Emulsifiable concentrate (EC) formulation

Abstract

The present invention relates to emulsifiable concentrate formulations comprising the herbicides pyrasulfotole and bromoxynil.

Description

[0001] Emulsifiable Concentrate (EC) formulation

[0002] Technical field

[0003] The present invention relates to the field of crop protection compositions. In particular, the invention relates to emulsifiable concentrate (EC) formulations comprising bromoxynil or a bromoxynil ester or mixtures thereof and pyrasulfotole.

[0004] Background

[0005] In general, active compounds for crop protection are not employed in pure form. Depending on the area of use and the type of use, and on physical, chemical and biological parameters, the active compound is used as an active compound formulation in a mixture with customary auxiliaries and additives. Also known are combinations with further active compounds for widening the activity spectrum and / or for protecting crop plants (for example by safeners, antidotes).

[0006] Formulations of individual active compounds, like formulations of combinations of a plurality of active compounds for crop protection, should generally be easy to apply and easy to use and have broad biological action combined with high selectivity with respect to the active compounds used, and should additionally be easy to formulate in the preparation process. Of particular importance here is high chemical and physical stability (in particular storage stability) of the formulation.

[0007] Typical formulations in crop protection are concentrated suspensions (active compound suspensions) in which the active compound particles (discontinuous phase) are suspended in an external liquid phase (continuous phase). Depending on the nature of the external phase, the suspensions are classified as suspension concentrates (SC), where the main component of the external phase is water, or in oil dispersions (OD), where the main component of the external phase is an organic solvent. The choice of the respective external phase is frequently determined by the stability of the active compounds in question. In general, active compounds which are unstable in water are formulated as OD, and active compounds which are unstable in organic solvents are formulated as SC.

[0008] The herbicides pyrasulfotole (CAS 365400-11-9) and bromoxynil, such as in form of bromoxynil ester or mixed esters (CAS 1689-84-5; 1689-99-2 (Octanoate); 56634-95-8 (Heptanoate); 3861-41-4 (Butyrate)) are known in the art, as are formulations thereof.

[0009] US8642508 describes emulsifiable concentrate formulations comprising pyrasulfotole and bromoxynil mixed esters.

[0010] While such emulsifiable concentrate (EC) formulations usually allow for an easy preparation and handling, the efficacy against weeds in the field may not be sufficient. Therefore, adjuvants usually need to be added to the formulations, e.g. as tank mix partners, to improve efficacy. Typically, ammonium sulfate (AMS) is applied as adjuvant. While AMS may boost the activity against weeds, it disadvantageously leads to an increased salt impact on the ground, and ground water.

[0011] WO2023023817A1 describes EC formulations comprising bromoxynil, and exemplifies further combinations of bromoxynil and fluroxypyr. Contrary to the active ingredients exemplified in WO2023023817A1, pyrasulfotole is difficult to solubilize, and requires a different system of solvents and adjuvants to be provided in an EC formulation.

[0012] Therefore, it was an object of the present invention to provide an improved formulation of crop protection agents, in particular of pyrasulfotole and bromoxynil, bromoxynil ester, or bromoxynil mixed esters with high efficacy against weeds in the field while limiting the impact on the salt balance in the ground, and which allows a high degree of formulation (emulsion) stability with both ingredients fully dissolved in the carrier solvent.

[0013] Summary

[0014] This object is achieved by the specific emulsifiable concentrate (EC) formulation of the present invention.

[0015] Accordingly, the present invention relates to an emulsifiable concentrate (EC) formulation comprising a) pyrasulfotole, b) bromoxynil or an agrochemically acceptable bromoxynil ester or a mixture thereof, c) an adjuvant system comprising

[0016] (i) a tris-ester of phosphoric acid with aliphatic or aromatic alcohols selected from tris-(2-ethylhexyl) phosphate, tris-n-octyl phosphate and tris- butoxyethyl phosphate,

[0017] (ii) a fatty acid ester, d) one or more water-miscible solvents, e) one or more water-immiscible solvents, f) one or more emulsifiers.

