STABILIZATION OF DIMPROPYRIDAZ SUSPENSIONS BY TRIETHYLAMONIUM CHLORIDE

Abstract

The invention relates to an aqueous pesticide composition comprising (a) suspended particles comprising dimpropyridaz and (b) triethylammonium chloride. It also relates to a method for producing the pesticide composition; a method for treating plant propagation material; the use of triethylammonium chloride to inhibit the crystal growth of dimpropyridaz particles suspended in a pesticide composition; a method for treating or protecting an animal from infestation or infection by invertebrate pests, comprising bringing the animal into contact with a pesticide-effective amount of the pesticide composition; and a method for combating or controlling invertebrate pests, the method comprising bringing the pest or its food supply, habitat, or breeding grounds into contact with a pesticide-effective amount of the pesticide composition.a method for protecting growing plants from attack or infestation by invertebrate pests, the method comprising bringing a plant, or soil or water in which the plant is growing, into contact with a pesticide-effective amount of the pesticide composition.

Description

STABILIZATION OF DIMPROPYRIDAZ SUSPENSIONS BY TRIETHYLAMONIUM CHLORIDE The invention relates to an aqueous pesticide composition; a process for producing the pesticide composition; the use of triethylammonium chloride to inhibit the growth of crystals of dimpropyridaz particles suspended in an aqueous pesticide composition; a method of treating plant propagation material; a method for treating or protecting an animal from infestation or infection by invertebrate pests; a method for combating or controlling invertebrate pests; and a method for protecting growing plants from attack or infestation by invertebrate pests. Suspension concentrates are a common formulation type for pesticide compounds. Pesticide suspension concentrates have a continuous aqueous phase in which particles of at least one pesticide are homogeneously dispersed. Suspension concentrates are desirable formulations because they do not contain high concentrations of organic solvents. Therefore, suspension concentrates are considered environmentally friendly compared to other formulation types, such as emulsion concentrates or oil dispersions. However, a serious drawback of suspension concentrates is their tendency for particle growth during storage. Particle growth in aqueous suspensions is caused by a process called Ostwald ripening. Ostwald ripening describes a process in which small particles dissolve, while larger particles increase in size and weight. The driving force behind Ostwald ripening is a difference in solubility between small and large particles. Ostwald ripening is particularly pronounced for particles of compounds with moderate water solubility. Dimpropyridaz is a pesticide with a water solubility of approximately 4-5% by weight at 25°C. The comparatively high water solubility of dimpropyridaz makes Ostwald ripening a critical issue for dimpropyridaz suspension concentrates. Surprisingly, it was discovered that adding at least 0.3 wt% triethylammonium chloride to an aqueous suspension of dimpropyridaz stabilizes the suspended dimpropyridaz particles. Crystal growth is significantly reduced by the addition of triethylammonium chloride. Furthermore, no sedimentation or caking of the pesticide is observed. The stabilizing effect can be observed at a triethylammonium chloride concentration of at least 0.3 wt% based on the total weight of the pesticide composition. Therefore, the invention relates to an aqueous pesticide composition comprising a) suspended particles comprising dimpropiridaz; b) triethylammonium chloride; ZQCQnn / 77Π7 / Β / YILI where the concentration of triethylammonium chloride is at least 0.3% by weight based on the total weight of the pesticide composition. Dimpropyridaz is the common name for the compound 1-[1,2-dimethylpropyl]- / V-ethyl-5-methyl- / V-pyridazin-4-yl-1 / 7-pyrazol-4-carboxamide. Dimpropyridaz has one center of chirality, and two enantiomers have been described (see ip.com IPCOM000256756D): 1-[(1 n)-1,2-dimethylpropyl]- / V-ethyl-5-methyl- / / -pyridazin-4-yl-1 / 7-pyrazol-4-carboxamide (hereinafter referred to as the R enantiomer), and 1-[(1 S)-1,2-dimethylpropyl]- / / -ethyl-5-methyl- / / pyridazin-4-yl-1 / 7-pyrazol-4-carboxamide (hereinafter referred to as the S enantiomer). The S enantiomer and the R enantiomer are represented by Formulas lA and lB, respectively: ζοροηη / ζζηζ / Ε / γίΛΐ Accordingly, the term dimpropyridaz as used herein refers to the S enantiomer, the R enantiomer, and racemic mixtures thereof. Preferably, the term dimpropyridaz refers to racemic mixtures of the S enantiomer and the R enantiomer. The aqueous pesticide composition contains suspended particles comprising dimpropyridaz. Preferably, the suspended particles consist of dimpropyridaz. The suspended particles are typically crystalline particles of dimpropyridaz. Dimpropyridaz exists in at least two crystalline forms, hereinafter referred to as polymorph A and polymorph