Emulsion (EC) formulation containing thiencarbazone-methyl

Abstract

The present invention relates to an emulsion formulation comprising thiencarbazone-methyl or a pesticide-acceptable salt thereof, one or more organic water-immiscible solvents, one or more organic water-miscible solvents selected from linear and cyclic carbamate esters, one or more emulsifiers, and one or more organic bases, wherein the formulation exhibits a pH of 5.5 to 9.

Description

[Technical Field]

[0001] The present invention relates to the field of crop protection compositions. In particular, the present invention relates to emulsifiable concentrate (EC) formulations containing herbicidal active compounds from the group of sulfonylaminocarbonyltriazolinones. [Background technology]

[0002] Generally, active compounds for crop protection are not used in their pure form. Depending on the application area and type of use, as well as the physical, chemical, and biological parameters, active compounds are used as formulations in mixtures with conventional auxiliaries and additives. Combinations with further active compounds to broaden the activity spectrum and / or protect the crop plant (e.g., by phytotoxicity reducers, antidotes) are also known.

[0003] Formulations of individual active compounds, such as combinations of multiple active compounds for crop protection, should generally be easy to apply, easy to use, possess high selectivity for the active compounds used, and have a broad biological effect in combination with them, and should also be easy to formulate in the preparation method. Of particular importance here is the high chemical and physical stability (storage stability) of the formulation.

[0004] Typical formulations for crop protection are concentrated suspensions (active compound suspensions) in which particles of the active compound (discontinuous phase) are suspended in an outer liquid phase (continuous phase). Depending on the properties of the outer phase, suspensions are classified as suspension concentrates (SCs), where the main component of the outer phase is water, or oil dispersions (ODs), where the main component of the outer phase is an organic solvent. The choice of each outer phase is often determined by the stability of the active compound being targeted. Generally, active compounds that are unstable in water are formulated as ODs, and active compounds that are unstable in organic solvents are formulated as SCs.

[0005] Sulfonylaminocarbonyltriazolinones are a class of highly effective and selective herbicides described in WO01 / 05788, WO03 / 026426, and WO03 / 026427. Thiencarbazone methyl (methyl 4-[(4,5-dihydro-3-methoxy-4-methyl-5-oxo-1H-1,2,4-triazole-1-yl)carbonylsulfamoyl]-5-methylthiophene-3-carboxylate; CAS 317815-83-1) also belongs to the aforementioned class of sulfonylaminocarbonyltriazolinones. These herbicides are typically formulated as oil-dispersible wettable powders, as described in WO2005 / 051082. Suspensions of sulfonylaminocarbonyltriazolinones are also known (e.g., EP2170041). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 01 / 05788 Pamphlet [Patent Document 2] International Publication No. 03 / 026426 Pamphlet [Patent Document 3] International Publication No. 03 / 026427 Pamphlet [Patent Document 4] International Publication No. 2005 / 051082 Pamphlet [Patent Document 5] European Patent No. 2170041 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] While sulfonylaminocarbonyltriazolinone OD and SC formulations have been shown to offer adequate storage stability and broad biological activity, these formulations are generally difficult to prepare and handle.

[0008] Therefore, the object of the present invention was to provide an improved formulation of a crop protection agent, particularly sulfonylaminocarbonyltriazolinones, which has high chemical and physical stability and is easy to handle in terms of manufacturing and field application. [Means for solving the problem]

[0009] This objective is achieved by a specific emulsion (EC) formulation of the present invention.

[0010] Therefore, the present invention relates to an emulsion (EC) formulation, a) One or more herbicidal compounds selected from the group of sulfonylaminocarbonyltriazolinones, preferably thiencarbazone-methyl or a pesticide-acceptable salt thereof. b) One or more organic water-immiscible solvents, c) One or more organic water miscible solvents, d) One or more emulsifiers, e) One or more organic bases Includes, Here, the present invention relates to a formulation that exhibits a pH between pH 5.5 and pH 9.

[0011] The pH of the formulation can be measured after diluting the emulsion formulation with distilled water to obtain a 10% w / w mixture.

[0012] The pH of the formulation can be measured, in particular, by the following method: - Dilute the emulsion formulation with distilled water to obtain a 10% w / w mixture; - Stir the mixture using a magnetic stirrer at 1500 RPM for 10 minutes at 25°C; and - Measure the pH of the mixture stirred at 25°C using a pH meter until the measured pH stabilizes for 10 seconds.

[0013] pH measurement can be performed using a Knick 766 pH meter (Calimatic, Knick SE 100N).

[0014] EC formulations may further include one or more of the following: f) One or more pharmacokinetic mitigating agents, g) One or more pesticide active ingredients different from a) and f), h) Further adjuvants, wetting agents and / or other additives suitable for the pesticide formulation.

[0015] The term “emulsifiable concentrate” (abbreviated as “EC”) is known in the art. Emulsifiable concentrate (EC) formulations typically contain an active ingredient, one or more surfactants that act as emulsifiers when the EC is diluted with water, and a water-immiscible solvent.

[0016] The term "water miscible" means that a compound or solvent may have a solubility in water of at least 5 g / l, preferably at least 20 g / l, more preferably at least 50 g / l, and especially at least 100 g / l at 20°C.

[0017] The term "water immiscible" means that the compound or solvent may have a solubility in water up to 100 g / l, preferably up to 50 g / l, more preferably up to 20 g / l, and particularly up to 5 g / l at 20°C.

[0018] Sulfonylaminocarbonyltriazolinones are described in WO01 / 05788. Sulfonylaminocarbonyltriazolinones have general formula (I) [ka] [In the formula, Q 1 represents O (oxygen) or S (sulfur), Q 2 represents O (oxygen) or S (sulfur), R 1 In each case, represents an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl, or heterocyclylalkyl which may be optionally substituted. R 2This represents hydrogen, cyano, nitro, halogen, or, in each case, optionally substituted alkyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkenyl, alkynyl, alkenyloxy, or alkynyloxy. R 3 , represents hydrogen, hydroxyl, mercapto, amino, cyano, halogen, or, in each case, optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylthio, alkylamino, alkylcarbonylamino, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio, alkenylamino, alkynylamino, dialkylamino, azilidino, pyrrolidino, piperidino, morpholino, cycloalkyl, cycloalkenyl, cycloalkyloxy, cycloalkylthio, cycloalkylamino, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylalkylthio, cycloalkyl-alkylamino, aryl, arylalkyl, aryloxy, arylalkoxy, arylthio, arylalkylthio, arylamino or arylalkylamino, and R 4 This represents hydrogen, hydroxyl, amino, cyano, alkylideneamino, or, in each case, optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylamino, alkyl-carbonylamino, alkenyloxy, dialkylamino, cycloalkyl, cycloalkylamino, cycloalkylalkyl, aryl, or arylalkyl. R 3 and R 4 [represents an arcanediil that may be branched or otherwise separated.] This relates to compounds represented by formula (I) and salts of compounds represented by formula (I).

[0019] Thienocarbazone-methyl (methyl 4-[(4,5-dihydro-3-methoxy-4-methyl-5-oxo-1H-1,2,4-triazole-1-yl)carbonylsulfamoyl]-5-methylthiophene-3-carboxylate; CAS No. 317815-83-1) is also described in WO01 / 05788. Thienocarbazone-methyl can be provided in the form of its salt, preferably in the form of its sodium salt.

[0020] Preferably, the EC formulation exhibits a pH of 6.0 to 8.5, more preferably 6.5 to 8.0, and even more preferably 6.8 to 7.7. The pH can be measured as described above.

[0021] The pH of the EC is preferably adjusted by at least one organic base.

[0022] It has been found that EC formulations containing sulfonylaminocarbonyltriazolinone, preferably thiencarbazone-methyl, require a specific pH for chemical stability. If the pH is excessively acidic or excessively basic, sulfonylaminocarbonyltriazolinone decomposes to a considerable extent. The use of organic bases allows for appropriate pH adjustment, enabling storage-stable EC formulations.

[0023] In further embodiments, the emulsion according to the present invention is a) 0.01 to 5% by weight, preferably 0.1 to 2% by weight, more preferably 0.3 to 1% by weight, of one or more herbicidal compounds from the group of sulfonylaminocarbonyltriazolinones, preferably thiencarbazone-methyl or a pesticide-acceptable salt thereof; and / or b) 5-95% by weight, preferably 10-70% by weight, more preferably 20-60% by weight of one or more organic water-immiscible solvents; and / or c) 5-95% by weight, preferably 10-60% by weight, more preferably 20-40% by weight of one or more organic water-miscible solvents; and / or d) 0.1 to 30% by weight, preferably 1 to 25% by weight, more preferably 5 to 20% by weight of one or more emulsifiers; and / or e) 0.1 to 10% by weight, preferably 0.2 to 5% by weight, more preferably 0.5 to 2% by weight of an organic base may be included.