[0018] The term “emulsifiable concentrate” (abbreviated with “EC”) is known in the art. Emulsifiable concentrate (EC) formulations conventionally contain an active ingredient, one or more surfactants which act as emulsifiers upon dilution of the EC with water, and a water immiscible solvent.

[0019] The term “water miscible” means the compound or solvent may have a solubility in water at 20 °C of at least 5 g / 1, preferably of at least 20 g / 1, more preferably at least 50 g / 1, and in particular of at least 100 g / 1. The term “water immiscible” means the compound or solvent may have a solubility in water at 20 °C of up to 100 g / 1, preferably of up to 50 g / 1 °C, more preferably up to 20 g / 1, and in particular of up to 5 g / 1.

[0020] Pyrasulfotole is an herbicide known in the art (CAS 365400-11-9).

[0021] Bromoxynil is an herbicide known in the art and can be provided in different forms, such as bromoxynil (CAS 1689-84-5), or as bromoxynil ester (CAS 1689-99-2 (Octanoate); 56634-95-8 (Heptanoate); 3861- 41-4 (Butyrate)), or in form of mixed esters, such as bromoxynil-octanoate and bromoxynil-heptanoate. Preferred is a mixture of bromoxynil-octanoate and bromoxynil-heptanoate.

[0022] Here and in the entire description, the term “% by weight” refers to the relative weight of the component in question based on the total weight of the formulation, unless defined otherwise.

[0023] The water-immiscible solvent may be an organic water-immiscible solvent, in particular a hydrocarbon, which may be unsubstituted or substituted.

[0024] Preferred organic water-immiscible solvents are aromatic hydrocarbons and / or aliphatic hydrocarbons.

[0025] The water-immiscible solvent can be present on its own or in a mixture of different water-immiscible solvents.

[0026] Examples for water-immiscible solvents are aromatic hydrocarbons, for example mono- or poly alkylsubstituted benzenes, such as toluene, xylenes, mesitylene, ethylbenzene, or mono- or polyalkylsubstituted naphthalenes, such as 1 -methylnaphthalene, 2-methylnaphthalene or dimethylnaphthalene, or other benzene-derived aromatic hydrocarbons, such as indane or Tetralin®, or mixtures thereof; aliphatic hydrocarbons, for example straight-chain or branched aliphatics, for example of the formula CrTEn+z, such as pentane, hexane, octane, 2-methylbutane or 2,2,4-trimethylpentane, or cyclic, optionally alkylsubstituted aliphatics, such as cyclohexane or methylcyclopentane, or mixtures thereof, such as solvents of the Exxsol® D series, Isopar® series or Bayol® series, for example Bayol® 82 (ExxonMobil Chemicals), or the Isane® IP series or Hydroseal®G series (TotalFinaElf); mixtures of aromatic and aliphatic hydrocarbons, such as solvents of the Solvesso® series, for example Solvesso®100, Solvesso®150 or Solvesso® 200 (ExxonMobil Chemicals), of the Solvarex® / Solvaro® series (TotalFinaElf) or the Caromax® series, for example Caromax® 28 (Petrochem Carless); or halogenated hydrocarbons, such as halogenated aromatic and aliphatic hydrocarbons, such as chlorobenzene or methylene chloride.

[0027] The water-miscible solvent may be an organic water-miscible solvent, and is preferably a linear or cyclic alkyl carbonate, in particular methyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate and isomers thereof, propylene carbonate, glycerol- 1 ,2-carbonate and butylene carbonate. Further preferably, the water-miscible solvent is propylene carbonate.

[0028] The emulsifiable concentrate further comprises a combination of two different adjuvants, namely (i) a bisester of phosphoric acid with aliphatic or aromatic alcohols selected from tris-(2-ethylhexyl) phosphate, tris-n-octyl phosphate and tris-butoxyethyl phosphate, and (ii) a fatty acid ester.

[0029] It has been found that such combination surprisingly improves activity on weeds after field application, rendering moot the addition of further adjuvants, such as ammonium sulfate.

[0030] Preferably, the tris-ester of phosphoric acid is tris-(2-ethylhexyl) phosphate.