B. Dimpropyridaz, its activity against arthropod pests, and general processes for its production are known from WO 2012 / 143317. Applying these general processes to the production of dimpropyridaz yields this compound as a glassy fusion containing polymorph A. Suspended particles comprising dimpropyridaz generally consist of suspended crystalline particles of dimpropyridaz that are of polymorph A, polymorph B, or a mixture thereof. In one embodiment, the suspended particles comprising dimpropyridaz consist of suspended crystalline particles of dimpropyridaz in the form of polymorph A. In another embodiment, the suspended particles comprising dimpropyridaz consist of suspended crystalline particles of dimpropyridaz in the form of polymorph B. Polymorph A can be identified and distinguished from form B by powder x-ray diffraction. The PXRD pattern of polymorph A form recorded using CuKa (1.54178 Å) radiation at 25°C shows at least 3 of the following reflections, cited as 2Θ values: 16.16 ± 0.10°, 20.36 ± 0.10°, 23.92 ± 0.10°, 24.29 ± 0.10°, and 27.43 ± 0.10°. These reflections are not present in form B. In addition to these 5 reflections, polymorph A may show in such a diagram one or more, in particular at least 2, often at least 4, in particular at least 6 or at least 8 reflections and, in particular, all the reflections cited hereafter as 2Θ values: 7.95 ± 0.10°, 10.16 ± 0.10°, 12.40 ± 0.10°, 15.31 ± 0.10°, 15.89 ± 0.10°, 16.53 ± 0.10°, 18.02 ± 0.10°, 19.25 ± 0.10°, 20.93 ± 0.10°, 23.44 ± 0.10°, 23.70 ± 0.10°, 26.16 ± 0.10°, 30.71 ± 0.10° and 32.92 ± 0.10°. Among the peaks of the PXRD pattern of polymorph A, those at the following 20 values ​​are the most prominent: 10.16 ± 0.10°, 15.31 ± 0.10°, 15.89 ± 0.10°, 16.16 ± 0.10°, 16.53 ± 0.10°, 19.25 ± 0.10°, 20.36 ± 0.10°, 20.93 ± 0.10°, 23.44 ± 0.10°, 23.70 ± 0.10°, 23.92 ± 0.10°, 224.29 ± 0.10°, 26.16 ± 0.10°, 30.71 ±0.10° and 32.92 ±0.10°. When analyzed by differential scanning calorimetry (DSC), polymorph A exhibits a thermogram with a characteristic endothermic peak, also known as the melting peak. The melting point, determined as the onset of the melting peak, is typically in the range of approximately 82°C to 87°C. The values ​​reported herein refer to values ​​determined by DSC using a sealed aluminum vessel with a sample size of 1 to 10 mg and a heating rate of 10 K / min. Thermogravimetric analysis, hereafter also referred to as TGA, revealed that there was no weight loss during heating, indicating that form A does not contain solvent. Polymorph B can be obtained as described in EP application number 19151447.0. Polymorph B can be identified by powder X-ray diffractometry based on its powder X-ray diffraction pattern, hereinafter also referred to as the powder X-ray diffraction pattern or PXRD pattern, of polymorph B recorded using Cu-Ka (1.54178 Å) radiation at 25°C showing the following 3 reflections, cited as 20 values: 20.69 ± 0.10°, 24.15 ± 0.10° and 30.52 ± 0.10°. In addition to these 3 reflections, polymorph B may show in such a PXRD pattern one or more, in particular at least 2, often at least 4, in particular at least 6 or at least 8 reflections and, in particular, all the reflections cited below as 20 values: 7.99 ± 0.10°, 10.07 ± 0.10°, 12.38 ± 0.10°, 15.31 ± 0.10°, 15.97 ± 0.10°, 16.50 ± 0.10°, 18.03 ± 0.10°, 19.29 ± 0.10°, 20.22 ± 0.10°, 20.96 ± 0.10°, 23.40 ± 0.10°, 23.70 ±0.10°, 26.09 ±0.10°, 27.26 ± 0.10° and 32.91 ± 0.10°. Among these reflections, preferably at least 1, in particular at least 2, more particularly at least 4, especially at least 6 or all of the following reflections, cited as 20 values, can be observed in such a PXRD pattern: 10.07 ± 0.10°, 15.31 ± 0.10°, 15.97 ± 0.10°, 16.50 ± 0.10°, 19.29 ± 0.10°, 20.22 ± 0.10°, 20.96 ± 0.10° and 26.09 ± 0.10°. In addition to these reflections, preferably at least 1, in particular at least 2, more particularly at least 4, especially at least 6 or all of the following reflections, cited as 20 values, can be observed in such a PXRD pattern: 7.99 ± 0.10°, 12.38 ± 0.10°, 18.03 ± 0.10°, 23.40 ± 0.10°, 23.70 ± 0.10°, 27.26 ± 0.10° and 32.91 ±0.10°. Frequently, a PXRD pattern of the polymorph B shape recorded using Cu-Ka (1.54178 Å) radiation at 25°C shows the following 3 reflections, cited as 20 values: 20.69 ± 0.10°, 24.15 ± 0.10° and 30.52 ± 0.10° and, in addition, the following reflections, cited as 20 values: 15.31 ± 0.10°, 15.97 ± 0.10° and 16.50 ±0.10°. Alternatively, a PXRD pattern of the polymorph B shape recorded using Cu-Ka (1.54178 Å) radiation at 25°C shows the following 3 reflections, cited as 20 values: ζοροηη / ζζηζ / Ε / γίΛΐ 20.69 ± 0.10o, 24.15 ± 0.10° and 30.52 ± 0.10oy, in addition, the following reflections, cited as 20 values: 23.40 ± 0.10° and 23.70 ± 0.10°. In particular, a PXRD pattern of the polymorph B shape recorded using Cu-Ka (1.54178 Å) radiation at 25°C shows the following 3 reflections, cited as 20 values: 20.69 ± 0.10°, 24.15 ± 0.10° and 30.52 ± 0.10° and, in addition, the following reflections, cited as 20 values: 15.31 ± 0.10°, 15.97 ± 0.10°, 16.50 ± 0.10°, 23.40 ± 