[0024] The EC formulation may further include one or more of the following: f) 0 to 10% by weight, preferably 1 to 8% by weight, more preferably 2 to 6% by weight of one or more phytotoxicity reducing agents; and / or g) 0 to 40% by weight, preferably 5 to 30% by weight, more preferably 10 to 25% by weight of one or more pesticide active ingredients different from a) and f); and / or h) 0 to 40% by weight, preferably 5 to 30% by weight, more preferably 10 to 20% by weight of further adjuvants, wetting agents and / or other additives compatible with the pesticide formulation.

[0025] Here, and throughout this description, the term "weight %" refers to the relative weight of the component based on the total weight of the formulation, unless otherwise defined.

[0026] The organic water-immiscible solvent b) may be a hydrocarbon which may be unsubstituted or substituted.

[0027] Examples of the organic water-immiscible solvent b) are aromatic hydrocarbons such as mono- or polyalkyl-substituted benzenes such as toluene, xylene, mesitylene, ethylbenzene, or mono- or polyalkyl-substituted naphthalenes such as 1-methylnaphthalene, 2-methylnaphthalene or dimethylnaphthalene, or other benzene-derived aromatic hydrocarbons such as indane or Tetralin (registered trademark), or mixtures thereof; aliphatic hydrocarbons such as pentane, hexane, octane, 2-methylbutane or 2,2,4-trimethylpentane, for example of the formula C n H 2n+2Linear or branched aliphatic compounds, or cyclic, optionally alkyl-substituted aliphatic compounds such as cyclohexane or methylcyclopentane, or mixtures thereof, for example, solvents of the Exxsol® D series, Isopar® series, or Bayol® series, for example, Bayol® 82 (ExxonMobil Chemicals), or Isane® IP series or Hydroroseal® G series (TotalFinaElf); mixtures of aromatic and aliphatic hydrocarbons, for example, solvents of the Solvesso® series, for example, Solvesso® 100, Solvesso® 150, or Solvesso® 200 (ExxonMobil Chemicals), Solvarex® / Solvaro® series (TotalFinaElf), or Caromax® series, for example, Caromax® 28 (Petrochem). Carless; or halogenated hydrocarbons, such as halogenated aromatics and aliphatic hydrocarbons, such as chlorobenzene or methylene chloride.

[0028] Alternatively, the organic water-immiscible solvent b) can be selected from fatty acid esters, for example, naturally derived ones, such as natural oils, such as animal or vegetable oils, or synthetic ones, such as the Edenor® series, such as Edenor® MEPa or Edenor® MESU, or the Agnique® ME series or Agnique® AE series (Cognis), Salim® ME series (Salim), Radia® series, such as Radia® 30167 (ICI), Prilube® series, such as Prilube® 1530 (Petrofina), Stepan® C series (Stepan), or Witconol® 23 series (Witco). The fatty acid ester is preferably C 10 ~C 22 -, preferably C 12 ~C 20-It is an ester of a fatty acid. C 10 ~C 22 - Fatty acid esters are, for example, unsaturated or saturated C 10 ~C 22 - Fatty acids, especially those having an even number of carbon atoms, such as erucic acid, lauric acid, palmitic acid, and especially C 18 - Fatty acids, such as esters of stearic acid, oleic acid, linoleic acid, or linolenic acid. C 10 ~C 22 - Examples of fatty acid esters, such as fatty acid esters, are C 10 ~C 22 - Glycerol and glycol esters of fatty acids such as fatty acids, or their transesterification products, for example, C 10 ~C 22 -Fatty acid C1~C 20 - These are fatty acid alkyl esters such as alkyl esters, for example, C 10 ~C22 fatty acid esters and the above-mentioned glycerol or glycol fatty acid esters and C1~C 20 -It can be obtained by transesterification with an alcohol (e.g., methanol, ethanol, propanol, or butanol). Transesterification can be carried out by known methods, such as those described in Roempp Chemie Lexikon, 9th edition, Vol. 2, p. 1343, Thieme Verlag Stuttgart. Preferred fatty acid alkyl esters, for example C 10 ~C 22 -Fatty acid C1~C 20 -Alkyl esters include methyl esters, ethyl esters, propyl esters, butyl esters, 2-ethylhexyl esters, and dodecyl esters. Preferred glycols and glycerol fatty acid esters, for example, C 10 ~C 22 - Fatty acid esters are C 10 ~C 22 - Fatty acids, especially fatty acids having an even number of carbon atoms, such as erucic acid, lauric acid, palmitic acid, especially C 18 - Homogeneous or mixed glycol esters and glycerol esters of fatty acids, such as stearic acid, oleic acid, linoleic acid, or linolenic acid.

[0029] Animal oils are generally known and commercially available. For the purposes of this invention, the term "animal oil" should be understood to mean oils of animal origin, such as whale oil, cod liver oil, musk oil, or mink oil.

[0030] Vegetable oils are generally known and commercially available. For the purposes of this invention, the term "vegetable oil" should be understood to mean oils from oily plant species such as soybean oil, rapeseed oil, corn oil, sunflower oil, cottonseed oil, linseed oil, coconut oil, palm oil, thistle oil, walnut oil, peanut oil, olive oil, or castor oil, and especially rapeseed oil, where vegetable oil also includes their transesterification products, such as alkyl esters such as rapeseed oil methyl ester or rapeseed oil ethyl ester.

[0031] Vegetable oil is preferably C 10 ~C 22 -, preferably C 12 ~C 20 -It is an ester of a fatty acid. C 10 ~C 22 - Fatty acid esters are, for example, unsaturated or saturated C, particularly those having an even number of carbon atoms. 10 ~C 22 - Fatty acids, such as erucic acid, lauric acid, palmitic acid and especially C 18 - Fatty acids, such as esters of stearic acid, oleic acid, linoleic acid, or linolenic acid.

[0032] Examples of vegetable oils include glycerol or glycol and C 10 ~C 22 - with fatty acids 10 ~C 22 - Fatty acid esters, or, for example, the above-mentioned glycerol or glycol C 10 ~C 22 - Fatty acid esters and C1~C 20 -C can be obtained by transesterification with an alcohol (e.g., methanol, ethanol, propanol, or butanol). 10 ~C 22 -Fatty acid C1~C20 -It is an alkyl ester. Transesterification can be carried out by known methods, such as those described, for example, in Roempp Chemie Lexikon, 9th edition, Vol. 2, p. 1343, Thieme Verlag Stuttgart.

[0033] Vegetable oils include, for example, commercially available vegetable oils, especially rapeseed oil, such as rapeseed oil methyl ester, such as Phytorob® B (Novance, France), Edenor® MESU and Agnique® ME series (Cognis, Germany), Radia® series (ICI), Prilube® series (Petrofina), or in the form of biodiesel, or commercially available vegetable oil-containing formulation additives, especially those based on rapeseed oil, such as rapeseed oil methyl ester, such as Hasten® (Victorian Chemical Company, Australia, hereinafter referred to as Hasten, main component: rapeseed oil ethyl ester), Actirob® B (Novance, France, hereinafter referred to as Actirob B, main component: rapeseed oil methyl ester), Rako-Binol® (Bayer) It may be contained in the adjuvant according to the present invention in the form of AG, Germany (hereinafter referred to as Rako-Binol, main component: rapeseed oil), Renol® (Stefes, Germany, hereinafter referred to as Renol, vegetable oil component: rapeseed oil methyl ester), or Stefes Mero® (Stefes, Germany, hereinafter referred to as Mero, main component: rapeseed oil methyl ester).

[0034] Examples of synthetic fatty acid esters include, for example, C 11 ~C 21 - These are derived from fatty acids that have an odd number of carbon atoms, such as fatty acid esters.

[0035] A preferred organic water-immiscible solvent (b) is an aromatic hydrocarbon and / or an aliphatic hydrocarbon.

[0036] Organic water-immiscible solvents (b) can exist alone or in a mixture of different water-immiscible solvents.

[0037] The organic water miscible solvent c) is preferably a linear or cyclic alkyl carbonate, particularly methyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate and their isomers, propylene carbonate, glycerol-1,2-carbonate and butylene carbonate, or a mixture thereof.