[0031] The fatty acid ester may be of natural origin, for example natural oils, such as animal oils or vegetable oils, or of synthetic origin, for example the Edenor® series, for example Edenor® MEPA or Edenor® MESU, or the Agnique® ME series or Agnique® AE series (Cognis), the Salim® ME series (Salim), the Radia® series, for example Radia® 30167 (ICI), the Prilube® series, for example Prilube® 1530 (Petrofina), the Stepan® C series (Stepan) or the Witconol®23 series (Witco). The fatty acid esters are preferably esters of C10-C22-, with preference C12-C20-, fatty acids. The Cio-C22-fatty acid esters are, for example, esters of unsaturated or saturated Cio-C22-fatty acids, in particular those having an even number of carbon atoms, for example erucic acid, lauric acid, palmitic acid, and in particular Cis-fatty acids, such as stearic acid, oleic acid, linoleic acid or linolenic acid. Examples of fatty acid esters such as C10-C22- fatty acid esters are glycerol and glycol esters of fatty acids such as Cio-C22-fatty acids, or transesterification products thereof, for example fatty acid alkyl esters such as Cio-C22-fatty acid C1-C20- alkyl esters, which can be obtained, for example, by transesterification of the abovementioned glycerol or glycol fatty acid esters such as Cio-C22-fatty acid esters with Ci-C2o-alcohols (for example methanol, ethanol, propanol or butanol). The transesterification can be carried out by known methods, as described, for example, in Roempp Chemie Lexikon, 9th edition, volume 2, page 1343, Thieme Verlag Stuttgart. Preferred fatty acid alkyl esters such as Cio-C22-fatty acid Ci-C2o-alkyl esters are methyl esters, ethyl esters, propyl esters, butyl esters, 2-ethylhexyl esters and dodecyl esters. Preferred glycol and glycerol fatty esters such as Cio-C22-fatty acid esters are the uniform or mixed glycol esters and glycerol esters of Cio-C22-fatty acids, in particular of such fatty acids having an even number of carbon atoms, for example erucic acid, lauric acid, palmitic acid and in particular Cis-fatty acids such as stearic acid, oleic acid, linoleic acid or linolenic acid.

[0032] Animal oils are generally known and commercially available. For the purpose of the present invention, the term “animal oils” is to be understood as meaning, for example, oils of animal origin such as whale oil, cod-liver oil, musk oil or mink oil.

[0033] Vegetable oils are generally known and commercially available. For the purpose of the present invention, the term “vegetable oils” is to be understood as meaning, for example, oils of oleaginous plant species, such as soybean oil, rapeseed oil, corn oil, sunflower oil, cottonseed oil, linseed oil, coconut oil, palm oil, thistle oil, walnut oil, arachis oil, olive oil or castor oil, in particular rapeseed oil, where the vegetable oils also include their transesterification products, for example alkyl esters, such as rapeseed oil methyl ester or rapeseed oil ethyl ester.

[0034] The vegetable oils are preferably esters of C10-C22-, preferably C12-C20-, fatty acids. The Cio-C22-fatty acid esters are, for example, esters of unsaturated or saturated Cio-C22-fatty acids having, in particular, an even number of carbon atoms, for example erucic acid, lauric acid, palmitic acid and in particular, Cis-fatty acids such as stearic acid, oleic acid, linoleic acid or linolenic acid.

[0035] Examples of vegetable oils are Cio-C22-fatty acid esters of glycerol or glycol with Cio-C22-fatty acids, or Cio-C22-fatty acid Ci-C2o-alkyl esters which can be obtained, for example, by transesterification of the glycerol or glycol Cio-C22-fatty acid esters mentioned above with Ci-C2o-alcohols (for example methanol, ethanol, propanol or butanol). The transesterification can be carried out by known methods as described, for example, in Roempp Chemie Lexikon, 9th edition, volume 2, page 1343, Thieme Verlag Stuttgart.

