Aqueous suspension concentrate formulation of agrochemical active substances

Abstract

The present invention relates to an aqueous agrochemical suspension concentrate formulation comprising a) from 1 wt% to 30 wt%, based on the total weight of the agrochemical suspension concentrate formulation, of at least one first agrochemically active compound, in particular pyroxasulfone, in the form of particles suspended in an aqueous phase (component a); b) from 5 wt% to 75 wt%, based on the total weight of the agrochemical suspension concentrate formulation, of at least one second agrochemically active compound, in particular a salt of dicamba or a salt of an imidazolinone herbicide (component b) dissolved in the aqueous phase; c) a thickener system (component c) comprising c.1) xanthan gum, c.2) guar gum and c.3) a cellulose-based thickener, d) an aqueous phase comprising water (component d). The invention also relates to the production of the aqueous agrochemical suspension concentrate formulation according to the invention, to the use of the aqueous agrochemical suspension concentrate formulation according to the invention in agriculture, and to a method for controlling undesired vegetation and / or phytopathogenic organisms such as phytopathogenic fungi or invertebrate pests and / or for regulating the growth of plants, wherein the agrochemical suspension concentrate formulation according to the invention is allowed to act on the respective pests, their environment, the crop plants to be protected from the respective pests, the plant propagation material of the crop plants and / or the environment of the crop plants.

Description

[0001] The present invention relates to an aqueous agrochemical suspension concentrate formulation, which comprises:

[0002] a) at least one first agrochemical active compound, in particular pyroxasulfone, in the form of particles suspended in the aqueous phase, in an amount of 1 wt% to 40 wt%, in particular 2 wt% to 35 wt%, preferably 5 wt% to 30 wt%, especially 7 wt% to 28 wt%, based on the total weight of the agrochemical suspension concentrate formulation;

[0003] b) at least one second agrochemical active compound, in particular a salt of dicamba and / or a salt of an imidazolinone herbicide, dissolved in the aqueous phase, in an amount of 5 wt% to 75 wt%, in particular 10 wt% to 70 wt%, preferably 12 wt% to 65 wt%, especially 15 wt% to 60 wt%, based on the total weight of the agrochemical suspension concentrate formulation.

[0004] The present invention also relates to a method for producing an aqueous agrochemical suspension concentrate formulation and its use in agriculture.

[0005] The concentrated agrochemical formulation is advantageous for the applicator because the volume and weight of the concentrate can be significantly reduced. The concentrated agrochemical products can be formulated in different ways depending on the physico-chemical properties of the agrochemical active compounds contained therein. Agrochemical active compounds with limited solubility in water are usually formulated as wettable powders (WP) or water-dispersible granules (WG), emulsifiable concentrates (EC), emulsions (EW), suspo-emulsions (SE), microemulsions (ME) or aqueous suspension concentrates (SC). Agrochemical active compounds with good solubility in water are often formulated as soluble liquids.

[0006] For agroactive substances that are insoluble in water, formulations as aqueous suspension concentrates (SC) are highly desirable because SC formulations do not require large amounts of organic solvents. In addition, they can be easily prepared by grinding the agroactive substances in an aqueous medium. On the other hand, SC formulations are thermodynamically unstable and tend to agglomeration, sedimentation and caking of the agroactive substances, which is obvious at high concentrations of agrochemical active compounds. The presence of a high concentration of additional agrochemical active compounds in dissolved form and a small amount of water in the composition further hinders the stabilization of the suspended particles. Therefore, SC formulations are usually stabilized by dispersants and / or thickeners.

[0007] It is mainly known to add thickeners to aqueous suspension concentrates for stabilization. In aqueous systems, carbohydrate-based thickeners can be used.

[0008] For example, WO 2015 / 124330 A1 discloses an aqueous pesticidal suspension which contains a suspended pesticidal compound and a thickener, the thickener comprising a cellulose ether in combination with xanthan gum or with an inorganic thickener, such as methylcellulose and hydroxypropylmethylcellulose. JP 2013-155137 A discloses an aqueous suspension concentrate of an agroactive substance for improving the adhesion of a spraying formulation to rice plants, the aqueous suspension concentrate containing xanthan gum as a thickener and a protective colloid such as polyvinyl alcohol, methylcellulose or hydroxypropylmethylcellulose.

[0009] When attempting to co-formulate a water-insoluble agroactive substance with a water-soluble agroactive substance into an aqueous suspension concentrate as described at the beginning using the thickeners described in the prior art, the aqueous suspension concentrate becomes unstable during storage, especially when the water-insoluble pesticidal agent is pyroxasulfone and / or when the water-soluble agroactive substance is present at a concentration of 20 wt% or higher. In particular, irreversible separation or coagulation is observed.

[0010] Now it has been found that these problems are solved by incorporating a combination of three carbohydrate thickeners, in particular xanthan gum, guar gum and a cellulose-based thickener (in particular methylcellulose and / or hydroxypropylmethylcellulose), into an aqueous suspension concentrate formulation as described at the beginning. This combination of carbohydrate-based thickeners (hereinafter referred to as the thickener system) imparts improved physical stability to the aqueous agrochemical suspension, and this effect is achieved even at high loadings of the respective agroactive substances and thus at low water contents, for example up to or below 50 wt% based on the total weight of the suspension concentrate. Specifically, the agrochemical suspension concentrate has very good storage stability even at high salt concentrations and there is no particle size growth or reduced particle size growth.

[0011] Accordingly, in a first aspect, the present invention relates to an aqueous agrochemical suspension concentrate formulation comprising:

[0012] a) at least one first agrochemical active compound, in particular pyroxasulfone (component a), in the form of particles suspended in an aqueous phase, in an amount of 1 wt% to 40 wt%, in particular 2 wt% to 35 wt%, preferably 5 wt% to 30 wt%, especially 7 wt% to 25 wt%, based on the total weight of the aqueous agrochemical suspension concentrate formulation;

[0013] b) at least one second agrochemical active compound, in particular a salt of dicamba and / or a salt of an imidazolinone herbicide, dissolved in the aqueous phase, in an amount of 5 wt% to 75 wt%, in particular 10 wt% to 70 wt%, preferably 12 wt% to 65 wt%, especially 15 wt% to 60 wt%, based on the total weight of the aqueous agrochemical suspension concentrate formulation;

[0014] c) A thickener system (component c), which comprises:

[0015] c.1) Xanthan gum,

[0016] c.2) Guar gum and

[0017] c.3) A cellulose-based thickener,

[0018] d) An aqueous phase containing water (component d).

[0019] The second aspect of the present invention relates to the production of the aqueous agrochemical suspension concentrate formulation of the present invention, which comprises the following steps:

[0020] A) Providing a liquid aqueous suspension comprising the suspension particles of the at least one first agrochemical active substance and a part of the thickener system;

[0021] B) Providing a liquid aqueous solution comprising the at least one second agrochemical active compound;

[0022] C) Providing the remaining part of the thickener system;

[0023] D) Mixing the suspension provided in step A), the solution provided in step B) and the remaining part of the thickener system in any given order.

[0024] A further aspect of the present invention relates to

[0025] - The use of the aqueous agrochemical suspension concentrate formulation of the present invention in agriculture, in particular for controlling unwanted vegetation and / or phytopathogenic organisms such as phytopathogenic fungi or invertebrate pests and / or for regulating the growth of plants and / or for treating plant propagation materials;

[0026] - A method for controlling unwanted vegetation and / or phytopathogenic organisms such as phytopathogenic fungi or invertebrate pests and / or for regulating the growth of plants, wherein the agrochemical suspension concentrate formulation of the present invention is allowed to act on the corresponding pests, their environment, crop plants to be protected from the corresponding pests, the plant propagation materials of these crop plants and / or the environment of these crop plants;

[0027] - A method for treating plant propagation materials, which comprises treating the plant propagation materials with the aqueous agrochemical suspension concentrate formulation of the present invention;

[0028] - Use of a thickener system comprising components c.1, c.2 and c.3 as disclosed herein for stabilizing aqueous agrochemical suspension concentrate formulations, in particular for improving their storage stability, wherein the aqueous agrochemical suspension concentrate formulation comprises at least one first agrochemical active compound in the form of particles suspended in an aqueous phase and at least one second agrochemical active compound dissolved in the aqueous phase.

[0029] The present invention is associated with several benefits. The aqueous agrochemical suspension concentrate formulations of the present invention have high physical stability even at high loadings of the corresponding agroactive substances and high salt concentrations. In particular, they have very good storage stability even at high temperatures and do not show significant particle size growth or agglomeration of the dispersed first agrochemical active compound. In addition, the viscosity of the aqueous agrochemical suspension concentrate formulations of the present invention does not change significantly during storage. Furthermore, the aqueous agrochemical suspension concentrates can be easily diluted with water and have a low formation of small droplets during spraying application. Moreover, the aqueous agrochemical suspension concentrates of the present invention are compatible with other agroformulations, in particular formulations of water-soluble biocides such as imidazolinones, glyphosate or glufosinate or their salts, in tank mix applications. In addition, cleaning the formulation from agricultural machinery is very user-friendly, reducing primary and secondary losses of the active compound. Another advantage is the reduced phytotoxicity to crop plants and the increased biological efficiency against pests.

[0030] In the context of the present invention, the terms "aqueous agrochemical suspension concentrate formulation", "aqueous agrochemical suspension concentrate", "suspension concentrate formulation", "suspension concentrate" and "SC formulation" are used synonymously and refer to the aqueous agrochemical suspension concentrate formulations of the present invention.

[0031] Herein and hereinafter, the terms "wt%" and "% by weight" are used synonymously and refer to the weight-based concentration of a specific compound in the aqueous agrochemical suspension concentrate.

[0032] The term "agrochemical active compound" refers to a substance that imparts the desired biological activity to the aqueous agrochemical suspension concentrate. Typically, the agrochemical active compound is a biocide. The agrochemical active compound can generally be selected from fungicides, insecticides, nematicides, herbicides, safeners, nitrification inhibitors, urease inhibitors, plant growth regulators, micronutrients and / or biopesticides. Such biocides are familiar to the person skilled in the art and can be found, for example, in Pesticide Manual, 16th Edition (2013), British Crop Protection Council, London.

[0033] In one embodiment, the agrochemical active compound comprised in the aqueous agrochemical suspension concentrate comprises at least one insecticide.