0.10° and 23.70 ± 0.10°. When analyzed by differential scanning calorimetry (DSC), the polymorph B of the present invention exhibits a thermogram with a characteristic endothermic peak, also referred to as the melting peak. The melting point, determined as the onset of the melting peak, is generally in the range of approximately 80°C to 90°C, particularly in the range of 82°C to 89°C. The values ​​quoted herein refer to those determined by DSC using a closed aluminum vessel with a sample size of 1 to 10 mg and a heating rate of 10 K / min. Thermogravimetric analysis (TGA) revealed no weight loss during heating, confirming the findings of single-crystal X-ray studies that polymorph B is solvent-free. Suspended particles comprising dimpropiridaz can be characterized by their size distributions, which can be determined using dynamic light scattering methods. The D50 value is a statistical figure indicating a maximum particle diameter that characterizes 50% by volume of all particles. In other words, 50% (v / v) of all particles have a diameter equal to or less than the D50 value. The D50 value for the particles in this case is typically up to 30 pm, preferably up to 25 pm, more preferably up to 20 pm, most preferably up to 10 pm, and especially preferably up to 7 pm. The D50 value for the particles is normally at least 0.1 pm, preferably at least 0.8 pm, more preferably at least 1 pm. The D50 value for the particles is typically from 0.5 to 10 pm, preferably from 1 to 8 pm, more preferably from 1 to 5 pm. The pesticide composition generally contains the suspended particles a) at a concentration of 5 to 60% by weight, preferably 10 to 50% by weight, more preferably 10 to 40% by weight, based on the total weight of the pesticide composition. The pesticide composition may contain the suspended particles a) at a concentration of at least 1% by weight, preferably at least 15% by weight, based on the total weight of the pesticide composition. The pesticide composition may contain the suspended particles a) at a concentration of up to 45% by weight, preferably up to 35% by weight, more preferably up to 25% by weight, based on the total weight of the pesticide composition. The pesticide composition is an aqueous pesticide composition, meaning the continuous liquid phase is an aqueous liquid. The pesticide composition may contain at least 5% by weight of water, preferably at least 10% by weight, more preferably at least 15% by weight, most preferably at least 30% by weight, and especially preferably at least 50% by weight of water, based on the total weight of the pesticide composition. The pesticide composition may contain up to 99% by weight of water, preferably up to 95% by weight, more preferably up to 90% by weight, and particularly up to 80% by weight of water, based on the total weight of the pesticide composition. The pesticide composition normally contains from 30 to 90% by weight of water, preferably from 50 to 80% by weight of water, based on the total weight of the pesticide composition. The pesticide composition also contains triethylammonium chloride, which can be identified by CAS number 554-68-7. Triethylammonium chloride is the adduct of triethylamine and hydrochloric acid (HCl). Consequently, it can also be referred to as (CH₃CH₂ZN-HCl). The pesticide composition contains triethylammonium chloride at a concentration of at least 0.3% by weight, preferably at least 0.4% by weight, based on the total weight of the pesticide composition. The pesticide composition may contain triethylammonium chloride at a concentration of up to 10% by weight, preferably up to 5% by weight, more preferably up to 2% by weight, and especially preferably up to 1.5% by weight, for example, up to 1% by weight. The pesticide composition typically contains triethylammonium chloride at a concentration of 0.3% to 3% by weight, preferably from 0.35% to 2% by weight, more preferably from 0.4% to 1% by weight. The triethylammonium chloride is normally present in dissolved form at 20°C in the pesticide composition. The weight ratio of suspended particles a) to triethylammonium chloride b) in the pesticide composition is typically from 5:1 to 200:1, preferably from 10:1 to 100:1, and in particular from 15:1 to 50:1. The weight ratio of suspended particles a) to triethylammonium chloride b) may be at least 2:1, preferably at least 3:1, more preferably at least 10:1. The weight ratio of suspended particles a) to triethylammonium chloride b) is typically up to 80:1, preferably up to 70:1. In one embodiment, the pesticide composition contains a) 10 to 99% by weight of water b) 1 to 60% by weight of suspended particles; and c) 0.3 to 10% by weight of triethylammonium chloride; each time depending on the total weight of the pesticide composition. In another embodiment, the pesticide composition contains a) 10 to 95% by weight of water a) 5 to 40% by weight of suspended particles; and c) 0.3 to 2% by weight of triethylammonium chloride; each time depending on the total weight of the pesticide composition. In another embodiment, the pesticide composition contains a) 