EP2866561A1

EP2866561A1 - Herbicidal formulation

Info

Publication number: EP2866561A1
Application number: EP13732959.5A
Authority: EP
Inventors: Gerhard Schnabel; Bernd Sievernich; Torsten MEID
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2012-07-02
Filing date: 2013-07-02
Publication date: 2015-05-06
Also published as: AU2013286010A1; MX2015000247A; IN2015DN00020A; US20150189877A1; CA2877455A1; EA201590137A1; WO2014006026A1; BR112015000134A2; CN104470360A

Abstract

Disclosed is a herbicidal formulation containing: (a1) at least one herbicidal active substance from the class of ACC inhibitors; (a2) optionally at least one safener; (a3) optionally at least one further herbicidal active substance that is different to (a1) and (a2); (b) one or a plurality of solvents of formula (I), R-CO-NR¹R², in which R is a C₃-C₁₈ hydrocarbon radical, and R¹ and R² are both or individually a Ci-Cu hydrocarbon radical or a C₁-C₁₄ hydroxyl hydrocarbon radical; one or a plurality of aromatic solvents; one or a plurality of surfactants from the group of C₈-C₂₂ alkyl alcohols which are alcoxylated, the terminal hydroxyl groups of these compounds optionally being closed by an alkyl-, cycloalkyl- or acryl radical with 1-24 carbon atom end groups; (e) one or a plurality of emulsifiers; (f) optionally one or a plurality of additives and (g) optionally water. The herbicidal formulation is particularly suited for combatting undesired grasses.

Description

herbicide formulation

The invention relates to a herbicidal formulation comprising an ACCase inhibitor and an alkylcarboxylic acid amide, a process for their preparation and their use for controlling unwanted plant growth.

Herbicides, whose mechanism of action is based on an inhibition of acetyl-CoA-carboxylase (ACC) (ACC inhibitors), have been used successfully for many years to combat unwanted monocotyledonous plants such as grasses (graminids). Exemplary of this class of drugs is clodinafop-propargyl, which is used as a post-emergence systemic grass herbicide (graminicide). Although good results are already achieved with the known formulations of these active ingredients, there is still room for improvement, for example as regards the constancy of action. In addition, these formulations often show a loss of activity when combined with products against unwanted dicotyledonous plants, in particular synthetic auxins such as dicamba and 2,4-D.

It was therefore the object to develop further formulations for ACC inhibitors, with which the disadvantages mentioned are at least reduced.

It has been found that formulations of ACC inhibitors which, in addition to the active ingredient, contain at least one C3-C18-alkylcarboxylic acid amide, a C8-C28-alkylalkoxylate, an emulsifier and a water-insoluble aromatic solvent, are particularly suitable for controlling unwanted grasses.

Formulations containing individual ones of these components, especially alkylcarbonic acid amides, are already known, see e.g. WO201 1/003534, WO2010 / 145772, WO2007 / 140332, WO2006 / 040022, WO2005 / 104844 and US2009 / 0215797. However, an indication of the combination of components according to the invention does not result from this.

The invention therefore provides a herbicidal formulation comprising a1) at least one herbicidally active compound from the class of ACC inhibitors, such as aryloxyphenoxypropionates, in particular clodinafop-prorpargyl; a2) optionally at least one safener; a3) optionally at least one further herbicidal active ingredient other than (a1) and (a2); one or more solvents of the formula (I), R-CO-NR ² R (I) wherein

R is a C3-C18 hydrocarbon radical, such as C3-C18-alkyl, C3-C18-alkenyl, C3-C18-alkynyl, C3-Cis-cycloalkyl, C3-C18-cycloalkenyl or C3-C18-cycloalkynyl,

R ¹ , R ^{2 are} identical or different and are a C 1 -C hydrocarbon radical such as C 1 -C 4 -alkyl, C 2 -C 14 -alkenyl, C 1 -C 4 -alkynyl, C 4 -C 14 -cycloalkyl, C 4 -C 14 -cycloalkenyl or C 4 -C 14 -cycloalkynyl or a C 2 -C 14 -hydroxyhydrocarbyl radical such as C 1 -C 4 -hydroxyalkyl, C 2 -C 14 -hydroxyalkenyl, C 2 -C 4 -hydroxyalkynyl, C 4 -C 14 -hydroxycycloalkyl, C 4 -C 14 -hydroxycycloalkenyl or C 4 -C 14 -hydroxycycloalkynyl; one or more aromatic solvents such as toluene, xylenes, naphthalene derivatives, C6-C16 aromatic mixtures, chlorobenzene and anisaldehyde acetates; one or more surfactants from the group of C8-C22-alkyl alcohols which are alkoxylated, for example with 1-60 alkylene oxide units, preferably 1-60 EO and / or 1-30 PO and / or 1-15 BO in any order, wherein the terminal hydroxy groups of these compounds are optionally end-capped by an alkyl, cycloalkyl, acyl or carboxylate (COOR) radical of 1 to 24 carbon atoms; one or more emulsifiers, such as ionic emulsifiers (e1) and nonionic emulsifiers (e2);

optionally one or more auxiliaries, for example defoamers and / or compatibilizers, and g) optionally water.