[0038] More preferably, the organic water miscible solvent c) is propylene carbonate and / or glycerol-1,2-carbonate, and even more preferably propylene carbonate.

[0039] Surprisingly, sulfonylaminocarbonyltriazolinones, preferably thiencarbazone-methyl, were found to be significantly chemically stabilized in two-phase solvent systems containing both water-immiscible and water-miscible solvents, the latter of which were linear or cyclic carbonates. Such carbonates, when combined with a suitable pH of 5.5–9, preferably 6–8.5, more preferably 6.5–8.0, and even more preferably 6.8–7.7, effectively prevent the chemical degradation of the active ingredient (ai) over time.

[0040] The EC formulation according to the present invention also includes, as an additional essential component d), at least one suitable emulsifier component that enables the formation of an aqueous emulsion (an oil-in-water emulsion) when the EC formulation of the present invention is added to water.

[0041] The emulsifier may be an ionic (cationic or anionic), amphoteric, or nonionic surfactant, such as an ionic, nonionic, or amphoteric emulsifier or a mixture thereof, and may include standard surface-active substances present in formulations of active pesticide components.

[0042] The emulsifier may be at least one nonionic surfactant selected from the group consisting of alkoxylated alcohols, ethoxylated alcohols, etopropoxylated alcohols, alkylphenol ethoxylates, alkoxylated tristyrylphenols, alkoxylated tributylphenols, alkylamine ethoxylates, ethoxylated vegetable oils (including their hydrogenated products), polyadditives of ethylene oxide and propylene oxide (e.g., polyoxyethylene-polyoxypropylene block copolymers and their derivatives), ethoxylated fatty acids, nonionic polymer surfactants (e.g., polyvinyl alcohol, polyvinylpyrrolidone, polymethacrylates and their derivatives), sorbitan esters and their ethoxylates, sorbitol esters, propylene glycol esters of fatty acids, and polyglycerol esters.

[0043] Examples of preferred nonionic surfactants include ethoxylated alcohols (e.g., Brij 020-SO-(MV), Croda), ethopropoxylated alcohols (e.g., Agnique KE 3551, BASF), alkoxylated tristyrylphenols, ethoxylated tristyrylphenols (e.g., Soprophor TS / 16, Rhodia), ethopropoxylated tristyrylphenols (e.g., Soprophor 796 / P, Rhodia), and ethoxylated vegetable oils (e.g., Tanemul® KS, Tanatex Chemicals).

[0044] Suitable anionic surfactants include salts of polyacrylic acid, polymer salts of acrylic acid / acrylate ester mixtures, polymer salts of acrylic acid / styrene mixtures, salts of lignosulfonic acid (such as sodium lignosulfonate), salts of phenolsulfonic acid, salts of condensation products of phenolsulfonic acid and formaldehyde, salts of naphthalenesulfonic acid, salts of condensation products of naphthalenesulfonic acid and formaldehyde, salts of condensed naphthalene or alkylnaphthalene sulfonates, and dodecyl- and tridecylbenzene. Salts of sulfonates, salts of sulfosuccinate or sulfosuccinate esters, salts of alkyl sulfates, salts of alkyl polyethoxylated and / or polypropoxylated sulfates, salts of paraffin sulfonates, salts of alkyl sulfonates, salts of alkyl polyethoxylated and / or polypropoxylated sulfonates, salts of aryl sulfates, salts of aryl polyethoxylated and / or polypropoxylated sulfates, salts of aryl sulfonates, salts of aryl polyethoxylated and / or polypropoxylated sulfonates Examples of such substances include, but are not limited to, salts of nates, salts of alkylaryl sulfates, salts of alkylaryl polyethoxylated and / or polypropoxylated sulfates, salts of alkylaryl sulfonates, salts of alkylaryl polyethoxylated and / or polypropoxylated sulfonates, salts of diphenyl sulfonates and diphenyl oxide sulfonates, salts of alpha-olefin sulfonates, salts of fatty acid and oil sulfonates, salts of alpha-sulfonated methyl esters, salts of taurine derivatives (preferably alkyl taurates), salts of isethionates, salts of alkyl phosphate esters, salts of aryl phosphate esters, salts of alkylaryl phosphate esters, salts of polyethoxylated and / or polypropoxylated aliphatic linear or branched alcohol phosphate esters, salts of polyethoxylated and / or polypropoxylated aryl alcohol phosphate esters, protein hydrolysates, lignosulfite wastewater, salts of polystyrene sulfonic acid, salts of polyvinyl sulfonic acid, salts of carboxylates, and salts of ether carboxylates.

[0045] Examples of such surfactants or emulsifiers include: ether carboxylates, sulfonates, sulfates, and phosphates, and their inorganic (e.g., alkali metal, alkaline earth metal, or ammonium salts) and organic (e.g., amine- or alkanolamine-based salts), e.g., Genapol® LRO, Sandopan® products, Hostaphat / Hordaphos® products from Clariant, Servoxyl® products from Elementis, Agnique® SLS products (Cognis); salts of aliphatic, alicyclic, and olefinic and polycarboxylic acids, as well as alpha-sulfo fatty acid esters, sulfosuccinates, alkanesulfonates, paraffin sulfonates, and olefinic sulfonates, also available from Cognis, and their inorganic (e.g., alkali metal and alkaline earth metal) and organic (e.g., amine- or alkanolamine-based) salts, e.g., Netzer from Clariant. IS (registered trademark), Hoe (registered trademark) S1728, Hostapur (registered trademark) OS, Hostapur (registered trademark) SAS, Triton (registered trademark) GR7ME and GR5 from Dow, Empimin (registered trademark) products from Huntsman, Marlon (registered trademark)-PS65 from Condea, sulfosuccinamates, for example, Aerosol (registered trademark) products from Cytec or Empimin (registered trademark) products from Huntsman, surfactant polyacrylic acid and polymethacrylic acid derivatives, for example, Sokalan (registered trademark) products from BASF.

[0046] Preferred anionic emulsifiers include phosphorylated or sulfated (poly)alkylphenol alkoxylates, phosphorylated or sulfated poly(arylalkyl)-phenol alkoxylates, (poly)alkyl- and poly(arylalkyl)-benzenesulfonates in acidic or salt form, and sulfosuccinates.

[0047] More preferred anionic emulsifiers are those based on calcium salts of dodecylbenzenesulfonic acid, such as Rhodacal® 60BE (Rhodia) or Calsogen® 4814 (Clariant), Atlox® 4838B X-MSU (Croda), Ninate® 60E X-MSU (Stepan), or Nansa® EVM70 / 2E (Huntsman).

[0048] One or more organic bases e) may be selected from amine-based organic compounds, preferably alkylamines, amino alcohols, alkylamino alcohols, aromatic amines, (poly)ethoxylated amines, and (poly)ethoxylated / propoxylated amines.

[0049] Organic bases are used to adjust the pH of the formulation. By adjusting the pH to a range of 5.5 to 9, preferably 6.0 to 8.5, and more preferably 6.5 to 8.0, the active ingredient (ai) is chemically stabilized.

[0050] Organic bases, particularly amine-based organic compounds, are preferably soluble in a two-phase solvent system comprising a water-immiscible solvent and a water-miscible solvent, especially within a specified concentration range.

[0051] The alkylamine may be, for example, triethylamine, and the aromatic amine may be, for example, pyridine. The amino alcohol may be, for example, triethanolamine.

[0052] Preferably, the organic base is of the following formula (II) [ka] [In the formula, R 1’ This is a linear or branched alkyl group, preferably an unsubstituted linear C2~ 24 It is alkyl, R 2’ is -(CH2-CH2-O) x H and R 3’ is -(CH2-CH2-O) yH is the value, and x+y is between 2 and 20. These are (poly)ethoxylated amines, such as fatty amine ethoxylates. Examples include stearylamines with 8 mol of EO (e.g., Genamin S080 by Clariant) and amine ethoxylates based on coconut fatty amines (e.g., Genamin C050 by Clariant).

[0053] In further embodiments, one or more organic bases are selected from amine-based organic bases, and one or more organic water-miscible solvents are selected from methyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate and their isomers, propylene carbonate, glycerol-1,2-carbonate, and butylene carbonate. Preferably, one or more organic bases are ethoxylated amines, and one organic water-miscible solvent is propylene carbonate.