40 to 80% by weight of water a) 15 to 30% by weight of suspended particles; and a) 0.4 to 1% by weight of triethylammonium chloride; each time depending on the total weight of the pesticide composition. The pesticide composition may contain another active pesticide ingredient. The active ingredient may be selected from the group of fungicides, insecticides, nematicides, herbicides, protectants, ZQCQnn / 77P7 / B / YILI micronutrients, biopesticides, nitrification inhibitors, urease inhibitors, and / or growth regulators. In one embodiment, the pesticide is an insecticide. In another embodiment, the pesticide is a fungicide. In yet another embodiment, the pesticide is a herbicide. The average person in the trade is familiar with such pesticides, which can be found, for example, in the Pesticide Manual, 16th ed. (2013), The British Crop Protection Council, London. Suitable insecticides include carbamate insecticides, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosyns, avermectins, milbemycin, juvenile hormone analogues, alkyl halides, organotin compounds, nereistoxin analogues, benzoylureas, diacylhydrazines, METI acaricides, and insecticides such as chloropicrin, pymetrozine, flonicamid, clofentezine, hexythiazox, and ethoxazole.diafenthiuron, propargite, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnon, acequinocil, fluacripyrim, rotenone or derivatives thereof. Suitable fungicides are fungicides from the classes of dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzylcarbamates, carbamates, carboxamides, carboxylic acid diamides, chloronitriles, cyanoacetamide oximes, cyanoimidazoles, cyclopropancarboxamides, dicarboximides, dihydrodioxazines, dinitrophenylcrotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolcarboxamides, guanidines, hydroxy-(2-amino)pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganic substances, isobenzofuranones, methoxyacrylates, methoxycarbamates, morpholines, N-phenylcarbamates, oxazolidinediones, oxyminoacetates, oxyminoacetamides, peptidylpyrimidinenucleosides, phenylacetamides,phenylamides, phenylpyrroles, phenylureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamides, pyrimidinamines, pyrimidines, pyrimidinonehydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfonamides, sulfamoyltriazoles, thiazolcarboxamides, thiocarbamates, thiophanates, thiophencarboxamides, toluamides, triphenyltin compounds, triazines, triazoles. Suitable herbicides are herbicides from the classes of acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazines, bipyridyl, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ethers, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines,phosphinic acids, phosphoroamidates, phosphorodithioates, phthalates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinidiones, pyrimidineyl(thio)benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils, ureas. Suitable plant growth regulators include antiauxins, auxins, cytokinins, defoliants, ethylene modulators, ethylene releasers, gibberellins, growth inhibitors, morphactins, growth retardants, growth stimulators, and other unclassified plant growth regulators. ζοραηη / ζζηζ / Ε / γίΛΐ The appropriate micronutrients are compounds that include boron, zinc, iron, copper, manganese, chlorine, and molybdenum. The concentration of the additional active pesticide ingredient in the pesticide composition is generally at least 5% by weight, preferably at least 10% by weight, most preferably at least 15% by weight, most preferably at least 20% by weight, most preferably at least 25% by weight, and in particular at least 30% by weight, based on the total weight of the pesticide composition. The concentration of the additional active pesticide ingredient in the pesticide composition is generally up to 95% by weight, preferably up to 85% by weight, most preferably up to 75% by weight, most preferably up to 75% by weight, and in particular up to 65% by weight, based on the total weight of the pesticide composition. The pesticide composition generally contains the additional active pesticide ingredient at a concentration of 10 to 90% by weight, preferably 15 to 60% by weight, with 20 to 50% by weight being more preferable, depending on the total weight of the pesticide composition. The pesticide composition is typically prepared by bringing triethylammonium chloride, particles comprising dimpropyridaz, and water into contact. The triethylammonium chloride, the particles, and the water can be brought into contact in any order; for example, in the first stage, the particles can be brought into contact with water, and then the triethylammonium chloride can be added. The pesticide composition can be prepared in a known way, such as that 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. Suitable auxiliaries include solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, antifreeze agents, antifoaming agents, colorants, tackifiers, and binders. Suitable liquid solvents and carriers are water and organic solvents, such as mineral oil fractions with a medium to high boiling