[0034] In another embodiment, the agrochemical active compound comprised in the aqueous agrochemical suspension concentrate comprises at least one insecticide.

[0035] In yet another particularly preferred embodiment, the agrochemical active compound comprised in the aqueous agrochemical suspension concentrate comprises at least one herbicide. In particular, both the first agrochemical active compound and the second agrochemical active compound are selected from the group of herbicides.

[0036] Suitable insecticides are insecticides from the following classes: carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosin, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin compounds, nereistoxin analogs, benzoylureas, diacylhydrazines, METI acaricides and insecticides such as chloropicrin, pymetrozin, flonicamid, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, chlorfenson, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, indoxacarb, acequinocyl, fluacrypyrim, rotenone, or derivatives thereof.

[0037] Suitable fungicides are fungicides from the following classes: dinitroanilines, allylamines, azole fungicides, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzyl carbamates, carbamates, carboxamides, carboxylic diamides, chloronitriles, cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrocinnamate, dithiocarbamates, dithiolanes, ethyl phosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy-(2-amino)pyrimidines, hydroxyanilines, imidazoles, imidazolinones, inorganic substances, isobenzofuranones, methoxyacrylates, methoxycarbamates, morpholines, N-phenylcarbamates, oxazolidinediones, oxime acetates, oxime acetamides, peptidylpyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles, phenylureas, phosphonates, thiophosphates, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridylmethylbenzamides, pyrimidinamines, pyrimidines, pyrimidinone hydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfonamides, sulfamoyl triazoles, strobulurins, thiazolecarboxamides, thiocarbamates, thiophanates, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines, triazoles.

[0038] Suitable herbicides are herbicides from the following classes: acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofurans, benzoic acids, benzothiadiazinones, bipyridiniums, carbamates, chloroacetamides, chloro carboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenols, diphenyl ethers, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N - phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalimides, pyrazoles, pyridazinones, pyridines, picolinic acids, picolinamides, pyrimidinediones, (thio)benzoic acid pyrimidinyl esters, quinolinic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazoloformamides, triazolo pyrimidines, triones, uracils, ureas.

[0039] Preferred herbicides include

[0040] - water - soluble herbicide compounds selected from glufosinate, especially L - glufosinate or its salts, glyphosate or its salts, imidazolinones such as imazapic, imazethapyr, imazamox, imazaquin and imazethapyr, benzoic acid herbicides such as dicamba and chloramben, phenoxyacetic acid herbicides such as 2,4 - D, quinolone carboxylic acids such as propanil and clomazone, and especially their salts;

[0041] - water - insoluble pesticides selected from pendimethalin, atrazine, isoxaflutole, indaziflam, pyraflufen - ethyl, mesotrione, flazasulfuron, pyroxasulfone, benzobicyclon, mesotrione, pinoxaden, picloram, flufenacet, mesosulfuron - methyl, metominostrobin, pyraclonil and flufenpyr - ethyl.

[0042] Suitable plant growth regulators are antigibberellins, auxins, cytokinins, defoliants, ethylene regulators, ethylene - releasing agents, gibberellins, growth inhibitors, morphactins, growth retardants, growth stimulants and other unclassified plant growth regulators. Suitable micronutrients are compounds containing boron, zinc, iron, copper, manganese, chlorine and molybdenum.

[0043] Suitable nitrification inhibitors are linoleic acid, α-linolenic acid, methyl p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl)propionate (MHPP), karanjin, brachialacton, sorgoleone, 2-chloro-6-(trichloromethyl)-pyridine (chloridazon or N-serve), dicyandiamide (DCD, DIDIN), 3,4-dimethylpyrazole phosphate (DMPP, ENTOC), 4-amino-1,2,4-triazole hydrochloride (ATC), 1-amino-2-thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercapto-benzothiazole (MBT), 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (dazomet, basamid), 2-sulfamoylthiazole (ST), ammonium thiosulfate (ATU), 3-methylpyrazole (3-MP), 3,5-dimethylpyrazole (DMP), 1,2,4-triazole thiourea (TU), N-(1H-pyrazolyl-methyl)acetamide such as N-((3(5)-methyl-1H-pyrazol-1-yl)methyl)acetamide and N-(1H-pyrazolyl-methyl)formamide such as N-((3(5)-methyl-1H-pyrazol-1-yl)methylformamide, N-(4-chloro-3(5)-methyl-pyrazol-1-ylmethyl)-formamide, N-(3(5),4-dimethyl-pyrazol-1-ylmethyl)-formamide, neem, products based on neem ingredients, cyanamide, melamine, catechol, benzoquinone, sodium tetraborate, zinc sulfate, 2-(3,4-dimethyl-1H-pyrazol-1-yl)succinic acid (hereinafter referred to as "DMPSA1") and / or 2-(4,5-dimethyl-1H-pyrazol-1-yl)succinic acid (hereinafter referred to as "DMPSA2"), and / or its derivatives, and / or its salts; the glycolic acid addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazolium glycolate, hereinafter referred to as "DMPG"), and / or its isomers, and / or its derivatives; the citric acid addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazolium citrate, hereinafter referred to as "DMPC"), and / or its isomers, and / or its derivatives; the lactic acid addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazolium lactate, hereinafter referred to as "DMPL"), and / or its isomers, and / or its derivatives; the mandelic acid addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazolium mandelate, hereinafter referred to as "DMPM"), and / or its isomers, and / or its derivatives; 1,2,4-triazole (hereinafter referred to as "TZ"), and / or its derivatives, and / or its salts; 4-chloro-3-methylpyrazole (hereinafter referred to as "ClMP"), and / or its isomers, and / or its derivatives, and / or its salts; the reaction adduct of dicyandiamide, urea and formaldehyde, or the triazinone-formaldehyde-dicyandiamide adduct;2-cyano-1-((4-oxo-1,3,5-triazinan-1-yl)methyl)guanidine, 1-((2-cyanoguanidino)methyl)urea; 2-cyano-1-((2-cyanoguanidino)methyl)guanidine; 3,4-dimethylpyrazole phosphate; allylthiourea, and chlorate.;

[0044] Examples of envisaged urease inhibitors include N-(n-butyl)thiophosphoric triamide (NBPT, Agrotain), N-(n-propyl)thiophosphoric triamide (NPPT), 2-nitrophenylphosphoric triamide (2-NPT), further NXPT known to the person skilled in the art, phenylphosphorodiamidate (PPD / PPDA), hydroquinone, ammonium thiosulfate and mixtures of NBPT and NPPT (see, for example, US8,075,659). Such mixtures of NBPT and NPPT can contain NBPT in an amount of 40 wt.-% to 95 wt.-%, and preferably 60 wt.-% to 80 wt.-%, based on the total amount of the active substances. Such mixtures are sold as LIMUS, which is a composition comprising approximately 16.9 wt.-% NBPT and approximately 5.6 wt.-% NPPT and approximately 77.5 wt.-% of other components (including solvents and adjuvants).

[0045] Preferably, both the first agrochemical active compound and the second agrochemical active compound have a melting point of at least 60 °C, for example in the range from 60 °C to 300 °C. This will result in a reduced volatility of the active compounds in the liquid aqueous agrochemical suspension concentrate formulation. Furthermore, in the case of the first (insoluble) agrochemical active compound, a melting point of at least 60 °C is preferred, since this will ensure that it does not melt at high storage temperatures, which would otherwise lead to sedimentation and / or phase separation. The suspension particles of the first agrochemical active compound can be present in the form of crystalline or amorphous particles. Preferably, they are crystalline.

[0046] The first agrochemical active compound comprises any one or any combination of the above agrochemical active compounds, provided that they are sufficiently insoluble in water. Generally, the first agrochemical active compound can have a water solubility of less than 2 g / l, preferably less than 1 g / l, in particular at most 0.5 g / l, in deionized water at 20 °C, 1 bar and pH 7.

[0047] In the SC formulation of the present invention, the first agrochemical active compound is present in the aqueous phase of the SC formulation in the form of suspension particles. Typically, at least 90 wt%, preferably at least 95 wt%, more preferably at least 98 wt% of the first agrochemical active compound is present as solid particles, based on the total weight of the first agrochemical active compound in the SC formulation.

[0048] The particles of the first agrochemical active compound can be characterized by their size distribution, which can be determined by laser scattering techniques in accordance with ISO 13320-1:2020. Among other things, suitable laser scattering measurement devices are produced under the trade names Malvern Mastersizer 3000 and Malvern Mastersizer 2000. The particles of the first agroactive compound can be characterized by their median diameter, which is commonly abbreviated as the D50 value. The D50 value refers to a specific particle size, below which half of the particle population is smaller by volume. The D50 value is typically determined by applying the Mie model to laser diffraction data in accordance with ISO 13320-1:2020. Generally, the particles of the first agrochemical active compound have a D50 value in the range of 0.1 μm to 30 μm, often in the range of 0.2 μm to 20 μm, preferably in the range of 0.5 to 20 μm, more preferably in the range of 0.5 μm to 15 μm, especially in the range of 0.8 μm to 10 μm. Preferably, at least 90% by volume of the particles have a particle size not greater than 30 μm.

[0049] Based on the total weight of the SC formulation, the concentration of the first agrochemical active compound is typically in the range of 1 wt% to 40 wt%, preferably in the range of 2 wt% to 35 wt%, more preferably in the range of 5 wt% to 30 wt%, especially in the range of 7 wt% to 28 wt% by weight.

[0050] Preferably, the first agrochemical active compound is a herbicide compound. In particular, it is selected from the group consisting of pendimethalin, atrazine, isoxazoles, indaziflam, pyraflufen-ethyl, metsulfuron-methyl, flazasulfuron, pyroxasulfone, isoxaflutole, mesotrione, clodinafop-propargyl, picloram, flufenican, mesosulfuron-methyl, metamifop, pyrazole, and flufenpyr-ethyl. In particular, the first herbicide compound is pyroxasulfone.

[0051] The at least one second agrochemical active compound is present in solution in the continuous aqueous phase. The at least one second agrochemical active compound is typically readily soluble in water. The second agrochemical active compound generally has a water solubility of at least 50 g / l, especially at least 100 g / l or at least 200 g / l, in deionized water at 20 °C, or is completely miscible with deionized water.

