Stabilization of zincpropylidaz suspensions with triethylammonium chloride.

Abstract

The present invention relates to an aqueous pesticide composition comprising a) suspended particles containing dinpropylidaz and b) triethylammonium chloride. The invention also relates to a method for making the pesticide composition, a method for treating plant propagation material, the use of triethylammonium chloride to inhibit crystal growth of dinpropylidaz particles suspended in the pesticide composition, a method for treating or protecting animals from invertebrate pest infestation or infection, comprising contacting the animal with a pesticidally effective amount of the pesticide composition, a method for eradicating or controlling invertebrate pests, comprising contacting the pest, its food supply, habitat, or breeding grounds with a pesticidally effective amount of the pesticide composition, and a method for protecting growing plants from invertebrate pest attack or infestation, comprising contacting the plant, or the soil or water in which the plant is growing, with a pesticidally effective amount of the pesticide composition.

Description

[Technical field]

[0001] The present invention relates to aqueous pesticide compositions, methods for making pesticide compositions, the use of triethylammonium chloride to inhibit crystal growth of particles of zincpropyridaz suspended in the aqueous pesticide composition, methods for treating plant propagation material, methods for treating or protecting animals from infestation or infection by invertebrate pests, methods for eliminating or controlling invertebrate pests, and methods for protecting growing plants from attack or infestation by invertebrate pests. [Background technology]

[0002] Suspension concentrates are a common formulation type for pesticide compounds. Pesticide suspension concentrates have an aqueous continuous phase in which particles of at least one pesticide are uniformly dispersed. Suspension concentrates are desirable formulations because they do not contain high concentrations of organic solvents. Thus, suspension concentrates are considered environmentally friendly compared to other formulation types, such as emulsion concentrates or oil dispersions.

[0003] However, a significant drawback of suspension concentrates is their tendency to grow on storage. Particle growth in aqueous suspensions is caused by a process called Ostwald ripening. Ostwald ripening describes the process whereby smaller particles dissolve while larger particles increase in size and weight. The driving force behind Ostwald ripening is the difference in solubility between small and large particles. Ostwald ripening is particularly pronounced in particles of compounds with moderate water solubility.

[0004] Zinpropyridaz is a pesticide with a water solubility at 20° C. of approximately 4-5 wt % at 25° C. The water solubility of zinpropyridaz is relatively high, so Ostwald ripening presents a significant problem for zinpropyridaz suspension concentrates. Summary of the Invention [Means for solving the problem]

[0005] It has been surprisingly discovered that adding at least 0.3 wt% triethylammonium chloride to an aqueous suspension of dinpropyridaz can stabilize suspended dinpropyridaz particles. Crystal growth is significantly reduced by the addition of triethylammonium chloride. No settling or solidification of the pesticide is then observed. The stabilizing effect can be observed at a concentration of at least 0.3 wt% triethylammonium chloride, based on the total weight of the pesticide composition.

[0006] Therefore, the present invention provides a) suspended particles containing zincpropylidaz; b) Triethylammonium chloride Including, The concentration of triethylammonium chloride is at least 0.3 wt. % based on the total weight of the pesticide composition; The present invention relates to an aqueous pesticide composition. This specification includes the following. [1] An aqueous pesticide composition comprising: a) suspended particles comprising dinpropylidaz; and b) triethylammonium chloride, wherein the concentration of triethylammonium chloride is at least 0.3 wt. %, based on the total weight of the pesticide composition. [2] The pesticide composition according to [1] above, wherein the suspended particles a) have a D50 value of 1 to 5 μm. [3] The pesticide composition according to either [1] or [2] above, wherein the concentration of triethylammonium chloride is up to 2 wt%. [4] A pesticide composition according to any one of [1] to [3] above, wherein the suspended particles are suspended crystalline particles. [5] The pesticide composition according to any one of [1] to [4] above, 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 [1] to [5] above, comprising a) 40 to 95 wt% water, b) 5 to 40 wt% suspended particles, and c) 0.3 to 2 wt% triethylammonium chloride, each based on the total weight of the pesticide composition. [7] The pesticide composition according to any one of [1] to [6], wherein triethylammonium chloride is present in dissolved form. [8] A pesticide composition according to any one of [1] to [7] above, which contains a further pesticidal active ingredient. [9] A method for producing a pesticide composition according to any one of [1] to [8] above, comprising the step of contacting particles containing triethylammonium chloride, dinpropylidaz, and water.

