Herbicidal mixture comprising L-glufosinate-ammonium or salt thereof and second herbicide

Abstract

The present invention relates to a herbicidal mixture comprising L-glufosinate-ammonium or a salt thereof and a herbicidal compound II, the weeding compound II is selected from the group consisting of beflubutamid-M, tetrafluoramid, dimethyl sulfonamide, quinolinone, dicarfentrazone-ethyl, bicyclopyrone, pyrimetribuzin, topramezone, pyrimidinafop-m, triazole sulcotrione, fluonafop-oxalic acid, fluoro-chlorantraniliprole, fluoro-pyrimidinafop-methyl, fluridone, florfenoxam, triazole oxamid, isoxamid, pyrazol-quinolinafop-ethyl and bromazone. Furthermore, the invention relates to a method for controlling undesired vegetation in killing plans, in industrial vegetation management and forestry, in inter-row crops, vegetables and perennial crops, and in turf and lawn.

Description

[0001] The present invention relates to a herbicidal mixture comprising L-phosphinothricin or a salt thereof and a herbicidal compound II selected from the group consisting of fluazifop-M, fluazifop-butyl, dimesulfazet, quinclorac, bispyribac, cypermethrin, dioxopyritrione, fenpyrazone, rimisoxafen, triazosulfuron, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, iptriazopyrid, isoxaclopyrid, quinclorac-butyl and bromoquinoxaline. In addition, the present invention relates to a method for controlling unwanted vegetation in pest control programs, in industrial vegetation management and forestry, in vegetables and perennial crops, and in turf and lawns.

[0002] Weed control, i.e., the complete removal of weeds from the soil by applying herbicides before crops are planted or emerge, is an important means of modern weed management. Weeds present at the planting site generally grow much faster than crop plants and therefore compete very early in the growing season, thereby damaging crop plants and reducing crop yields. It is therefore desirable to plant crops in weed-free seedbeds or to ensure that there are essentially no weeds present when crops emerge. Weed control may also require weed control on fallow farmland.

[0003] In industrial weed management and forestry, it is desirable to control large numbers of weeds for a longer period of time. It may also be desirable to control large weeds, or taller species such as shrubs or trees. Industrial weed management includes, for example, railroad and right-of-way management, fence lines and non-agricultural land such as industrial and building land, gravel areas, roads or sidewalks. Forestry includes, for example, the clearing of existing forests or bushes, the removal of regenerated vegetation after mechanical forest felling, or the management of weeds under forestry plantations. In the latter case, it may be desirable to protect the desired trees from contact with a spray solution containing the herbicidal mixture according to the invention.

[0004] Vegetable crops include, for example, aubergine, beans, bell peppers, cabbage, peppers, cucumbers, eggplant, lettuce, melon, onions, potatoes, sweet potatoes, spinach and tomatoes. For weed control in vegetable crops, it may be desirable to protect the crops from contact with a spray solution containing the herbicidal mixture according to the invention.

[0005] Row crops can be planted in sufficiently wide rows to allow them to be cultivated or otherwise grown by agricultural machinery, machinery customized for seasonal activities of row crops. The particularity of row crops is that they are planted and cultivated based on season or year. Therefore, such crops produce products and profits relatively quickly and predictably. Row crops are crops produced from plants that last for many seasons, rather than crops that are planted again after each harvest. The example of row crops includes soybean, corn, canola, cotton, cereals or rice, as well as sunflower, potato, dry beans, peas, flax, safflower, buckwheat and beet. Usually, the row crops that can be processed according to the present invention can be conventional sources or can be herbicide tolerant row crops.

[0006] Perennial crops include tree, nut and vine crops, such as almonds, apples, apricots, avocados, cashews, cherries, Christmas trees, durian, oranges, pitayas, grapes, guavas, longans, mangoes, olives, papayas, peaches, pears and other pome fruits, pistachios, plums, pomegranates, grapefruits and quinces, and citrus crops including, for example, clementines, grapefruits, lemons, limes, mandarins and nectarines, and nut crops including, for example, hazelnuts, macadamia nuts and walnuts; and plantation crops such as bananas, cocoa, coconuts, coffee, oil palm, pepper and other spices, plantains, rubber, sugar cane and tea. Also included are ornamental plants, such as azaleas, rhododendron, roses and nursery plants. For weed control in perennial crops, it may be desirable to protect the crop from contact with a spray solution containing the herbicidal mixture according to the invention.

[0007] The compositions according to the invention can also be used for weed control in turf and lawns, provided that the desired grass species tolerates the herbicidal mixture. In particular, such mixtures can be used in desired grasses that have been rendered tolerant to glufosinate by mutagenesis or genetic engineering.

[0008] Glufosinate and its salt are non-selective systemic herbicides with good post-emergence activity for multiple weeds and can therefore be used in killing plans, in industrial vegetation management and forestry, in row crops, vegetables and perennial crops, and in turf and lawns. However, only using glufosinate usually obtains unsatisfactory weed control, and usually requires several applications and / or high dosage rates. In addition, glufosinate is not sufficiently effective to some weeds.

[0009] Therefore, it is often recommended to use a combination of glufosinate and at least one other herbicide. However, the effectiveness of such a combination is usually unsatisfactory and realizes acceptable weed control and still needs a high application rate. In addition, the reliability and persistence of such a combination depend to a great extent on climatic conditions and can avoid some difficulties in controlling weed species. In addition, the herbicidal activity of these mixtures only lasts for a short time, so that only in the short time range before the planting of crops, effective killing is achieved.

[0010] Therefore, the object of the present invention is to provide a herbicidal mixture which allows efficient and reliable control of grasses and broadleaf weeds in pest control programs, in industrial vegetation management and forestry, in row crops, vegetables and perennial crops, and in turf and lawns. In addition, the persistence of the herbicidal activity of the mixture should be long enough to achieve weed control over a sufficiently long period of time, thereby allowing a more flexible application. The mixture should also have a lower toxicity to humans or other mammals. The mixture should also show an accelerated effect on harmful plants, that is, it should achieve damage to harmful plants more quickly than the application of individual herbicides.

[0011] Glufosinate is a racemate of two enantiomers, only one of which shows sufficient herbicidal activity (see, e.g., US 4265654 and JP92448 / 83). Although various methods for preparing L-Glufosinate (and corresponding salts) are known, mixtures known in the art do not point to stereochemistry, which means that racemates exist (e.g., WO 2013154396).

[0012] Surprisingly, it has been found that mixtures of L-glufosinate or its salts with the herbicide compound II show higher activity in pest control programs, in industrial vegetation management and forestry, in row crops, vegetables and perennial crops, and in turf and lawns compared to L-glufosinate alone.

[0013] Surprisingly, it has been found that mixtures of L-glufosinate or its salts with the herbicide compound II show higher activity in pest control programs, in industrial vegetation management and forestry, in row crops, vegetables and perennial crops, and in turf and lawns compared to the use of mixtures of racemic glufosinate and the herbicide compound II.

[0014] The present invention therefore relates to the following herbicidal mixtures:

[0015] 1) L-phosphinothionyl ammonium or a salt thereof as compound I, and

[0016] 2) A herbicidal compound II as compound II selected from the group consisting of fluazifop-M, fluazifop-butyl, dimethoate, quinclorac, bispyribac, cypermethrin, pyridazione, benzafluazione, pyridazine, fluazifop-butyl, triazosulfuron, fluclorac, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, triazosulfuron, isoxaclorac, quinclorac-butyl and bromoxynil.

[0017] In a preferred embodiment, the above invention relates to a herbicidal mixture as described above, wherein L-glufosinate-ammonium contains more than 70% by weight of the L-enantiomer.

[0018] Glufosinate (common name [DL-4-[hydroxy(methyl)phosphonyl]-DL-homoalaninate]) and its salts (e.g. glufosinate ammonium) and their herbicidal activity have been described, for example, by F. Schwerdtle et al., Z. Pflanzenkr. Pflanzenschutz [Journal of Plant Diseases and Plant Protection], 1981, Special Issue IX, pp. 431-440. Glufosinate and its salts in racemic form are available under the trade name Basta TM and Liberty TM Commercially available from Bayer CropScience.

[0019] The L-glufosinate used in the present invention contains more than 70% by weight of the L-enantiomer; preferably more than 80% by weight of the L-enantiomer; more preferably more than 90% of the L-enantiomer, most preferably more than 95% of the L-enantiomer, and can be prepared as mentioned above. L-glufosinate can be prepared according to methods known in the art, for example as described in WO 2006 / 104120, US 5530142, EP 0127429 and J. Chem. Soc. Perkin Trans. [Journal of the Chemical Society] 1, 1992, 1525-1529.

[0020] L-Glufosinate, also known as glufosinate-P, is (2S)-2-amino-4-[hydroxy(methyl)phosphinoyl]butanoic acid (CAS Reg. No. 35597-44-5). Related salts of L-Glufosinate are L-Glufosinate-ammonium (also known as glufosinate-P-ammonium salt), which is (2S)-2-amino-4-(methylphosphinoyl)butanoic acid ammonium (CAS Reg. No. 73777-50-1); L-Glufosinate-sodium (also known as glufosinate-P-sodium), which is (2S)-2-amino-4-(methylphosphinoyl)butanoic acid sodium (CAS Reg. No. 70033-13-5), and L-Glufosinate-potassium (also known as glufosinate-P-potassium), which is (2S)-2-amino-4-(methylphosphinoyl)butanoic acid potassium.

[0021] In the present disclosure, compound I is the acid form or salt of the enantiomer L-phosphinothricin (phosphinothricin-P, compound I.1), or a mixture of acid forms and salts of X% w / w L-phosphinothricin and Y% w / w D-phosphinothricin, wherein X is ≥70, preferably ≥80, more preferably ≥90, and most preferably ≥95, and wherein X+Y is 100.

[0022] The following are examples of suitable Compound I for administration with Compound II:

[0023] Compound I:

[0024] I.1: Enantiomers L-phosphinothricin

[0025] I.1.a: Enantiomers L-glufosinate ammonium

[0026] I.1.b: Enantiomers of L-glufosinate sodium

[0027] I.1.c: Enantiomers of L-phosphinothricin potassium

[0028] I.2: A mixture of X% w / w L-glufosinate and Y% w / w D-glufosinate, wherein X ≥ 95 and Y ≤ 5, and wherein X + Y is 100.

[0029] I.2.a: A mixture of X% w / w L-ammonium glufosinate and Y% w / w D-ammonium glufosinate, wherein X ≥ 95 and Y ≤ 5, and wherein X + Y is 100.

[0030] I.2.b: A mixture of X% w / w L-glufosinate sodium and Y% w / w D-glufosinate sodium, wherein X ≥ 95 and Y ≤ 5, and wherein X + Y is 100.

[0031] I.2.c: A mixture of X% w / w L-glufosinate-potassium and Y% w / w D-glufosinate-potassium, wherein X ≥ 95 and Y ≤ 5, and wherein X + Y is 100.

[0032] I.3: A mixture of X% w / w L-glufosinate and Y% w / w D-glufosinate, wherein X ≥ 90 and Y ≤ 10, and wherein X + Y is 100.

[0033] I.3.a: A mixture of X% w / w L-ammonium glufosinate and Y% w / w D-ammonium glufosinate, wherein X ≥ 90 and Y ≤ 10, and wherein X + Y is 100.

[0034] I.3.b: A mixture of X% w / w L-glufosinate sodium and Y% w / w D-glufosinate sodium, wherein X ≥ 90 and Y ≤ 10, and wherein X + Y is 100.

[0035] I.3.c: A mixture of X% w / w L-glufosinate-potassium and Y% w / w D-glufosinate-potassium, wherein X ≥ 90 and Y ≤ 10, and wherein X + Y is 100.

[0036] I.4: A mixture of X% w / w L-glufosinate and Y% w / w D-glufosinate, wherein X ≥ 80 and Y ≤ 20, and wherein X + Y is 100.