[0052] Based on the total weight of the SC formulation, the concentration of the second agrochemical active compound is typically in the range of 5 wt% to 75 wt%, especially in the range of 10 wt% to 70 wt%, preferably in the range of 12 wt% to 65 wt%, especially in the range of 15 wt% to 60 wt% or 40 wt% to 60 wt%.

[0053] In the SC formulation of the present invention, the second agrochemical active compound is dissolved and present in the aqueous phase of the SC formulation. Typically, at least 90 wt%, preferably at least 95 wt%, more preferably at least 98 wt% or the total amount of the second agrochemical active compound is dissolved and present based on the total weight of the second agrochemical active compound in the SC formulation.

[0054] Preferably, the second agrochemical active compound is a herbicide compound. In particular, it is selected from the group consisting of: glufosinate, especially salts of L-glufosinate, salts of glyphosate, imidazolinones such as salts of imazapic, imazethapyr, imazapyr, imazaquin and imazethapyr, salts of benzoic acid herbicides such as salts of dicamba and chloramben, salts of phenoxyacetic acid herbicides such as salts of 2,4-D, and salts of quinolone carboxylic acids such as salts of propanil and clomazone. In particular, the second agrochemical active compound is selected from the group consisting of: salts of dicamba, salts of glufosinate, salts of glyphosate and salts of imidazolinone herbicides. In particular, the second agrochemical active compound is a salt of dicamba.

[0055] In particular, the first agrochemical active compound is oxasulfuron, and the second agrochemical active compound is selected from the group consisting of: salts of dicamba, salts of glufosinate, salts of glyphosate and salts of imidazolinone herbicides.

[0056] In a particularly preferred group of embodiments 1, the present invention relates to an aqueous agrochemical suspension concentrate formulation comprising:

[0057] a) 1 wt% to 30 wt%, especially 2 wt% to 25 wt%, preferably 5 wt% to 20 wt%, especially 7 wt% to 15 wt% of oxasulfuron in the form of particles suspended in the aqueous phase (component a) based on the total weight of the agrochemical suspension concentrate formulation;

[0058] b) at least one second agrochemical active compound selected from salts of dicamba, dissolved in the aqueous phase, of 5 wt% to 75 wt%, especially 10 wt% to 70 wt%, preferably 20 wt% to 65 wt%, especially 40 wt% to 60 wt% based on the total weight of the agrochemical suspension concentrate formulation (component b), wherein the salt of dicamba is especially a salt of dicamba with a water-miscible amine;

[0059] c) a thickener system as described herein (component c); and

[0060] d) an aqueous phase containing water (component d).

[0061] In a particularly preferred group of embodiments 2, the present invention relates to an aqueous agrochemical suspension concentrate formulation comprising:

[0062] a) Pyroxasulfone (component a) in the form of particles suspended in the aqueous phase, in an amount of 2 wt% to 40 wt%, particularly 5 wt% to 35 wt%, preferably 10 wt% to 30 wt%, especially 15 wt% to 28 wt%, based on the total weight of the agrochemical suspension concentrate formulation;

[0063] b) At least one second agrochemical active compound (component b) selected from salts of imidazolinone herbicides, dissolved in the aqueous phase, in an amount of 5 wt% to 50 wt%, particularly 10 wt% to 40 wt%, preferably 10 wt% to 30 wt%, especially 12 wt% to 25 wt%, based on the total weight of the agrochemical suspension concentrate formulation, wherein the salts of imidazolinone herbicides are especially salts of imidazolinone with alkali metal ions or ammonium ions;

[0064] c) A thickener system as described herein (component c); and

[0065] d) An aqueous phase containing water (component d).

[0066] Suitable salts of the second agrochemical active compound include those in which the counterion is an agriculturally acceptable cation. In one embodiment, the pesticidal agent is a metal salt of dicamba, such as the lithium, sodium, potassium, magnesium or calcium salt. In another embodiment, the dicamba salt is preferably the ammonium salt of dicamba, i.e., the salt of dicamba with ammonia or with an amine miscible with water. In this context, the term "miscible with water" means completely miscible with deionized water at a temperature of 25 °C and 1 bar or an amine that dissolves in water in an amount of at least 100 g / l at a temperature of 25 °C and 1 bar.

[0067] Suitable water-miscible organic amines are those having at least one amino group, where 1, 2 or 3 of the amino hydrogen atoms are replaced by alkyl, hydroxyalkyl, alkoxyalkyl, hydroxyalkoxyalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, N-(aminoalkyl)aminoalkyl, N-(N',N'-dialkylaminoalkyl)aminoalkyl, etc. In this context, the alkyl and alkoxy groups preferably have 1 to 4 carbon atoms, especially 1 or 2 carbon atoms, while the substituted alkyl moieties of alkoxyalkyl, hydroxyalkoxyalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, N-(aminoalkyl)aminoalkyl and N-(N',N'-dialkylaminoalkyl)aminoalkyl preferably have 2 to 4 carbon atoms.

[0068] Preferred are amines having a primary or secondary amino group and at least one additional functional group selected from primary amino, secondary amino, tertiary amino, hydroxy and ether groups.

[0069] Examples of suitable amines that are water-miscible include, but are not limited to, dimethylamine, diethylamine, n-propylamine, isopropylamine, 2-hydroxyethylamine (ethanolamine or MEA), 2-(2-hydroxyethoxy)ethan-1-amine (diethylene glycol amine or DGA), bis(2-hydroxyethan-1-yl)amine (diethanolamine), tris(2-hydroxyethyl)amine (triethanolamine), tris(3-propanol)amine, tris(hydroxypropyl)amine (tripropanolamine), N-(3-aminopropyl)-N-methylamine, N,N-bis-(3-aminopropyl)-N-methylamine (bispropylamine, BAPMA), N,N-dimethyldipropylenetriamine (DMAPAPA). Further examples are oligomeric amines having a number average molecular weight in the range of 200 to 500 g / mol, such as polyetheramines, like Jeffamine types having a number average molecular weight in the range of 200 to 500 g / mol, and oligomeric polyamines, such as polyalkyleneimines and N-substituted polyalkyleneimines, such as poly-N,N-bis-(3-aminopropyl)methylamine (MPPI).

[0070] Preferred are such formulations, wherein the second agrochemical active compound is a salt of dicamba with an amine selected from the group consisting of: monoalkanolamines, N,N-dialkanolamines, N-(diethylene glycol)amines and N-(aminoalkyl)alkylamines, N,N-bis(aminoalkyl)alkylamines and N-(N,N-dialkylaminoalkylamino)alkylamines, especially selected from the group consisting of: mono-C2-C4-alkanolamines, N,N-bis(C2-C4-alkanol)amines, N-(di-C2-C4-alkyleneglycol)amines and N-(amino-C2-C4-alkyl)-C1-C2-alkylamines, N,N-bis(amino-C2-C4-alkyl)-C1-C2-alkylamines, N-(N',N'-di-C1-C2-alkylamino-C2-C4-alkyl)-C1-C2-alkylamines, and in particular selected from the group consisting of: N-(di-C2-C4-alkyleneglycol)amines and N,N-bis(amino-C2-C4-alkyl)-C1-C2-alkylamines.

[0071] Among these, preferred are such formulations, wherein the second agrochemical active compound is a salt of dicamba with an amine selected from the group consisting of: 2-hydroxyethylamine (ethanolamine or MEA), 2-(2-hydroxyethoxy)ethan-1-amine (diethylene glycol amine or DGA), bis(2-hydroxyethan-1-yl)amine (diethanolamine), tris(2-hydroxyethyl)amine (triethanolamine), N-(3-aminopropyl)-N-methylamine, N,N-bis-(3-aminopropyl)N-methylamine (BAPMA) and N,N-dimethyldipropylenetriamine (DMAPAPA), and wherein the amine is especially DGA or BAPMA.

[0072] In particular, the second agrochemical active compound is the N,N-bis-(3-aminopropyl)methylammonium salt of dicamba (or "dicamba-BAPMA").

[0073] In particular, the present invention relates to an SC formulation, wherein the at least one first agrochemical active compound is pyroxasulfone and the at least one second agrochemical active compound is dicamba or a salt thereof, as defined above.

[0074] The SC formulation contains water, which is used to dissolve the second agrochemical active compound and the thickener system and optionally additional ingredients. The water is thus part of the aqueous phase. The amount of water in the SC formulation is typically at least 10 wt%, in particular at least 15 wt%, especially at least 20 wt% or at least 25 wt% based on the total weight of the SC formulation. Based on the total weight of the SC formulation, this amount is typically up to 90 wt%. Each time based on the total weight of the suspension, the agrochemical composition preferably contains up to 80 wt% of water, more preferably up to 70 wt%, especially up to 60 wt% of water.

[0075] According to the present invention, the SC formulation contains a thickener system, which comprises xanthan gum, guar gum and a cellulose-based thickener. The SC formulation may contain the thickener system at a concentration of 0.1 to 20 g / l, preferably 0.5 to 15 g / l, more preferably 1 to 10 g / l.

[0076] Guar gum (CAS No. 9000-30-0) (also known as guaran) is a galactomannan polysaccharide that can be obtained from guar beans. It is composed of the sugars galactose and mannose.

[0077] Typically, the SC formulation contains guar gum at a concentration of 0.01 g / l to 5 g / l, preferably 0.1 to 2 g / l, more preferably 0.1 to 1 g / l. The SC formulation may contain guar gum at a concentration of up to 10 g / l, preferably up to 3 g / l, more preferably up to 1.5 g / l, most preferably up to 0.8 g / l, such as up to 0.6 g / l. The SC formulation may contain guar gum at a concentration of at least 0.05 g / l, preferably at least 0.2 g / l.

[0078] Xanthan gum (CAS No. 11138-66-2) is a polysaccharide known to those skilled in the art. It is composed of a pentasaccharide repeating unit containing glucose, mannose, and glucuronic acid. SC formulations typically contain xanthan gum at a concentration of 0.01 g / l to 5 g / l, preferably 0.05 to 2 g / l, more preferably 0.05 to 1 g / l. SC formulations can contain xanthan gum at a concentration of up to 2 g / l, preferably up to 0.5 g / l, more preferably up to 0.3 g / l, most preferably up to 0.2 g / l. SC formulations can contain xanthan gum at a concentration of at least 0.05 g / l, preferably at least 0.1 g / l.