[0054] The emulsion according to the present invention may include, as component f), a phytotoxicity reducing agent suitable for reducing or preventing damage to crop plants. Suitable phytotoxicity reducing agents are known, for example, from WO-A-96 / 14747 and the literature cited therein. In organic solvents, the phytotoxicity reducing agent exists in a soluble form.

[0055] S1) Compound from the group of heterocyclic carboxylic acid derivatives (Formula S1) [ka] [In the formula, symbols and subscripts are defined as follows: n A is an integer value in the range of 0 to 5, preferably 0 to 3; R A 1 These are halogens, (C1-C4)-alkyls, (C1-C4)-alkoxys, nitros, or (C1-C4)-haloalkyls; W Ais an unsubstituted or substituted divalent heterocyclic moiety selected from the group of partially unsaturated or aromatic 5-membered heterocycles having 1 to 3 heteroatoms selected from the group of nitrogen (N) and oxygen (O), and having at least 1 N atom and 1 or less O atoms in the ring, preferably from groups (WA1) to (WA4) [Chemical formula] m A is 0 or 1; R A 2 is OR A 3 SR A 3 or NR A 3 R A 4 or contains up to 3 heteroatoms in combination with at least 1 N atom and preferably other heteroatoms from the group of O (oxygen) and S (sulfur), is bonded to the carbonyl group in (S1) via a nitrogen atom, and is unsubstituted or a moiety selected from the group of (C1-C4)-alkyl, (C1-C4)-alkoxy or optionally substituted phenyl, preferably OR A 3 NHR A 4 or N(CH3)2, particularly OR A 3 substituted saturated or unsaturated 3- to 7-membered heterocycle; R A 3 is hydrogen or preferably an unsubstituted or substituted aliphatic hydrocarbon moiety containing 1 to 18 C atoms; R A 4 is hydrogen, (C1-C6)-alkyl, (C1-C6)-alkoxy or substituted or unsubstituted phenyl; R A 5 is hydrogen, (C1-C8)-alkyl, (C1-C8)-haloalkyl, (C1-C4)-alkoxy-(C1-C8)-alkyl, cyano or COOR A 9 (where R A9 is hydrogen, (C1-C8)-alkyl, (C1-C8)-haloalkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl, (C1-C6)-hydroxyalkyl, (C3-C 12 )-cycloalkyl or tris-(C1-C4)-alkylsilyl; R A 6 , R A 7 , R A 8 are independently hydrogen, (C1-C8)-alkyl, (C1-C8)-haloalkyl, (C3-C 12 )-cycloalkyl or substituted or unsubstituted phenyl; R A 10 is hydrogen, (C3-C 12 )-cycloalkyl, substituted or unsubstituted phenyl, or substituted or unsubstituted heteroaryl); is a 5-membered heterocyclic moiety selected from

[0056] S1 a ) compounds of the dichlorophenylpyrazoline-3-carboxylic acid type (S1 a ), preferably compounds such as 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic acid, ethyl 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate (S1-1) (“mephenpyr-diethyl”), and related compounds (these are described in WO-A-91 / 07874); S1 b ) derivatives of dichlorophenylpyrazolecarboxylic acid (S1 b), preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (S1-2), ethyl 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (S1-3), and ethyl 1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate (S1-4), as well as related compounds (these are described in EP-A-333131 and EP-A-269806); S1 c ) Derivatives of 1,5-diphenylpyrazole-3-carboxylic acid (S1 c ), preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-5), methyl 1-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-6), and related compounds (these are described, for example, in EP-A-268554); S1 d ) Triazolecarboxylic acid type compounds (S1 d ), preferably fenchlorazole (-ethyl ester), i.e., compounds such as ethyl 1-(2,4-dichlorophenyl)-5-trichloromethyl-1H-1,2,4-triazole-3-carboxylate (S1-7), and related compounds (these are described in EP-A-174562 and EP-A-346620); S1 e ) Compounds of the type 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid (S1 ePreferably, compounds such as 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate ethyl (S1-8) or 5-phenyl-2-isoxazoline-3-carboxylate ethyl (S1-9) and related compounds (these are described in WO-A-91 / 08202), or 5,5-diphenyl-2-isoxazolinecarboxylic acid (S1-10) or 5,5-diphenyl-2-isoxazoline-3-carboxylate ethyl (S1-11) ("isoxadifen-ethyl") or 5,5-diphenyl-2-isoxazoline-3-carboxylate n-propyl (S1-12) or 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate ethyl (S1-13) (these are described in patent application WO-A-95 / 07897).

[0057] S1 f ) Triazolyloxyacetic acid type compounds (S1 f Preferably, methyl-{[1,5-bis(4-chloro-2-fluorophenyl)-1H-1,2,4-triazole-3-yl]oxy}acetate (S1-14) or {[1,5-bis(4-chloro-2-fluorophenyl)-1H-1,2,4-triazole-3-yl]oxy}acetic acid (S1-15) or methyl-{[5-(4-chloro-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazole-3-yl]oxy}acetate (S1-16) or {[5-(4-chloro-2-fluorophenyl)-1 Compounds such as -(2,4-difluorophenyl)-1H-1,2,4-triazole-3-yl]oxy}acetic acid (S1-17) or methyl-{[1-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1H-1,2,4-triazole-3-yl]oxy}acetate (S1-18) or {[1-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1H-1,2,4-triazole-3-yl]oxy}acetic acid (S1-19) (these are described in patent application WO2021105101).

[0058] S2) Compounds from the group of 8-quinoline oxy derivatives (S2): S2 a ) 8-Quinoline oxyacetic acid type compound (S2 a Preferably 1-methylhexyl(5-chloro-8-quinolineoxy)acetate ("chloroquintoset-mexyl") (S2-1), 1,3-dimethylbuta-1-yl(5-chloro-8-quinolineoxy)acetate (S2-2), 4-allyloxybutyl(5-chloro-8-quinolineoxy)acetate (S2-3), 1-allyloxypropane-2-yl(5-chloro-8-quinolineoxy)acetate (S2-4), ethyl(5-chloro-8-quinolineoxy)acetate (S2-5), methyl(5-chloro-8-quinolineoxy)acetate (S2-6), allyl(5-chloro-8-quinolineoxy)acetate (S2-7), 2-(2-propyridene) Iminoxy)-1-ethyl(5-chloro-8-quinolineoxy)acetate (S2-8), 2-oxopropa-1-yl(5-chloro-8-quinolineoxy)acetate (S2-9) and related compounds (these are described in EP-A-86750, EP-A-94349 and EP-A-191736 or EP-A-0492366), as well as (5-chloro-8-quinolineoxy)acetic acid (S2-10), its hydrates and salts, such as its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts (these are described in WO-A-2002 / 34048); S2 b ) (5-chloro-8-quinoline oxy)malonic acid type compound (S2 b Preferably, compounds such as (5-chloro-8-quinolineoxy) diethyl malonate, (5-chloro-8-quinolineoxy) diallyl malonate, (5-chloro-8-quinolineoxy) methyl ethyl malonate and related compounds (these are described in EP-A-0582198).

[0059] S3) Dichloroacetamide-type active ingredients (S3) are frequently used as pre-emergence phytotoxicity reducers (soil-acting phytotoxicity reducers), for example, "Dichlormid" (N,N-diallyl-2,2-dichloroacetamide) (S3-1), Stauffer's "R-29148" (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) (S3-2), Stauffer's "R-28725" (3-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine) (S3-3), "Benoxacol" (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4), "PPG-1292" (N-allyl-N-[(1,3-dioxolan-2-yl)methyl]dichloroacetamide) (S3-5) from PPG Industries, "DKA-24" (N-allyl-N-[(allylaminocarbonyl)methyl]dichloroacetamide) (S3-6) from Sagro-Chem, "AD-67" or "MON 4660" (3-dichloroacetyl-1-oxa-3-azaspiro[4.5]decane) (S3-7) from Nitrokemia or Monsanto, "TI-35" (1-dichloroacetylazepane) from TRI-Chemical RT, "Diclonon" (or "BAS145138" or "LAB145138") (S3-9) ((RS)-1-dichloroacetyl-3,3,8a-trimethylperhydropyrrolo[1,2-a]pyrimidine-6-one) from BASF, "Flirazole" or "MON13900" ((RS)-3-dichloroacetyl-5-(2-furyl)-2,2-dimethyloxazolidine) (S3-10), and its (R) isomer (S3-11).