[0037] I.4.a: A mixture of X% w / w L-ammonium glufosinate and Y% w / w D-ammonium glufosinate, wherein X ≥ 80 and Y ≤ 20, and wherein X + Y is 100.

[0038] I.4.b: A mixture of X% w / w L-glufosinate sodium and Y% w / w D-glufosinate sodium, wherein X ≥ 80 and Y ≤ 20, and wherein X + Y is 100.

[0039] I.4.c: A mixture of X% w / w L-glufosinate-potassium and Y% w / w D-glufosinate-potassium, wherein X ≥ 80 and Y ≤ 20, and wherein X + Y is 100.

[0040] I.5: A mixture of X% w / w L-glufosinate and Y% w / w D-glufosinate, wherein X ≥ 70 and Y ≤ 30, and wherein X + Y is 100.

[0041] I.5.a: A mixture of X% w / w L-ammonium glufosinate and Y% w / w D-ammonium glufosinate, wherein X ≥ 70 and Y ≤ 30, and wherein X + Y is 100.

[0042] I.5.b: A mixture of X% w / w L-glufosinate sodium and Y% w / w D-glufosinate sodium, wherein X ≥ 70 and Y ≤ 30, and wherein X + Y is 100.

[0043] I.5.c: A mixture of X% w / w L-glufosinate-potassium and Y% w / w D-glufosinate-potassium, wherein X ≥ 70 and Y ≤ 30, and wherein X + Y is 100.

[0044] The compounds II as well as their pesticidal action and their methods of production are generally known, for example, from the Compendium of Pesticide Common Names (https: / / pesticidecompendium.bcpc.org), and from other sources.

[0045] In the mixture of the present invention, the weight ratio of compound I to compound II is preferably from 1000:1 to 1:500, 400:1 to 1:40, more preferably 500:1 to 1:250, in particular from 200:1 to 1:20, even more preferably from 100:1 to 1:10, most preferably 50:1 to 1:5, 50:1 to 10:1, 50:1 to 5:1, 50:1 to 2:1, 400:1 to 5:1. :1 to 1:5, 40:1 to 10:1, 40:1 to 5:1, 40:1 to 2:1, 30:1 to 1:5, 30:1 to 10:1, 30:1 to 5:1, 30:1 to 2:1, 20:1 to 1:5, 20:1 to 10:1, 20:1 to 5:1, 20:1 to 2:1, 10:1 to 1:5, 10:1 to 5:1, 10:1 to 2:1, 2:1 to 1:1.

[0046] In addition, mixtures containing L-glufosinate ammonium or L-glufosinate sodium in the form of L-glufosinate salts, or L-glufosinate in the form of free acid are preferred. Particularly preferred are mixtures containing L-glufosinate ammonium in the form of L-glufosinate salts.

[0047] Preferred compounds II are fluazifop-M, tetraflupyralid, quinclorac, bispyribac, pyridazione, benzafluazione, triazosulfuron, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, triazosulfuron, isocyanate, quinclorac, pyraclostrobin and bromoxynil.

[0048] In one embodiment of the present invention, compound II is fluazifop-M.

[0049] In another embodiment of the present invention, compound II is tetrafluthrin.

[0050] In one embodiment of the present invention, compound II is oxadiazine.

[0051] In one embodiment of the present invention, compound II is quinpyraclostrobin.

[0052] In one embodiment of the present invention, Compound II is bromoxynil.

[0053] Therefore, a preferred mixture according to the present invention is a mixture of L-glufosinate ammonium or L-glufosinate sodium in the form of L-glufosinate salt or L-glufosinate in the form of free acid and a compound II selected from the group consisting of fluazifop-M, tetraflupyralid, quinclorac, bispyribac, pyridazione, benzafluazione, triazosulfuron, fluclorac, fluazifop-butyl, flupyralid, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, triazosulfuron, isoxaflutamide, pyraclostrobin and bromoxynil.

[0054] Preferred mixtures according to the invention are mixtures of L-glufosinate ammonium or L-glufosinate sodium in the form of L-glufosinate salts or L-glufosinate in the form of free acids and at least one herbicidal compound II selected from the group consisting of fluazifop-M, tetraflupyralid, quinclorac, bispyribac, triazosulfuron, benzafluazione, pyridazione, fluazifop-butyl, fluazifop-butyl and isoxadiazine.

[0055] A more preferred mixture of the present invention is a mixture of L-glufosinate ammonium or L-glufosinate sodium in the form of L-glufosinate salt or L-glufosinate in the form of free acid and a herbicidal compound II selected from the group consisting of fluazifop-M, tetrafluthrin and isoxadiazine.

[0056] Even more preferred mixtures of the present invention are mixtures of L-glufosinate ammonium and a herbicidal compound II selected from the group consisting of fluazifop-M, tetrafluthrin and isoxadiazine.

[0057] All preferred mixtures are listed in Table 2, wherein the following abbreviations are used in Table 1:

[0058] Table 1

[0059]

[0060]

[0061] Table 2

[0062]

[0063]

[0064] In another embodiment of the present invention, the mixture is a mixture of L-glufosinate ammonium or L-glufosinate sodium in the form of L-glufosinate salt or L-glufosinate in the form of free acid and fluazifop-M, tetrafluthrin or isoxadiazine as compound II.

[0065] In a preferred embodiment of the present invention, the mixture is a mixture of L-glufosinate ammonium or L-glufosinate sodium in the form of L-glufosinate salt or L-glufosinate in the form of free acid and fluazifop-M as compound II.

[0066] In another preferred embodiment of the present invention, the mixture is a mixture of L-glufosinate ammonium or L-glufosinate sodium in the form of L-glufosinate salt or L-glufosinate in the form of free acid and tetrafluthrin as compound II.

[0067] In another preferred embodiment of the present invention, the mixture is a mixture of L-glufosinate ammonium or L-glufosinate sodium in the form of L-glufosinate salt or L-glufosinate in the form of free acid and isoxadiazole as compound II.

[0068] Preference is therefore given to mixtures M-1, M-2, M-17, M-20, M-21, M-36, M-40, M-41 and M-58.

[0069] All the above-mentioned mixtures are referred to below as "mixtures according to the invention".

[0070] The mixtures according to the invention may further contain one or more insecticides, fungicides, herbicides.

[0071] The mixtures of the present invention can be converted into conventional types of agrochemical mixtures, such as solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressed products, capsules and mixtures thereof. Examples of mixture types are suspensions (e.g., SC, OD, FS), emulsifiable concentrates (e.g., EC), emulsions (e.g., EW, EO, ES, ME), capsules (e.g., CS, ZC), pastes, pastilles, wettable powders or dusts (e.g., WP, SP, WS, DP, DS), pressed products (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), insecticide preparations (e.g., LN), and gel formulations (e.g., GF) for treating plant propagation materials such as seeds. These and additional mixture types are defined in "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th edition, May 2008, CropLife International.

[0072] These mixtures are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

[0073] Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, antifreeze agents, defoamers, colorants, tackifiers and adhesives.

[0074] Suitable solvents and liquid carriers are water and organic solvents, such as medium to high boiling mineral oil fractions, for example kerosene, diesel; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, for example toluene, paraffins, tetralin, alkylated naphthalenes; alcohols, for example ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, for example cyclohexanone; esters, for example lactates, carbonates, fatty acid esters, γ-butyrolactone; fatty acids; phosphonates; amines; amides, for example N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.

[0075] Suitable solid carriers or fillers are mineral earths, for example silicates, silica gel, talc, kaolin, limestone, lime, chalk, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, for example cellulose, starch; fertilizers, for example ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; products of plant origin, for example cereal flour, bark flour, wood flour, nut shell flour and mixtures thereof.

[0076] Suitable surfactants are surface-active compounds such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifiers, dispersants, solubilizers, wetting agents, penetration enhancers, protective colloids, or adjuvants. Examples of surfactants are listed in McCutcheon's, Volume 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International or North American Edition).

[0077] Suitable anionic surfactants are alkali metal salts, alkaline earth metal salts or ammonium salts of sulfonates, sulfates, phosphates, carboxylates and mixtures thereof. The example of sulfonates is alkyl aryl sulfonates, diphenyl sulfonates, α-olefin sulfonates, lignin sulfonates, fatty acids and oily sulfonates, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalene, sulfonates of dodecyl- and tridecylbenzene, sulfonates of naphthalene and alkylnaphthalene, sulfosuccinates or sulfosuccinamates. The example of sulfates is sulfates of fatty acids and oily sulfates, sulfates of ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols or sulfates of fatty acid esters. The example of phosphates is phosphate esters. The example of carboxylates is alkyl carboxylates and carboxylated alcohols or alkylphenol ethoxylates.

[0078] Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters that have been alkoxylated by 1 to 50 equivalents. Ethylene oxide and / or propylene oxide can be used for alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerides or monoglycerides. Examples of sugar-based surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters or alkyl polyglucosides. Examples of polymeric surfactants are homopolymers or copolymers of vinyl pyrrolidone, vinyl alcohol or vinyl acetate.

[0079] Suitable cationic surfactants are quaternary ammonium surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups or salts of long-chain primary amines. Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable block polymers are AB or ABA type block polymers comprising blocks of polyethylene oxide and polypropylene oxide, or ABC type block polymers comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polyalkalis. The example of polyacids is the alkali metal salt of polyacrylic acid or polyacid comb-like polymers. The example of polyalkalis is polyvinylamine or polyvinylamine.

[0080] Suitable adjuvants are compounds which have negligible pesticidal activity or even no pesticidal activity and which improve the biological performance of the inventive mixture on the target. Examples are surfactants, mineral or vegetable oils, and other adjuvants. Additional examples are listed in Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, Chapter 5.

[0081] Suitable thickeners are polysaccharides (eg xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates and silicates.

[0082] Suitable bactericides are bronopol and isothiazolinone derivatives, such as alkylisothiazolinones and benzisothiazolinones.

[0083] Suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerol.

[0084] Suitable defoamers are silicones, long-chain alcohols and salts of fatty acids.

[0085] Suitable colorants (e.g., red, blue or green) are pigments with low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g., iron oxide, titanium oxide, iron hexacyanoferrate) and organic colorants (e.g., alizarin colorants, azo colorants and phthalocyanine colorants).

[0086] Suitable tackifiers or binders are polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylates, biological or synthetic waxes and cellulose ethers.

[0087] Examples of mixture types and their preparation are:

[0088] i) Water-soluble concentrates (SL, LS)

[0089] 10 wt% to 60 wt% of the mixture according to the invention and 5 wt% to 15 wt% of a wetting agent (eg alcohol alkoxylate) are dissolved in water and / or a water-miscible solvent (eg alcohol) added to 100 wt%. The active substance dissolves on dilution with water.

[0090] ii) Dispersible Concentrate (DC)

[0091] 5 wt% to 25 wt% of the mixture of the present invention and 1 wt% to 10 wt% of a dispersant (eg, polyvinyl pyrrolidone) are dissolved in an organic solvent (eg, cyclohexanone) added to 100 wt%, and diluted with water to obtain a dispersion.

[0092] iii) Emulsifiable concentrates (EC)

[0093] 15-70 wt% of the mixture of the present invention and 5-10 wt% of an emulsifier (eg calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in a water-insoluble organic solvent (eg aromatic hydrocarbon) added to 100 wt%, and diluted with water to obtain an emulsion.

[0094] iv) Emulsion (EW, EO, ES)

[0095] 5 wt% to 40 wt% of the mixture of the present invention and 1 wt% to 10 wt% of an emulsifier (e.g., calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20 wt% to 40 wt% of a water-insoluble organic solvent (e.g., aromatic hydrocarbon). The mixture is introduced into 100 wt% of water by an emulsifier and made into a uniform emulsion. The emulsion is diluted with water to obtain an emulsion.