[0079] Cellulose-based thickeners are known to those skilled in the art and are commercially available. Typically, cellulose-based thickeners are cellulose ethers. Examples of cellulose-based thickeners are methylcellulose, hydroxypropyl methylcellulose, hydroxyethyl cellulose, hydroxyethyl methylcellulose, hydroxypropyl cellulose, carboxymethyl cellulose, and mixtures thereof. Preferably, cellulose-based thickeners are non-ionic and do not carry carboxyl groups. In a preferred embodiment, the cellulose-based thickener is selected from hydroxypropyl methylcellulose and methylcellulose. In particular, the cellulose-based thickener is hydroxypropyl methylcellulose. In another embodiment, the cellulose-based thickener is methylcellulose.

[0080] In the case where the cellulose-based thickener is hydroxypropyl methylcellulose, it typically has a methoxy group content of 10 wt% to 40 wt%, preferably 15 wt% to 35 wt%, more preferably 18 wt% to 30 wt% based on the total weight of the hydroxypropyl methylcellulose.

[0081] In the case where the cellulose-based thickener is hydroxypropyl methylcellulose, it typically has a hydroxypropoxy group content of 5 wt% to 15 wt%, preferably 6 wt% to 13 wt%, more preferably 7 wt% to 12 wt% based on the total weight of the hydroxypropyl methylcellulose.

[0082] In the case where the cellulose-based thickener is methylcellulose, it typically has a methoxy group content of 10 wt% to 40 wt%, preferably 15 wt% to 35 wt%, more preferably 18 wt% to 30 wt% based on the total weight of the methylcellulose.

[0083] In the case where the cellulose-based thickener is methylcellulose, it can typically have a methoxy group content of 25 wt% to 35 wt%, preferably 27 wt% to 32 wt%.

[0084] The amounts of methoxy groups in methylcellulose and hydroxypropylmethylcellulose and hydroxypropoxy groups in hydroxypropylmethylcellulose can be determined according to the United States Pharmacopeia (USP30 NF25), United States Pharmacopoeia Convention, Inc., 2007, page 2323 using the so-called Zeisler alkoxy reaction including treatment with hydroiodic acid, followed by quantitative gas chromatography of the released methyl iodide and 2-propyl iodide (see Dow Analytical Method DOWM 100755-ME0OB, Dow Chemical Company, 2002) or preferably by 1 1 1H-NMR spectroscopy as described in §§204-206 of US2011 / 0319383.

[0085] The dynamic viscosity of a 2 wt% solution of a hydroxypropylmethylcellulose thickener in water at 20 °C is typically 3000 to 6000 cP, preferably 3500 to 5600 cP. The dynamic viscosity can be measured according to EN ISO 3219 using a viscometer, such as a rotational viscometer or an Ubbelohde viscosimeter.

[0086] The dynamic viscosity of a 2 wt% solution of a methylcellulose thickener in water at 20 °C is typically 3000 to 6000 cP, preferably 3000 to 5600 cP, more preferably 3800 to 4200 cP. The dynamic viscosity can be measured according to EN ISO 3219 using a viscometer, such as a rotational viscometer or an Ubbelohde viscosimeter.

[0087] The SC formulation can contain a cellulose-based thickener at a concentration of 0.5 to 20 g / l, preferably 1 to 10 g / l, more preferably 2 to 8 g / l. The SC formulation can contain a cellulose-based thickener at a concentration of at least 0.1 g / l, preferably at least 1.5 g / l. The SC formulation can contain a cellulose-based thickener at a concentration up to 15 g / l, preferably up to 6 g / l.

[0088] The weight ratio of the cellulose-based thickener to guar gum is typically 1:2 to 50:1, preferably 1:1 to 20:1, more preferably 2:1 to 15:1, such as 3:1 to 12:1.

[0089] The weight ratio of guar gum to xanthan gum is typically 1:2 to 10:1, preferably 1:1 to 20:1, more preferably 3:1 to 15:1.

[0090] The SC formulation may further contain an inorganic or organic buffer (component e) to stabilize the pH of the aqueous spray liquid obtained by diluting the SC formulation with water. As determined by CIPAC MT 75.3, the pH of a 1.39 wt% aqueous dilution of the buffered SC formulation is typically in the range of 7 to 10, preferably in the range of 8 to 10, such as in the range of 8.5 to 9.5.

[0091] The buffer is typically a carbonate- or citrate-based buffer or a mixture thereof, which is particularly selected from alkali metal carbonates and alkali metal citrates. For example, the buffer can be potassium carbonate (K2CO3) or potassium citrate (tripotassium citrate) or a mixture thereof.

[0092] The SC formulation may contain the buffer at a concentration of 5 wt% to 25 wt%, preferably 8 wt% to 20 wt%, especially 10 wt% to 15 wt%.

[0093] The SC formulation may further contain at least one anionic dispersant F (component f), which carries at least one anionic group selected from sulfonate, sulfate, phosphonate, and phosphate groups. Suitable anionic dispersants F include, but are not limited to, the following groups of dispersants:

[0094] F.1 Aryl- and C1-C 16 -alkylarylsulfonates such as naphthalenesulfonates, mono-, di-, and tri-C1-C 16 -alkylnaphthalenesulfonates such as dibutylnaphthalenesulfonate, dodecyldiphenyl ether sulfonate, mono-, di-, and tri-C1-C 16 -alkylphenylsulfonates such as cumenesulfonate, octylbenzenesulfonate, nonylbenzenesulfonate, dodecylbenzenesulfonate, and tridecylbenzenesulfonate;

[0095] F.2 Aryl ether sulfates, especially aryl poly(C2-C3-alkylene oxide) ether sulfates, such as sulfates of (poly)ethoxylated di- or triphenylvinylphenols and sulfates of (poly)ethoxylated-co-propoxylated di- or triphenylvinylphenols;

[0096] F.3 Aryl ether phosphates, especially aryl poly(C2-C3-alkylene oxide) ether phosphates, such as phosphates of (poly)ethoxylated di- or triphenylvinylphenols and phosphates of (poly)ethoxylated-co-propoxylated di- or triphenylvinylphenols;

[0097] F.4 Condensates of arylsulfonic acids such as naphthalenesulfonic acid or phenolsulfonic acid with formaldehyde and condensates of arylsulfonic acids such as naphthalenesulfonic acid or phenolsulfonic acid with formaldehyde and urea.

[0098] The anionic dispersant F is typically present in the formulations of the present invention as its salts, especially ammonium salts, alkali metal salts such as sodium or potassium salts, and alkaline earth metal salts, especially calcium salts.

[0099] Among the surfactant group F.1, preferred are mono- or di-C4-C8-alkylnaphthalenesulfonic acids and mono- or di-C4-C 16 -alkylbenzenesulfonic acids and their ammonium salts, alkali metal salts such as sodium or potassium salts, and alkaline earth metal salts, especially calcium salts. Particularly suitable examples are EFW (Akzo Nobel), etc.

[0100] Among the surfactant group F.2, preferred are sulfates of (poly)ethoxylated di- or triphenylvinylphenols, especially ammonium salts, alkali metal salts, and alkaline earth metal salts of those having 5 to 70, especially 10 to 60 or 15 to 50 ethylene oxide repeating units. Particularly suitable examples of sulfates of (poly)ethoxylated di- or triphenylvinylphenols are those of Solvay 4D384, etc.

[0101] Among the surfactant group F.3, preferred are phosphates of (poly)ethoxylated di- or triphenylvinylphenols, especially ammonium salts and alkali metal salts of those having 5 to 50, especially 10 to 50 or 15 to 50 ethylene oxide repeating units.

[0102] Among the surfactant group F.4, preferred are ammonium salts and alkali metal salts of naphthalenesulfonic acid formaldehyde condensates and naphthalenesulfonic acid urea formaldehyde condensates.

[0103] Preferred anionic dispersants F are those of groups F.3 and F.4 and combinations thereof. In a particularly preferred set of embodiments, the SC formulations of the present invention contain at least one anionic dispersant of group F.3 and at least one anionic dispersant of group F.4.

[0104] The total concentration of the dispersant F (if present in the SC formulations of the present invention) is typically in the range of 0.1 wt% to 5 wt%, especially in the range of 0.3 wt% to 3 wt%, based on the total weight of the SC formulation.

[0105] In addition to the mandatory components a, b, and c, water (component d), and the optional components e and f, the SC formulations of the present invention may also contain water-immiscible organic solvents (component g). Here, the term "water-immiscible solvent" refers to an organic solvent having a solubility of no more than 1 g / L in deionized water at 20 °C and 1 bar. Suitable water-immiscible organic solvents include, but are not limited to, vegetable oils, aromatic hydrocarbons, fatty acid alkyl esters, especially C8-C 26C1-C8-alkyl esters of fatty acids, such as methyl or ethyl esters, fatty acid amides, especially C8-C 26 -di-C1-C4-alkyl amides of fatty acids and mixtures thereof. Typically, the concentration of component g) is not more than 10 wt% based on the total weight of the SC formulation and is often in the range of 1 wt% to 10 wt% (if present).

[0106] The SC formulation may also contain one or more nonionic surfactants, especially if the SC formulation contains component g. Generally, the polymeric dispersant D has a hydrophilic-lipophilic balance, i.e., an HLB value in the range of 3 to 18, especially in the range of 5 to 15. Herein and hereinafter, the HLB value refers to the HLB value according to Griffin (W.C. Griffin, J. Soc. Cosmet. Chem. [Journal of the Society of Cosmetic Chemists] 1 (1950), page 311 and J. Soc. Cosmet. Chem. [Journal of the Society of Cosmetic Chemists] 5 (1954), page 249).

[0107] Examples of suitable nonionic surfactants having an HLB within the above range include alkyl ethoxylates, alkyl ethoxylate-co-propoxylates, alkylphenol ethoxylates, alkylphenol ethoxylate-co-propoxylates, tributylphenol ethoxylates, tributylphenol ethoxylate-co-propoxylates, triphenylvinylphenol ethoxylates, triphenylvinylphenol ethoxylate-co-propoxylates, ethylene oxide-co-propylene oxide block copolymers, fatty acid polyethylene glycol esters, fatty acid polyglycerol esters, fatty acid polyglycerol ester ethoxylates, fatty acid polyglycerol ester ethoxylate-co-propoxylates, sorbitan ester ethoxylates, sorbitan ester ethoxylate-co-propoxylates and of course castor oil ethoxylates and castor oil ethoxylate-co-propoxylates and mixtures thereof.