[0036] The vegetable oils can be contained in the adjuvants according to the invention for example in the form of commercially available vegetable oils, in particular rapeseed oils, such as rapeseed oil methyl ester, for example Phytorob® B (Novance, France), Edenor® MESU and the Agnique® ME series (Cognis, Germany), the Radia® series (ICI), the Prilube® series (Petrofina), or biodiesel or in the form of commercially available, plant-oil-containing formulation additives, in particular those based on rapeseed oils, such as rapeseed oil methyl esters, for example Hasten® (Victorian Chemical Company, Australia, hereinbelow referred to as Hasten, main ingredient: rapeseed oil ethyl ester), Actirob® B (Novance, France, hereinbelow referred to as ActirobB, main ingredient: rapeseed oil methyl ester), Rako-Binol® (Bayer AG, Germany, hereinbelow referred to as Rako-Binol, main ingredient: rapeseed oil), Renol® (Stefes, Germany, hereinbelow referred to as Renol, vegetable oil ingredient: rapeseed oil methyl ester) or Stefes Mero® (Stefes, Germany, hereinbelow referred to as Mero, main ingredient: rapeseed oil methyl ester).

[0037] Examples of synthetic fatty acid esters are, for example, those derived from fatty acids having an odd number of carbon atoms, such as Cn-C2i-fatty acid esters.

[0038] Preferably, the fatty acid ester is a rapeseed oil methyl ester.

[0039] The EC formulation according to the invention comprises as an additional essential component also at least one suitable emulsifier component enabling an oil-in-water emulsion to be formed when the EC formulation of the invention is added to water. The emulsifier can be an ionic (cationic or anionic), amphoteric or non-ionic surfactant, such as ionic or non-ionic or amphoteric emulsifier or a mixture thereof, including standard surface-active substances present in formulations of active agrochemical ingredients.

[0040] The emulsifier may be at least one non-ionic surfactant selected from the group of alkoxylated alcohols, ethoxylated alcohols, ethopropoxylated alcohols, alkylphenolethoxylates, alkoxylated tristyrylphenols, alkoxylated tributylphenols, alkylaminethoxylates, ethoxylated vegetable oils including their hydrogenates, polyadducts of ethylene oxide and propylene oxide (e.g. polyoxyethylenepolyoxypropylene block copolymers and their derivatives), ethoxylated fatty acids, nonionic polymeric surfactants (e.g. polyvinylalcohol, polyvinylpyrrolidone, polymethacrylates and their derivatives), sorbitan esters and their ethoxylates, sorbitolesters, propylene glycol esters of fatty acids and poly glycerolesters .

[0041] Examples of preferred non-ionic surfactants are 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).

[0042] Examples of suitable anionic surfactants include, but are not limited to, salts of polyacrylic acid, salts of polymers of mixtures of acrylic acid / acrylate esters, salts of polymers of mixtures of acrylic acid / styrene, salts of lignosulfonic acid (such as sodium lignosulfonate), salts of phenolsulfonic acid, salts of condensation products of phenolsulphonic acid and formaldehyde, salts of naphthalenesulfonic acid, salts of naphthalenesulphonic acid and formaldehyde condensation products, salts of sulfonates of condensed naphtalenes or alkyl napthtalenes, salts of sulfonates of dodecyl- and tridecylbenzenes, salts of sulfosuccinic or sulfosuccinamate 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, 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 of diphenyloxide sulfonates, salts of alphaolefinsulfonates, salts of sulfonates of fatty acids and oils, salts of alpha-sulfonated methyl esters, salts of taurine derivatives (preferably alkyl taurates), salts of isethionates, salts of alkyl phosphoric esters, salts of aryl phosphoric esters, salts of alkylaryl phosphoric esters, salts of phosphoric esters of polyethoxylated and / or polypropoxylated aliphatic linear or branched alcohols, salts of phosphoric esters of polyethoxylated and / or polypropoxylated aryl alcohols, protein hydrolysates, lignosulfite waste liquors, salts of polystyrenesulphonic acids, salts of polyvinylsulphonic acids, salts of carboxylates, salts of ether carboxylates. Examples for such surfactants or emulsifiers are: Ether carboxylates, sulfonates, sulfates, and phosphates, and their inorganic salts (e.g., alkali metal, alkaline earth metal or ammonium salts) and organic salts (e.g., amine- or alkanolamine -based salts), such as Genapol®LRO, Sandopan® products, Hostaphat / Hordaphos® products from Clariant, Servoxyl® products from Elementis, Agnique® SLS products (Cognis); salts of aliphatic, cycloaliphatic, and olefinic carboxylic acids and polycarboxylic acids, and also alpha-sulfo fatty acid esters as obtainable from Cognis, Sulfosuccinates, alkanesulfonates, paraffinsulfonates and olefinsulfonates and their inorganic (e.g., alkali metal and alkaline earth metal) and organic (e.g., amine- or alkanolamine -based) salts such as Netzer IS®, Hoe®S1728, Hostapur®OS, Hostapur®SAS from Clariant, Triton®GR7ME and GR5 from Dow, Empimin® products from Huntsman, Marlon®-PS65 from Condea, Sulfosuccinamates such as the Aerosol® products from Cytec or the Empimin® products from Huntsman, Surface-active polyacrylic and polymethacrylic derivatives such as the Sokalan® products from BASF.