The invention further provides a process for preparing a herbicidal formulation according to the invention, wherein the said components are mixed together.

The invention likewise relates to the use of the herbicidal formulation according to the invention for controlling undesired plant growth and to a method for controlling unwanted plant growth, wherein an effective amount of a herbicidal formulation according to the invention is applied to the unwanted plants or the sites in which they occur.

Advantages of the formulation according to the invention are a higher effect with good selectivity, good miscibility, tank mix compatibility, good stability of the spray liquors over a wide concentration range, good physical and chemical stability, low-temperature stability and advantageous spray behavior. When combining the invention A reduced antagonism occurs in the case of ACC inhibitors used with dicot ethylene herbicides such as auxin derivatives, in some cases even a synergistic effect on the activity of co-applied herbicides such as Dicamba can be observed. The preferred, particularly preferred and especially preferred features described below are to be understood as meaning that the preferences are either independent of one another or in combination with one another.

The herbicidal formulation according to the invention preferably has the following composition (in% by weight):

(a) 2-60, preferably 2.5-45, more preferably 3.75-25,

(a1) 2 to 30, preferably 2 to 16, particularly preferred 3 to 10,

(a2) 0-10, preferably 0.5-4, more preferably 0.75-2.5,

(a3) 0-50, preferably 0-25, particularly preferably 0-12.5,

(b) 5-60, preferably 7.5-45, more preferably 10-35,

(c) 5-60, preferably 7.5-45, more preferably 10-35,

(d) 5-60, preferably 7.5-45, more preferably 10-35,

(e) 3 to 30, preferably 3 to 20, more preferably 6 to 18

(e1) 0-30, preferably 0-20, more preferably 3-15

(e2) 0-30, preferably 0-20, more preferably 3-15,

(f) 0-20, preferably 0.01-10, more preferably 0.5-6,

(f1) O - Compatibility Compound, preferably 0.5-10, especially 1

(f2) 0-5 defoamer, preferably 0.02-2, especially 0.05-2 and

(g) 0-50, preferably 0-5, more preferably 0-1

In a preferred embodiment, the herbicidal formulation according to the invention consists of the components (a) - (g). In a further embodiment, the herbicidal formulation according to the invention consists of components (a) - (f).

The herbicidal formulation according to the invention contains at least one herbicidal active ingredient from the group of the ACC inhibitors (a1), preferably from the class of the aryloxyphenoxypropionates (FOPs), such as clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl, diclofop-P-methyl, feno- xaprop-P-ethyl, Fluazifop-butyl, Fluazifop-P-butyl, Haloxyfop, Haloxyfop-P, Haloxyfop-B-methyl, Propaquizafop, Quizalofop, Quizalofop-ethyl, Quizalofop-P, Quizalofop-P-ethyl and Quizalofop-P -tefuryl; cyclohexanedione oximes (DIMs), such as alloxydim, butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, and tralkoxydim; and phenylpyrazolines (DENs), such as pinoxaden. Especially preferred are FOP, especially preferred is clodinafop-propargyl. Preferably, the herbicidal formulation according to the invention contains one or two more preferably an ACC inhibitor. Particularly in the case of the FOPs, the herbicidal formulation according to the invention preferably contains one or more safeners (a2), preferably from the group Cloquintocet-mexyl, Fencholazole-ethyl and Mefenpyr-diethyl, particularly preferably Cloquintocet-mexyl. If the herbicidal formulation according to the invention contains one or more safeners, this is preferably a safener.

Preferred combination of ACC inhibitor and safener is the combination Clodinafoppropargyl / Cloquintocet-mexyl.

In a further embodiment, the herbicidal formulation according to the invention contains, in addition to at least one ACC inhibitor and optionally at least one safener, at least one further herbicidal active ingredient a3), preferably from the group of (synthetic) auxines, such as dicamba or 2,4-D and their salts , eg organic ammonium salts; 4-HPPD inhibitors such as Topramezone Benzobicyclone, Benzofenap, Bicyclopyrone, Clomazone, Isoxalflutole, Pyrasulfofole, Pyrazolinate, Pyrazoxyten, Mesotrione, Sulcotrione, Tefuryltrione and Tembotrione; Benzonitriles such as bromoxynil and loxynil; and / or sulfonylureas such as amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metsulfuron-methyl, Nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, triberuron, trifloxysulfuron, triflusulfuron, tritosulfuron, bensulfuron-methyl, chlorimuron, ethametsulfuron, ethametsulfuron-methyl, flupyrsulfuron-methyl-sodium, Halosulfuron-methyl, iodosulfuron-methyl-sodium, lofensulfuron, iofensulfuron-sodium, metazosulfuron, metsulfuron, orthosulfamuron, primisulfuron-methyl, propyrisulfuron, pyrazosulfuron-ethyl, sulfometuron-methyl, thifensulfuron-methyl, tribenuron-methyl, triflusulfuron-methyl and 1 - ((2-chloro-6-propylimidazo [1,2-b] pyridazin-3-yl) sulfonyl) -3- (4,6-dimethoxypyrimidin-2-yl) urine off. Preferred as component a3) are (synthetic) auxins, in particular Dicamba and 2,4-D, and 4-HPPD inhibitors