point, e.g., kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic, and aromatic hydrocarbons, e.g., toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g., ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, e.g., cyclohexanone; esters, e.g., lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g., N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof. Suitable solid carriers or filling agents are mineral earths, for example silicates, silica gels, talc, kaolin, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, for example cellulose, starch; fertilizers, for example ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, for example cereal flour, bark flour, wood flour, nutshell flour and mixtures thereof. ζοροηη / ζζηζ / Ε / γίΛΐ Suitable surfactants are surfactant compounds, such as anionic, cationic, nonionic, and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifiers, dispersants, solubilizers, wetting agents, penetration enhancers, protective colloids, or adjuvants. Examples of surfactants are listed in McCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (international or North American edition). Suitable anionic surfactants are alkali, alkaline earth, or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates include alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, fatty acid and oil sulfonates, ethoxylated alkylphenol sulfonates, alkoxylated arylphenol sulfonates, condensed naphthalene sulfonates, dodecylbenzene and tridecylbenzene sulfonates, naphthalene and alkylnaphthalene sulfonates, sulfosuccinates, and sulfosuccinamates. Examples of sulfates include fatty acid and oil sulfates, ethoxylated alkylphenol sulfates, alcohol sulfates, ethoxylated alcohol sulfates, and fatty acid ester sulfates. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and alkylphenol ethoxylates or carboxylated alcohols. Suitable nonionic surfactants include alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids, or fatty acid esters that have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and / or propylene oxide can be used for alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucoamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters, or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, glucose-sucrose esters, or alkyl polyglucosides. Examples of polymeric surfactants are homopolymers or copolymers of vinylpyrrolidone, vinyl alcohols, or vinyl acetate. Suitable cationic surfactants are quaternary surfactants, for example, quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetaines and imidazolines. Suitable block polymers are AB or ABA type block polymers comprising polyethylene oxide and polypropylene oxide blocks, or ABC type block polymers comprising alkanol, polyethylene oxide, and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacid comb polymers or polyacrylic acid. Examples of polybases are polyvinylamines or polyethyleneamines. Suitable adjuvants are compounds that have minimal or no pesticidal activity and that enhance the biological performance of compound I on the target. Examples include surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed in Knowles, Adjuvants and Additives, Agrow Reports DS256, T&F Informa UK, 2006, Chapter 5. Suitable thickeners are polysaccharides (e.g., xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones. Suitable antifreeze agents are ethylene glycol, propylene glycol, urea, and glycerin. Suitable antifoaming agents are silicones, long-chain alcohols, and fatty acid salts. Suitable colorants (e.g., in red, blue, or green) are pigments with low water solubility and water-soluble dyes. Examples include inorganic dyes (e.g., iron oxide, titanium oxide, iron hexacyanoferrate) and organic dyes (e.g., alizarincyanin, azocyanin, and phthalocyanine dyes). Suitable sticking agents or binders are polyvinylpyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers. Seed treatment solutions (STS), suspensions (STS), and fluid concentrates (FCTs) are generally used for treating plant propagation materials, particularly seeds. These compositions, after dilution two to ten times, provide active substance concentrations of 0.01 to 60% by weight, preferably 0.1 to 40% by weight, in ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying the pesticide composition to plant propagation material, especially seeds, include coating, pelleting, spraying, soaking, and furrow application. Preferably, the pesticide composition is applied to the plant propagation material by a method that does not induce germination, such as coating, pelleting, or spraying. When used for plant protection, the amounts of active ingredient applied vary, according to the type of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, with greater preference from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha. In the treatment of plant propagation materials such as seeds, for example, by spraying, coating or soaking seeds, quantities of active ingredient of 0.1 to 1000 g are generally required, preferably 1 to 1000 g, with greater preference 1 to 100 g and with maximum preference 5 to 100 g, per 100 