[0108] The total concentration of component g (if present) in the SC formulation of the present invention is typically in the range of 0.1 wt% to 5 wt%, especially in the range of 0.3 wt% to 3 wt% based on the total weight of the SC formulation.

[0109] The formulations of the present invention may contain one or more additives which are commonly included in aqueous formulations of pesticidal compounds. These additives include, but are not limited to, antifreeze agents, defoaming agents, dyes, pigments and preservatives to prevent microbial spoilage.

[0110] In particular, the formulation comprises at least one antifreeze. Suitable antifreezes are typically water-soluble solvents, including alcohols such as ethanol, ethylene glycol, propylene glycol, and glycerol. The amount of such antifreeze can depend on the type of antifreeze and is typically in the range of 0.5 wt.-% to 10 wt.-% based on the total weight of the formulation (if present).

[0111] Defoamers suitable for the formulations according to the invention are, for example, silicone emulsions (such as Silicone SRE-PFL from Wacker or ) from Bluestar Silicones), long-chain alcohols, fatty acids, organofluorine compounds, and mixtures thereof. The amount of such defoamer can depend on the type of defoamer and is typically in the range of 0.01 wt.-% to 0.5 wt.-% based on the total weight of the formulation (if present).

[0112] Suitable preservatives for preventing microbial spoilage of the compositions of the invention include formaldehyde, alkyl esters of p-hydroxybenzoic acid, sodium benzoate, 2-bromo-2-nitropropane-1,3-diol, o-phenylphenol, thiazolinones (such as 1,2-benzisothiazol-3(2H)-one, 5-chloro-2-methyl-4-isothiazolinone (CIT), methylisothiazolinone (MIT)), pentachlorophenol, 2,4-dichlorobenzyl alcohol, and mixtures thereof. Commercially available preservatives based on isothiazolinones are, for example, sold under the trademark (ArchChemical), grades (such as MV, MBS, and B20) (Thor Chemie) and MK (Rohm & Haas). 2-Bromo-2-nitropropane-1,3-diol is commercially available as L30.

[0113] The SC formulations of the invention are typically shear-thinning, i.e., their dynamic viscosity decreases as the shear rate increases. Typically, the dynamic viscosity of the formulations of the invention determined at a shear rate of 100 s -1 at 20 °C does not exceed 2000 mPa·s, especially 200 mPa·s, and is typically in the range of 20 to 1000 mPa·s.

[0114] SC formulations can be prepared analogously to known methods, as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

[0115] In one aspect, the present invention relates to a method for preparing an SC formulation as defined above, the method comprising the steps of:

[0116] A) providing a liquid aqueous suspension comprising suspended particles of at least one first agrochemical active substance and a portion of a thickener system, in particular xanthan gum;

[0117] B) providing a liquid aqueous solution comprising at least one second agrochemical active compound;

[0118] C) providing the remaining portion of the thickener system, in particular guar gum and a cellulose-based thickener;

[0119] D) mixing the suspension provided in step A), the solution provided in step B) and the remaining portion of the thickener system in any given order.

[0120] In step A) of the method according to the invention, an aqueous suspension of at least one first agrochemical active substance, in particular oxasulfuron, is provided, which aqueous suspension contains a portion of a thickener system, in particular xanthan gum. Typically, the suspension contains at least one of the dispersants D, in particular at least one dispersant F, in order to stabilize the suspension during production and storage. The suspension may also contain an antifoaming agent to avoid foaming during production.

[0121] Generally, the order of combining the individual components of the combined suspension is not critical. However, it can be advantageous to carry out step A by first mixing water and a portion of the dispersant F and a portion of the thickener until a homogeneous mixture is obtained, and then adding at least one first agrochemical active substance, in particular pyroxasulfone, to the homogeneous mixture under shear. This results in a mixture containing these components, in which the first active substance is present in the form of solid particles, which are dispersed in the homogeneous aqueous phase formed by water and the dispersant F. The mixture is then typically subjected to suitable means for reducing the particle size of the pyrithiobac-sodium and pyroxasulfone particles present in the mixture to an average particle size D[v,0.5] typically below 10 μm, preferably below 7 μm and in particular below 5 μm. This step can be carried out by any physical grinding method, such as milling, crushing or grinding, in particular by wet milling or wet grinding, including for example bead milling, hammer milling, jet milling, air classification milling, pin milling, cryogenic grinding processes, etc. Mixing and particle size reduction are typically then carried out. However, these steps can also be carried out together. Step A is typically carried out at a temperature in the range from 10 °C to 60 °C.

[0122] In step B of the process according to the invention, an aqueous solution of the at least one second agrochemical active compound is provided. The aqueous solution can contain a further portion of the thickener. The aqueous solution can also contain buffer E (if present). The aqueous solution can also contain one or more bactericides and / or antifreeze agents. However, the final SC formulation can also be blended with one or more bactericides and / or antifreeze agents. The aqueous solution can also contain an antifoaming agent to avoid foaming during the production of the emulsion in step D. The aqueous solution can be prepared simply by mixing the components of the aqueous solution in any order. Step (B) is typically carried out at a temperature in the range from 10 °C to 70 °C and preferably in the range from 15 °C to 60 °C.

[0123] In step C of the process according to the invention, the remaining portion of the thickener system is provided, in particular guar gum and cellulose-based thickeners. Preferably, the remaining portion of the thickener system, in particular guar gum and cellulose-based thickeners, is activated by mixing with water, typically at a temperature in the range from 10 °C to 40 °C, for a period of preferably 10 minutes to 5 hours before use.

[0124] In step D) of the process according to the invention, the suspension provided in step A), the solution provided in step B) and the remaining portion of the thickener system are mixed in any given order. The mixing in step D) can be achieved by mixing, shaking, homogenizing or wet grinding, preferably to achieve the median particle size as described herein. Optionally, one or more of the additional ingredients, such as an antifoaming agent, an antifreeze agent, a bactericide and / or water, are added at this stage.

[0125] The invention also relates to a method for controlling unwanted vegetation and / or for regulating the growth of plants, in which an SC formulation is made to act on the corresponding pests, their environment, or on crop plants, soil and / or crop plants and / or their environment to be protected against the corresponding pests.

[0126] SC formulations are generally applied to crop plants, soil and / or crop plants and / or their environment to be protected against pests or unwanted vegetation. In one embodiment, the SC formulation is applied to the soil. In another embodiment, the SC formulation is applied to the leaves.

[0127] When used for plant protection, depending on the type of desired effect, the total application rate of the first and second agroactive compounds is from 0.010 to 3 kg / ha, preferably from 0.050 to 2 kg / ha, more preferably from 0.2 to 1.5 kg / ha.

[0128] The application of the formulation according to the invention or of the formulation or co-formulation of the individual herbicides of the combination according to the invention can be carried out using water or liquid nitrogen fertilizer as a spraying carrier. For this purpose, the corresponding formulation is diluted with water or liquid nitrogen fertilizer to obtain a liquid spraying solution. Frequently, the amount of water used is at least 20 L / ha, especially at least 25 L / ha, and can be up to 2000 L / ha.

[0129] The spraying solution can be applied in a conventional manner using techniques familiar to the person skilled in the art. Suitable techniques include spraying, atomizing, dusting, broadcasting or watering. The type of application depends in a known manner on the intended purpose; in any case, they should ensure the finest possible distribution of the active ingredient according to the invention.

[0130] The user generally applies the SC formulation according to the invention by means of a pre-dosing device, a knapsack sprayer, a spray tank, a spraying aircraft, or an irrigation system. Generally, the SC formulation is made up with water, buffer and / or additional adjuvants to the desired application concentration, and thus a ready-to-use spraying solution or agrochemical composition according to the invention is obtained.

[0131] The formulation or combination according to the invention can also be applied in the form of fertilizer granules which have been impregnated with the formulation according to the invention or with the formulation of the individual components.

[0132] In order to achieve a broader activity spectrum, the formulation according to the invention or the combination according to the invention can be co-applied with additional herbicides. The application can also be combined.

[0133] A variety of types of oils, wetting agents, adjuvants, fertilizers, or micronutrients, as well as additional pesticidal agents (such as herbicides, insecticides, fungicides, growth regulators, safeners) can be added to the SC formulation as a premix, or, if appropriate, added until immediately prior to use (tank mix). These reagents can be mixed with the SC formulation according to the invention in a weight ratio of 1:100 to 100:1.

[0134] The formulations of the present invention can be applied together with adjuvants as activity enhancers. Particularly preferred adjuvants are described in WO 00 / 53014 and WO 2010 / 037734. The adjuvants are a combination of C5-C 22 -alkanoic acid C1-C5-alkyl esters, C 10 -C 20 -carboxylic acids, partial phosphoric or sulfuric acid esters of monohydroxy-functional polyalkylene ethers, and alkyl polyalkylene oxide polyethers. Preferred C5-C 22 -alkanoic acid C1-C5-alkyl esters are methyl oleate, methyl palmitate, and ethyl oleate and mixtures thereof. Specifically, the C5-C 22 -alkanoic acid C1-C5-alkyl esters contain at least 70% by weight of methyl oleate or a mixture of methyl oleate and methyl palmitate. Such an activity enhancer system is commercially available under the name For example HC from BASF Corporation, USA. Other activity enhancers include, but are not limited to, those adjuvants conventionally used in combination with glyphosate, such as non-ionic surfactants (NIS), ammonium sulfate, C 6-18 alkyl sulfates of C 6-18 alkanols such as sodium dodecyl sulfate, alkyl ether sulfates of C

[0135] In the case where the first and second agroactive compounds are from the herbicide group, the SC formulations of the present invention are suitable for controlling unwanted plant growth, especially unwanted plant growth in crops. For this purpose, the aqueous formulation is applied to the unwanted plants or the area in which the unwanted plants will grow.