[0096] v) Suspension (SC, OD, FS)

[0097] In a stirred ball mill, 20-60 wt% of the mixture according to the invention are comminuted with addition of 2-10 wt% of dispersants and wetting agents (e.g. sodium lignin sulfonate and alcohol ethoxylate), 0.1-2 wt% of thickener (e.g. xanthan gum) and up to 100 wt% of water to give a good suspension of active substance. Dilution with water gives a stable suspension of active substance. For FS-type mixtures, a maximum of 40 wt% of binder (e.g. polyvinyl alcohol) is added.

[0098] vi) Water dispersible granules and water soluble granules (WG, SG)

[0099] 50 wt % to 80 wt % of the mixture according to the invention is finely ground with the addition of 100 wt % of dispersants and wetting agents (e.g. sodium lignin sulfonate and alcohol ethoxylate) and made into water-dispersible or water-soluble granules by means of technical devices (e.g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.

[0100] vii) Water dispersible powders and water soluble powders (WP, SP, WS)

[0101] 50 wt % to 80 wt % of the mixture according to the invention are ground in a rotor-stator mill with addition of 1 wt % to 5 wt % of a dispersant (e.g. sodium lignin sulfonate), 1 wt % to 3 wt % of a wetting agent (e.g. alcohol ethoxylate) and up to 100 wt % of a solid carrier (e.g. silica gel). Dilution with water gives a stable dispersion or solution of the active substance.

[0102] viii) Gel (GW, GF)

[0103] In a stirred ball mill, 5-25 wt% of the mixture according to the invention is comminuted with addition of 3-10 wt% of a dispersant (e.g. sodium lignin sulfonate), 1-5 wt% of a thickener (e.g. carboxymethyl cellulose) and up to 100 wt% of water to give a fine active substance suspension. Dilution with water gives a stable active substance suspension.

[0104] ix) Microemulsion (ME)

[0105] 5-20 wt% of the mixture of the present invention is added to 5-30 wt% of an organic solvent blend (e.g., fatty acid dimethylamide and cyclohexanone), 10-25 wt% of a surfactant blend (e.g., alcohol ethoxylate and arylphenol ethoxylate) and to 100 wt% of water. The mixture is stirred for 1 hour to spontaneously generate a thermodynamically stable microemulsion.

[0106] x) Microcapsules (CS)

[0107] An oil phase comprising 5 wt% to 50 wt% of the mixture of the invention, 0 wt% to 40 wt% of a water-insoluble organic solvent (e.g., aromatic hydrocarbons), 2 wt% to 15 wt% of acrylic monomers (e.g., methyl methacrylate, methacrylic acid, and diacrylates or triacrylates) is dispersed in an aqueous solution of a protective colloid (e.g., polyvinyl alcohol). Free radical polymerization initiated by a free radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5 wt% to 50 wt% of the mixture of the invention, 0 wt% to 40 wt% of a water-insoluble organic solvent (e.g., aromatic hydrocarbons) and isocyanate monomers (e.g., diphenylmethylene-4,4'-diisocyanate) is dispersed in an aqueous solution of a protective colloid (e.g., polyvinyl alcohol). Addition of a polyamine (e.g., hexamethylenediamine) results in the formation of polyurea microcapsules. The amount of monomers is 1 wt% to 10 wt%. wt% relative to the total CS mixture.

[0108] xi) Dustable powders (DP, DS)

[0109] 1 wt% to 10 wt% of the mixture according to the invention is finely ground and mixed intimately with up to 100 wt% of a solid carrier (eg finely divided kaolin).

[0110] xii) Granules (GR, FG)

[0111] 0.5 wt% to 30 wt% of the mixture of the invention is finely ground and combined with a solid carrier (eg silicate) added to 100 wt%. Granulation is achieved by extrusion, spray drying or fluidized bed.

[0112] xiii) Ultra Low Volume Liquids (UL)

[0113] 1 wt% to 50 wt% of the mixture of the present invention is dissolved in an organic solvent (eg aromatic hydrocarbon) added to 100 wt%.

[0114] Mixture types i) to xiii) may optionally contain further auxiliaries, such as 0.1 wt% to 1 wt% of bactericides, 5 wt% to 15 wt% of antifreeze agents, 0.1 wt% to 1 wt% of antifoams, and 0.1 wt% to 1 wt% of colorants.

[0115] The resulting agrochemical mixtures generally contain between 0.01% and 95%, preferably between 0.1% and 90%, in particular between 0.5% and 75% by weight of active substances. The active substances are employed in a purity (according to the NMR spectrum) of from 90% to 100%, preferably from 95% to 100%.

[0116] Solutions (LS), suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually used for the purpose of treating plant propagation materials, especially seeds. After two to ten times dilution, the active substance concentration in the ready-to-use preparations of the mixtures in question is from 0.01% to 60% by weight, preferably from 0.1% to 40%. Application can be carried out before or during sowing. Methods for applying the mixtures of the present invention and mixtures thereof, respectively, to plant propagation materials, especially seeds, include seed dressing, coating, granulation, dusting, soaking and in-furrow application methods of the propagation materials. Preferably, the mixtures of the present invention or mixtures thereof, respectively, are applied to the plant propagation materials by a method that does not induce germination, for example by seed dressing, granulation, coating and dusting.

[0117] The present invention also relates to herbicidal formulations comprising a herbicidally active mixture as defined herein and at least one carrier material (including liquid and / or solid carrier materials).

[0118] Various types of oils, wetting agents, adjuvants, fertilizers, or micronutrients and additional pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) can be added to the active substance or the mixture according to the invention comprising the active substance as a premix or, if appropriate, not until just before use (tank mix). These agents can be admixed with the mixture according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

[0119] The user usually applies the mixture according to the present invention by a pre-dosing device, a backpack sprayer, a spray tank, a spray aircraft or an irrigation system. Usually, the agrochemical mixture is made to the desired application concentration with water, a buffer, and / or an additional adjuvant, and thus obtains the instant spray liquid or agrochemical mixture according to the present invention. Usually, 20 to 2000 liters, preferably 50 to 400 liters of instant spray liquid are applied per hectare of agricultural available area.

[0120] As mentioned above, the present invention also relates to the use of the mixture as defined herein for controlling undesirable vegetation in pest control programs, in industrial vegetation management and forestry, in vegetables and perennial crops, and in turf and lawns, wherein the mixture according to the invention can be applied before or after emergence, i.e. before, during and / or after the emergence of the undesirable plants. Preferably, it is applied as a post-emergence treatment, i.e. during and / or after the emergence of the undesirable plants. Herein, the mixture according to the invention is applied to the site where the crop is to be planted before the crop is planted or before emergence.

[0121] Therefore, the present invention also relates to a method for killing unwanted vegetation in crops, which method comprises applying the mixture of the present invention to the site where the crops are to be planted before planting (or sowing) or emergence of the crops. Herein, the mixture of the present invention is applied to unwanted vegetation or its site.

[0122] The present invention therefore relates to a method for controlling unwanted vegetation, which method comprises applying the mixture according to the invention to a locus where unwanted vegetation is present or is expected to be present, wherein the application can be carried out before, during and / or after the emergence of the unwanted vegetation, preferably during and / or after the emergence of the unwanted vegetation.

[0123] As used herein, the terms "control" and "controlling" are synonymous.

[0124] As used herein, the terms "unwanted vegetation," "unwanted species," "unwanted plants," "noxious plants," "unwanted weeds," or "noxious weeds" are synonyms.

[0125] As used herein, the term "locus" means an area, typically a field, where vegetation or plants are growing or will grow.

[0126] In such killing plan, the mixture of the present invention can be before the crop plant sowing (planting) or after the crop plant sowing (or planting) but before the crop plant emerges, particularly before sowing. The mixture of the present invention is preferably used before the crop plant sowing. For killing, the mixture of the present invention will usually be used at most 9 months, often at most 6 months, preferably at most 4 months before the planting crop. Killing can be carried out on a date of 1 day before the crop plant emerges, and preferably on a date before the crop plant sowing / planting, preferably at least one day before planting, preferably at least 2 days and particularly at least 4 days, or 6 months to 1 day before emerging, particularly 4 months to 2 days before emerging and more preferably 4 months to 4 days before emerging. Of course, killing can be repeated within this time frame and used once or repeatedly, for example once, twice, three times, four times or five times.

[0127] The special benefit of the mixture of the present invention is that it has very good post-emergence herbicide activity, i.e. it shows good herbicidal activity for the undesirable plants that have emerged. Therefore, in a preferred embodiment of the present invention, the mixture of the present invention is applied after the emergence of the undesirable plants, i.e. during and / or after the emergence of the undesirable plants. When the undesirable plants start from leaf development to flowering, it is particularly advantageous to apply the mixture of the present invention after emergence. The mixture of the present invention is particularly useful for controlling undesirable vegetation that has developed to a state that is difficult to control with conventional killing mixtures, i.e. when the individual weeds are higher than 10 cm (4 inches) or even higher than 15 cm (6 inches) and / or for controlling heavy weed populations.

[0128] In the case of post-emergence treatment of plants, the inventive mixtures are preferably applied by foliar application.

[0129] If the active compounds I and II are not well tolerated by certain crop plants, an application technique can be used in which the herbicidal composition is sprayed with the aid of spray equipment in such a way that as little contact as possible with the leaves of sensitive crop plants is avoided, while the active compound reaches the leaves of unwanted plants growing below, or the exposed soil surface (post-directed, lay-by). In addition, spray hoods can be used.

[0130] Application can be carried out, for example, by customary spraying techniques, using water as carrier, using spray mixtures in amounts of generally from 10 to 2000 l / ha, in particular 50 to 1000 l / ha.

[0131] The required application rate of the pure active compound mixture depends on the density of the undesirable vegetation, the development stage of the plants, the climatic conditions of the location where the mixture is used and the application method. Usually, the application rate of the mixture is from 55 to 6000 g / ha, preferably from 100 to 5000 g / ha, from 200 to 4000 g / ha and more preferably from 300 to 3000 g / ha of active ingredient (ai).

[0132] When using the inventive mixture in the method according to the invention, the active compounds present in the inventive mixture can be applied simultaneously or sequentially where undesirable vegetation may occur. In this context, it is not important whether the individual compounds present in the inventive mixture are formulated jointly or separately and applied jointly or separately, and in the case of separate application, the order in which the application is carried out is also not important. It is only necessary that the individual compounds present in the inventive mixture are applied within a time frame that allows the active ingredients to act simultaneously on the undesirable plants.

[0133] As mentioned above, the mixtures according to the invention have several advantages, namely an enhanced herbicidal action compared to mixtures of racemic glufosinate and the herbicide compound II.

[0134] In addition, the present invention mixture demonstrates lasting herbicidal activity, even under difficult climatic conditions, allows to use more flexibly in killing and using and minimize the risk of weeds escaping thus.In addition, the present invention mixture and some conventional crop plants and with herbicide tolerant crop plants demonstrate excellent crop compatibility, that is, it is used for these crops so that the damage of crop plants is reduced and / or the damage of crop plants can not be increased.Therefore, the present invention mixture can also be used after crop plants emerge.The present invention mixture can also show the acceleration to harmful plants, that is, compared with the mixture of racemic glufosinate-ammonium and herbicidal compounds II, they can realize the damage to harmful plants faster.