kilograms of plant propagation material (preferably seeds). When used for the protection of stored materials or products, the amount of active ingredient applied depends on the type of application area and the desired effect. The amounts typically applied for material protection are 0.001 g / 2 kg, preferably 0.005 g / 1 kg, of active substance per cubic meter of treated material. Various types of oils, wetting agents, adjuvants, fertilizers or micronutrients, and additional pesticides (e.g., herbicides, insecticides, fungicides, growth regulators, protectants) can be added to the pesticide composition, either as premixes or, if appropriate, only immediately before use (tank mix). These agents can be mixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1. In general, the user applies the composition according to the invention using a pre-dosing device, a backpack sprayer, a spray tank, a spray aircraft, or an irrigation system. The pesticide composition typically consists of water, a buffer, and / or additional auxiliaries at the desired application concentration, resulting in the ready-to-use spray liquor or pesticide composition according to the invention. Generally, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of usable agricultural area. According to one embodiment, the user can mix the individual components of the composition according to the invention, such as parts of a kit or parts of a binary or ternary mixture, in a spray tank and additional auxiliaries can be added, if appropriate. The invention also relates to the use of triethylammonium chloride to inhibit the crystal growth of dimpropyridaz particles suspended in an aqueous pesticide composition. The inhibition of crystal growth can be measured by comparing a pesticide composition to which triethylammonium chloride has been added with a pesticide composition that does not contain triethylammonium chloride. Typically, the two compositions are incubated at 40°C for 4 weeks, and the particle size is measured, for example, by laser diffraction. The invention further relates to a method for treating plant propagation material comprising the step of bringing the plant propagation material into contact with the pesticide composition. Another object is a method for treating or protecting an animal from infestation or infection by invertebrate pests comprising putting the animal in contact with an effective amount of the pesticide composition. Another additional object is a method for combating or controlling invertebrate pests, the method comprising bringing said pest or its food supply, habitat or breeding areas into contact with a pesticide-effective amount of the pesticide composition as defined in accordance with any of the claims. Another additional object is a method for protecting growing plants against attacks or infestation by invertebrate pests, the method comprising bringing a plant, or soil or water in which the plant is growing, into contact with a pesticide-effective amount of the pesticide composition. The pesticide composition is suitable for use in protecting crops, plants, plant propagation materials such as seeds, or soil or water in which plants grow, from attack or infestation by animal pests. The pesticide composition is effective through contact and ingestion. Furthermore, the pesticide composition can be applied at all developmental stages, such as egg, larva, pupa, and adult. ζοροηη / ζζηζ / Ε / γίΛΐ The application can be carried out both before and after infestation by pests of crops, plants, plant propagation materials such as seeds, soil or area, material or environment. Suitable application methods include, but are not limited to, soil treatment, seed treatment, furrow application, and foliar application. Soil treatment methods include soaking the soil, drip irrigation (drip application to the soil), dipping roots, tubers, or bulbs, or soil injection. Seed treatment techniques include seed coating, seed dusting, seed soaking, and seed pelleting. Furrow applications typically involve forming a furrow in cultivated soil, sowing seeds in the furrow, applying the pesticide composition to the furrow, and closing the furrow. Foliar application refers to applying the pesticide composition to the foliage of plants, for example, using spray equipment.In the case of foliar applications, it can be advantageous to modify pest behavior by using pheromones in combination with the pesticide. The appropriate pheromones for specific crops and pests are known to mid-level practitioners and are publicly available in pheromone and semiochemical databases, such as http: / / www.pherobase.com. As used herein, the expression "to put in contact" includes both direct contact (applying the pesticide composition directly onto the animal or plant pest, usually on the foliage, stem, or roots of the plant) and indirect contact (applying the pesticide composition to the locus, i.e., the habitat, breeding area, plant, seed, soil, area, material, or environment where a pest is growing or may grow). The term "effective quantity" indicates an amount of the active ingredient