[0060] S4) Compounds from the class of acylsulfonamides (S4): S4 a ) Equation (S4 a ) [ka] [During the ceremony, R A 1 These are (C1-C6)-alkyl and (C3-C6)-cycloalkyl, where the latter two groups are from the group of halogen, (C1-C4)-alkoxy, (C1-C6)-haloalkoxy and (C1-C4)-alkylthio. A It is substituted by a substituent, and in the case of a cyclic group, it is also substituted by (C1-C4)-alkyl and (C1-C4)-haloalkyl groups; R A 2 These are halogens, (C1-C4)-alkyls, (C1-C4)-alkoxys, and CF3; m A is either 1 or 2; v A [is 0, 1, 2, or 3] Compounds and salts thereof (these are described in WO-A-97 / 45016); S4 b ) Equation (S4 b ) [ka] [During the ceremony, R B 1 , R B 2 These are independently hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, and (C3-C 6) -Alkenyl, (C3-C6)-Alkinyl, R B 3 This refers to halogens, (C1-C4)-alkyls, (C1-C4)-haloalkyls, or (C1-C 4) -It is an alkoxy, and m B is either 1 or 2, For example, the following: R B 1 =Cyclopropyl, R B 2 = Hydrogen and (R B3 ) = 2-OMe("Cyprosulfamide", S4-1), R B 1 =Cyclopropyl, R B 2 = Hydrogen and (R B 3 ) = 5-Cl-2-OMe(S4-2), R B 1 = ethyl, R B 2 = Hydrogen and (R B 3 ) = 2 - OMe(S4-3), R B 1 = Isopropyl, R B 2 = Hydrogen and (R B 3 )=5-Cl-2-OMe(S4-4) and R B 1 = Isopropyl, R B 2 = Hydrogen and (R B 3 ) = 2 - OMe(S4-5) Compounds of the 4-(benzoylsulfamoyl)benzamide type and salts thereof (these are described in WO-A-99 / 16744); S4 c ) Formula (S4) described in EP-A-365484 c ) [ka] [During the ceremony, R C 1 , R C 2 These are independently hydrogen, (C1-C8)-alkyl, (C3-C8)-cycloalkyl, (C3-C6)-alkenyl, and (C3-C6)-alkynyl. R C 3 These are halogens, (C1-C4)-alkyls, (C1-C4)-alkoxys, CF3, and m Cis either 1 or 2; for example, 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea, 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea, 1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea] Compounds from the class of benzoylsulfamoylphenylurea; S4 d ) is equation (S4 d ) [ka] [During the ceremony, R D 4 These are halogens, (C1-C4)-alkyls, (C1-C4)-alkoxys, and CF3; m D is either 1 or 2; R D 5 These are hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, and (C5-C6)-cycloalkenyl. N-phenylsulfonyl terephthalamide type compounds and their salts (these are known, for example, from CN101838227), S5) Active ingredients (S5) from the class of hydroxyaromatic compounds and aromatic-aliphatic carboxylic acid derivatives, e.g., ethyl 3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicylic acid, 2-hydroxycinnamic acid, 2,4-dichlorocinnamic acid (these are described in WO-A-2004 / 084631, WO-A-2005 / 015994, and WO-A-2005 / 016001).

[0061] S6) Active ingredients from the class of 1,2-dihydroquinoxarin-2-ones (S6), e.g., 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxarin-2-one, 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxarin-2-thione, 1-(2-aminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxarin-2-one hydrochloride, 1-(2-methylsulfonylaminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxarin-2-one (these are described in WO-A-2005 / 112630).

[0062] S7) Compounds from the class of diphenylmethoxyacetic acid derivatives (S7), e.g., methyl diphenylmethoxyacetate (CAS registry no. 41858-19-9) (S7-1), ethyl diphenylmethoxyacetate, or diphenylmethoxyacetic acid (these are described in WO-A-98 / 38856).

[0063] S8) Formula (S8) [ka] [In the formula, symbols and subscripts are defined as follows: R D 1 These are halogens, (C1-C4)-alkyls, (C1-C4)-haloalkyls, (C1-C4)-alkoxys, and (C1-C4)-haloalkoxys. R D 2 is hydrogen or (C1-C4)-alkyl, R D 3 is hydrogen, (C1-C8)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, or aryl, where each of the above carbon-containing groups is unsubstituted or substituted with one or more, preferably up to three identical or different groups selected from the group consisting of halogens and alkoxys; or is a salt thereof. n D [This is an integer between 0 and 2.] The compounds (these are described in WO-A-98 / 27049).

[0064] S9) Active ingredients (S9) from the class of 3-(5-tetrazolylcarbonyl)-2-quinolones, e.g., 1,2-dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS registry number: 219479-18-2), 1,2-dihydro-4-hydroxy-1-methyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS registry number 95855-00-8) (these are listed in WO-A-1999 / 000020).

[0065] S10) Formula (S10 a ) or (S10 b ) [ka] [During the ceremony, R E 1 These are halogen, (C1-C4)-alkyl, methoxy, nitro, cyano, CF3, and OCF3. Y E , Z E These are independently O or S, n E is an integer from 0 to 4, R E 2 (C1-C 16 )-alkyl, (C2-C6)-alkenyl, (C3-C6)-cycloalkyl, aryl; benzyl, halobenzyl, R E 3 [is hydrogen or (C1-C6)-alkyl] The compounds (these are described in WO-A-2007 / 023719 and WO-A-2007 / 023764).

[0066] S11) An oxyimino compound type active ingredient (S11) known as a seed coating agent, for example, "Oxavethrinil" ((Z)-1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile) (S11-1), is known as a seed powder phytotoxicity mitigating agent for millet / sorghum against damage caused by metrachlor. "Fluxofenim" (1-(4-chlorophenyl)-2,2,2-trifluoro-1-ethanone O-(1,3-dioxolan-2-ylmethyl)-oxime) (S11-2), is known as a seed powder phytotoxicity mitigating agent for millet / sorghum against damage caused by metrachlor, and "Siometrinil" or "CGA-43089" ((Z)-cyanomethoxyimino(phenyl)acetonitrile) (S11-3), is known as a seed powder damage mitigation agent for millet / sorghum damage caused by metrachlor.

[0067] S12) An active ingredient (S12) selected from the class of isothiochromanones, for example, [(3-oxo-1H-2-benzothiopyran-4(3H)-ylidene)methoxy]methyl acetate (CAS registry no. 205121-04-6) (S12-1) and related compounds (from WO-A-1998 / 13361).

[0068] S13) One or more compounds from group (S13): "Naphthalic anhydride" (1,8-naphthalenedicarboxylic acid anhydride) (S13-1), is known as a seed powder damage mitigating agent for corn against damage caused by thiocarbamate herbicides. "Fenchlorim" (4,6-dichloro-2-phenylpyrimidine) (S13-2) is known as a phytotoxicity-reducing agent for pretilachlor in sown rice. "Flurazole" (2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate benzyl) (S13-3), is known as a seed powder phytotoxicity mitigating agent for millet / sorghum against damage caused by alachlor and metrachlor. "CL304415" (CAS Registry Number 31541-57-8) (4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid)(S13-4) from American Cyanamid is known as a phytotoxicity mitigating agent for maize against damage caused by imidazolinones. Nitrokemia's "MG191" (CAS registry number 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) is known as a phytotoxicity reducer for corn. "MG838" (CAS Registry Number 133993-74-5) (2-propenyl-1-oxa-4-azapiro[4,5]decane-4-carboditioate) from Nitrokemia (S13-6) "Disulfone" (O,O-diethyl S-2-ethylthioethyl phosphorodithioate) (S13-7), "dietholate" (O,O-diethyl O-phenylphosphorothioate) (S13-8), "Mephenate" (4-chlorophenyl methylcarbamate) (S13-9).

[0069] S14) Active ingredients that, in addition to their herbicidal effect on harmful plants, also have an effect of reducing phytotoxicity to crop plants such as rice, for example, "Dimethiperate" or "MY-93" (S-1-methyl-1-phenylethylpiperidine-1-carbothioate) is known as a phytotoxicity mitigating agent for rice plants affected by the herbicide molinate. "Daimlon" or "SK23" (1-(1-methyl-1-phenylethyl)-3-p-tolylurea), is known as a phytotoxicity reducer for rice plants affected by the herbicide imazosulfuron. "Kumiluron" = "JC-940" (3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenylethyl)urea, see JP-A-60087254), is known as a phytotoxicity reducer for rice plants affected by several herbicides. "Methoxyphenone" or "NK049" (3,3'-dimethyl-4-methoxybenzophenone) is known as a phytotoxicity reducer for rice against damage from several herbicides. Kumiai's "CSB" (1-bromo-4-(chloromethylsulfonyl)benzene) (CAS registry number 54091-06-4) is known as a phytotoxicity mitigating agent for damage caused by several herbicides in rice.