[0135] In the method of the present invention, L-glufosinate alone as well as the mixtures of the present invention are suitable for controlling a large number of harmful plants in crops, including monocotyledonous weeds, in particular annual weeds, such as grass weeds (grasses), including Echinochloa species, such as Echinochloa crusgalli var. crus-galli, Echinchloa walteri (Pursh) Heller, Jungle rice / Echinochloa colona, ​​Echinochloa crus-pavonis, Echinochloa oryzicola; Digitaria species, such as crabgrass / Digitaria sanguinalis, Digitaria horizontalis, sourgrass (Digitaria insularis) or naked crabgrass / Digitaria nuda; Setaria species, such as Digitaria sanguinalis, Digitaria horizontalis, sourgrass (Digitaria insularis) or naked crabgrass (Digitaria nuda); Setaria species, such as Digitaria spp. species, such as green foxtail (Setaria viridis), big foxtail (Setaria faberii), golden foxtail (Setaria glauca or Setaria pumila), or barbed foxtail (Setaria verticillata); sorghum, such as johnsongrass (Sorghumhalepense Pers.)); Avena, such as wild oats (Avena fatua), Avenasterillis or Avena strigosa; Terrestris, such as field sandbur (Cenchrus pauciflorus) or Cenchrus echinatus; Bromus, such as Japanese brome (Bromus japonicus Thunb), poor brome (Bromus sterilis) or dry brome (Bromustectorum); Lolium; Phalaris, such as Phalaris brachystachys, Phalaris minor or Phalaris persicaria; Panicum; Panicum, such as fallpanicum (Panicum dichotomiflorum), Panicum fasciculatum, or Panicum maximum; Brachiaria; annual bluegrass (Poa annua); Alopecurus spp., such as blackgrass (Alopecurus myosuroides), Alopecurusaequalis Sobol, or Alopecurus japonicus Steud; Aegilops spp., such as Aegilops cylindrica or Aegylops tauschii; Apera spica-venti; Eleusine indica; Cynodon dactylon; couch grass (Agropyron repens or Elymus repens); Agrostis alba); Beckmannia syzigachne (Steud.) Fernald; Chloris spp., such as Chloris virgata; Commelina spp., such as Commelina benghalensis, Commelina communis, Commelina diffusa or Commelina erecta; Dactyloctenium aegyptium; Hordeum jubatum, Hordeum leporinum; Imperata cylindrica; Ischaemum rogusum, Ixophorus unisetus; Leerisa hexandra; Leersia japonica; Leptochloa spp., such as Leptochloa chinensis, Leptochloa tuftica fascicularis, Leptochloa afiliformis or Leptochloa panicoides; Lolium spp., such as Lolium multiflorum, Lolium perenne, Lolium persicum or Lolium rigidum; Luziola subintegra; Murdannia nudiflora (L.) Brenan; Oryza latifolia, Oryza rufipogon; Paspalum distichum, Paspalum spp.; Pennisetum americanum, Pennisetum purpureum; Phleum paniculatum; Phragmites australia; Ploypogon fugax.N.; Poa spp., such as Poa annua or Poa trivialis L.; Puccinellia distans; Rott boellia cochinchinensis; Sclerochloa kengiana (Ohwi) Tzvel.); Trichloris crinita; Urochloa or Brachiaria, such as Brachiaria decumbens, Brachiaria plantaginea, Brachiaria platyphylla; Urochloa panicoides, Urochloa ramosa, etc.

[0136] L-Glufosinate alone and the mixtures of the invention are also suitable for controlling a large number of dicotyledonous weeds, especially broadleaf weeds including Polygonum, such as wild buckwheat (Polygonum convolvolus), Pennsylvanian Polygonum (Polygonumpensilvanicum), Spring Polygonum (Polygonum persicaria) or prostrate knotweed (Polygonum aviculare); Amaranth, such as pigweed (Amaranthus retroflexus), Palmer amaranth (Amaranthus palmeri), tall waterhemp (Amaranthus tuberculatus or Amaranthus rudis), redroot pigweed (Amaranthus retroflexus), green amaranth (Amaranthus hybridus), purple amaranth (Amaranthus lividus), prickly amaranth (Amaranthus spinosus) or green amaranth (Amaranthus quitensis); Chenopodium species, such as common goosefoot (Chenopodium album L.), small-leaved goosefoot (Chenopodium serotinum) or quinoa (Chenopodium quinoa); Ambrosia species, such as prickly sida (Sida spinosa L.); Ambrosia species, such as common ragweed (Ambrosia artemisiifolia) or giant ragweed (Ambrosia trifida); Acanthos permum species; Anthemis species, such as Anthemis arvensis or Anthemis cotula; Atriplex species; Cirsium species, such as Cirsium arvense; Convolvulus species, such as field bindweed (Convolvulus arvensis);Conyza species, such as horseweed (Conyza canadensis / Erigeroncanadensis) or hairy fleabane (Conyza bonariensis / Erigeronbonariensis); Cassia species; Datura species, such as jimsonweed (Datura stramonium); Euphorbia species, such as toothed spurge (Euphorbia dentata), Euphorbia hirta, Euphorbia helioscopia or gorilla grass (Euphorbia heterophylla); Geranium species, such as Geranium longroot (Geranium stramonium). donianum or Geranium pusillum; Galinsoga species; morning glory (Ipomoea species); Lamium species, such as henbit dead-nettle (Lamium amplexicaule); Malva species, such as dwarf mallow (Malva neglecta) or cheeseweed (Malwa parviflora); Matricaria species, such as chamomile (Matricaria chamomilla) or light chamomile (Matricaria inodora); Sysimbrium species; Solanum species, such as black nightshade (Solanum nigrum); Xanthium species; Veronica species. species, such as Veronica polita; Viola species; common chickweed (Stellaria media);velvetleaf (Abutilon theophrasti); Sesbania species, such as Sesbania exaltata, Sesbania herbacea, or hemp sesbania (Sesbania exaltata Cory); Anodacristata; Bidens species, such as Bidens frondosa or Bidens pilosa; Brassica kaber; Capsella species, such as Capsella media or Capsella bursa-pastoris; Centaurea cyanus; Hemp nettle (Galeopsis tetrahit); Galium aparine; sunflower (Helianthus annuus); South American mountain leech (Desmodium tortuosum); Kochia scoparia; Mercurialis indigo (Mercurialisannua); forget-me-not (Myosotis arvensis); corn poppy (Papaver rhoeas); Raphanus species, such as wild radish (Raphanus raphanistrum); Salsola species, such as Salsola tragus or Salsola kali; wild mustard (Sinapis arvensis); Sonchus species, such as Sonchus asper, Sonchus arvensis or Sonchus oleraceus; Thlaspi arvense; Tagetes minuta; Richarddia species, such as Richardia scabra or Richardia brasiliensis; Aeschynomeme species, such as Aeschynomene denticulata, Aeschynomene indica or Aeschynomene rudis;Alisma species, such as Alisma canaliculatum or Alisma plantago-aquatica; Borreria species, such as Borreria verticillata; Brassica rapa; Carduus acanthoides; Parietaria debilis; Portulaca oleracea; Ipomoea species, such as I pomoea grandifolia, I pomoea hederacea, Ipomoea indivisa, Ipomoea lacunose, Ipomoea lonchophylla or Ipomoea wrightii; Senna obtusifolia; sida) (Sida rhombifolia) or Sida spinosa; Spermacoce latifolia; Tridax procumbens; Trianthema portulacastrum; Parthenium hysterophorus; Portulaca oleracea; Acalypha australis; Ammi majus; Atriplex; Orobanche species; Indigofera spp.; Silk Road thistle; Calystegia sepium; Chickweed; Lamium species; Viola species; Celosia argentea; Melampodium divaricatum; Cleome viscosa; Molugo verticilatus; Borhevia erecta; Gomphrena species; Nicandra physalodes; Ricinus communis; Geranium dissectum;Alternantheraspecies, such as Althernanthera philoxeroides or Alternantheratenella; Ammannia species, such as Ammania coccinea; Anacamtodon fortunei Mitt.; Anagallis arvensis; Aneilemakeisak; Arenaria serpyllifolia; Argemone mexicana; Asphodelus tenuifolius; Atriplex patula; Bacoparotundifolia; Brassica napus; Caperonia species, such as Caperonia castaneifolia or Caperonia sibiricum. palustris; Cephalanthus segetum; Corynopus didymus; Crepiscapillaris; Crepis tectorum; Croton lobatus; Descuminia sophia (L.); Descurainia pinnata; Echinodorus grandiflorus; Eclipta alba; Eclipta prostrata; Eichhorniacrassipes; Eleocharis species; Equisetum arvense; Fallopia convolvulus; Heteranthera limosa; Jussiaea species; Kallstroemia maxima; Lactuca serriola; Lathyrus aphaca; Launea mudicaulis; Leucas chinensis; Limnocharis flava; Lindernia dubia;Lindernia pyxidaria; Litospermum arvense; Ludwigia species, such as Ludwigia octovallis; Macroptilium lathyroides; Malachium aquaticum (L.); Melilotus species; Merremia aegyptia; Momordica charantia; Monochoria hastate; Monochoria vaginalis; Mucuna species; Murdannia nudiflora; Oxalis neaei; Phylanthus species; Physalis species; Pistia stratiotes; Potamogeton distinctus; Rorippa islandica; Rotalaindica; Rotala ramosior; Rumex dentatus; Rumex obtusifolius; Sagittaria montevidensis, Sagittaria pygmaea Miq., Sagittaria sagittifolia, Sagittaria trifolia L.; Senecio vulgaris; Sicyos polyacanthus; Silene gallica; chenopo Sisymbrium, such as Sisymbrium oficinale; Solanum; Spergula arvensis; Sphenoclea zeylanica; Trianthem spp.); Tripleurospermum inodorum; Veronica, such as Veronica persica or Veronica polita; Vicia sativa, etc.;

[0137] L-Glufosinate alone and the mixtures of the present invention are useful for controlling a wide variety of annual and perennial weeds in the Cyperaceae family, including Cyperus species, such as purple nutsedge (Cyperus rotundus L.), yellow nutsedge (Cyperus esculentus L.), hime-kugu (Cyperus brevifolius H.), sedge weeds (Cyperus microiria Steud), rice flatsedge (Cyperus iria L.), Cyperus difformis, Cyperus difformis L., Cyperus esculentus, Cyperus ferax, Cyperus flavus, Cyperus serratus, Cyperus ferax ... iria), Cyperus lanceolatus, Cyperus odoratus, Cyperus rotundus, Cyperus serotinus Rottb., Eleocharis acicularis, Eleocharis kuroguwai, Fimbristylis dichotoma, Fimbristylismiliacea, Scirpus grossus, Scirpus juncoides, Scirpusjuncoides Roxb, Scirpus or Bolboschoenus maritimus, Scirpus or Schoenoplectus mucronatus, Scirpus planiculmis Fr. Schmidt, etc.