that is sufficient to control harmful fungi on cultivated plants or in the protection of materials without causing substantial damage to the treated plants. This amount can vary widely and depends on several factors, such as the pest species to be controlled, the treated material or cultivated plants, climatic conditions, and the specific active ingredient used. The term "invertebrate pest" includes arthropods, gastropods, and nematodes. The preferred animal pests according to the invention are arthropods, preferably insects and arachnids, particularly insects. Insects of particular importance to crops are generally referred to as crop pests. The term plant includes cereals, for example, durum wheat and other types of wheat, rye, barley, triticale, oats, rice, or zea mays (fodder zea mays and sweet zea mays / fodder and sweet maize); beets, for example, sugar beets or fodder beets; fruits, such as pomes, stone fruits, or berries, for example, apples, pears, plums, peaches, nectarines, almonds, cherries, papayas, strawberries, raspberries, blackberries, or gooseberries; leguminous plants, such as beans, lentils, peas, alfalfa, or soybean seeds; oilseed plants, such as rapeseed, turnip, mustard, olives, sunflowers, coconut, cocoa beans, castor plants, palm oil, peanuts, or soybeans; Cucurbits, such as squash, pumpkins, cucumbers or melons; fiber plants, such as cotton, flaxseed, hemp or jute; citrus fruits, such as oranges, lemons, grapefruits or tangerines;Vegetables, such as eggplant, spinach, lettuce (e.g., iceberg lettuce), chicory, cabbage, asparagus, kale, carrots, onions, garlic, leeks, tomatoes, potatoes, cucurbits, or bell peppers; laurel plants, such as avocados, cinnamon, or camphor; energy and raw material plants, such as corn, soybeans, rapeseed, sugar cane, or palm oil; tobacco; nuts, for example, walnuts; pistachios; coffee; tea; bananas; vines (table grapes and juice grape vines); hops; sweet herb (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers (e.g., carnations, petunias, geraniums / pelargoniums, pansies and impatiens), shrubs, broadleaf trees (e.g., poplars) or evergreen trees, e.g., conifers; eucalyptus; lawns; grass;Grass, such as pasture for animal feed or ornamental uses. Preferred plants include potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, canola, legumes, sunflowers, coffee, or sugarcane; fruits; vines; ornamental plants; or vegetables, such as cucumbers, tomatoes, beans, or squash. The term plant also includes cultivated plants. It should be understood that the expression cultivated plants includes plants that have been modified by mutagenesis or genetic engineering to provide a new trait to a plant or to modify a trait already present. Advantages: The pesticide composition is characterized by very high storage stability, reduced particle growth (e.g., crystal growth), reduced sedimentation, reduced gelation, an advantageous rheological profile, and high biological efficacy. The following examples illustrate the invention. Examples The following ingredients were used to prepare the pesticide compositions in the examples. Insecticide A: 1-[(1 ñS)-1,2-dimethylpropyl]- / \ / -ethyl-5-methyl-A / -pyridazin-4-yl-1 / - / -pyrazol-4-carboxamide. Wetting agent: ethoxylated castor oil, 40 polymerized ethylene oxide units per molecule on average, saponification value 58-66 (according to ISO 3657) Polymeric additive A: sulfomethylated lignosulfonate, organic sulfur content of approximately 9% by weight, mass average molecular weight of 20 to 50 kDa. Antifoaming agent: dimethylsiloxane emulsion in silica particles, 20% by weight of foam remover content Biocide A: glycol-based benzisothiazolinone solution Biocide B: aqueous composition of benzisothiazolinones and 5-chloro-2-methylisothiazolin-3-one Additive A: hydrophobic fumed silica, surface modified with dimethyldichlorosilane, surface area of ​​130 m2 / g Stabilizer A: polyarylphenyl ether sulfate, ammonium salt, viscous liquid at 20°C Example 1: Preparation of suspension concentrates The suspension concentrates containing the ingredients were prepared according to Table A, 7QCQnn / 77n7 / B / YIAI, shows that the suspension concentrates differed depending on the type and concentration of stabilizer used. For each type of stabilizer, suspension concentrates were produced with 0.0 wt, 0.1 wt, 0.2 wt, 0.4 wt, 0.6 wt, 0.8 wt, and 1 wt of the respective stabilizer. The stabilizers tested were triethylammonium chloride, sodium chloride, ammonium chloride, ammonium sulfate, triethylammonium bromide, Stabilizer A, and tetraethylammonium iodide. In the first stage, a premix containing 3% xanthan gum by weight was prepared by adding xanthan gum, part of biocide A, and biocide B to water. The premix was blended with a capped knife until the xanthan gum was fully hydrated and the premix was homogeneous. In a second stage, stabilizer solutions were prepared containing 10% by weight of a given stabilizer as indicated in Table B by diluting the respective stabilizer in water with stirring. In a third stage, a milling base was prepared by adding