[0070] S15) Formula (S15) [ka] [During the ceremony, R H 1 is a (C1-C6)-haloalkyl group, and R H 2 is hydrogen or halogen, and R H 3 , R H 4 Independently, hydrogen, (C1-C 16 )-alkyl, (C2-C 16 )-alkenyl or (C2-C 16 )-alkynyl, where each of the latter three groups is unsubstituted or substituted with one or more groups from the group consisting of halogen, hydroxyl, cyano, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkylthio, (C1-C4)-alkylamino, di[(C1-C4)-alkyl]amino, [(C1-C4)-alkoxy]carbonyl, [(C1-C4)-haloalkoxy]carbonyl, unsubstituted or substituted (C3-C6)-cycloalkyl, unsubstituted or substituted phenyl, and unsubstituted or substituted heterocyclyl. or (C3-C6)-cycloalkyl, (C4-C6)-cycloalkenyl, (C3-C6)-cycloalkyl condensed to a 4- to 6-membered saturated or unsaturated carbon ring on one side of the ring, or (C4-C6)-cycloalkenyl condensed to a 4- to 6-membered saturated or unsaturated carbon ring on one side of the ring, and Here, each of the latter four groups is either unsubstituted or substituted with one or more groups from the group consisting of halogen, hydroxyl, cyano, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkylthio, (C1-C4)-alkylamino, di[(C1-C4)-alkyl]amino, [(C1-C4)-alkoxy]carbonyl, [(C1-C4)-haloalkoxy]carbonyl, unsubstituted or substituted (C3-C6)-cycloalkyl, unsubstituted or substituted phenyl, and unsubstituted or substituted heterocyclyl. or R H 3 These are (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C2-C6)-alkynyloxy, or (C2-C4)-haloalkoxy. R H 4 is hydrogen or (C1-C4)-alkyl, or R H 3 and R H 4 This represents a 4- to 8-membered heterocyclic ring together with the directly bonded nitrogen atom, which may contain, in addition to the nitrogen atom, up to two additional ring heteroatoms, preferably from the group N, O, and S, and which is either unsubstituted or substituted with one or more groups from the group halogen, cyano, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, and (C1-C4)-alkylthio. Compounds of or tautomers thereof (these are described in WO-A-2008 / 131861 and WO-A-2008 / 131860).

[0071] S16) Active ingredients that are mainly used as herbicides but also have the effect of reducing phytotoxicity to crops, for example, (2,4-Dichlorophenoxy)acetic acid (2,4-D), (4-chlorophenoxy)acetic acid, (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop), 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB), (4-chloro-o-tolyloxy)acetic acid (MCPA), 4-(4-chloro-o-tolyloxy)butyric acid, 4-(4-chlorophenoxy)butyric acid, 3,6-Dichloro-2-methoxybenzoic acid (dicamba), 1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate (lactidichlor-ethyl).

[0072] Preferred phytotoxicity reducing agents to be combined with the herbicide combination of the present invention are croquintoset-mexil, cyprosulfamide, fenchlorazole ethyl ester, isoxadifen-ethyl, mefenpyr-diethyl, fenchlorim, cumilon, S4-1 and S4-5, and particularly preferred phytotoxicity reducing agents are croquintoset-mexil, cyprosulfamide, isoxadifen-ethyl and mefenpyr-diethyl.

[0073] One or more pesticide active ingredients g) different from a) and f) are diflufenican, pyroxasulfone, metrivudine, mesotrione, acroniphen, bromoxynyl, bromoxynyl-butyrate, -potassium, -heptanoate, and -octanoate, benzofenap, butachlor, 2,4-D, 2,4-D-butotyl, -butyl, -dimethylammonium, -diolamine, -ethyl, -2-ethylhexyl, -isobutyl, -isooctyl, -isopropylammonium, -potassium, -triisopropanolammonium, and -trolamine, diflufenican, dimethenamide, ethoxysulfuron, phenoxaprop, phenoxaprop-P, phenoxaprop-ethyl, phenoxaprop-P- The following may be selected: ethyl, fenquinotrione, fentrazamide, florathram, fluphenacet, fluroxypyr, fluroxypyr-meptyl, horamsulfuron, iodosulfuron, iodosulfuron-methyl-sodium, isoproturone, isoxaflutol, mefenacet, mesosulfuron, mesosulfuron-methyl, metrachlor, S-metrachlor, metrivudine, metoslam, nicosulfuron, oxaziargyl, oxadiazone, petoxamide, prosulfocarb, pyrasulfotol, piroxyslam, tefuryltrione, tenbotrione, triafamone, bendimethalin, propoxycarbazone, harauxifen-methyl, and 2-methyl-4-chlorophenoxyacetic acid (MCPA).

[0074] Preferably, the further pesticide active ingredient is fluroxypyr-meptil.

[0075] The emulsion formulation may further include common adjuvants and additives h) known in the art and compatible with pesticide formulations. Such additives may be stabilizers, e.g., antifreezes, preservatives, antioxidants, light stabilizers, especially UV stabilizers, and other agents that improve chemical and / or physical stability.

[0076] Other additives include defoamers, such as silicone defoamers and magnesium stearate, silicone oils, silicone oil preparations, and especially nonionic aqueous polydimethylsiloxane emulsions (dimethylsiloxane and silicone, CAS number 63148-62-9). Examples include Silcolapse® 426 and 432 from Bluestar Silicones, Silfoam® SRE and SC132 from Wacker, and SAG1572 and SAG30 from Momentive.

[0077] Other additives include penetration enhancers, such as ethoxylated linear and / or branched fatty alcohols having 2 to 20 EO units (e.g., Clariant's Genapol® X-type); methyl-terminated ethoxylated linear and / or branched fatty alcohols containing 2 to 20 EO units (e.g., Clariant's Genapol® XM-type); and ethoxylated coconut alcohols containing 2 to 20 EO units (e.g., Claria Genapol® C-type from nt; ethoxylated C12 / 15 alcohols containing 2 to 20 EO units (e.g., Synperonic® A-type from Croda); branched or linear propoxyethoxylated alcohols, e.g., Antarox® B / 848 from Solvay, Atlas® G5000 from Croda, Lucramul® HOT5902 from Levaco, Break-Thru from Evonik Vibrant; Me-terminated propoxy-ethoxylated fatty acids, e.g., Lion's Leofat® OC0503M; alkyl ether citrate surfactants (e.g., Adsee CE range, Akzo Nobel); alkyl polysaccharides (e.g., BASF's Agnique® PG8107, PG8105; Croda's Atplus® 438, AL-2559, AL-2575); ethoxylated mono or diesters of glycerin containing fatty acids having 8 to 18 carbon atoms and an average of 10 to 40 EO units (e.g., Croda's Crovol® product range); castor oil ethoxylates containing an average of 5 to 40 EO units (e.g., Nouryon's Berol® range, Clariant's Emulsogen® EL range); and block copolymers of polyethylene oxide and polypropylene oxide (e.g., BASF's Pluronic range).

[0078] Other additives include wetting agents, spreading agents, and retaining agents, such as ethoxylated branched alcohols having 2 to 20 EO units (e.g., Genapol® X-type); methyl-terminated ethoxylated branched alcohols containing 2 to 20 EO units (e.g., Genapol® XM-type); branched or linear propoxy-ethoxylated alcohols, such as Antarox® B / 848, Atlas® G5000, Lucramul® HOT5902; organically modified polysiloxanes, such as BreakThru® OE444, BreakThru® S240, Silwett® L77, Silwet® 312, Silwett® 408, Silwet® 806; mono and diesters of sodium sulfosuccinate salts with branched or linear alcohols containing 1 to 10 carbon atoms, such as Geropon DOS; Ethoxylated diacetylenediol, for example, Surfynol® 4xx-diol.