[0138] L-Glufosinate alone as well as the mixtures according to the invention are also suitable for controlling weeds which are resistant to customary herbicides, such as, for example, glyphosate-resistant weeds, weeds resistant to auxin inhibitor herbicides, such as, for example, 2,4-D or dicamba, weeds resistant to photosynthesis inhibitors, such as, for example, atrazine, weeds resistant to ALS inhibitors, such as, for example, sulfonylureas, imidazolinones or triazolopyrimidines, weeds resistant to ACCase inhibitors, such as, for example, clodinafop-butyl, clethodim or pinoxaden, or weeds resistant to protoporphyrinogen-IX-oxidase inhibitors, such as, for example, sulfentrazone, fluazifop-butyl, fomesafen or acifluorfen, for example, the weeds listed in the International Weed Resistant Survey (http: / / www.weedscience.org / Summary / SpeciesbySOATable.aspx). In particular, they are suitable for controlling resistant weeds listed in the International Survey of Resistant Weeds, for example ACCase-resistant barnyard grass, wild oats, large-eared foxtail grass, bald barnyard grass, Japanese foxtail grass, upland brome, wild barley (Hordeum murinum), field duckbill (Ischaemum rugosum), green foxtail, false sorghum, foxtail grass (Alopecurus aequalis), Apira grass, false wild oats (Avena sterilis), wild grass, double male brome, crabgrass, paddy field barnyard grass, water barnyard grass (Echinochloaphyllopogon), small son phalaris, strange phalaris (Phalaris paradoxa), French foxtail, green foxtail, two-spiked short-spoils grass, double male brome, poor brome, foreign foxtail (Cynosurus echinatus), two-ear grass, hemostatic crabgrass, Leptochloa chinensis, hygrophila, Rochegrass, Digitaria ciliaris, Ehrharta longiflora, Eriochloa punctata, Leptochloa chinensis, European ryegrass, Polypogon fugax, Gunn's hard grass, Snowdenia polystacha, Sorghum sudanese, and Brachiaria plantaine; ALS inhibitor-resistant barnyard grass, bluegrass, wild oats, big-eared foxtail, bald barnyard grass, green-spiked amaranth, long-horned amaranth, western amaranth, suman white wine grass, retroflex amaranth, dwarf ragweed (Ambrosia artemisifolia), small pampas grass, Kochia scoparia, wild radish, spring groundsel (Seneciovernalis), Japanese alopecuroides, Bidens pilosa, Bromus chinensis, Chenopodium album, fragrant silk grass, wild barley, field duckbill, European groundsel, green foxtail grass, Oriental garlic mustard (Sisymbriumorientale), false sorghum, brown-stamen foxtail (Alopecurusaequalis), concave-headed amaranth (Amaranthus blitum), Bower's amaranth (Amaranthus powellii), Apera, false wild oats, turnip, two-sex brome, Descurainia sophia, crabgrass, water barnyard grass, water barnyard grass, white-budded orangutan, sawtooth lettuce, small-headed phragmites, miraculous phragmites, French foxtail, green foxtail, wild mustard, nightshade, sow thistle, chickweed, North American amaranth (Amaranthus blitoides), spiny amaranth, wrinkled amaranth (Amaranthus viridis), three-lobed ragweed, Bidens pilosa (Bidens subalternans), Bromus subalternus, Bromus subalternus, Shepherd's purse, Blue cornflower, Setaria officinalis, Cyperus heterophyllus, Water lice, Hemp nettle, Proto-Laura vine, Galium spurium, Sunflower, Hirschfeldia incana, Yellow rush, Limnophila erecta, Corn poppy, Guayule, Hygrophila hygrophila, Polygonum convoluted, Polygonum sorrel, Polygonum verum, Ranunculus acris, Rochefoymus, Salix montendonii, Salpinia spinulosa, Schoenoplectus mucronatus, Setaria officinalis, Xanthium strumarium, Ageratum conyzoides, Alisma orientalis, Alisma orientalis, Ammannia auriculata), long-leaved water amaranth, field water amaranth (Ammannia arvensis), stinking chamomile, round-leaved saxifraga, Biforaradians, Blyxa aubertii, Brassica tournefortii, Bromus japonicus, Bromus secalinus, Lithospermum arvense, Camelina microcarpa, Chamaesyce maculata, Chrysanthemum coronarium, Clidemia hirta, Cuscuta pentagona, Cyperus brevifolis, Cyperus sedge (Cyperus compressus), Cyperus oleifera, Cyperus rotundus, Cyperus rotundus, Damasonium minus, Diplotaxiserucoides), Diplotaxis tenuifolia, Dopatrum junceum, Echium plantaine, Elatine triandra, Felt, Erucaria hispanica, Erysimum repandum, Galium tricornutum, Iva xanthifolia, Setaria uniflora, Loblolly grass, Limnophilia sessiliflora, Lindernia micrantha, Lindernia procumbens, Ludwigia prostrata, Matricariarecutita, Mesembryanthemum crystallinum, Monochoriakorsakowii, Duck tongue grass, Myosoton aquaticum, Neslia paniculata), red rice (Oryza sativa var.sylvatica), Pentzia suffruticosa, Picrisheiracioides, Raphanus sativus, Rapistrum rugosum, Rorippaindica, Rotala indica, Rotala pusilla, Rumex dentata, Sagittaria guayensis, dwarf arrowhead, wild arrowhead, Schoenoplectus fluviatilis, Schoenoplectus juncoides, Schoenoplectus wallichii, yellow-flowered sedge, white-flowered sedge, Sinapis alba, Sisymbrium thellungii), Sorghum bicolor, Macroclaw, Imperata, Xinjiang Trifoliate Fruit, Vaccariahispanica) and wild peas; photosynthesis inhibitor resistant barnyard grass, bluegrass, big spike foxtail, bald barnyard, green spike amaranth, long-horned amaranth, western amaranth, Sumatran wine grass, retroflex amaranth, dwarf ragweed, small pampas grass, Kochia, wild radish, spring groundsel, Japanese foxtail, three-leaf Bidens, dry brome, quinoa, fragrant silk grass, field duckbill, European groundsel, green foxtail, oriental garlic mustard, concave head amaranth, Bao's amaranth, Apira grass, weed, turnip, crabgrass, white gorilla grass, small phragmites, strange phragmites, French foxtail, green foxtail, wild mustard, nightshade, chickweed, North American amaranth, wrinkled fruit amaranth, three-leaf Bidens, two spike short-stalked grass, Mengren grass (Chloris barbata), Cyperus heteroflorus, Echinochloa erecta (Echinochloa erecta), Epilobium ciliatum, Polygonum ciliatum, Polygonum voluteum, Polygonum sorrel, Polygonum schoenoides, Purslane, Water hair flower, Golden foxtail, Solanum nigrum, Ghost chicory, Populus sphaerocephalus, Vulpia bromoides, Abutilon, Amaranthus albus, Amaranthus cruentus, Arabidopsis, Heartless cabbage, Bidens tripartita, Chenopodium ficifolium, Chenopodium polyspermum, Crypsis schoenoides, Datura stramonium, Epilobium tetragonum, Galinsoga ciliata, Matricaria discoidea), Panicum capillare, Panicum lagopus, Plantago lagopus, Polygonum hydopiper, Polygonum pensylvanicum, Polygonum monspeliensis, Rostraria, smyrnacea, Rumex sylvatica, Setaria barbata, and Urtica foetida; PS-I electron transport inhibitor-resistant bluegrass, Sumatran white wine grass, Psoralea corylifolia, Japanese foxtail grass, Bidens pilosa, Fragrant silk grass, wild barley, field duckbill, Amaranthus chinensis, Solanum nigrum, Arctotheca calendula, Willow herb, Hedyotis verticillata, Solanum nigrum, European Foxtail fescue, Field bindweed, Crassocephalum crepidioides, Cupheacarthagensis), Erigeron philadelphicus, Gamochaeta pensylvanica, Landoltia punctata, Lepidium virginicum, Mazus fauriei, Mazus pumilus, Mitracarpus hirtus, Sclerochloadura, Solanum americanum, and Youngia japonica; glyphosate-resistant bluegrass, barnyard grass, green-fringe amaranth, long-horned amaranth, western amaranth, sumatrae, dwarf ragweed, small ragweed, kochia, wild radish, three-leafed bidens, fragrant silk grass, wild barley, false sorghum, turnip, two-sex brome, sawtooth lettuce, endive, spiny amaranth, three-lobed ragweed, two-eared grass, round-stemmed grass, sunflower, silver guayule, long-leaved plantain, spiny sand sedge, millet grass, arm grass (Brachiariaeruciformis), red brome (Bromus rubens), tiger tail grass (Chloris elata), truncated tiger tail grass (Chloristruncata), tiger tail grass (Chloris virgata), rough hair triproot grass (Cynodon hirsutus), willow lettuce (Lactuca saligna), slender Leptochloa (Leptochloa virgata), Paspalum paniculatum, and Long-stalked Chrysanthemum; microtubule assembly inhibitor-resistant barnyard grass, bluegrass, wild oats, large-spiked foxtail, long-horned amaranth, green foxtail, false sorghum, brown-stamen foxtail, sedge grass, and dense blue pansy (Fumaria densiflora); auxin herbicide-resistant barnyard grass, bald barnyard grass, green-spiked amaranth, western amaranth, white wine grass, Kochia scoparia, wild radish, quinoa, oriental garlic mustard, sowwort, sawtooth lettuce, wild mustard, chicory, chickweed, South African marigold, blue knapweed, hemostatic crabgrass, sunshine wafting grass (Fimbristylis miliacea), hemp nettle, original hyacinth, cleaver, short-pod mustard, yellow ash, upright skinktail, corn poppy, long-leaved plantain, tall buttercup, musk starfish (Carduus nutans), Carduus pycnocephalus, Centaurea soltitialis, Centaurea stoebe ssp. Micranthos, Silk Road thistle, knotweed, peacock barnyard grass, Solivasessilis and Sphenocleazeylanica; HPPD inhibitor-resistant Amaranthus oleraceus and Amaranthus chinensis; PPO inhibitor-resistant Amaranthus ferox, Amaranthus spicata, Amaranthus oleraceus, Amaranthus retroflexus, Amaranthus occidentalis, Dwarf ragweed, Avena sativa, Avena sativa, Artemisia selengensis, Gypsophila paniculata and Glechoma longituba; carotene biosynthesis inhibitor-resistant Hydrilla verticillata, Radish radish, Glechoma longituba and Oriental garlic mustard; VLCFA inhibitor-resistant Alopecurus macrostachya, Avena sativa and Echinochloa crusgalli.

[0139] The mixtures according to the invention are suitable for combating / controlling common harmful plants in fields where useful plants are to be grown (i.e. in crops). The mixtures according to the invention are generally suitable for combating undesirable vegetation in fields of the following crops:

[0140] - Cereal crops, including e.g.

[0141] - Cereals (small cereals) such as wheat (Triticum aestivum) and wheat-like crops such as durum (T. durum), einkorn (T. monococcum), emmer (T. dicoccon) and spelt (T. spelta), rye (Secale cereale), triticale (Tritiosecale), barley (Hordeum vulgare);

[0142] - maize (corn; Zea mays);

[0143] - Sorghum (e.g., Sorghum bicolor);

[0144] - rice (Oryza species, such as Oryza sativa and O. sativa); and

[0145] -sugar cane;

[0146] - pulses (Fabaceae), including, for example, soybeans (Glycine max.), peanuts (Arachis hypogaea) and pulse crops, such as peas, including peas (Pisum sativum), pigeon peas and cowpeas, beans, including broad beans (Vicia faba), Vigna spp. and Phaseolus spp., and lentils (Lens culinaris var.);

[0147] - the family Cruciferae, including, for example, canola (Brassica napus), rapeseed (OSR, Brassica napus), cabbage (B. oleracea var.), mustard such as B. juncea, B. campestris, B. narinosa, B. nigra and B. tournefortii; and turnip (Brassica rapa var.);

[0148] - other broadleaf crops, including, for example, sunflower, cotton, flax, linseed, sugar beet, potato and tomato;

[0149] - TNV crops (TNV: trees, nuts and vines), including, for example, grapes, citrus, pome fruits, for example, apples and pears, coffee, pistachios and oil palm, stone fruits, for example, peaches, almonds, walnuts, olives, cherries, plums and apricots;

[0150] -turf, pasture and pasture;

[0151] - Onions and garlic;

[0152] - Ornamental bulbs, such as tulips and daffodils;

[0153] - coniferous and deciduous trees, such as pine, fir, oak, maple, dogwood, hawthorn, crabapple and buckthorn (sea buckthorn); and

[0154] - Ornamental garden plants such as roses, petunias, marigolds and snapdragons.

[0155] The mixtures of the invention are particularly suitable for combating undesirable vegetation in fields of the following crop plants: small cereals such as wheat, barley, rye, triticale and durum wheat, rice, maize (corn), sugar cane, sorghum, soybeans, legumes such as peas, beans and lentils, peanuts, sunflowers, sugar beets, potatoes, cotton, Brassica crops such as rape, canola, mustard, cabbage and turnips, turf, pasture, pasture, grapes, pome fruits such as apples and pears, stone fruits such as peaches, almonds, walnuts, pecans, olives, cherries, plums and apricots, citrus, coffee, pistachios, garden ornamentals such as roses, petunias, marigolds, snapdragons, bulb ornamentals such as tulips and daffodils, coniferous and deciduous trees such as pine, fir, oak, maple, dogwood, hawthorn, crabapple and sea buckthorn.