[0043] Preferred anionic emulsifiers are: phosphated or sulfated (poly)alkylphenol alkoxylates, phosphated or sulfated poly(arylalkyl)-phenol alkoxylates, (poly)alkyl- and poly(arylalkyl)-benzenesulfonates in acidic or salt form and sulfosuccinates.

[0044] More preferred anionic emulsifiers are emulsifiers based on calcium salt of dodecylbenzenesulfonic acid, such as Rhodacal® 60 BE (Rhodia) or Calsogen® 4814 (Clariant), Atlox® 4838B X-MSU (Croda), Ninate® 60E X-MSU (Stepan) or Nansa® EVM 70 / 2E (Huntsman).

[0045] The emulsifiable concentrate formulation may further comprise common adjuvants and additives known in the art. Such additives may be for example stabilizers, such as antifreeze, preservatives, antioxidants, light stabilizers, in particular UV stabilizers, other agents which improve chemical and / or physical stability.

[0046] Other additives are antifoams, such as silicone antifoams and magnesium stearate, -silicone oils, silicone oil preparations, particularly nonionic aqueous polydimethylsiloxane -based emulsions (dimethyl siloxanes and silicones, CAS No. 63148-62-9). Examples are Silcolapse® 426 and 432 from Bluestar Silicones, Silfoam® SRE and SC132 from Wacker, SAG 1572 and SAG 30 from Momentive.

[0047] The herbicidal compositions have outstanding herbicidal activity against a broad spectrum of economically important monocoty ledonous and dicotyledonous harmful plants. Even perennial weeds which produce shoots from rhizomes, rootstocks or other perennial organs and which are difficult to control are controlled well. In this context, it does not matter whether the herbicidal compositions are applied before sowing, pre -emergence or post-emergence. Specific examples may be mentioned of some representatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the herbicidal compositions, without the enumeration being a restriction to certain species. Examples of weed species on which the herbicidal compositions act efficiently are, from amongst the monocotyledonous weed species, 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. such as Bromus catharticus, Bromus secalinus, Bromus erectus, Bromus tectorum and Bromus japonicus, and Cyperus species from the annual group, and, among the perennial species, Agropyron, Cynodon, Imperata and Sorghum and also perennial Cyperus species. In the case of the dicotyledonous weed species, the spectrum of action extends to genera such as, for example, Abutilon spp., Amaranthus spp., Chenopodium spp., Chrysanthemum spp., Galium spp. such as Galium aparine, Ipomoea spp., Kochia spp., Lamium spp., Matricaria spp., Pharbitis spp., Polygonum spp., Sida spp., Sinapis spp., Solanum spp., Stellaria spp., Veronica spp. and Viola spp., Xanthium spp., among the annuals, and Convolvulus, Cirsium, Rumex and Artemisia in the case of the perennial weeds.

[0048] If the herbicidal compositions are applied to the soil surface before germination, the weed seedlings are either prevented completely from emerging or else the weeds grow until they have reached the cotyledon stage, but then their growth stops, and, eventually, after three to four weeks have elapsed, they die completely.

[0049] If the herbicidal compositions are applied post-emergence to the green parts of the plants, growth likewise stops drastically a very short time after the treatment, and the weed plants remain at the growth stage of the point of time of application, or they die completely after a certain time, so that in this manner competition by the weeds, which is harmful to the crop plants, is eliminated very early and in a sustained manner.