[0136] The formulations of the present invention and the combinations of the present invention can be applied to many crops. Crops particularly include field corn, including field corn grown for the production of grain, seed or silage, popcorn, sweet corn, soybeans, chickpeas, edible peas, field peas, lentils (including green and red types), perennial grasses (especially when grown for seed production), alfalfa (especially in established dormant alfalfa stands, in cereal, legume and oilseed cover crops). These formulations are active against broadleaf and grass weeds without causing substantial damage to the crop plants. To this end, the formulations and combinations of the present invention are preferably applied pre-emergence, i.e., before the emergence of unwanted plants. Pre-emergence application in crops can be carried out shortly before or after crop planting, but is preferably carried out before the emergence of the crop plants.

[0137] The formulations of the present invention and the combinations of the present invention can be applied to crops that have been modified by mutagenesis or genetic engineering to provide new traits to the plant or to modify existing traits. Mutagenesis includes random mutagenesis techniques using X-rays or mutagenic chemicals, but also targeted mutagenesis techniques to generate mutations at specific loci in the plant genome. Targeted mutagenesis techniques often use oligonucleotides or proteins such as CRISPR / Cas, zinc finger nucleases, TALENs or meganucleases to achieve a targeted effect. Genetic engineering typically uses recombinant DNA techniques to generate modifications in the plant genome that cannot be easily obtained in nature by hybridization, mutagenesis or natural recombination. Typically, one or more genes are integrated into the genome of the plant to increase or improve traits. These integrated genes are also referred to as transgenes in the art, and plants containing such transgenes are referred to as transgenic plants. The plant transformation process typically results in several transformation events that differ in the genomic loci where the transgene has been integrated. A plant containing a specific transgene at a specific genomic locus is typically described as containing a specific "event", which is referred to by a specific event name. Traits that have been introduced into or modified in plants particularly include herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions such as drought.

[0138] Examples of genetically modified crops in which the formulations and combinations can be used particularly include corn and soybeans:

[0139] Transgenic soybean events containing a herbicide tolerance gene are, for example, but not excluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21, A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS-81419-2, GU262, W62, W98, FG72 and CV127.

[0140] Transgenic cotton events comprising a herbicide tolerance gene are, for example, but not limited to, 19-51a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN10224, MON1445, MON1698, MON88701, MON88913, GHB119, GHB614, LLCotton25, T303-3 and T304-40.

[0141] In the case where the first and second agroactive compounds are from the herbicide group, the SC formulations and combinations of the present invention provide very good vegetation control during the fallow period (i.e., the period after harvest and before planting the next crop).

[0142] In the case where the first and second agroactive compounds are from the herbicide group, the SC formulations of the present invention also provide very good vegetation control in non-crop areas, especially at high application rates.

[0143] In the case where the SC formulation contains pyroxasulfone as the first agrochemical compound and dicamba or its salt as the second agrochemical compound, the SC formulation and combination of the present invention provide very good control of the following plants, which include broadleaf weeds such as Palmer amaranth (Amaranth, Palmer) (Amaranthus palmeri), Powell amaranth (Amaranth, Powell) (Amaranthus powellii), catchweed bedstraw (Bedstraw, catchweed) (Galium aparine), hairy beggarticks (Beggarticks, hairy) (Bidens pilosa), Florida beggarweed (Beggarweed, Florida) (Desmodium tortuosum), field bindweed (Bindweed, field) (Convolvulus arvensis), wild buckwheat (Buckwheat, wild) (Polygonum convolvulus), buffalobur (Buffalobur) (Solanum rostratum), C. burcucumber (C. Burcucumber) (Sicyos angulatus), all types of volunteer canola (S, Canola, volunteer) (rape) (Brassica spp.), carpetweed (Carpetweed) (Mollugo verticillata), mayweed chamomile (Chamomile, mayweed) (Anthemis cotula), common chickweed (Chickweed, common) (Stellaria media), common cocklebur (Cocklebur, common) (Xanthium strumarium), Virginia copperleaf (Copperleaf, Virginia) (Acalypha virginica), volunteer cotton (Cotton,volunteer)(Gossypium hirsutum), Cowcockle (Vaccaria pyramidata), Dandelion (Taraxacum officinale), Devil's-claw (Proboscidea louisiana), Eclipta (Eclipta prostrata), Eveningprimrose, cutleaf (Oenothera laciniata), Galinsoga, smallflower (Galinsoga parviflora), Falseflax, smallseed (Camelina macrocarpa), Filaree, redstem (Erodium cicutarium), Fleabane, hairy (Conyza bonariensis), Flixweed (Descurainia sophia), Groundcherry, cutleaf (Physalis angulate), Groundsel, common (Senecio vulgaris), Hawksbeard, narrowleaf (Crepis tectorum), Hemlock, poison (Conium maculatum), Henbit (Lamium amplexicaule), Horseweed (Conyza canadensis), Jimsonweed (Datura stramonium), Knotweed, prostrate (Polygonum aviculare), Kochia (Kochia scoparia), Ladysthumb (Polygonum persicaria), Lambsquarters,common)(Chenopodium album), Lambsquarters, narrowleaf)(Chenopodium pratericola), Lettuce, prickly)(Lactuca serriola), Mallow, common)(Malva neglecta), Mallow, little)(cheeseweed)(Malva parviflora), Mallow, Venice)(Hibiscus trionum), Conyza canadensis)(Canada fleabane), Morningglory, entireleaf)(Ipomoea hederacea var. integriuscula), Morningglory, ivyleaf)(Ipomoea hederacea), Morningglory, palmleaf)(Ipomoea wrightii), Morningglory, pitted)(Ipomoea lacunose), Morningglory, tall)(Ipomoea purpurea), Mustard, black)(Brassica nigra), Mustard, tumble)(Sisymbrium altissimum), Mustard, wild)(Sinapis arvensis), Nettle, burning)(Urtica urens), Nightshade, black)(Solanum nigrum), Nightshade, cutleaf)(Solanum triflorum), Nightshade, Eastern black)(Solanum ptycanthum), Nightshade, hairy)(Solanumhairy)(Solanum sarrachoides), Parthenium (Parthenium hysterophorus), Pennycress, field (Thlaspi arvense), Pigweed, prostrate (Amaranthus blitoides), Pigweed, redroot (Amaranthus retroflexus), Pigweed, smooth (Amaranthus hybridus), Pigweed, tumble (Amaranthus albus), Puncturevine (Tribulus terrestris), Purslane, common (Portulaca oleracea), Pusley, Florida (Richardia scabra), Ragweed, common (Ambrosia artemisiifolia), Ragweed, giant (Ambrosia trifida), Rocket, London (Sisymbrium irio), Sesbania, hemp (Sesbania exaltata), Shepherds-purse (Capsella bursa-pastoris), Sida, prickly (Sida spinosa), Smartweed, Pennsylvania (Polygonum pennsylvanicum), Sowthistle, annual (Sonchus arvensis), Spurge, nodding (Chamaesyce nutans), Spurge, spotted (Chamaesyce maculate), Starbur, bristly (Acanthospermum hispidum), Sunflower,common)(Sunflower (Helianthus annuus)), Tansymustard, pinnate (Descurainia pinnata), Texasweed (Caperonia palustris), Thistle, Canada (Cirsium arvense), Thistle, Russian (Salsola kali), Velvetleaf (Abutilon theophrasti), Waterhemp (Amaranthus tuberculatus), and Willowweed (Epilobium adenocaulon);,

[0144] Annual gramineous weeds, such as Barley, hare (Hordeum murinum spp. leporinum); Barnyardgrass (Echinochloa crus-galli), Bluegrass, annual (Poa annua), Bluegrass, roughstalk (Poa trivialis), Brome, California (Bromus carinatus), Brome, downy (Bromus tectorum), Brome, Japanese (Bromus japonicus), Canarygrass (Phalaris canariensis), Cheat (Bromus secalinus), Crabgrass, large (Digitaria sanguinalis), Crabgrass, smooth (Digitaria ischaemum), Crowfootgrass (Dactyloctenium aegyptium), Cupgrass, Southwestern (Eriochloa gracilis), Cupgrass, woolly (Eriochloa villosa), Fescue, rattail (Vulpia myuros), Foxtail, giant (Setaria faberi), Foxtail, green (Setaria viridis), Foxtail, yellow (Setaria pumila), Goosegrass (Eleusine indica), Johnsongrass, seedling (Sorghum halepense), Millet, Texas (Urochloa texana), Wild millet,wild proso (Panicum miliaceum), wild oat (Avena fatua), fall panicum (Panicum dichotomiflorum), Texas panicum (Panicum texanum), red rice (Oryza sativa), Italian ryegrass (Lolium multiflorum), rigid ryegrass (Lolium rigidum), sandbur (Cenchrus spp.), shattercane (Sorghum bicolor), broadleaf signalgrass (Brachiaria platyphylla), witchgrass (Panicum capillare), rice flatsedge (Cyperus iria), and yellow nutsedge (Cyperus esculentus).

[0145] The application of the formulations of the invention can vary according to a rate which can depend on the type of ground on which the formulation is applied and which is typically in the range from 1 to 100 kg / ha, in particular in the range from 5 to 50 kg / ha.

[0146] The application rate of pyroxasulfone alone is typically in the range from 5 to 250 g / ha, in particular in the range from 15 to 120 g / ha.

[0147] The application rate of dicamba alone is typically in the range from 50 to 1500 g / ha, in particular in the range from 120 to 1200 g / ha.

[0148] In the case where the first and second agroactive compounds are from the group of herbicides, the SC formulations of the invention can be applied pre-planting, pre-emergence or as a non-selective application (in particular in the fall). The pre-planting application can be carried out on the surface or by incorporating the formulation or the individual herbicides of the combination into the ground.

[0149] Pre-plant surface applications are typically made by broadcast application onto the soil surface. Pre-plant surface applications are usually made within 30 days of planting and before crop emergence. For pre-plant incorporation (PPI) applications, the formulated product or individual herbicides of the combination are typically incorporated into the topsoil, e.g., to a depth of 2 to 6 cm, preferably within 14 days of planting. Incorporation can be done by shallow incorporation, including field cultivators, harrows, rolling cultivators or finishing disks.