Active substances of groups (a1), (a2) and (a3) are commercially available and are known, for example, from the publications mentioned above and from "The Pesticide Manual", 15th edition, 2009, The British Crop Protection Council, "Agricultural Chemicals Book II - Herbicides - ", by. W. T. Thompson, Thompson Publications, Fresno CA, USA 1990 and "Farm Chemicals Handbook '90", Meister Publishing Company, Willoughby OH, USA, 1990.

As a solvent, the herbicidal formulation according to the invention comprises one or more amides of the formula (I),

R-CO-NR R ² (I) wherein

R ¹ , R ^2, identically or differently, a C 1 -C hydrocarbon radical such as C 1 -C 4 -alkyl, C 2 -C 14

Alkenyl, C 1 -C 4 -alkynyl, C 4 -C 14 -cycloalkyl, C 4 -C 14 -cycloalkenyl or C 4 -C 14 -cycloalkynyl, or a C 2 -C 14 -hydroxy hydrocarbon radical such as C 1 -C 4 -hydroxyalkyl, C 2 -C -hydroxyalkenyl, C 2 -C 4 -cycloalkyl Hydroxyalkynyl, C4-C4 hydroxycycloalkyl, C4-C14 hydroxycycloalkenyl or C4-C4 hydroxycycloalkynyl;

In the formula (I), the hydrocarbon radicals R, R ¹ and R ² and the hydroxy hydrocarbon radicals R ¹ and R ^{2 may be} straight-chain, branched or cyclic. The hydrocarbon radicals R, R ¹ and R ² and the hydroxy hydrocarbon radicals R ¹ and R ² may be substituted. Substituted hydrocarbon radicals and hydroxy hydrocarbon radicals, eg. For example, substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, hydroxyalkyl, hydroxyaklenyl, hydroxyalkinyl, for example, a radical derived from the substituted parent substituted radical, wherein the substituents for example one or more, preferably 1, 2 or 3 radicals from the Halogen, alkoxy, haloalkoxy, alkylthio, amino, nitro, carboxy, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylamino-cabonyl, substituted amino, such as acylamino, mono- and diaklylamino, and alkylsulfinyl, haloalkylsulfinyl, Alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals, also alkyl, hydroxy and haloalkyl, and the said saturated hydrocarbon-containing radicals corresponding unsaturated aliphatic radicals, such as alkenyl, alkynyl, alkenyloxy, alkynyloxy, etc.

If the alkyl radicals R, R ¹ and R ² and the hydroxyalkyl radicals R ¹ and R ² in formula (I) are substituted, then by C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 4 -C 18 -cycloalkyl, C 4 -C 18 -alkyl, Cycloalkenyl or C4-Ci9-cycloalkynyl. Alkyl radicals, also in the composite meanings such as alkoxy, haloalkyl, etc., mean, unless stated otherwise, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, tert- or sec-butyl, pentyl, hexyl, such as n -Hexyl, iso-hexyl and 1, 3-dimethylbutyl or heptyl, such as n-heptyl, 1-methylhexyl and 1, 4-demethylpentyl; Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals; Alkenyl is, for example, allyl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-ene-yl, 1 Methyl-but-3-en-1-yl and 1-meth-but-2-en-1-yl; Alkynyl is, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl.

Cycloalkyl denotes a carbocyclic, unsaturated ring system, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Cycloalkenyl and cycloalkynyl mean the corresponding unsaturated ring systems. Examples of alkyl radicals R are propyl, such as n-propyl or isopropyl, butyl, such as n-butyl or branched pentyl, such as isopentyl or neopentyl, hexyl, such as n-hexyl or branched hexyl, heptyl, such as n-heptyl or branched heptyl, octyl, such as n-butyl or n-propyl. Octyl or branched octyl such as isooctyl, nonyl such as n-nonyl or branched nonyl, decyl such as n-decyl or branched decyl, undecyl such as n-undecyl or branched undecyl, dodecyl such as n-dodecyl or branched dodecyl, tridecyl such as n-tridecyl or branched tridecyl.

Examples of alkyl radicals R ¹ and R ² are methyl, ethyl, propyl, such as n-propyl or isopropyl, butyl, such as n-butyl or branched butyl, such as sec-butyl, isobutyl or tert-butyl, pentyl and n-butyl. Pentyl or branched pentyl such as isopentyl or neopentyl, hexyl such as n-hexyl or branched hexyl, heptyl such as n-heptyl or branched heptyl, octyl such as n-octyl or branched octyl such as isooctyl, nonyl such as n-nonyl or branched nonyl, decyl such as n Decyl or branched decyl, undecyl such as n-undecyl or branched undecyl, dodecyl such as n-dodecyl or branched dodecyl, tridecyl such as n-tridecyl or branched tridecyl and the corresponding hydroxyalkyl radicals such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, Hydroxyhexyl, hydroxyheptyl, hydroxyoctyl, hydroxynonyl, hydroxydecyl, hydroxyundecyl, hydroxydodecyl or hydroxytridecyl.