[10] Use of triethylammonium chloride to inhibit crystal growth of zincpropyridaz particles suspended in an aqueous pesticide composition.

[11] A method for treating plant propagation material, comprising the step of contacting the plant propagation material with a pesticide composition according to any one of [1] to [8] above.

[12] A method for treating or protecting an animal from infestation or infection by an invertebrate pest, comprising contacting the animal with a pesticidally effective amount of a pesticide composition described in any of [1] to [8] above.

[13] A method for eradicating or controlling an invertebrate pest, comprising contacting the pest, or its food supply, habitat, or breeding grounds, with a pesticidally effective amount of a pesticide composition described in any of [1] to [8] above.

[14] A method for protecting growing plants from attack or infestation by invertebrate pests, comprising contacting the plants, or the soil or water in which the plants are growing, with a pesticidally effective amount of a pesticide composition according to any of [1] to [8] above. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] Zinpropyridaz is the generic name for the compound 1-[1,2-dimethylpropyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-1H-pyrazole-4-carboxamide. Zinpropyridaz has a chiral center and two enantiomers have been described (see ip.com IPCOM000256756D): 1-[(1R)-1,2-dimethylpropyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-1H-pyrazole-4-carboxamide (hereinafter referred to as the "R enantiomer") and 1-[(1S)-1,2-dimethylpropyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-1H-pyrazole-4-carboxamide (hereinafter referred to as the "S enantiomer"). The S and R enantiomers are depicted by formulas IA and IB, respectively.

[0008] [ka]

[0009] Thus, the term "zinpropyridaz" as used herein refers to the S enantiomer, the R enantiomer and a racemic mixture thereof. Preferably, the term zinpropyridaz refers to a racemic mixture of the S and R enantiomers.

[0010] The aqueous pesticide composition contains suspended particles comprising dinpropyridaz. Preferably, the suspended particles consist of dinpropyridaz. The suspended particles are typically suspended crystalline particles of dinpropyridaz.

[0011] Zinpropyridaz occurs in at least two crystalline forms, hereinafter referred to as "polymorph A" and "polymorph B". Zinpropyridaz, its activity against arthropod pests and general procedures for its preparation are known from WO 2012 / 143317. These general procedures are applied to the preparation of zinpropyridaz to produce the compound as a glassy melt containing polymorph A. The suspended particles comprising zinpropyridaz typically relate to suspended crystalline particles of zinpropyridaz in polymorph A form, polymorph B or a mixture thereof. In one embodiment, the suspended particles comprising zinpropyridaz relate to suspended crystalline particles of zinpropyridaz in polymorph A form. In another embodiment, the suspended particles comprising zinpropyridaz relate to suspended crystalline particles of zinpropyridaz in polymorph B form.

[0012] Polymorph A can be confirmed and distinguished from Form B by powder X-ray diffraction. The PXRD pattern of polymorph Form A recorded at 25° C. using Cu-Kα radiation (1.54178 Å) displays at least three of the following reflections quoted 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 do not appear in Form B. In addition to these five reflections, Polymorph A may display in such a diagram one or more, in particular at least two, often at least four, in particular at least six or at least eight, especially all of the reflections hereinafter quoted 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°.

[0013] Among the peaks in the PXRD pattern of Polymorph A, the following 2θ 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°.

[0014] When analyzed by differential scanning calorimetry (DSC), polymorph A displays a thermogram with a characteristic endothermic peak, also called the melting peak. The melting point is determined as the onset of the melting peak and is typically in the range of about 82° C. to 87° C. Values ​​quoted herein relate to values ​​determined by DSC using an aluminium sealed cup with a sample size of 1 to 10 mg and applying a heating rate of 10 K / min.

[0015] Thermogravimetric analysis, hereinafter also referred to as TGA, revealed that no weight loss occurred upon heating, indicating that Form A does not contain solvent.

[0016] Polymorph B can be obtained as described in European Patent Application No. 19151447.0. Based on the powder X-ray diffraction diagram, hereinafter also referred to as the powder X-ray diffraction pattern or PXRD pattern, of polymorph B recorded at 25° C. using Cu-Kα radiation (1.54178 Å), polymorph B ascertainable by powder X-ray diffraction techniques displays the following three reflections, quoted as 2θ values: 20.69±0.10°, 24.15±0.10° and 30.52±0.10°. In addition to these three reflections, Polymorph B may display in such a PXRD pattern one or more, especially at least two, often at least four, especially at least six or at least eight, and especially all, of the following reflections quoted as 2θ 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°.