[0150] SC formulations are particularly advantageous in minimizing off-target movement. Reducing the off-target movement of the pesticidal agent from the treated area minimizes potential negative environmental impacts and maximizes the efficacy of the pesticidal agent where it is most needed. By their nature, herbicides affect sensitive plants, and reducing their off-target movement reduces their impact on neighboring crops and other vegetation while maximizing weed control in the treated field. Off-target movement can occur by a variety of mechanisms, which are generally classified into primary losses (direct losses from the application equipment before reaching the intended target) and secondary losses (indirect losses from the treated plants and / or soil) categories. Primary losses from the spraying equipment typically occur as fine dust or spray droplets, which take a longer time to settle and can be more easily blown off-target. The off-target movement of the spray particles or droplets is typically referred to as'spray drift'. Primary losses can also include the unintentional application of a sensitive crop using contaminated equipment. Contamination can occur when a product (i.e., a pesticidal agent) is not adequately cleaned from the spraying equipment and the contaminated equipment is subsequently used to apply a different product to a sensitive crop, resulting in crop damage. Secondary losses describe the off-target movement of the pesticidal agent after it has contacted the target soil and / or foliage and has moved from the treated surface by means including airborne dust (e.g., crystalline pesticidal agent particles or pesticidal agent bound to soil or plant particles), volatility (i.e., the change in state from the applied solid or liquid form to a gas), or runoff in rain or irrigation water. Off-target movement is typically mitigated by appropriate application techniques (e.g., spray nozzle selection, nozzle height and wind limits) and improved pesticidal agent formulations. The same is true for dicamba, where appropriate application techniques reduce potential primary losses and equipment contamination. By developing formulations using improved dicamba salts such as the N,N-bis-(3-aminopropyl)methylammonium ("BAPMA") salt of dicamba, secondary losses of dicamba are further reduced. SC formulations have favorable primary and secondary loss characteristics, are safe for applicators, and have high biological activity.

[0151] The following examples illustrate the invention.

[0152] Abbreviations

[0153] BAPMA N,N-Bis-(3-aminopropyl)methylamine

[0154] EO Ethylene Oxide

[0155] HPMC Hydroxypropyl Methylcellulose

[0156] PO Propylene Oxide

[0157] SC Suspension Concentrate

[0158] % w / w Percent by weight

[0159] Materials used:

[0160] Dispersant A: Triphenylvinylphenol-polyoxyethylene phosphate, FLK, Solvay

[0161] Dispersant B: High molecular weight alkylnaphthalenesulfonate condensate, D809, Nouryon

[0162] Dispersant C: Mixture of salts of naphthalenesulfonate condensate and phenolsulfonate condensate, DN, BASF SE

[0163] Dispersant D: EO / PO block polymer, PE 10500, BASF SE

[0164] Surfactant: Ethoxylated castor oil, VO / 2003, Solvay

[0165] Antifoam 1: Polydimethylsiloxane emulsion, SRE, Wacker Chemie AG

[0166] Antifoam 2: Polydimethylsiloxane emulsion, Wacker Silicon SRE-PFL, Wacker Chemie AG

[0167] HPMC: Hydroxypropyl methylcellulose, methoxy content 19% - 24%, hydroxypropoxy content 7% - 22%, dynamic viscosity at 20 °C in water at a concentration of 2 wt% is 3500 to 5600 cP, K4M, Dow Chemical Company

[0168] Methylcellulose: Methoxy content 27 wt% to 32 wt%, dynamic viscosity at 20 °C at a concentration of 2 wt% is 4000 cP, A4M, Dow Chemical Company

[0169] Auxiliary agent A: A non-ionic auxiliary agent composition containing dimethyl polysiloxane, alkanolamide, fatty acid, and alkyl aryl polyoxyalkylene ether.

[0170] Xanthan gum: Xanthan gum, G, Solvay S.A.

[0171] Biocide 1: A mixture of chloromethyl isothiazolinone and methyl isothiazolinone, MV, Thor GmbH.

[0172] Biocide 2: A 2-bromo-2-nitro-1,3-propanediol solution based on diol, L 30, Thor GmbH.

[0173] Biocide 3: A benzisothiazolinone solution based on diol, B 20, Thor GmbH.

[0174] Dicamba-SL: A 600 g / l solution of the N,N-bis-(3-aminopropyl) methylammonium salt of dicamba in water.

[0175] If not otherwise stated, the viscosity of the SC formulation is measured at 20 °C at a shear rate of 100 s -1 using an HR-10 Discovery hybrid rheometer (TA Waters).

[0176] If not otherwise stated, the particle size is determined by static light scattering of a 10% w / w - 20% w / w aqueous dilution of the SC formulation using a Malvern Mastersizer 3000.

[0177] If not otherwise stated, the pH value in the undiluted aqueous formulation is determined using a glass electrode at 22 °C and 1 bar.

[0178] Example - 1: Manufacture of the SC formulation

[0179] Step A: Liquid SC formulation

[0180] Produce a liquid aqueous suspension having the composition according to Table 1. For this purpose, the components are mixed until a homogeneous composition is obtained, and then it is ground in a bead mill until an average particle size (D50) below 1.5 microns is obtained.

[0181] Table 1: Components of the liquid SC formulation

[0182]

[0183]

[0184] Step B: Liquid agrochemical solution

[0185] Mix water, the BAPMA salt of dicamba, potassium carbonate and optionally potassium citrate (ternary, monohydrate) until a homogeneous solution of the salts with a concentration of 754 g / l is obtained.

[0186] Step C

[0187] Mix the SC formulation of Step A and the agrochemical solution of Step B with a biocide, an antifoaming agent 1 and optionally additional ingredients and / or methylated soybean oil. Activate the guar gum and cellulose-based thickeners by adding water and incubating at room temperature for about 20 minutes. Subsequently, mix the liquid agrochemical composition and the activated thickeners until homogeneous, and screen the resulting mixture through a 150 μm sieve to obtain homogeneous SC formulations SC-1 to SC-7 with the ingredients summarized in Table 2.

[0188] Table 2: Ingredients of the final liquid SC formulations SC-1 to SC-7

[0189]

[0190]

[0191] Example 2: Temperature stability of the SC formulation

[0192] Evaluate the storage stability of the SC-1 sample by incubating it at 54 °C for two weeks. The sample remained homogeneous without sedimentation or clear liquid formation.

[0193] Example 3: Particle size measurement

[0194] Incubate the SC-1 sample at various temperatures and time periods, where the particle sizes (D50 and D90) are measured as indicated in Table 3.

[0195] Table 3: Storage conditions and particle size measurements of SC-1

[0196]

[0197] Example 4: Spraying characteristics

[0198] The specific characteristics of the fine droplets of the diluted soluble concentrates SC-3 to SC-5 mixed with glyphosate were analyzed. For this purpose, 0.93 L of the suspensions SC-3 to SC-5 were mixed with 2.07 L of a soluble concentrate containing 540 g / l of potassium glyphosate, and the mixture was diluted with water to a total volume of 94 L. The resulting spraying solution was then sprayed using an AIXR 110 04 nozzle ("AirInduction XR FlatSpray Tip") at a pressure of 2.76 bar or using a TTI 110 03 nozzle ("Turbo TeeJetInduction FlatSpray Tip") at a pressure of 4.8 bar. The droplet size distribution was measured using a Sympatec Helos KF laser diffraction device. The measurement was carried out in 31 particle size classes from 18 to 3500 μm. The measurement was carried out at a distance of 30.5 cm from the nozzle. The analysis of the data was based on 10 measurement values collected in two runs. The lens was cleaned in between if necessary.

[0199] For comparison, a spraying solution was prepared by mixing 0.93 L of an aqueous soluble concentrate (SL-C1) containing 754 g / L of dicamba N,N-bis-(3-aminopropyl)methylammonium with 2.07 L of a soluble concentrate containing 540 g / L of potassium glyphosate and diluting with water to a total volume of 94 L. Table 4 shows the fractions of fine droplets of different nozzle types and the tested suspensions SC-3 to SC-5 compared to SL-C1.

[0200] Table 4: Measured values of the ratio of fine droplets <100 μm of SC-3, SC-4 and SL-1 after mixing with potassium glyphosate and dilution with water

[0201]

[0202]

[0203] Example 5:

[0204] Analyze the volatility of suspensions SC-1 to SC-3 in the presence of potassium glyphosate. For this purpose, 0.93 L of suspensions SC-1 to SC-3 were mixed with 2.07 L of a soluble concentrate containing 540 g / l of potassium glyphosate, and the mixture was diluted with water to a total volume of 94 L. The samples were further diluted with water to ensure that the amount of active compound per unit area in the test tubes was similar to that obtained by spraying the active compound at the recommended application rate in the field. Then the samples were incubated in glass tubes contained in a water bath. The samples were incubated at 70 °C for 24 days. The volatile sample material was continuously removed from the tube through an air duct. The residual amount of dicamba was determined relative to the application rate. The reported volatility was [1 - (residual amount / application rate)], expressed as a percentage. The results are summarized in Table 5 below.

[0205] Table 5: Volatility of samples SC-1 to SC-3 measured in Büchi Multivapor P-12

[0206] Sample SC-1 SC-2 SC-3 SC-6 SC-7 Volatility [%] 5.7 6.3 5.3 5.7 Not measured

[0207] Example 6:

[0208] As described in Example 6, analyze the volatility of suspensions SC-3 to SC-5 in the presence of potassium glyphosate. The results are summarized in Table 6 below.

[0209] Table 6: Volatility of samples SC-3 to SC-5 measured in Büchi Multivapor P-12

[0210] Sample SC-3 SC-4 SC-5 SC-6 SC-7 Volatility [%] 3.2 4.6 3.1 3.2 Not measured

[0211] Example 7:

[0212] Conduct the Humi-Dome study. For this purpose, place two treated glass plates in a plastic tray covered with a transparent plastic humidity dome (total dimensions 25 cm wide x 50 cm long x 20 cm high, Hummert International). The humidity dome is equipped with an air sampling filter cassette containing fiberglass and cotton pad filter media, which is connected to a vacuum pump with a flow rate of 2 liters per minute. Place individual humidity domes representing different study treatments and replicates in a controlled growth chamber environment at 35 °C and 25% to 40% humidity. Test suspensions SC-1 to SC-4 in a tank mix of water, 0.25 vol-% adjuvant A, and the glyphosate-containing product Roundup PowerMAX II (1120 grams acid equivalent per hectare). Apply the treatments to the glass plates using a laboratory track sprayer with a TeeJet 95015E nozzle through the spray system and a spray volume of 146 L / ha. The application rate of dicamba is 560 grams acid equivalent per hectare. After 24 hours of air sampling, collect the filters, extract, and analyze the dicamba content using gas chromatography-mass spectrometry. Then divide the total amount of dicamba captured by the total volume of air flowing through the filter to calculate the total amount of dicamba captured / unit volume of air, as summarized in Table 7.