Preference is given to solvents of the formula (I) in which R is C 6 -C 12 -alkyl, preferably C 1 -C 10 -alkyl, and R ¹ , R ^{2 are} identical or different, preferably identical, C ¹ -C 6 -alkyl (for example methyl, Ethyl, propyl, such as n-propyl or iso-propyl, butyl, such as n-butyl, or branched butyl, such as sec-butyl, isobutyl or tert-butyl, pentyl, such as n-pentyl or branched pentyl, such as isopentyl or neopentyl, Hexyl such as n-hexyl or branched hexyl), C 4 -C 10 -cycloalkyl (eg cyclobutyl, cyclopentyl or cyclohexyl) or C 1 -C 6 -hydroxyalkyl.

Preference is furthermore given to solvents of the formula (I) in which R is C ₆ -C 12 -alkyl, preferably C 12 -C 12 -alkyl, and R ¹ is equal to R ² and is C ₁ -C ₆ -alkyl, preferably methyl.

Solvents b) contained in the herbicidal formulation according to the invention are e.g. Decane acid dimethylamide (for example, available as Genagen® 4296 from Clariant), mixtures of Cs / C 16 fatty acid dimethylamides (e.g., available as Genagen® 4166 and Genagen® 4231 from Clariant) and dodecanoic acid dimethylamide e.g. available as Agnique® AMD 12 from BASF SE).

In one embodiment, the herbicidal formulation of the invention contains a compound of formula (I). In a further preferred embodiment, the herbicidal formulation according to the invention contains several, typically 2-4, compounds of the formula (I). In particular, when amides of fatty acids are used from natural raw materials, mixtures of compounds of formula (I) are usually present, with a compound often dominating. As component (c), the herbicidal formulation according to the invention contains one or more water-insoluble aromatic solvents. "Water-insoluble" means according to the invention a water solubility of less than 1 g / l at 25 ° C and atmospheric pressure, in particular less than 0.2 g / l.

Preferred water-insoluble aromatic solvents are aromatic hydrocarbons, such as toluene, xylenes and naphthalene derivatives, in particular 1-methylnaphthalene, 1-methylnaphthalene, C6-C16-aromatic mixtures, such as e.g. the Solvesso series (ESSO) with types Solvesseo® 100 (bp 162-177 ° C), Solvesso® 150 (bp 187-207X) and Solvesso® 200 (bp 219-282), Solvesso 200 ND, Solvesso 150 ND and halogenated aromatic hydrocarbons such as chlorobenzene or anisaldehyde acetals such as anisaldehyde dimethyl acetal.

Preferred aromatic solvents (c) are mixtures of C 6 -C 16 aromatics, in particular those in which the content of naphthalene has been depleted (<1%), and also anisaldehyde dimethyl acetal. As component d), the herbicidal formulation according to the invention contains one or more tensides from the group of C 8 -C 22 -alkyl alcohols which have been alkoxylated, e.g. with 1-60 Alkylenoxidein- units, preferably 1-60 EO and / or 1-30 PO and / or 1-15 BO in any order, wherein the terminal hydroxy groups of these compounds optionally by an alkyl, cycloalkyl, acyl or carboxylate with 1 -24 carbon atoms are end-capped.

Examples of such compounds are: Plurafac® and Lutensol®A, AT, ON, TO products from BASF, Genapol®C, L, O, T, DU, UDD, X products from Clariant, Marlipal®24 and 013 products from Condea, Dehypon® products from Henkel, Ethylan® products from Akzo-Nobel such as Ethylan®CD 120.

Preferred as component (d) are alkyl alkoxylates of the formula (I I),

R ³ -O- [R ⁴ O] _m R ⁵ (II) where

R ^{3 is} a linear or branched, saturated or unsaturated, unsubstituted or substituted with one or more hydroxy groups (C 8 -C 22) hydrocarbon radical;

R ^{4 is} an ethylene, propylene or butylene group or a mixture of two or three of said groups;

R ⁵ is H, _(Ci-C24) alkyl, (C ₂ -C ₂₄₎ -acyl, (C ₂ -C ₂₄₎ -0-acyl or (C ₃ -C ₈₎ cycloalkyl, and m is a natural number from 3 to 100 is.

The symbols in the formula (II) particularly preferably have the following meanings: R ³ is preferably C 12 -C 16 -alkyl, particularly preferably a C 12 -C 14 -alkyl mixture and very particularly preferably C 13 -alkyl.

R ⁴ is preferably ethyl and / or propyl, more preferably and most preferably ethyl.