[0156] The mixtures of the present invention are most useful for combating undesirable vegetation in fields of the following crop plants: small cereals such as wheat, barley, rye, triticale and durum wheat, rice, maize, sugar cane, soybeans, pulse crops such as peas, beans and lentils, peanuts, sunflowers, cotton, Brassica crops such as rapeseed and canola, turf, pasture, pasture, grapes, stone fruits such as peaches, almonds, walnuts, pecans, olives, cherries, plums and apricots, citrus and pistachios.

[0157] The invention further relates to the use of a mixture as defined herein for controlling unwanted vegetation in crops in a pest control program, wherein the crops are genetically engineered or produced by breeding to be resistant to one or more herbicides and / or pathogens such as phytopathogenic fungi, and / or to insect attack; preferably resistant to glufosinate-ammonium.

[0158] Thus, as used in the present invention, the term "crops" as used herein also includes (crop) plants which have been modified by mutagenesis or genetic engineering in order to provide the plants with new traits or to modify already existing traits.

[0159] Mutagenesis includes random mutagenesis techniques using X-rays or mutagenic chemicals, but also targeted mutagenesis techniques to generate mutations at specific loci in the plant genome. Targeted mutagenesis techniques often use oligonucleotides or proteins like CRISPR / Cas, zinc finger nucleases, TALENs or meganucleases to achieve targeted effects.

[0160] Genetic engineering usually uses recombinant DNA technology to produce modifications in plant genomes, and this modification can not be easily obtained by hybridization, mutagenesis or natural recombination under natural environment.Typically, one or more genes are integrated into the genome of plants to increase traits or improve traits.These integrated genes are also referred to as transgenic in the art, and the plants comprising such transgenic are called transgenic plants.Plant transformation process usually produces several transformation events, and they are different on the genomic locus of transgenic that have been integrated therein.Plants comprising specific transgenic on specific genomic locus are usually described as comprising specific "events", which are referred to by specific event names.Properties introduced into plants or modified particularly include herbicide tolerance, insect resistance, yield of improvement and tolerance to abiotic conditions like drought.

[0161] Herbicide tolerance has been generated by the use of mutagenesis as well as by genetic engineering. Plants that have been rendered tolerant to the acetolactate synthase (ALS) inhibitor herbicides by conventional mutagenesis and breeding methods include those that may be named Commercially available plant varieties. However, most herbicide tolerance traits have been generated through the use of transgenics.

[0162] Herbicide tolerance has been developed to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbicides like bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitor herbicides, and 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors like isoxathiapiprolin and mesotrione.

[0163] Transgenics that have been used to provide herbicide tolerance traits include: for glyphosate tolerance: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601, gat4621 and goxv247, for glufosinate tolerance: pat and bar, for 2,4-D tolerance: aad-1 and aad-12, for dicamba tolerance: dmo, for oxynil herbicide tolerance: bxn, for sulfonylurea herbicide tolerance: zm-hra, csr1-2, gm-hra, S4-HrA, for ALS inhibitor herbicide tolerance: csr1-2, for HPPD inhibitor herbicide tolerance: hppdPF, W336 and avhppd-03.

[0164] Transgenic maize events comprising herbicide tolerance genes are, for example, but not exclusively, DAS40278, MON801, MON802, MON809, MON810, MON832, MON87411, MON87419, MON87427, MON88017, MON89034, NK603, GA21, MZHGOJG, HCEM485, 1981-5, 676, 678, 680, 33121, 4114, 59122, 98140, Bt10, Bt176, CBH-351, DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507 and TC6275.

[0165] Transgenic soybean events comprising herbicide tolerance genes are, for example, but not exclusively, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21, A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS-81419-2, GU262, W62, W98, FG72 and CV127.

[0166] Transgenic cotton events comprising a herbicide tolerance gene are, for example, but not exclusively, 19-51a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN10224, MON1445, MON1698, MON88701, MON88913, GHB119, GHB614, LLCotton25, T303-3, and T304-40.

[0167] Transgenic canola events comprising a herbicide tolerance gene are for example, but not exclusively, MON88302, HCR-1, HCN10, HCN28, HCN92, MS1, MS8, PHY14, PHY23, PHY35, PHY36, RF1, RF2 and RF3.

[0168] Insect resistance is mainly produced by transferring bacterial genes of insecticidal proteins into plants. The most commonly used transgenics are toxin genes of Bacillus species (Bacillus spec.) and synthetic variants thereof, such as cry1A, cry1Ab, cry1Ab-Ac, cry1Ac, cry1A.105, cry1F, cry1Fa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1, cry34Ab1, cry35Ab1, cry9C, vip3A (a), vip3Aa20. However, plant-derived genes are also transferred into other plants. In particular, genes encoding protease inhibitors, such as CpTI and pinII. Another method uses transgenics to produce double-stranded RNA in plants to target and lower insect genes. The example of this transgenic is dvsnf7.

[0169] Transgenic maize events comprising a gene for an insecticidal protein or double-stranded RNA are, for example, but not exclusively, Bt10, Bt11, Bt176, MON801, MON802, MON809, MON810, MON863, MON87411, MON88017, MON89034, 33121, 4114, 5307, 59122, TC1507, TC6275, CBH-351, MIR162, DBT418 and MZIR098.

[0170] Transgenic soybean events comprising a gene for an insecticidal protein are for example, but not exclusively, MON87701, MON87751 and DAS-81419.

[0171] Transgenic cotton events comprising a gene for an insecticidal protein are, for example, but not exclusively, SGK321, MON531, MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601, Event1, COT67B, COT102, T303-3, T304-40, GFM Cry1A, GK12, MLS 9124, 281-24-236, 3006-210-23, GHB119 and SGK321.

[0172] Increased yield is achieved by increasing ear biomass using the transgene athb17 present in maize event MON87403, or by enhancing photosynthesis using the transgene bbx32 present in soybean event MON87712.

[0173] Crops containing improved oil content have been produced by using the following transgenes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A, and fatb1-A. Soybean events containing at least one of these genes are: 260-05, MON87705, and MON87769.

[0174] Tolerance to abiotic conditions, in particular drought tolerance, has been demonstrated through the use of the transgene cspB contained in maize event MON87460 and through the use of the transgene cspB contained in soybean event The included transgenic Hahb-4 was produced.

[0175] Traits are usually combined by combining genes in a transformation event or by combining different events during the breeding process. Preferred combinations of traits are herbicide tolerance to different groups of herbicides, insect tolerance to different species of insects, in particular tolerance to Lepidoptera and Coleoptera, herbicide tolerance with one or several types of insect resistance, herbicide tolerance with increased yield and a combination of herbicide tolerance and tolerance to abiotic conditions.

[0176] Plants comprising single or stacked traits and genes and events providing these traits are well known in the art. For example, detailed information about induced mutations or integrated genes and corresponding events can be obtained from the website of the agency "International Service for the Application of Agri-biotech Applications (ISAAA)" (http: / / www.isaaa.org / gmapprovaldatabase) and "Center for Environmental Risk Assessment (CERA)" (http: / / cera-gmc.org / GMCropDatabase) and patent applications like EP 3028573 and WO2017 / 011288.

[0177] Use of the mixtures of the invention on crops may result in specific effects on the crops containing a gene or event. These effects may involve changes in growth behavior or altered resistance to biotic or abiotic stress factors. Such effects may include, in particular, increased yield, increased resistance or tolerance to insect, nematode, fungus, bacteria, mycoplasma, viral or viroid pathogens, and early vigour, early or delayed maturity, cold or heat tolerance, and altered amino acid or fatty acid profiles or contents.

[0178] Furthermore, plants containing altered amounts of components or new components by the use of recombinant DNA techniques, in particular to improve the production of raw materials, such as potatoes producing increased amounts of amylopectin (e.g. Potatoes, BASF SE, Germany).

[0179] Preferred are crops that are tolerant to glufosinate, wherein the glufosinate tolerant crop plants are preferably selected from the group consisting of rice, canola, soybean, corn and cotton plants.