[0213] Table 7: Reduction of dicamba captured in the filter as measured in the humidity dome assay.

[0214] Soluble concentrate <![CDATA[Reduction of dicamba captured in the filter [ng / m 3 > SC-3 32 SC-4 33 SC-5 39 SC-6 Not measured SC-7 Not measured

[0215] Example 8:

[0216] Conduct laboratory tests to evaluate the ease of dicamba removal applied via SC-3 to SC-5. For this purpose, mix SC-3 to SC-5 each with the glyphosate-containing product Roundup Power MAX II at a ratio of 1:2 (v / v), and incubate the mixture overnight in an 11" EPDM hose section. The next day, first rinse the hose section with water and then with pure methanol. Collect the methanol rinse for dicamba analysis using HPLC. The results show that the dicamba concentration in the methanol rinse is 1.6 - 1.9 ppm for the SC-3, SC-4, or SC-5 treatments.

[0217] Example 9: Influence of thickener combinations

[0218] A suspension of pyroxasulfone was produced in a similar manner to step A of Example 1, a solution of dicamba-BAPMA was provided in a similar manner to step B of Example 1, and the two mixtures were combined in a similar manner to step C of Example 1. The final composition and amounts are indicated in Table 8 below. The stability of the suspension is also indicated in Table 8. Run 1 was carried out according to the present invention, and Runs 2-4 were comparative examples.

[0219] Table 8: Long-term stability of SC formulations at high temperatures.

[0220]

[0221]

[0222] 1) Stored at 54 °C for 14 days

[0223] 2) Stored at 40 °C for 4 weeks

[0224] 3) Stored at 40 °C for 8 weeks

[0225] The results in Table 8 show that when using a combination of xanthan gum, guar gum, and cellulose-based thickeners, long-term stability of the SC formulation at high temperatures can be achieved.

[0226] Example 10: Influence of different thickener combinations

[0227] Example 9 was repeated with different percentages of thickener compositions. Run 1 was carried out according to the present invention, and Runs 2-8 were comparative examples. The final composition and results are shown in Table 9 below.

[0228] Table 9 indicates that increasing the concentration of one or two thickeners alone is less effective in stabilizing the SC formulation than the presence of all three thickeners simultaneously.

[0229] Table 9: Long-term stability of SC formulations at high temperatures

[0230]

[0231]

[0232] 1) Stored at 22 °C (room temperature) for 14 days

[0233] 2) Stored at 54 °C for 14 days

[0234] 3) Stored at 40 °C for 4 weeks

[0235] Table 9 (continued):

[0236]

[0237] Example 11: Manufacture of an SC formulation containing pyroxasulfone and imazethapyr

[0238] Step A: Liquid SC formulation

[0239] Produce a liquid aqueous suspension having the ingredients according to Table 10. To this end, mix the ingredients until a homogeneous composition is obtained, and then grind it in a bead mill until an average particle size (D50) of less than 1.5 μm is obtained.

[0240] Table 10: Ingredients of the liquid SC formulation

[0241] Ingredient Concentration, wt% Pyroxasulfone 41.46 Dispersant C 1.66 Dispersant D 2.49 1,2 - Propylene glycol 5.8 Defoamer 2 0.41 Biocide 1 0.1 Biocide 2 0.08 Biocide 3 0.19 Xanthan gum 0.17 Water Up to 100

[0242] Step B: Liquid agrochemical solution

[0243] Mix water, the potassium salt of imazethapyr, and an aqueous potassium hydroxide solution until a homogeneous solution with a salt concentration of 35 wt% is obtained.

[0244] Step C:

[0245] Mix the SC formulation of Step A and the agrochemical solution of Step B with a biocide and defoamer 2. Activate guar gum and HPMC by adding water and incubating at room temperature for about 20 minutes. Subsequently, mix the liquid agrochemical composition and the activated thickener until homogeneous, and screen the resulting mixture through a 150 μm sieve to obtain a homogeneous SC formulation SC-8 having the ingredients summarized in Table 11.

[0246] Table 11: Ingredients of the final liquid SC formulation SC-8

[0247]

[0248]

[0249] Check the storage stability of formulation SC-8 by incubating formulation samples at different temperatures for different time periods. Then visually evaluate the samples, measure their viscosity and pH values, and analyze the size of the particles contained in the samples. The results are shown in Table 12.

[0250] Table 12 Evaluation of SC-8 samples after different storage conditions

[0251]

[0252] 1) No upper phase separation;

[0253] 2) Liquid and homogeneous after shaking.

[0254] As is evident from the visual assessments summarized in Table 12, formulation SC-8 remained homogeneous under all conditions analyzed and, in particular, no phase separation and sedimentation occurred. In addition, the values of pH, viscosity and particle size given in Table 12 confirm that formulation SC-8 remained fairly stable under different storage conditions.

[0255] Another sample of formulation SC-8 was stored at a temperature of -20 °C for four weeks. Under these conditions, the sample became solid but returned to its original state after one hour at room temperature.

Claims

1. An aqueous agrochemical suspension concentrate formulation, comprising: a) at least one first agrochemical active compound in the form of particles suspended in an aqueous phase, based on 1 wt% to 40 wt% of the total weight of the formulation; b) at least one second agrochemical active compound dissolved in the aqueous phase, based on 5 wt% to 75 wt% of the total weight of the formulation; c) a thickener system, comprising: c.1) xanthan gum, c.2) guar gum and c.3) a cellulose-based thickener, d) an aqueous phase containing water.

2. The formulation according to claim 1, wherein The first agrochemical active compound is pyroxasulfone.

3. The formulation according to any one of the preceding claims, wherein, The at least one second agrochemical active compound is selected from the group consisting of salts of dicamba, salts of glufosinate, salts of glyphosate, and salts of imidazolinone herbicides.

4. The formulation according to claim 3, wherein, The second agrochemical active compound is a salt of dicamba, in particular the ammonium salt of dicamba.

5. The formulation according to any one of the preceding claims, wherein, Based on the total weight of the agrochemical suspension concentrate, the concentration of the first agrochemical active compound is in the range of 7 wt% to 28 wt%, and the concentration of the second agrochemical active compound is in the range of 15 wt% to 60 wt%.

6. The formulation according to any one of the preceding claims, wherein, The cellulose-based thickener is selected from methylcellulose and hydroxypropylmethylcellulose, and in particular the cellulose-based thickener is hydroxypropylmethylcellulose.

7. The formulation according to claim 6, wherein, The hydroxypropylmethylcellulose contains 15 wt% to 35 wt% of methoxy groups based on the total weight of the hydroxypropylmethylcellulose, and the hydroxypropylmethylcellulose contains 5 wt% to 15 wt% of hydroxypropoxy groups based on the total weight of the hydroxypropylmethylcellulose.

8. The formulation according to any one of the preceding claims, wherein, The weight ratio of the cellulose-based thickener to the guar gum is 2:1 to 10:1, wherein the weight ratio of the guar gum to the xanthan gum is 1:1 to 20:1, and the concentration of the thickener system is in the range of 0.1 to 10 g / l.

9. The formulation according to any one of the preceding claims, further comprising at least one anionic dispersant F, the anionic dispersant carrying at least one anionic group selected from sulfonate, sulfate, phosphonate, and phosphate groups.

10. The formulation according to any one of the preceding claims, further comprising at least one buffer, the buffer being particularly selected from alkali metal carbonates and alkali metal citrates, and in particular potassium carbonate.

11. The formulation according to any one of the preceding claims, wherein, Based on the total weight of the agrochemical suspension concentrate, the concentration of the inorganic buffer is particularly in the range of 5 wt-% to 30 wt-%.

12. The formulation according to any one of the preceding claims, having at least one of the following characteristics 12.1 to 12.3: 12.1 The at least one first agrochemical active compound has a water solubility of less than 2 g / l, particularly less than 1 g / l, in deionized water at 20 °C, 1 bar, and pH 7; 12.2 The suspended particles of the first agrochemical active compound have a D50 value in the range of 0.1 to 30 μm, particularly in the range of 0.5 μm to 20 μm, especially in the range of 0.8 to 10 μm, as measured by dynamic light scattering; 12.3 Based on the total weight of the agrochemical suspension concentrate, the concentration of water is from 10 wt% to 60 wt%, in particular from 20 wt% to 50 wt%.

13. A method for preparing an agrochemical suspension concentrate formulation as claimed in any one of claims 1 to 12, the method comprising the steps of: A) providing an aqueous suspension comprising the suspension particles of the at least one first agrochemical active substance and a part of the thickener system; B) providing a liquid aqueous solution comprising the at least one second agrochemical active compound; C) providing the remaining part of the thickener system; D) mixing the suspension provided in step A), the solution provided in step B) and the remaining part of the thickener system in any given order.

14. Use of an aqueous agrochemical suspension concentrate formulation as claimed in any one of claims 1 to 12 in agriculture, in particular for controlling unwanted vegetation and / or phytopathogenic organisms such as phytopathogenic fungi or invertebrate pests and / or for regulating the growth of plants and / or for treating plant propagation material.

15. A method for controlling unwanted vegetation and / or phytopathogenic organisms such as phytopathogenic fungi or invertebrate pests and / or for regulating the growth of plants, wherein an aqueous agrochemical suspension concentrate formulation as claimed in any one of claims 1 to 12 is made to act on these respective pests, their environment, crop plants to be protected from these respective pests, the plant propagation material of these crop plants and / or the environment of these crop plants.

16. A method for treating plant propagation material, the method comprising treating the plant propagation material with an aqueous agrochemical suspension concentrate formulation as claimed in any one of claims 1 to 12.

17. Use of a thickener system for stabilizing an aqueous agrochemical suspension concentrate formulation, the thickener system comprising: c.1) xanthan gum, c.2) guar gum and c.3) a cellulose-based thickener, the aqueous agrochemical suspension concentrate formulation comprising at least one first agrochemical active compound in the form of particles suspended in an aqueous phase and at least one second agrochemical active compound dissolved in the aqueous phase.

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