R ⁵ is preferably H, methyl, t-butyl, -COOMe or COMe, more preferably and most preferably H or methyl.

m is preferably 4 to 20, particularly preferably 5 to 15 and very particularly preferably 6 to 10. Preferred, particularly preferred and very particularly preferred are also compounds of the formula (II) in which R ³ , R ⁴ , R and m are all have the preferred, particularly preferred or very particularly preferred meanings.

The herbicidal formulation according to the invention contains as component (e) one or more emulsifiers, preferably from the groups of ionic emulsifiers (e1) and / or nonionic emulsifiers (e2):

Ionic emulsifiers (e1), preferably anionic surfactants, e.g. Alkali, alkaline earth or ammonium salts of fatty acids such as potassium stearate, alkyl sulfates, alkyl ether sulfates, alkyl or iso-alkyl sulfonates, alkylbenzenesulfonates such as Na dodecylbenzenesulfonate and Ca dodecylbenzenesulfonate, alkylnaphthalenesulfonates, Alkylmehtylestersulfonate, acylglutamates, Alkylbersteinsäureestersulfonate, sarcosinates such Natnumlauroylsarkosinat and taurates, and mixtures of several ionic emulsifiers.

Preferred ionic emulsifiers (e1) are the salts of the alkylbenzenesulfonates and the alkylsulfosuccinates. Particularly preferred ionic emulsifiers are the salts of alkylbenzenesulfonic acids, especially the calcium salt of dodecylbenzenesulfonic acid and the sodium salt of dioctylsulfosuccinate, in particular the calcium salt of dodecylbenzenesulfonic acid.

Particular preference is given to calcium p-dodecyl phenylsulfonate, which is obtainable, for example, under the designation Wettol®EM 1 from BASF SE.

Suitable nonionic emulsifiers (e2) are e.g. alkoxylated animal or vegetable fats and oils such as corn oil ethoxylates, castor oil ethoxylates, tallow fatty ethoxylates, glycerol esters such as glycerol monostearate, fatty alcohol alkoxylates and oxo alcohol alkoxylates, fatty acid alkoxylates such as oleic acid ethoxylates, alkylphenol alkoxylates such as isononyl, isooctyl, tributyl, tristearyl phenol ethoxylates, fatty amine alkoxylates, fatty acid amide alkoxylates, sugar surfactants such as sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate), polyoxyethylene sorbitan fatty acid esters, alkylpolyglycosides, N-alkylglucomannides, alkylmethylsulfoxides, alkyldimethylphosphine oxides such as tetracadecyldimethylphosphine oxide, and mixtures of such nonionic emulsifiers.

Preferred nonionic emulsifiers are ethoxylated or propoxylated naturally occurring carboxylic acids or alcohols, especially ethoxylated oils such as castor oil ethoxylate with 36 to 50 ethylene oxide units (available, for example, from BASF SE under the name Wettol®EM 31).

The herbicidal formulation according to the invention preferably contains at least one emulsifier of group (e1) and at least one emulsifier of group (e2). In this case, the weight ratio of the components (e1): (e2) is preferably 0.1 to 10: 1.

Suitable auxiliaries (f) are usually solvents or solubilizers, penetrants, protective colloids, adhesives, thickeners, humectants, compatibilizers, bactericides, antifreeze agents, foam inhibitors, colorants, adhesives and binders.

Other suitable solvents besides components (b) and (c) are, if appropriate, nonpolar or polar solvents, such as mineral or vegetable oils, aliphatic hydrocarbons, lactic acid esters, carboxylic acid esters, DMSO, gamma-butyrolactone, propylene carbonate, glycerol, propylene glycol and / or ethylene glycol

Suitable thickening agents are preferably polysaccharides (e.g., xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.

Suitable bactericides are preferably bronopol and isothiazolium derivatives such as alkylisothiazolinone and benzisothiazolinone. Suitable antifreeze agents are preferably ethylene glycol, propylene glycol, urea and glycerin.

Suitable humectants are e.g. Glycerin or sugar syrups such as the corn-derived "Com syrup" (available from, e.g., Cargill, USA).

Suitable compatibilizers are e.g. B dipropylene glycol, monopropylene glycol, butyldiglycol or polyethylene glycol having a M _w of 200, for example available as Pluriol® E 200 from BASF SE.

Suitable foam inhibitors are preferably silicones and long-chain alcohols and salts of fatty acids.

Suitable dyes (e.g., in red, blue, or green) are preferably pigments which are sparingly soluble in water and water-soluble dyes. Examples are inorganic colorants (e.g., iron oxide, titanium oxide, ferric hexacyanoferrate) and organic colorants (e.g., alizarin, azo, and phthalocyanine colorants).

Suitable adhesives or binders are preferably polyvinylpyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes and cellulose ethers. The herbicidal formulations according to the invention are preferably prepared as liquid formulations, such as emulsion concentrates (EC), microemulsions or microemulsion concentrates or emulsions (emulsion concentrate EW) or oil dispersions (OD). Particularly preferred are EC.