[0180] The transgenic maize event comprising the glufosinate tolerance gene is, for example, but not exclusively, 5307 x MIR604 x Bt11 x TC1507 x GA21 x MIR162 (Event Code: Gene: pat, for example, as Duracade TM 5222 commercially available), 59122 (event code: DAS-59122-7, gene: pat, e.g., as Herculex TM RW commercially available), 5307x MIR604 x Bt11 x TC1507 x GA21 (Event Code: Gene: pat, for example, as Duracade TM 5122 commercially available), 59122x NK603 (event code: Gene: pat, for example, as Herculex TM RW Roundup Ready TM 2 commercially available), Bt10 (gene: pat, for example, commercially available as Bt10), Bt11 (X4334CBR, X4734CBR) (event code: Gene: pat, for example, as Agrisure TMCB / LL commercially available), BT11 x 59122xMIR604 x TC1507 x GA21 (Event Code: Gene: pat, for example, as 3122 commercially available), Bt11 x GA21 (Event code: Gene: pat, for example, as Agrisure TM GT / CB / LL commercially available), Bt11 x MIR162 (Event Code: Gene: pat, for example, as Viptera TM 2100 commercially available), Bt11x MIR162 x GA21 (Event Code: Gene: pat, for example, as Viptera TM 3110 commercially available), BT11x MIR162x MIR604 (Event Code: Gene: pat, for example, as Viptera TM 3100 commercially available), Bt11x MIR162x MIR604 x GA21 (Event Code: Gene: pat, for example, as Viptera TM 3111, Viptera TM 4 commercially available), Bt11x MIR162x TC1507 x GA21 (Event Code: Gene: pat, for example, as Agrisure TM Viptera3220 commercially available), Bt11 x MIR604 (event code: Gene: pat, for example, as Agrisure TM CB / LL / RW commercially available), BT11 x MIR604 x GA21 (Event Code: Gene: pat, for example, as Agrisure TM 3000GT commercially available), Bt176 (176) (event code: SYN-EV176-9, gene: bar, for example, as NaturGard KnockOut TM, Maximizer TM Commercially available), CBH-351 (Event code: Gene: bar, for example, as Starlink TM Zea mays commercially available), DBT418 (event code: DKB-89614-9, gene: bar, e.g., as Bt Xtra TM corn commercially available), MON89034 x TC1507 x MON88017 x 59122 (Event Code: Gene: pat, for example, as SmartStax TM Commercially available), MON89034x TC1507 x NK603 (Event code: Gene:pat, for example, as PowerCore TM Commercially available), NK603x T25 (Event code: Gene: pat, for example, as Roundup Ready TM Liberty Link TM Corn was purchased from a commercial source), T14 (event code: Gene:pat, for example, as Liberty Link TM Corn was purchased from a commercial source), T25 (event code: Gene:pat, for example, as Liberty Link TM corn commercially available), T25 x MON810 (event code: Gene:pat, for example, as Liberty Link TM Yieldgard TM Corn was purchased commercially), TC1507 (event code: Gene: pat, for example, as Herculex TM I. Herculex TM CB commercially available), TC1507 x 59122x MON810x MIR604 x NK603 (Event code: Gene: pat, for example, as Optimum TM Intrasect Xtreme commercially available), TC1507 x 59122 (Event Code: Gene: pat, for example, as Herculex XTRA TMCommercially available), TC1507 x 59122x MON810 x NK603 (Event code: Gene: pat, for example, as Optimum TM Intrasect XTRA commercially available), TC1507 x59122x NK603 (event code: Gene: pat, for example, as Herculex XTRA TM RR commercially available), TC1507 x MIR604 x NK603 (Event Code: Gene: pat, for example, as Optimum TM TRIsect commercially available), TC1507 x MON810 x NK603 (Event Code: Gene: pat, for example, as Optimum TM Intrasect commercially available), TC1507 x NK603 (Event Code: Gene: pat, for example, as Herculex TM I RR commercially available), 3272x Bt11 (event code: Gene: pat), 3272x Bt11 x GA21 (Event code: Gene: pat), 3272x Bt11x MIR604 (Event code: Gene: pat), 3272x BT11xMIR604 x GA21 (Event code: Gene: pat), 33121 (event code: Gene: pat), 4114 (event code: Gene: pat), 59122x GA21 (event code: Gene: pat), 59122x MIR604 (event code: Gene: pat), 5307x MIR604 x Bt11 x TC1507 x GA21 xMIR162 (Event Code: , Gene: pat), 59122x MIR604 x GA21 (Event Code: Gene: pat), 59122x MIR604x TC1507 (Event Code: Gene: pat), 59122x MIR604 xTC1507 x GA21 (Event Code: , Gene: pat), (Event Code: Gene: pat), 59122x MON810 (event code: Gene: pat), 59122xMON810 x NK603 (Event Code: Gene: pat), 59122x TC1507x GA21 (Event code: Gene: pat), 676 (event code: Gene: pat), 678 (event code: Gene: pat), 680(Event code: Gene: pat), 98140x 59122(Event code: Gene: pat), 98140x TC1507 (event code: Gene: pat), 98140x TC1507 x 59122 (Event code: Gene: pat), 59122x MON88017 (event code: Gene: pat), Bt11x 59122 (event code: Gene: pat), Bt11x 59122x GA21 (Event code: Gene: pat), Bt11 x 59122xMIR604 (Event code: Gene: pat), Bt11x59122x MIR604 x GA21 (Event code: Gene: pat), Bt11 x 59122 x MIR604 x TC1507 (Event code: Bt11 x 59122 x MIR604 x TC1507, Gene: pat), Bt11 x 59122 x TC1507 (Event code: Gene: pat), Bt11x 59122x TC1507 x GA21 (Event code: Gene: pat), Bt11x MIR162 x TC1507 (Event code: Gene: pat), Bt11 x MIR604 x TC1507 (Event Code: Gene: pat), Bt11x TC1507 (event code: Gene: pat), Bt11x TC1507 x GA21 (Event code: Gene: pat), GA21x T25 (event code: Gene: pat), MIR162x TC1507 (event code: Gene: pat), MIR162x TC1507 x GA21 (Event code: Gene: pat), MIR604x TC1507 (event code: Gene: pat), (Event code: Gene: pat), MON89034x 59122 (event code: Gene: pat), MON89034 x 59122x MON88017 (Event Code: , Gene: pat), MON89034x TC1507 (Event Code: Gene: pat), (Event code: Gene: pat), MIR604 x TC1507 (Event code: Gene: pat), (Event code: Gene: pat), MON89034x 59122 (event code: Gene: pat), MON89034x 59122x MON88017 (Event Code: , Gene: pat), MON89034 x TC1507 (Event Code: Gene: pat), (Event code: Gene: pat), DLL25(B16)(Event code: gene: bar), MIR604 x TC1507 (event code: Gene: pat), (Event code: Gene: pat), MON89034x 59122 (event code: Gene: pat), MON89034x 59122x MON88017 (Event Code: Gene: pat), MON89034xTC1507 (event code: Gene: pat), MON89034x TC1507x59122 (event code: Gene: pat), MON89034 x TC1507 x MON88017 (Event Code: Gene: pat), MON89034x TC1507 x MON88017 x59122x DAS40278 (Event Code: Gene: pat), MON89034 x TC1507 x MON88017 x DAS40278 (Event Code: Gene: pat), MON89034x TC1507 x NK603 x DAS40278 (Event Code: Gene: pat), NK603x MON810 x 4114x MIR 604 (Event Code: MON-00603-6x MON-00810-6xDP004114-3x SYN-IR604-4, Gene: pat), TC1507 x MON810 x MIR604 x NK603 (Event Code: Gene: pat), TC1507 x 59122x MON810 (Event Code: Gene: pat), TC1507x 59122x MON88017 (Event Code: Gene: pat), TC1507 x GA21 (Event code: Gene: pat), TC1507 x MON810 (Event code: Gene: pat), TC1507x MON810 x MIR162 x NK603 (Event Code: Gene: pat), 3272x Bt11x MIR604 x TC1507 x 5307x GA21 (Event Code: Gene: pat), TC1507x MIR162 xNK603 (Event code: Gene: pat), TC1507x MON810 x MIR162 (Event Code: gene: pat), MON87419 (event code: MON87419-8, gene: pat), TC1507 x MON88017 (event code: Gene: pat), TC6275 (event code: Gene: bar), MZHG0JG (event code: Gene: pat), MZIR098 (event code: Gene: pat), Bt11x MIR162 x MON89034 (Event Code: Gene: pat) and (Event code: Gene: pat), 59122x DAS40278 (Event code: Gene: pat), 59122x MON810x MIR604 (Event Code: Gene: pat), 59122x MON810 xNK603 x MIR604 (Event Code: Gene: pat), 59122x MON88017x DAS40278 (Event Code: Gene: pat), 59122x NK603 xMIR604 (Event code: Gene: pat), Bt11x 5307 (event code: Gene: pat), Bt11x 5307x GA21 (Event code: Gene: pat), Bt11 xMIR162 x 5307 (Event code: Gene: pat), Bt11x MIR162 x 5307x GA21 (Event Code: Gene: pat), BT11 x MIR162 x MIR604 x 5307 (Event Code: Gene: pat), Bt11x MIR162 xMIR604 x 5307x GA21 (Event Code: Gene: pat), Bt11x MIR162 x MIR604 x MON89034 x 5307x GA21 (Event Code:

[0181] Gene: pat), BT11x MIR162 x MIR604xTC1507 (Event Code: Gene: pat), BT11x MIR162 x MIR604 x TC1507 x 5307 (Event Code: Gene: pat), Bt11x MIR162 x MIR604x TC1507 x GA21 (Event Code: Gene: pat), Bt11x MIR162 xTC1507 x 5307 (Event code: Gene: pat), BT11x MIR162 x MIR604x TC1507 x 5307 (Event Code: Gene: pat), Bt11x MIR162 x MIR604 x TC1507 x GA21 (Event Code: Gene: pat), Bt11x MIR162 x TC1507 x 5307 (Event Code: Gene: pat), Bt11x MIR162 xTC1507 x 5307x GA21 (Event Code: Gene: pat), Bt11 x MIR604 x 5307 (Event Code: Gene: pat), Bt11x MIR604 x 5307x GA21 (Event Code: Gene: pat), Bt11 x MIR604 x TC1507 x 5307 (Event Code: Gene: pat), Bt11x MIR604 xTC1507 x GA21 (Event Code: Gene: pat), Bt11x MON89034 (or )(Event code: Gene: pat), Bt11 xMON89034 x GA21 (Event code: Gene: pat), (Event code: Gene: pat), Bt11 x TC1507 x5307 (Event code: Gene: pat), Bt11xTC1507 x 5307x GA21 (Event code: Gene: pat), MIR162 x MIR604 x TC1507 x 5307 (Event Code: Gene: pat), MIR162x MIR604 xTC1507 x 5307x GA21 (Event Code: Gene: pat), MIR162 x MIR604 x TC1507 x GA21 (Event Code: Gene: pat), MIR162x TC1507 x5307 (event code: Gene: pat), MIR162x TC1507 x 5307x GA21 (Event code: Gene: pat), MIR604 x TC1507 x 5307 (Event code: Gene: pat), MIR162x TC1507 x 5307 (Event code: Gene: pat), MIR162 x TC1507 x5307x GA21 (Event code: Gene: pat), MIR604x TC1507 x5307 (event code: Gene: pat), MIR604x TC1507 x 5307xGA21 (Event Code: Gene: pat), MIR604 xTC1507 x GA21 (Event code: Gene: pat), MON87427x 59122 (Event code: MON-87427-7x DAS-59122-7, Gene: pat), MON87427 xMON89034 x59122 (Event code: Gene: pat), MON87427 x MON89034 x MON88017 x 59122 (Event Code: Gene: pat), MON87427 xMON89034 x TC1507 (Event Code: Gene: pat), MON87427x MON89034x TC1507 x 59122 (Event Code: Gene: pat), MON87427x MON89034 x TC1507 x MON87411 x 59122 (Event Code: Gene: pat), MON87427x MON89034x TC1507 x MON87411 x 59122x DAS40278 (Event Code: Gene: pat), MON87427x MON89034 x TC1507 xMON88017 (Event Code: Gene: pat), MON87427x TC1507 (Event code: Gene: pat), MON87427x TC1507x 59122 (Event code: Gene: pat), MON87427 x TC1507 xMON88017 (Event Code: Gene: pat), MON87427x TC1507 x MON88017 x 59122 (Event Code: Gene: pat), MON89034x 59122x DAS40278 (Event code: Gene: pat), MON89034 x 59122xMON88017 x DAS40278 (Event Code: Gene: pat), MON89034 x TC1507 x 59122x DAS40278 (Event Code: Gene: pat), MON89034 x TC1507 x DAS40278 (Event Code: Gene: pat), MON89034x TC1507 x NK603 x MIR162 (Event Code: Gene: pat), TC1507x 5307 (event code: Gene: pat), TC1507x 5307x GA21 (Event code: Gene: pat), TC1507 x 59122xDAS40278 (Event Code: Gene: pat), TC1507x 59122x MON810x MIR604 (Event Code: Gene: pat), TC1507x 59122x MON88017 x DAS40278 (Event Code: Gene: pat), TC1507x 59122x NK603 x MIR604 (Event code: , Gene: pat) TC1507xDAS40278 (Event Code: Gene: pat), TC1507x MON810 xMIR604 (Event Code: Gene: pat), TC1507x MON810 x NK603 x MIR604 (Event Code: Gene: pat), TC1507x MON88017x DAS40278 (Event Code: gene: pat) and TC1507 x NK603 x DAS40278 (event code: Gene: pat).

[0182] The transgenic soybean event containing the glufosinate tolerance gene is, for example, but not exclusively, A2704-12 (event code: Gene:pat, for example, as Liberty Link TM Soybeans were purchased commercially), A2704-21 (Event Code: Gene:pat, for example, as Liberty Link TMSoybeans were purchased commercially), A5547-127 (Event Code: Gene:pat, for example, as Liberty Link TM Soybeans were purchased commercially), A5547-35 (Event Code: Gene:pat, for example, as Liberty Link TM Soybeans were purchased commercially), GU262 (Event Code: Gene:pat, for example, as Liberty Link TM Soybeans purchased from commercial sources), W62 (Event code: Gene:pat, for example, as Liberty Link TM Soybeans purchased from commercial sources), W98 (Event Code: Gene:pat, for example, as Liberty Link TM soybean commercially available), DAS68416-4 (event code: DAS-68416-4, gene: pat, for example, as Enlist TM soybeans were purchased commercially), DAS44406-6 (Event Code: Gene: pat), DAS68416-4x MON89788 (Event code: DAS-68416-4x MON-89788-1, Gene: pat), (Event code: Gene: pat), DAS81419x DAS44406-6 (Event code: gene: pat) and FG72x A5547-127 (event code: Gene: pat).