[0017] Of these reflections, preferably at least one, especially at least two, more preferably at least four, especially at least six or all of the following reflections, quoted as 2θ values: 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°, may be observed in such a PXRD pattern. In addition to these reflections, preferably at least one, especially at least two, more preferably at least four, especially at least six or all of the following reflections, quoted as 2θ values: 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°, may be observed in such a PXRD pattern.

[0018] Frequently, a PXRD pattern for polymorph form B recorded using Cu-Kα radiation (1.54178 Å) at 25° C. displays the following three reflections, quoted as 2θ values: 20.69±0.10°, 24.15±0.10°, and 30.52±0.10°, in addition to the following reflections, quoted as 2θ values: 15.31±0.10°, 15.97±0.10°, and 16.50±0.10°.

[0019] Alternatively, the PXRD pattern of polymorph Form B recorded at 25° C. using Cu-Kα radiation (1.54178 Å) displays the following three reflections, quoted as 2θ values: 20.69±0.10°, 24.15±0.10°, and 30.52±0.10°, in addition to the following reflections, quoted as 2θ values: 23.40±0.10° and 23.70±0.10°.

[0020] In particular, the PXRD pattern of polymorph Form B recorded at 25° C. using Cu-Kα radiation (1.54178 Å) displays the following three reflections, quoted as 2θ values: 20.69±0.10°, 24.15±0.10°, and 30.52±0.10°, in addition to the following reflections, quoted as 2θ values: 15.31±0.10°, 15.97±0.10°, 16.50±0.10°, 23.40±0.10°, and 23.70±0.10°.

[0021] When analyzed by differential scanning calorimetry (DSC), polymorph B of the present invention displays a thermogram with a characteristic endothermic peak, also referred to as the melting peak. The melting point is determined as the onset of the melting peak and is typically in the range of about 80° C. to 90° C., in particular in the range of 82° C. to 89° C. The values ​​quoted herein relate to values ​​determined by DSC using an aluminium closed cup with a sample size of 1 to 10 mg and applying a heating rate of 10 K / min. Thermogravimetric analysis, hereinafter also referred to as TGA, revealed that no weight loss occurred upon heating, confirming the findings of the single crystal X-ray study that polymorph B is solvent-free.

[0022] Suspension particles containing dinpropyridaz can be characterized by their size distribution, which can be determined by dynamic light scattering. The D50 value is a statistical figure indicating the 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 of the particles in the present case is typically up to 30 μm, preferably up to 25 μm, more preferably up to 20 μm, most preferably up to 10 μm, especially preferably up to 7 μm. The D50 value of the particles is typically at least 0.1 μm, preferably at least 0.8 μm, more preferably at least 1 μm. The D50 value of the particles is typically 0.5 to 10 μm, preferably 1 to 8 μm, more preferably 1 to 5 μm.

[0023] The pesticide composition contains the suspended particles a) in a concentration of usually 5-60 wt%, preferably 10-50 wt%, more preferably 10-40 wt%, based on the total weight of the pesticide composition. The pesticide composition may contain the suspended particles a) in a concentration of at least 1 wt%, preferably at least 15 wt%, based on the total weight of the pesticide composition. The pesticide composition may contain the suspended particles a) in a concentration of up to 45 wt%, preferably up to 35 wt%, more preferably up to 25 wt%, based on the total weight of the pesticide composition.

[0024] The pesticide composition is an aqueous pesticide composition, i.e. the continuous liquid phase is an aqueous liquid. The pesticide composition may contain at least 5 wt% water, preferably at least 10 wt%, more preferably at least 15 wt%, most preferably at least 30 wt%, especially preferably at least 50 wt% water, based on the total weight of the pesticide composition. The pesticide composition may contain up to 99 wt% water, preferably up to 95 wt%, more preferably up to 90 wt%, especially up to 80 wt% water, based on the total weight of the pesticide composition. The pesticide composition usually contains 30-90 wt% water, preferably 50-80 wt% water, based on the total weight of the pesticide composition.

[0025] The pesticide composition also contains triethylammonium chloride, which can be identified by the CAS number 554-68-7. Triethylammonium chloride is an adduct of triethylamine and hydrochloric acid (HCl). Thus, it is sometimes referred to as (CH3CH2)3N-HCl.