Examples of the preparation of preferred formulations are:

Emulsion Concentrates (EC) and Microemulsion Concentrates Components (a), (b) and (d) - (f) are dissolved in the organic solvent (c) ad 100% by weight. Dilution with water gives an emulsion or microemulsion as a spray mixture.

emulsions

Components (a), (b) and (d) - (f) are dissolved in 20-40% by weight of water-insoluble organic solvent (c). This mixture is introduced with an emulsifier in water ad 100 wt .-% and processed to a homogeneous emulsion. Subsequent dilution with water gives an emulsion as a spray mixture.

microemulsions

Components (a) and (e) - (f) are added to 5-30% by weight of an organic solvent mixture (b) and (c), 10-25% by weight of a surfactant mixture (d) and water ad 100% given. This mixture is stirred for 1 h, which spontaneously forms a thermodynamically stable microemulsion.

When used in crop protection, the application rates of the active compounds (eg "fops") are generally from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.02 to 0.5 kg, depending on the nature of the desired effect ha, and in particular from 0.03 to 0.20 kg per ha.

Various types of oils, wetting agents, adjuvants, fertilizers or micronutrients as well as other pesticides (eg herbicides, insecticides, fungicides, growth regulators, safeners) can be added to the compositions according to the invention as premix or, if appropriate, shortly before use (tank mix) , These agents can be added to the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1. Pesticides containing at least one active compound selected from the group of herbicides, safeners, fungicides, insecticides, nematicides, and / or growth regulators are suitable as further pesticides, for example. Preferred pesticides are herbicides, fungicides, insecticides, and growth regulators. Also mixtures of pesticides consisting of two or more of the named classes can be used. One skilled in the art will be familiar with such pesticides as described, for example, in Pesticide Manual, 15th Ed. (2009), The British Crop Protection Council, London. Suitable herbicides are herbicides of the classes of acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ethers, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles , N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl (thio) benzoates , Quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils and ureas. Suitable insecticides are insecticides of the class of carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosines, avermectins, milbemycins, juvenile hormone analogs, alkylhalides, organotin compounds, nereistoxin analogs, benzoylureas, diacylhydrazines, METI acaricides, and insecticides such as chloropicrin, pymetrozine, flonicamide, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnone, acequinocyl, fluacrypyrim, rotenone, or their derivatives. Suitable fungicides are fungicides of the classes dinitroanilines, allylamines, anilinopyrimidine, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzylcarbamates, carbamates, carboxamides, carboxylic acid amides, chloronitriles, cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides , Dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy (2-amino) pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganics, isobenzofuranones, methoxyacrylates, methoxycarbamates, morpholines, N Phenylcarbamates, oxazolidinediones, oximinoacetates, oximinoacetamides, peptidylpyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles, phenylureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamide e, pyrimidineamines, pyrimidines, pyrimidinone-hydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles, thiazolecarboxamides, thiocarbamates, thiophanates, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines and triazoles.

The user typically applies the herbicidal formulation of the present invention from a predosing device, a backpack syringe, a spray tank, a spray plane or an irrigation system. Usually, the herbicidal formulation according to the invention is diluted with water, buffer and / or further excipients to the desired application concentration, whereby the ready-to-use spray liquid or herbicidal formulation according to the invention is obtained. Usually 20 to 2000 liters, preferably 50 to 400 liters, of ready-spray mixture are applied per hectare of agricultural land. According to one embodiment, individual components of the herbicidal formulation according to the invention, such as parts of a kit or parts of a two- or three-component mixture, may be mixed by the user himself in a spray tank, and further adjuvants may optionally be added.

In a further embodiment, either individual components of the herbicidal formulation according to the invention or partially premixed components may be mixed by the user in a spray tank and further adjuvants and additives may optionally be added.

In a further embodiment, either individual components of the herbicidal formulation of the invention or partially premixed components, e.g. Components comprising herbicides a) and / or other active ingredients, applied together (e.g., after mixing in the tank) or sequentially.

The herbicidal formulation according to the invention is suitable as a herbicide. It combats plant growth on non-crop surfaces very well, especially at high application rates. In crops such as cereals, especially wheat, rye, triticale and rice, soy and cotton, it acts against weeds and grass weeds without significantly damaging the crops. This effect occurs especially at low application rates.