insecticide A, 50% of the assigned wetting agent, polymeric additive, antifoaming agent, the remaining biocide A, the remaining biocide B, acetic acid, and additive A to the remaining water. The mixture was homogenized until uniform and then ground in a ball mill until an average particle size of 2–3 micrometers was achieved. After the ground base reached the particle size, it was mixed with the remaining wetting agent and premix to produce the final slurry concentrates. Once the final suspension concentrate was prepared, the volume of the suspension concentrate was divided into several subsamples and the respective stabilizing solution and water were added and mixed until homogeneous. ζοροηη / ζζηζ / Ε / γίΛΐ Component Concentration [% by weight] Insecticide A 20.91 Wetting agent 8.00 Polymeric additive 2.00 Antifoaming agent 0.40 Biocide A 0.20 Biocide B 0.10 Xanthan gum 0.13 Acetic acid 0.10 Additive A 1.00 Stabilizer As listed in Table B Water up to 100 Table A: Ingredients of SC-1, SC-C1, SC-C2, SC-C3, SC-C4, SC-C5, and SC-C6 suspension concentrates. Example 2: Stability assessment All suspension concentrates prepared in Example 1 were placed in a -10°C / 30°C cycling chamber (temperature cycles every 24 hours). After 8 or 16 weeks of storage, the samples were evaluated under a microscope to determine crystal growth. The results are summarized in Table B. Stabilizer Time in cycle chamber Microscopic observation Stabilizer concentration in suspension concentrates [% by weight] 0.00% 0.10% 0.20% 0.40% 0.60% 0.80% 1.00% Triethylammonium chloride 16 weeks Crystal growth Crystal growth Crystal growth No crystal growth No crystal growth No crystal growth No crystal growth Sodium chloride 8 weeks Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Ammonium chloride 8 weeks Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Ammonium sulfate 8 weeks Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Crystal growthTriethylammonium bromide crystal growth 8 weeks Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Stabilizer A 8 weeks Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Tetraethylammonium iodide 8 weeks Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Crystal growth Table B: Summary of the stability assessment of suspension concentrates containing different stabilizers at various concentrations.

Claims

1) An aqueous pesticide composition comprising a) suspended particles comprising dimpropyridaz; and b) triethylammonium chloride; wherein the concentration of triethylammonium chloride is at least 0.3% by weight based on the total weight of the pesticide composition. 2) The pesticide composition according to claim 1, wherein the suspended particles a) have a D50 value of 1 to 5 pm. 3) The pesticide composition according to any of claims 1 or 2, wherein the concentration of triethylammonium chloride is up to 2% by weight. 4) The pesticide composition according to any of claims 1 to 3, wherein the suspended particles are suspended crystalline particles. 5) The pesticide composition according to any of claims 1 to 4, wherein the weight ratio of the suspended particles a) to triethylammonium chloride is up to 70:

1. 6) The pesticide composition according to any one of claims 1 to 5, containing a) 40 to 95% by weight of water; b) 5 to 40% by weight of suspended particles; c) 0.3 to 2% by weight of triethylammonium chloride; each time depending on the total weight of the pesticide composition. 7) The pesticide composition according to any of claims 1 to 6, wherein triethylammonium chloride is present in dissolved form. 8) The pesticide composition according to any of claims 1 to 7, further comprising an active pesticide ingredient. 9) A process for producing the pesticide composition as defined according to any of claims 1 to 8, comprising the step of contacting triethylammonium chloride, particles comprising dimpropyridaz and water. 10) The use of triethylammonium chloride to inhibit the growth of crystals of dimpropyridaz particles that are suspended in an aqueous pesticide composition. 11) A method for treating plant propagation material comprising the step of bringing the plant propagation material into contact with the pesticide composition as defined according to any of claims 1 to 8. 12) A method for treating or protecting an animal from infestation or infection by invertebrate pests comprising bringing the animal into contact with a pesticide-effective amount of the pesticide composition as defined according to any one of claims 1 to 8. 13) A method for combating or controlling invertebrate pests, the method comprising bringing said pest or its food supply, habitat or breeding areas into contact with an effective pesticide quantity of the pesticide composition as defined in accordance with any one of claims 1 to 8. 14) A method for protecting growing plants against attack or infestation by invertebrate pests, wherein the method comprises bringing a plant, or soil or water in which the plant is growing, into contact with a pesticide-effective amount of the pesticide composition according to any one of claims 1 to 8.