[0050] The abovementioned properties and advantages are necessary for weed control practice to keep agricultural crops free from undesired competing plants, and thus to ensure and / or increase yield levels from the qualitative and quantitative angle. These novel herbicidal compositions markedly exceed the technical state of the art with a view to the properties described.

[0051] Owing to their herbicidal properties, the herbicidal compositions can also be employed for controlling harmful plants in crops of genetically modified plants which are known or yet to be developed. As a rule, the recombinant plants are distinguished by specific advantageous characteristics, for example by resistances to certain pesticides, in particular certain herbicides, resistances to plant diseases or the causative organisms of plant diseases such as specific insects or microorganisms such as fungi, bacteria or viruses. Other specific characteristics relate, for example, to the harvested material with regard to quantity, quality, storability, composition and specific constituents. Thus, for example, transgenic plants are known whose starch content is increased, or whose starch quality is altered, or those where the harvested material has a different fatty acid composition. The use of the herbicidal compositions in economically important transgenic crops of useful plants and ornamentals, for example of graminaceous crops such as wheat, barley, rye, oats, millet, rice and corn, or else crops of sugarbeet, cotton, soya, oilseed rape, potatoes, tomatoes, peas and other vegetables, is preferred. Preferably, the herbicidal compositions can be employed in crops of useful plants which resist the phytotoxic effects of the herbicides, or have been made to resist these effects by recombinant techniques.

[0052] When using the herbicidal compositions in transgenic crops, effects are frequently observed in addition to the effects against harmful plants to be observed in other crops, which are specific for the application in the transgenic crop in question, for example a modified or specifically widened weed spectrum which can be controlled, modified application rates which may be employed for application, preferably good combining ability with the further herbicidally active compounds to which the transgenic crop is resistant, and an effect on growth and yield level of the transgenic crop plants.

[0053] The present invention therefore also relates to a method for controlling undesired vegetation (harmful plants), preferably in crops of plants such as cereals (for example wheat, barley, rye, oats, rice, corn and millet), sugar beet, sugar cane, oilseed rape, cotton and soya, especially preferably in monocotyledonous plants such as cereals, for example wheat, barley, rye, oats, and their hybrids such as triticale, rice, corn and millet, wherein the formulations according to the invention or the herbicidal compositions obtainable therefrom are applied to the harmful plants, plant parts, seeds of the plants or the area on which the plants grow, for example the area under cultivation, in an effective amount.

[0054] The plants treated according to the invention are, as far as the use of herbicides is concerned, all types of harmful plants, such as weeds. With respect to the protection of crop plants by application of, for example, fungicides and insecticides, the use in economically important crops including, for example, also transgenic crops, of useful plants and ornamentals, for example of cereals, such as wheat, barley, rye, oats, millet, rice, manioc and corn, or else crops of peanut, sugar beet, cotton, soybean, oilseed rape, potato, tomato, pea and other vegetable species, is preferred.

[0055] The process for preparing the formulations according to the invention can be chosen from a number of processes known per se which describe the preparation of emulsifiable concentrates.

[0056] The formulations according to the invention have excellent chemical and physical stability during preparation and storage and are suitable in particular also for combinations of active compounds having different physicochemical properties. Overall, the formulations according to the invention have the longterm storage stability desired and are without fault from a technical point of view. Examples

[0057] The examples are meant to illustrate the invention and do not limit it to the processes and compounds described therein.

[0058] Starting materials: The compounds used in the examples are hereafter specified in Table 1.

[0059] Table 1: Chemicals used in the examples.

[0060] Example 1:

[0061] Emulsifiable concentrate formulations according to Table 2 below were prepared by first mixing all liquid components followed by adding the solid components to the mixture and eventually heating to 30 to 60 °C. In these formulations, different adjuvant systems were tested, namely Genapol X 090 and Disflamoll TOF versus Rapeseed Oil Methyl Ester and Disflamoll TOF.

[0062] Table 2: Example formulation and comparative formulation.