Harmful grasses that can be controlled with the herbicidal formulation according to the invention are, for example, Aegilops cylindrica, Alopecurus myosuroides, Agrostis stolonifera, Agropyron repens, Apera spica-venti, Avena fatua, Avena ludoviciana, Avena sterilis, Brachiaria brizantha, Brachiaria plantaginea, Brachiaria platyphylla, Brachiaria decumbens, Bromus arvense, Bromus inermis, Bromus mollis, Bromus secalinus, Bromus sterilis, Bromus tectorum, Cenchrus echinatus, Cenchrus incertus, Cynodon dactylon, Dactyloctenium aegyptium, Digitaria adscendens, Digitaria ciliaris, Digitaria horizontalis, Digitaris ischaemum, Digitaria sanguinalis, Echinochloa colonum, Echinochloa crus-galli, Echinochloa crus-pavonis, Echinochloa spp., Eleusine indica, Eriochloa gracilis, Eriochloa villosa, Imperata cylindria, Ischaemum rugosum, Leptochloa chinensis, Leptochloa fascicularis, Leptochloa filiformis, Lolium multiflorum, Lolium perenne, Lolium rigidum, lolium temulentum, panicum capillare, Panicum dichotomiflorum, Panicum maximum, Panicum miliaceum, Panicum repens, Panicum texanum, Phalaris brachystachys, Phalaris canariensis, Phalaris minor, Poa annua, Poa trivialis, Roettboellia exaltata, Setaria faberi, Setaria italica, Setaria lutescens (= glauca), Setaria verticilliata, Setaria viridis, Setaria spec., Sorghum bicolor, Sorghum halepense.

Alopecorus myosuroides, Avena fatua, Avena ludoviciana, Avena sterilis, Lolium multiflorum, Lolium perenne, Lolium rigidum, Lolium temulentum, Phalaris brachystachys, Phalaris canariensis, Phalaris minor, Roettboellia exaltata, Setaria faberi, Setaria italica, are preferred with the herbicidal formulation according to the invention. Setaria lutescens (= glauca), Setaria verticilliata, Setaria viridis and / or Setaria spec. fought. Depending on the particular method of application, the herbicidal formulation according to the invention can be used in a further number of crop plants for the removal of unwanted plants. For example, the following cultures may be considered: Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Avena satva, Beta vulgaris spec. altissima, Beta vulgaris spec. rapeseed, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Brassica nigra, Brassica oleracea, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica) , Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec. Pistacia vera, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Seeale cereale, Sinapis albal, Solanum tuberosum, S orghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticale, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays. In addition, the herbicidal formulation according to the invention can also be used in cultures produced by

Breeding, including genetic engineering methods against which the action of herbicides are tolerant, may be used.

The invention is explained in more detail by the examples without thereby restricting them

Examples

Preparation Examples The following herbicidal formulations were prepared:

Table 1 Formulations and Comparative Examples According to the Invention

Table 1

Genagen® 4296, ^** = Solvesso® 200ND, ^*** = Lutensol® T08, Plurafac® LF1300, ^***** = Calsogen® A 100 ND, ^****** = Emulan®EL40

II Application examples

The herbicidal action of the herbicidal formulation according to the invention was demonstrated by greenhouse experiments:

The culture vessels used were plastic pots with loamy sand with about 3.0% humus as substrate. The seeds of the test plants were sown separately by species.

For the postemergence treatment, the test plants were, depending on the growth form, first grown to a height of from 3 to 15 cm and then treated with the herbicidal formulation according to the invention. The cultivation of the test plants was carried out either by direct sowing in the test vessels or by sowing in seed shells with subsequent transplantation of the test plants in the test vessels a few days before treatment

The plants were kept species-specific at temperatures of 10 - 25 ° C and 20 - 35 ° C, respectively. The trial period lasted for 2 to 4 weeks. During this time, the plants were cared for, and their response to each treatment was evaluated.

The effect of the herbicidal formulation according to the invention on the test plants was evaluated in direct comparison with untreated test plants on the basis of a percentage scale (0 to 100%). 100% means no emergence of the plants or complete destruction of at least the aerial parts and 0% no damage or normal growth course.

The effect of the herbicidal formulation of Example 1 according to the invention on various test plants was compared with that of Comparative Example 1 (Table 2).

Table 2

= Echinocloa crus-galli (chicken millet)

= Setaria viridis (L) (Green Bristlecone) ^*** = Alopecurus myosuroides Huds. (Blackgrass)

* ^*** = Phaldris canariensis L (canary grass)

The herbicidal formulation of the invention shows a higher effect at a reduced application rate.

Application example 2 Tank mixes with Dicamba

Spray mixtures were prepared from the herbicidal formulations according to the invention and commercially available clodinafoppropargyl formulations and the amounts of dicamba stated were added. The activity was determined analogously to Application Example 1 on the specified harmful plants (Table 3).

Table 3

Harmful plant / effect in%

(Λ c c

13 13

13 (Λ (Λ

.Q -Q C C

o o o o

- -

CO CO>>

<<<<<Li. <Li.

N N N O O LU LU

Ol Ol Ol Ol _l _l>>

I-1-1 1- <<<<

Example 1 + 20 + 200 20 35 25 15 30 95 35 75

DICAMBA 10 + 200 15 20 20 15 20 90 40 70

5 + 200 15 15 25 15 20 85 20 40

2.5 + 200 10 10 20 0 15 50 10 0

Example 2 + 20 + 200 25 15 20 0 45 98 45 95

DICAMBA 10 + 200 25 10 25 5 25 90 90 75

5 + 200 25 5 25 10 10 60 60 50

2.5 + 200 25 5 30 15 15 25 25 20

^* Syngenta commercial product (240 g / l clodinafop-propargyl + 60 g / l cloquintocetmexyl)

^** Syngenta commercial product (80 g / l clodinafop-propargyl + 60 g / l cloquintocetmexyl)

TRZAW = Triticum aestivum L (winter wheat)

TRZAS = Triticum aestivum L (summer wheat)

ALOMY = Alopecurus myosuroides HUDS (field fox tail)

AVEFA = Avena fatua L (wild oats) The herbicidal formulations according to the invention show markedly reduced antagonism when co-applied with Dicamba.

