AxB 100 In this connection: A, B = respectively action of the component A or B in percent at a dosage of a or b grams ai/ha, 5 E = expected value in % at a dosage of a + b grams ai/ha. PAPRH Papaver rhoeas Action in postemergence Herbicide Dosage Herbicidal action Expected against PAPRH value Diflufenican 9 10% Pyroxsulam 1 0% Diflufenican + Pyroxsulam 9 + 1 30% 10% 10 Action in postemergence Herbicide Dosage Herbicidal action Expected against PAPRH value Diflufenican 9 10% Penoxsularn 3 0% Diflufenican + Penoxsujam 9 + 3 20% 10%

Claims (13)

1. A herbicide combination, which comprises A) diflufenican (component A), and 5 B) penoxsulam or pyroxsulam (component B).

2. The herbicide combination as claimed in claim 1, which comprises, as sole herbicidal active substances, diflufenican and penoxsulam. 10

3. The herbicide combination as claimed in claim 1, which comprises, as sole herbicidal active substances, diflufenican and pyroxsulam.

4. The herbicide combination as claimed in one of claims 1 to 3, wherein the ratio by weight of the components A and B to one another is from 2:1 to 100:1. 15

5. The herbicide combination as claimed in claim 4, wherein the ratio by weight of the components A and B to one another is from 2:1 to 20:1.

6. The herbicide combination as claimed in one of claims I to 5, which ?0 additionally comprises additives and/or formulation auxiliaries conventional in plant protection.

7. The herbicide combination as claimed in one of claims 1 to 6, which additionally comprises one or more additional components from the group of 5 agrochemical active substances consisting of insecticides, fungicides and safeners.

8. The herbicide combination as claimed in claim 7, which comprises a safener.

9. A process for combating undesirable plant growth, which comprises applying o the components A and B of the herbicide combination, defined according to one of claims 1 to 8, together or separately to the plants, plant parts, plant seeds or the area on which the plants are growing. WO 2009/106259 21 PCT/EP2009/001182

10. The process as claimed in claim 9 for the selective combating of harmful plants in crop plants. 5

11. The process as claimed in claim 10 for the combating of harmful plants in monocotyledonous crop plants.

12. The process as claimed in claim 10 or 11, wherein the crop plants are modified by genetic engineering or are obtained by mutation selection. 10

13. The use of the herbicide combination defined according to one of claims 1 to 8 for combating harmful plants.