[0063] Pyrasulfotole + Bromoxynil containing herbicide formulations according to Comparative Example and Example were evaluated for broad spectrum dicot weed control to determine if adjuvant based formulation differences could provide superior control of economically important weed species.

[0064] Specifically, the formulations were tested as follows:

[0065] Weed efficacy data were generated utilizing small-plot field trials. Herbicide application was carried out according to the local agricultural practice. Each trial was conducted with 3 to 4 fully randomized replicates. The plot size was approximately 2 meters by 6 meters. The formulations according to above table 2 were sprayed using a backpack sprayer at BBCH growth stage 12-19 and 5-10 cm. Application rate of the active ingredients was 400 g ai / ha Bromoxynil-Octanoate-Heptanoate and 25 g ai / ha Pyrasulfotole.

[0066] Activity against various weeds as per below table 3 was determined as follows: For the assessment of the herbicide performance, the level of control guidelines used was the PMRA document entitled “Value guidelines for new plant protection products and label amendments (2016)”. Table 3: Field test results of the formulations of table 2

[0067] As shown in above table 3, the example composition provides for a strong activity against a variety of weeds, while the comparative example is not as strong in weed control.

Claims

Claims:

1. Emulsifiable concentrate formulation comprising a) pyrasulfotole, b) bromoxynil or an agrochemically acceptable bromoxynil ester or a mixture thereof, c) an adjuvant system comprising(iii) a tris-ester of phosphoric acid with aliphatic or aromatic alcohols selected from tris-(2-ethylhexyl) phosphate, tris-n-octyl phosphate and tris- butoxyethyl phosphate,(iv) a fatty acid ester, d) one or more water-miscible solvents, e) one or more water-immiscible solvents, f) one or more emulsifiers.

2. Emulsifiable concentrate formulation according to claim 1 , wherein the tris-ester of phosphoric acid is tris-(2-ethylhexyl) phosphate.

3. Emulsifiable concentrate formulation according to claim 1 or 2, wherein the fatty acid ester is selected from esters of unsaturated or saturated Cio-Czz-fatty acids, or mixtures thereof.

4. Emulsifiable concentrate formulation according to any one of the preceding claims, wherein the adjuvant system comprises tris-(2-ethylhexyl) phosphate and mixed esters of unsaturated or saturated Cio-Czz-fatty acids.

5. Emulsifiable concentrate formulation according to any one of the preceding claims, wherein the one or more water-immiscible solvents is selected from aromatic and / or aliphatic hydrocarbons, preferably from aromatic hydrocarbons.

6. Emulsifiable concentrate formulation according to any one of the preceding claims, wherein the one or more water-miscible solvents is selected from methyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate and isomers thereof, propylene carbonate, glycerol- 1 ,2-carbonate and butylene carbonate, preferably propylene carbonate.

7. Emulsifiable concentrate formulation according to any one of the preceding claims, comprising a) 0.5 to 10 % by weight, preferably 1 to 5 % by weight, further preferably 2 to 3 % by weight pyrasulfotole, b) 10 to 50 % by weight, preferably from 20 to 45 % by weight, further preferably 30 to 40 % by weight bromoxynil or bromoxynil ester or mixtures thereof, c) (i) 5 to 30 % by weight, preferably 10 to 25 % by weight, further preferably 12 to 18 % by weight of the tris-ester of phosphoric acid with aliphatic or aromatic alcohols,(ii) 2 to 25 % by weight, preferably 5 to 20 % by weight, further preferably 8 to 12 % by weight of the fatty acid ester, d) 5 to 40 % by weight, preferably 10 to 30 % by weight, further preferably 12 to 18 % by weight of the one or more water-miscible solvents, e) 5 to 40 % by weight, preferably 10 to 30 % by weight, further preferably 12 to 18 % by weight of the one or more water-immiscible solvents, f) 0.1 to 30 % by weight, preferably 1 to 25 % by weight, further preferably 5 to 20 % by weight of the one or more emulsifiers.

8. Method of combating unwanted plants at a foliar locus comprising treating the foliar locus with a composition obtained from emulsifying an emulsifiable concentrate formulation according to any one of the claims 1 to 7 in water.

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