Use Example 3 Combination of herbicidal formulations according to the invention and commercially available clodinafop-propargyl formulations (TOPIK® 240EC) with post-emergence dicamba / tritosulfuron (ARRAT®) (Table 4). Table 4

^** BASF SE product (250 g / kg tritosulfuron + 500 g / kg dicamba)

CHEAL = Chenopodium album (white goosefoot)

POLAV = Polygonum aviculare L (bird knotweed) The experiments demonstrate a synergistic effect of the herbicidal formulation according to the invention from Example 1 on a mixture of dicamba and tritosulfuron.

Claims

claims

1 . A herbicidal formulation comprising a1) at least one herbicidal active ingredient from the class of ACC inhibitors; a2) optionally at least one safener; a3) if appropriate, at least one further active substance different from (a1) and (a2) herbicidal active substance; b) one or more solvents of the formula (I),

R-CO-NR ² R (I) wherein

R is a C3-C18 hydrocarbon radical,

R ¹ , R ^2, identically or differently, are a C 1 -C 6 -hydrocarbon radical or a C 1 -C -hydroxyhydrocarbon radical; c) one or more aromatic solvents; d) one or more surfactants from the group of C8-C22-alkyl alcohols which are alkoxylated, the terminal hydroxy groups of these compounds being optionally end-capped by an alkyl, cycloalkyl, acyl or carboxylate radical having 1 to 24 carbon atoms; e) one or more emulsifiers; f) optionally one or more auxiliaries and g) optionally water. A herbicidal formulation according to claim 1 containing the components (a) - (f) in the following amounts (wt%):

(a) 2 - 60,

(a1) 2 - 30,

(a2) 0-10, (a3) 0-50,

(b) 5-60,

(c) 5-60,

(d) 5 - 60,

(e) 3 - 30 and

(f) 0-20.

A herbicidal formulation according to claim 1 or 2, wherein the ACC inhibitor is a phenoxypropionate.

A herbicidal formulation according to claim 3, wherein the phenoxypropionate is clodinafop-propargyl.

A herbicidal formulation according to claim 4, wherein component (a2) is quintocet-mexyl.

A herbicidal formulation according to any one of claims 1 to 5, wherein the solvent (b) is selected from decanoic acid dimethylamide and mixtures of C ₀ / C 12 fatty acid dimethylamides and dodecanoic acid dimethylamide

A herbicidal formulation according to any one of claims 1 to 6, wherein the solvent (c) is selected from toluene, xylates, naphthalene derivatives, C6-C16 aromatic mixtures, chlorobenzene and anisaldehyde acetals.

A herbicidal formulation according to any one of claims 1 to 7, containing alkylalkoxylates of the formula (II),

R ³ -O- [R ⁴ O] _m R ⁵ (II) where

R ^{3 is} a linear or branched, saturated or unsaturated, unsubstituted or substituted by one or more hydroxy groups (C0-C22) - hydrocarbon radical;

R ^{5 is} H, (C ₁ -C ₂₄ ) -alkyl, (C ₂ -C ₂ 4) -acyl, (C ₂ -C ₂ 4) -O-acyl or (C ₃ -C ₈ ) -cycloalkyl and m is a natural number of 3 to 100.

9. A herbicidal formulation according to any one of claims 1 to 8, wherein the emulsifier component (e) contains at least one ionic (e1) and at least one nonionic emulsifier (e2).

10. A herbicidal formulation according to claim 9, containing one or more ionic emulsifiers (e1) from the group of alkali, alkaline earth or ammonium salts of fatty acids, alkyl sulfates, alkyl ether sulfates, alkyl or iso-alkyl sulfonates, alkylbenzenesulfonates, alkylmethyl ester sulfonates and taurates, and a or several nonionic emulsifiers (e2) from the group of corn oil ethoxylates, castor oil oxylates, tallow fatty ethoxylates, glycerol esters, fatty alcohol alkoxylates and oxoalkanol alkoxylates, fatty acid alkoxylates, alkylphenol alkoxylates. 1 1. A process for the preparation of a herbicidal formulation according to any one of claims 1 to 10, wherein the said components are mixed together.

12. A method for controlling undesired plant growth, wherein applying an effective amount of a herbicidal formulation according to any one of claims 1 to 10 on the unwanted plants or the places where they occur.

13. Use of a herbicidal formulation according to any one of claims 1 to 10 for combating undesirable plant growth.

14. Use according to claim 13, wherein the formulation is used together with at least one further herbicide.

Use according to claim 14, wherein the further herbicide is dicamba.