[0079] Typically, suitable adjuvants that function as uptake enhancers include oils, such as sunflower oil, rapeseed oil, corn oil, soybean oil, rice bran oil, and olive oil; ethylhexyl oleate, ethylhexyl palmitate, myristic acid / ethylhexyl laurate, ethylhexyl laurate, caprylic acid / ethylhexyl caprate, isopropyl myristate, isopropyl palmitate, methyl oleate, methyl palmitate, ethyl oleate, rapeseed oil methyl ester, soybean oil methyl ester, rice bran oil methyl ester; and mineral oils, such as Exxsol® D100 and Solvesso® 200ND. Adjuvants may also be selected from tris-alkyl phosphates, preferably tris(2-ethylhexyl) phosphate, such as Disflamoll® TOF.

[0080] The adjuvant may also be selected from the following group of compounds: ethoxylated branched alcohol having 2 to 20 EO units (e.g., Genapol® X-type); methyl-terminated capped ethoxylated branched alcohol containing 2 to 20 EO units (e.g., Genapol® XM-type); ethoxylated coconut alcohol containing 2 to 20 EO units (e.g., Genapol® C-type); ethoxylated C1 alcohol containing 2 to 20 EO units 2 / 15 alcohols (e.g., Synperonic® A-type); branched or linear propoxyethoxylated alcohols, e.g., Antarox® B / 848, Atlas® G5000, Lucramul® HOT5902; Me-terminated propoxyethoxylated fatty acids, e.g., Leofat® OC0503M; alkyl ether citrate surfactants (e.g., Adsee® CE range, Akzo Nobel); Ethoxylated mono or diesters of glycerin containing fatty acids having 8 to 18 carbon atoms and an average of 10 to 40 EO units (e.g., Crovol® range); Castor oil ethoxylates containing an average of 5 to 40 EO units (e.g., Berol® range, Emulsogen® EL range); Ethoxylated oleic acid containing 2 to 20 EO units (e.g., Alkamuls® A and AP); Ethoxylated sorbitan fatty acid esters containing fatty acids having 8 to 18 carbon atoms and an average of 10 to 50 EO units (e.g., Arlatone® T, Tween range).

[0081] Preferred uptake promoters according to the present invention are tris(2-ethylhexyl) phosphate, rapeseed oil methyl ester, ethoxylated coconut alcohol, propoxy-ethoxylated alcohol, and mineral oil.

[0082] The herbicide composition exhibits remarkable herbicidal activity against a wide range of economically important monocotyledonous and dicotyledonous weeds. Even perennial weeds that produce shoots from rhizomes, rootstocks, or other perennial organs and are difficult to control are effectively controlled. In this regard, it is not relevant whether the herbicide composition is applied before sowing, before emergence, or after emergence. Several representative examples of monocotyledonous and dicotyledonous weed flora that can be controlled by the herbicide composition can be given, but the enumeration is not limited to specific species.

[0083] Examples of weed species on which the herbicide composition acts effectively include monocotyledonous weeds from the annual group, such as Apera spica venti, Avena spp., Alopecurus spp., Brachiaria spp., Digitaria spp., Lolium spp., Echinochloa spp., Panicum spp., Phalaris spp., Poa spp., Setaria spp., and Bromus spp., for example, Bromus ruficollis. This includes species such as catharticus, Bromus secalinus, Bromus erectus, Bromus tectorum, and Bromus japonicus, as well as species of the genus Cyperus, and among perennial species, species of the genus Agropyron, Cynodon, Imperata, and Sorghum, as well as perennial species of the genus Cyperus.In the case of dicotyledonous weed species, the spectrum of action is, for example, among annuals, Abutilon spp., Amaranthus spp., Chenopodium spp., Chrysanthemum spp., Galium spp., for example, Galium aparine, Ipomoea spp., Kochia spp., Lamium spp., Matricaria spp., Pharbitis spp., Polygonum spp., Sida spp., and Sinapis spp. This includes species of the genera Solanum, Stellaria, Veronica, Viola, Xanthium, and in the case of perennial weeds, species of Convolvulus, Cirsium, Rumex, and Artemisia.

[0084] This herbicide composition is also highly effective against harmful plants found in rice under specific cultivation conditions, such as Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus, and Cyperus.

[0085] When the herbicide composition is applied to the soil surface before germination, the emergence of weed seedlings is completely prevented, or the weeds grow to the cotyledon stage but then their growth stops, and they eventually die completely after 3-4 weeks.

[0086] When the herbicide composition is applied to the green parts of plants after germination, growth is dramatically stopped very quickly after treatment, and the weed plants either remain in the growth stage at the time of application or die completely after a certain period of time. As a result, competition by weeds harmful to crop plants is eliminated very early and sustainably.

[0087] Herbicide compositions are distinguished by their rapid onset and long-lasting herbicidal action. Generally, the rainfastness of the active substances in the herbicide compositions is advantageous. A particular advantage is that the dose used in the herbicide composition and the effective dose of the herbicide compound can be adjusted to a low level such that their soil action is optimally low. This not only allows them to be used on sensitive crops, but also substantially avoids groundwater contamination. The combination of active compounds in this invention makes it possible to significantly reduce the required application rate of the active substance.

[0088] The aforementioned properties and advantages are necessary for weed control to maintain the absence of undesirable competing plants on crops and, therefore, to ensure and / or increase yield levels from both qualitative and quantitative perspectives. These novel herbicide compositions significantly exceed the state of the art in the field with respect to the properties described.

[0089] The herbicide composition exhibits significant herbicidal activity against monocotyledonous and dicotyledonous weeds, but economically important crops, such as dicotyledonous crops like soybeans, cotton, rapeseed, and sugar beets, or grass crops like wheat, barley, rye, oats, millet, rice, or maize, suffer only minimal damage, if any. For this reason, this herbicide composition is highly suitable for the selective control of undesirable plant growth in agricultural or ornamental plant plantations.

[0090] Herbicide compositions can also be used to control harmful plants in crops of genetically modified plants, whether known or not yet developed, due to their herbicidal properties. Generally, genetically modified plants are distinguished by specific advantageous characteristics, such as resistance to specific pesticides (especially specific herbicides), plant diseases or the organisms that cause plant diseases (e.g., specific insects or microorganisms, such as fungi, bacteria, or viruses). Other specific characteristics relate to the harvest in terms of quantity, quality, storability, composition, and specific components. Thus, for example, transgenic plants with increased starch content, transgenic plants with altered starch quality, or transgenic plants whose harvest has a different fatty acid composition are known.

[0091] The use of herbicide compositions is preferred in economically important transgenic crops of useful and ornamental plants, such as grasses, such as wheat, barley, rye, oats, millet, rice, and maize, or in crops of sugar beets, cotton, soybeans, rapeseed, potatoes, tomatoes, peas, and other vegetables. Preferably, the herbicide composition can be used in crops of useful plants that are resistant to the phytotoxic effects of herbicides or have been produced to be resistant to these effects by recombinant technology.

[0092] When using herbicide compositions on transgenic crops, in addition to the effects on harmful plants observed on other crops, effects specific to application on transgenic crops are often observed, such as a modified or specifically expanded weed spectrum that can be controlled, modified application rates that can be used, preferably good combination ability with further herbicidal compounds to which the transgenic crop is resistant, and effects on the growth and yield levels of the transgenic crop plants.

[0093] Accordingly, the present invention also relates to a method for controlling undesirable vegetation (harmful plants) in plant crops, preferably cereals (e.g., wheat, barley, rye, oats, rice, maize, and millet), sugar beets, sugarcane, rapeseed, cotton, and soybeans, and particularly preferably monocotyledonous plants, such as cereals like wheat, barley, rye, and oats, and their hybrids such as rye, rice, maize, and millet, comprising applying an effective amount of a formulation according to the present invention or a herbicide composition obtainable therefrom to harmful plants, plant parts, plant seeds, or areas where plants grow, such as cultivated areas.

[0094] The plant crops may also be genetically modified or obtained by mutational selection, and they are preferably resistant to acetolactate synthase (ALS) inhibitors.

[0095] The plants treated according to the present invention are all types of harmful plants, such as weeds, as far as the use of herbicides is concerned. For example, with regard to the protection of crop plants by the application of fungicides and insecticides, the use is preferred in useful and ornamental plants in economically important crops, including transgenic crops, such as cereals such as wheat, barley, rye, oats, millet, rice, cassava and maize, or in crops of peanuts, sugar beets, cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetable species.

[0096] A method for preparing a formulation according to the present invention can be selected from several methods known on their own that describe the preparation of an emulsion.

[0097] The formulations according to the present invention have excellent chemical and physical stability during preparation and storage, and are particularly suitable for combinations of active compounds having different physicochemical properties. Overall, the formulations according to the present invention have the desired long-term storage stability and are free from technical defects. [Examples]

[0098] Examples The examples provided are intended to illustrate the present invention and are not limited to the methods and compounds described herein.