[0183] The transgenic cotton event comprising the glufosinate tolerance gene is, for example, but not exclusively, 3006-210-23x281-24-236x MON1445 (event code: Gene: bar, for example, as WideStrike TM Roundup Ready TM Cotton purchased from a commercial source), 3006-210-23 x 281-24-236 x MON88913 (Event Code: Gene: bar, for example, as Widestrike TM Roundup Ready Flex TMCotton purchased from commercial sources), 3006-210-23x281-24-236x MON88913 x COT102 (Event Code: Gene: pat, for example, as Widestrike TM x Roundup Ready Flex TM x VIPCOT TM Cotton commercially available), GHB614 xLLCotton25 (Event Code: Gene: bar, for example, as GlyTol TM Liberty Link TM Commercially available), GHB614 x T304-40 x GHB119 (Event Code: Gene: bar, for example, as Glytol TM x Twinlink TM Commercially available), LLCotton25 (Event code: Gene: bar, for example, as Commercially available), GHB614x T304-40x GHB119x COT102 (Event Code: Gene: bar, for example, as Glytol TM x Twinlink TM x VIPCOT TM Cotton purchased from commercial sources), LLCotton25 x MON15985 (Event Code: Gene: bar, for example, as Fibermax TM LibertyLink TM Bollgard II TM Commercially available), T304-40 x GHB119 (Event Code: Gene: bar, for example, as a TwinLink TM Cotton commercially available), GHB614 x T304-40 x GHB119 x COT102 (Event Code: Gene: bar, for example, as Glytol TM xTwinlink TM x VIPCOT TM Cotton purchased from commercial sources), GHB119 (event code: Gene: bar), GHB614x LLCotton25 x MON15985 (Event Code: Gene: bar), (Event code: MON88701, gene: bar), T303-3 (Event code: Gene: bar), T304-40 (Event code: Gene: bar), (Event code: gene: bar), 81910 (event code: DAS-81910-7, gene: pat), MON8870 (event code: Gene: bar), MON88701 x MON88913 (Event Code: Gene: bar), MON88701x MON88913 x MON15985 (Event Code: Gene: bar), 281-24-236x 3006-210-23x COT102 x 81910 (Event Code: Gene: pat), COT102x MON15985 xMON88913 x MON88701 (Event Code: Gene: bar) and 3006-210-23x281-24-236x MON88913 x COT102 x 81910 (Event Code: Gene: pat).

[0184] A transgenic canola event comprising a glufosinate tolerance gene is, for example, but not exclusively, HCN10 (Topas 19 / 2) (Event Code: , Gene: bar, for example, as Liberty Link TM Independence TM Commercially available), HCN28 (T45) (Event code: Gene: pat, for example, as InVigor TM Canola (commercially available), HCN92 (Topas 19 / 2 (event code: Gene: bar, for example, as a LibertyLink TM Innovator TM Commercially available), MS1 (B91-4) (Event code: Gene: bar, for example, as InVigorTM Canola (commercially available), MS1 x RF1(PGS1) (Event Code: Gene: bar, for example, as InVigor TM Canola (commercially available), MS1 x RF2 (PGS2) (Event Code: Gene: bar, for example, as InVigor TM Canola (commercially available), MS1 x RF3 (Event Code: Gene: bar, for example, as InVigor TM Canola rapeseed commercially available), MS8 (event code: Gene: bar, for example, as InVigor TM Canola (commercially available), MS8 x RF3 (Event Code: Gene: bar, for example, as InVigor TM Canola (commercially available), RF1 (B93-101) (event code: Gene: bar, for example, as InVigor TM Canola (commercially available), RF2 (B94-2) (Event Code: Gene: bar, for example, as InVigor TM Canola rape was purchased commercially), RF3 (event code: Gene: bar, for example, as InVigor TM Canola (commercially available), MS1 x MON88302 (Event Code: Gene: bar, for example, as InVigor TM x TruFlex TM Roundup Ready TM Canola (commercially available), MS8 x MON88302 (Event Code: Gene: bar, for example, as InVigor TM x TruFlex TM Roundup Ready TM Canola (commercially available), RF1 xMON88302 (event code: Gene: bar, for example, as InVigor TM x TruFlex TM Roundup Ready TMCanola (commercially available), RF2 x MON88302 (Event Code: Gene: bar, for example, as InVigor TM x TruFlex TM Roundup Ready TM Canola (commercially available), HCN28 x MON88302 (Event Code: Gene: pat, for example, as InVigor TM x TruFlex TM Roundup Ready TM Canola (commercially available), HCN92 x MON88302 (Event Code: Gene: bar, for example, as a Liberty Link TM Innovator TM x TruFlex TM Roundup Ready TM Canola (commercially available), HCR-1 (gene: pat), MON88302 x MS8 x RF3 (event code: Gene: bar), MON88302x RF3 (Event Code: gene: bar), MS8x RF3 xGT73 (RT73) (event code: , gene: bar), PHY14 (event code: bar), PHY23 (gene: bar), PHY35 (gene: bar), and PHY36 (gene: bar), and 73496x RF3 (event code: Gene: bar).

[0185] The transgenic rice event comprising the glufosinate tolerance gene is, for example, but not exclusively, LLRICE06 (event code: For example, as a Liberty Link TM Rice commercially available), LLRICE601 (event code: For example, as a Liberty Link TM Rice commercially available) and LLRICE62 (event code: For example, as a Liberty Link TM Rice was purchased from a commercial supplier).

[0186] The mixtures of the invention can be applied in a conventional manner using techniques familiar to the skilled person. Suitable techniques include spraying, atomizing, dusting, broadcasting or watering. The type of application depends in a well-known manner on the intended purpose; in any case, they should ensure the finest possible distribution of the active ingredients according to the invention.

[0187] In one embodiment, the mixture of the invention is applied to the locus primarily by spraying, in particular foliar spraying, an aqueous dilution of the active ingredients of the mixture. Application can be carried out by conventional spraying techniques using, for example, water as a carrier and at a spray rate of about from about 10 to 2000 l / ha or 50 to 1000 l / ha (e.g., from 100 to 500 l / ha). Application of the mixture of the invention by low-volume and ultra-low-volume methods is possible because it is applied in microparticle form.

[0188] The required application rate of the pure active compound mixture depends on the density of the undesirable vegetation, the developmental stage of the plants, the climatic conditions at the location where the mixture is to be used and the method of application.

[0189] In general, the application rate of L-glufosinate is usually 50 g / ha to 3000 g / ha and preferably in the range of 100 g / ha to 2000 g / ha or 200 g / ha to 1500 g / ha of active substance (ai), and the application rate of the herbicide compound II is 1 g / ha to 2000 g / ha and preferably in the range of 5 g / ha to 1500 g / ha, more preferably in the range of 25 g / ha to 900 g / ha of active substance (ai).

[0190] The following examples illustrate the invention without imposing any limitations.

[0191] Biological Examples

[0192] Synergy can be described as an interaction in which the combined effect of two or more compounds is greater than the sum of the individual effects of each compound. The presence of synergy between two mixtures (X and Y) can be calculated using the Colby equation (Colby, SR, 1967, Calculating Synergistic and Antagonistic Responses in Herbicide Combinations, Weeds, 15, 21-22) in terms of percent control:

[0193]

[0194] When the observed combined control effect is greater than the expected (calculated) combined control effect (E), then the combined effect is synergistic.

[0195] The following tests demonstrate the control effects of the compounds, mixtures or compositions of the present invention on specific weeds. However, the weed control provided by these compounds, mixtures or compositions is not limited to these species. An analysis using the Colby equation to determine synergy or antagonism between mixtures or compositions.

[0196] greenhouse

[0197] Application Examples

[0198] The culture container used is a plastic flower pot containing sandy loam with about 3.0% humus as a matrix. For each species and / or resistant biotype, the seeds of the test plants are sown separately. For pre-emergence treatment, after sowing, the active ingredient suspended or emulsified in water is directly applied by means of a fine distribution nozzle. The container is gently irrigated to promote germination and growth and then covered with a transparent plastic cover until the plant takes root. This covering makes the test plant germinate uniformly unless it has been damaged by the active ingredient. For post-emergence treatment, depending on the plant habits, the test plant is first grown to a height of 3 to 15 cm, and then only treated with the active ingredient suspended or emulsified in water. For this purpose, the test plant is directly sown and grown in the same container, or first grown separately as a seedling and transplanted into the test container a few days before treatment. Depending on the species, these plants are kept at 10°C-25°C or 20°C-35°C respectively. The test period is extended to 20 days after treatment. During this time, these plants are taken care of and their response to individual treatments is evaluated. Evaluation is performed by using a scale from 0 to 100. 100 means that the plants have not emerged or at least the above-ground parts are completely destroyed, and 0 means no damage, or normal growth process.

[0199] product:

[0200] L-Glufosinate ammonium: 600g / l

[0201] Tetrafluthrin: 50mg / mL EC

[0202] Weeds studied:

[0203] EPPO code scientific name ABUTH Ramie AVEFA Wild Oats CHEAL Quinoa KCHSC Kochia POLAV Polygonum flatulum Volunteer Plants HORVS Volunteer Plant Barley

[0204] The results of these tests are given in Use Examples 1 and 2 below and demonstrate the synergistic effect of the mixture comprising compound I (L-phosphinothricin) and compound II (tetrafluthrin).

[0205] Assessments were performed after 7 or 20 days post-treatment (DAT) as indicated in each example.

[0206] Example 1: Post-emergence treatment with a mixture of L-phosphinothricin and tetrafluthrin (7 DAT)

[0207]

[0208] Example 2: Post-emergence treatment with a mixture of L-phosphinothricin and tetrafluthrin (20 DAT)

[0209]

Claims

1. A herbicidal mixture comprising a) L-glufosinate-ammonium and its salts as compound I; and b) herbicidal compound II; Wherein the L-glufosinate contains greater than 70% by weight of the L-enantiomer.

2. The herbicidal mixture according to claim 1, wherein compound I is selected from the group consisting of L-glufosinate ammonium and L-glufosinate sodium in the form of L-glufosinate salts and L-glufosinate in the form of free acid.

3. The herbicidal mixture as claimed in claim 1, wherein compound I is L-glufosinate-ammonium.

4. The herbicidal mixture according to any one of claims 1 to 3, wherein L-glufosinate-ammonium comprises more than 80% by weight, preferably more than 90% by weight, even more preferably more than 95% by weight of the L-enantiomer.

5. The herbicidal mixture according to any one of claims 1 to 4, wherein compound II is selected from the group consisting of fluazifop-M, fluazifop-butyl, dimethoate, quinclorac, bispyribac, cypermethrin, pyridazione, benzafluazione, pyridazine, fluazifop-butyl, triazosulfuron, fluclorac, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, triazosulfuron, isoxaclorac, quinclorac-butyl and bromopyralid, Preferably, compound II is selected from the group consisting of fluazifop-M, tetrafluanid, quinclorac, bispyribac, triazosulfuron, benfenac, pyridazione, fluazifop-butyl, fluazifop-butyl and isoxadiazine.

6. The herbicidal mixture according to any one of claims 1 to 5, wherein compound II is selected from the group consisting of fluazifop-M, tetrafluthrin and isoxadiazine.

7. The herbicidal mixture as claimed in any one of claims 1 to 6, wherein the weight ratio of compound I to compound II is from 1000:1 to 1:

500.

8. The herbicidal mixture as claimed in any one of claims 1 to 7, wherein the weight ratio of compound I to compound II is from 50:1 to 1:

5.

9. A pesticidal composition comprising a liquid or solid carrier and the mixture according to any one of claims 1 to 8.

10. A method for controlling undesirable vegetation, the method comprising applying a mixture according to any one of claims 1 to 8 to a locus where undesirable vegetation is present or is expected to be present.

11. A method as claimed in claim 10, comprising applying a mixture as claimed in any one of claims 1 to 8 before crop emergence.

12. The method of claim 10, which comprises applying the mixture of any one of claims 1 to 8 before planting crops.

13. The method of any one of claims 10 to 12, wherein the crop is selected from rice, maize, pulse crops, cotton, canola, small grains, soybeans, peanuts, sugar cane, sunflowers, plantation crops, tree crops, nuts and grapes.

14. The method of any one of claims 10 to 13, wherein the crop is selected from glufosinate-tolerant crops.

15. The method according to any one of claims 10 to 14, wherein compounds I and II in the mixture according to any one of claims 1 to 7 are administered simultaneously, ie jointly or separately, or sequentially.

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