[0099] Starting materials: The compounds used in the examples are shown in Table 1 below.

[0100] Table 1: Chemical substances used in the examples. [Table 1]

[0101] Example 1: The emulsion formulations shown in Table 2 below were prepared by first mixing all the liquid components, then adding the solid components to the mixture, and finally heating to 30-60°C. These formulations were tested with different organic water-miscible solvents, namely propylene carbonate, glycerol-1,2-carbonate, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and acetamide, and N-[2-(acetyloxy)ethyl)]-N-methyl (Steposol EA).

[0102] The formulations were tested for stability at 54°C after two weeks by measuring the thiencarbazone-methyl content via HPLC. The chemical degradation (%) in Table 2 below shows the relative loss of thiencarbazone-methyl compared to the initial amount (day 0).

[0103] Table 2: Examples of EC formulations [Table 2]

[0104] Propylene carbonate and glycerol-1,2-carbonate resulted in improved stability of the formulation after 2 weeks of storage at 54°C, with propylene carbonate showing only 6.98% degradation (indicated as "-6.98"), whereas other tested polar aprotic solvents, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and Steposol EA (acetamide, N-[2-(acetyloxy)ethyl)]-N-methyl), provided insufficient stability after 2 weeks of storage at 54°C, with a loss of up to 63.64% of thiencarbazone-methyl compared to the initial thiencarbazone-methyl content measured immediately after formulation preparation (=day 0).

[0105] Example 2: Further EC formulations were prepared as described above for Example 1, and the chemical stability of thiencarbazone-methyl was tested using the components shown in Table 3 below, as described in Example 1.

[0106] Table 3: Further examples of EC formulations [Table 3]

[0107] As can be seen from the table above, formulation #7, which has a pH < 5 and does not contain organic bases, exhibits insufficient stability after storage at 54°C for two weeks. Specifically, the chemical degradation of thiencarbazone-methyl exceeds 10% compared to the initial thiencarbazone-methyl content measured immediately after preparation (= Day 0), while the other formulations show less than 10% degradation (i.e., less than 10% loss of thiencarbazone-methyl), providing suitable storage stability. The pH of each formulation is measured after (i) diluting the formulation to a 10% w / w formulation with distilled water, (ii) stirring the mixture with a magnetic stirrer at 1,500 RPM for 10 minutes at 25°C, and (iii) measuring the pH of the stirred mixture at 25°C with a pH meter until the measured pH stabilizes for 10 seconds. pH is measured with a Knick pH meter 766 (Calimatic, Knick SE 100N).

[0108] Example 3: Further EC formulations were prepared using the components shown in Table 4 below, in accordance with the description in Example 1. The pH was determined as described in Example 2.

[0109] Table 4: Further examples of EC formulations [Table 4]

[0110] The formulations described in Examples #15 to #17 offer excellent storage stability and weed control after field application, such as control against wild oats, green foxtail, and yellow foxtail.

Claims

1. It is an emulsion formulation, a) Thiencarbazone-methyl or its pesticide-permissible salts, b) One or more organic water-immiscible solvents, c) One or more organic water-miscible solvents selected from linear and cyclic carbonate esters, d) One or more emulsifiers, e) One or more organic bases Includes, Here, the formulation is a formulation exhibiting a pH of 5.5 to 9.

2. The emulsion formulation according to claim 1, wherein the formulation exhibits a pH of 6.0 to 8.5, preferably 6.5 to 8.0, and more preferably 6.8 to 7.

7.

3. The emulsion formulation according to claim 1 or 2, wherein the pH is adjusted by one or more organic bases (e).

4. An emulsion formulation according to any one of the preceding claims, wherein one or more organic bases are selected from amine-based organic bases.

5. The emulsion formulation according to the preceding claim, wherein one or more organic bases are ethoxylated amines.

6. An emulsion formulation according to any one of the preceding claims, wherein one or more organic water-immiscible solvents are selected from aromatic and / or aliphatic hydrocarbons.

7. An emulsion formulation according to any one of the preceding claims, wherein one or more organic water-miscible solvents are selected from methyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate and its isomers, propylene carbonate, glycerol-1,2-carbonate and butylene carbonate, or mixtures thereof.

8. The emulsion formulation according to the preceding claim, wherein one or more organic water-miscible solvents are propylene carbonates.

9. An emulsion formulation according to any one of the preceding claims, wherein one or more organic bases are selected from amine-based organic bases, and one or more organic water-miscible solvents are selected from methyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate and its isomers, propylene carbonate, glycerol-1,2-carbonate, and butylene carbonate.

10. An emulsion formulation according to any one of the preceding claims, wherein the organic base is an ethoxylated amine and the organic water miscible solvent is propylene carbonate.

11. below: a) One or more pharmacokinetic mitigating agents, b) One or more pesticide active ingredients different from a) and f), c) Further adjuvants, wetting agents and / or other additives suitable for the pesticide formulation. An emulsion formulation according to any one of the preceding claims, further comprising one or more of the above.

12. The emulsion formulation according to claim 11, wherein the drug-induced harm reduction agent is selected from cloquintoset-mexil, cyprosulfamide, fenchlorazole ethyl ester, isoxadifen-ethyl, mefenpyr-diethyl, fenchlorim, and cumilon, and preferably the drug-induced harm reduction agent is mefenpyr-diethyl.

13. One or more pesticide active ingredients different from a) and f) are: diflufenican, pyroxasulfone, metrivudine, mesotrione, acroniphen, bromoxynyl, bromoxynyl-butyrate, -potassium, -heptanoate, and -octanoate, benzofenap, butachlor, 2,4-D, 2,4-D-butotyl, -butyl, -dimethylammonium, -diolamine, -ethyl, -2-ethylhexyl, -isobutyl, -isooctyl, -isopropylammonium, -potassium, -triisopropanolammonium, and -trolamine, diflufenican, dimethenamide, ethoxysulfuron, phenoxaprop, phenoxaprop-P, phenoxaprop-ethyl, phenoxaprop-P-ethyl, fenquinotrione, fentrazamide, florathram, and flufenace. An emulsion formulation according to any one of the preceding claims 11 or 12, wherein the pesticide active ingredient is selected from fluroxypyr, fluroxypyr-meptyl, phoramsulfuron, iodosulfuron, iodosulfuron-methyl-sodium, isoproturone, isoxaflutol, mefenacet, mesosulfuron, mesosulfuron-methyl, metrachlor, S-metrachlor, metrivudine, metoslam, nicosulfuron, oxaziargyl, oxadiazone, petoxamide, prosulfocarb, pyrasulfotol, piroxislam, tefuryltrione, tenbotrione, triafamone, bendimethalin, propoxycarbazone, harauxifen-methyl, and 2-methyl-4-chlorophenoxyacetic acid (MCPA), and preferably, different from a) and f), is fluroxypyr-meptyl.

14. a) 0.01 to 5% by weight, preferably 0.1 to 2% by weight, more preferably 0.3 to 1% by weight of thiencarbazone-methyl or a pesticide-acceptable salt thereof, b) 5 to 95% by weight, preferably 10 to 70% by weight, more preferably 20 to 60% by weight of one or more organic water-immiscible solvents, c) 5 to 95% by weight, preferably 10 to 60% by weight, more preferably 20 to 40% by weight of one or more organic water-miscible solvents, d) One or more emulsifiers in an amount of 0.1 to 30% by weight, preferably 1 to 25% by weight, and more preferably 5 to 20% by weight. e) 0.1 to 10% by weight, preferably 0.2 to 5% by weight, more preferably 0.5 to 2% by weight of an organic base, f) One or more phytotoxicity reducing agents in an amount of 0 to 10% by weight, preferably 1 to 8% by weight, and more preferably 2 to 6% by weight. g) 0 to 40% by weight, preferably 5 to 30% by weight, more preferably 10 to 25% by weight, one or more pesticide active ingredients different from a) and f), h) Further adjuvants, wetting agents and / or other additives suitable for a pesticide formulation in an amount of 0 to 40% by weight, preferably 5 to 30% by weight, and more preferably 10 to 20% by weight. An emulsion formulation according to any one of the preceding claims, including the following:

15. A method for eradicating undesirable plants on the leaf surface, comprising treating the leaf surface with a composition obtained by emulsifying an emulsion formulation according to any one of claims 1 to 14 in water.

Images