[0026] The pesticide composition contains triethylammonium chloride at a concentration of at least 0.3 wt%, preferably at least 0.4 wt%, based on the total weight of the pesticide composition. The pesticide composition may contain triethylammonium chloride at a concentration of up to 10 wt%, preferably up to 5 wt%, more preferably up to 2 wt%, particularly preferably up to 1.5 wt%, for example up to 1 wt%. The pesticide composition typically contains triethylammonium chloride at a concentration of 0.3 to 3 wt%, preferably 0.35 to 2 wt%, more preferably 0.4 to 1 wt%. Triethylammonium chloride is typically present in the pesticide composition in a dissolved form at 20°C.

[0027] The weight ratio of suspended particles a) to triethylammonium chloride b) in the pesticide composition is typically 5:1 to 200:1, preferably 10:1 to 100:1, in particular 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.

[0028] In one embodiment, the pesticide composition comprises: a) 10 to 99 wt% water, b) 1 to 60 wt% suspended particles and c) 0.3 to 10 wt % of triethylammonium chloride, Each is included based on the total weight of the pesticide composition.

[0029] In another embodiment, the pesticide composition comprises: a) 10 to 95 wt% water, b) 5-40 wt% suspended particles and c) 0.3 to 2 wt % of triethylammonium chloride, Each is included based on the total weight of the pesticide composition.

[0030] In another embodiment, the pesticide composition comprises: a) 40 to 80 wt% water, b) 15-30 wt% suspended particles and c) 0.4 to 1 wt % of triethylammonium chloride, Each is included based on the total weight of the pesticide composition.

[0031] The pesticide composition may contain further pesticidal active ingredients. The active ingredients may be selected from the group of fungicides, insecticides, nematicides, herbicides, safeners, 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 skilled person is familiar with such pesticides and can be found, for example, in the Pesticide Manual, 16th Edition (2013), The British Crop Protection Council, London. Suitable insecticides are insecticides from the classes of carbamates, organophosphates, organochlorines, phenylpyrazoles, pyrethroids, neonicotinoids, spinosyns, avermectins, milbemycins, juvenile hormone analogues, alkyl halides, organotin compounds, nereistoxin analogues, benzoylureas, diacylhydrazines, METI acarizides, and insecticides such as chloropicrin, pymetrozine, flonicamid, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, rotenone, or derivatives thereof.Suitable bactericides include dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzyl carbamates, carbamates, carboxamides, carboxylic acid diamides, chloronitrile cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethyl phosphonates, ethylaminothiazole carboxamides, guanidines, hydroxy-(2-amino)pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganic substances, isobenzofuranones, methoxyacrylates, methoxy Fungicides from the classes of carbamates, morpholines, N-phenylcarbamates, oxazolidinediones, oximinoacetates, oximinoacetamides, peptidylpyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles, phenylureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamides, pyrimidineamines, pyrimidines, pyrimidinone hydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles, thiazolecarboxamides, thiocarbamates, thiophanates, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines, triazoles.Suitable herbicides include acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofurans, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanedione, dinitroanilines, dinitrophenols, diphenyl ethers, glycine, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinedione, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenyl Herbicides from the classes of: pyridazines, phosphinic acids, phosphoramidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl (thio)benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils, ureas.

[0032] Suitable plant growth regulators are antiauxins, auxins, cytokinins, defoliants, ethylene regulators, ethylene releasing agents, gibberellins, growth inhibitors, morphactins, growth retardants, growth stimulants and further unclassified plant growth regulators.

[0033] Suitable micronutrients are compounds containing boron, zinc, iron, copper, manganese, chlorine and molybdenum.

[0034] The concentration of the further pesticidal active ingredient in the pesticide composition is typically at least 5 wt%, more preferably at least 10 wt%, most preferably at least 15 wt%, particularly preferably at least 20 wt%, most preferably at least 25 wt%, particularly preferably at least 30 wt%, based on the total weight of the pesticide composition. The concentration of the further pesticidal active ingredient in the pesticide composition is typically up to 95 wt%, preferably up to 85 wt%, more preferably up to 75 wt%, particularly preferably up to 75 wt%, especially up to 65 wt%, based on the total weight of the pesticide composition. The pesticide composition contains the further pesticidal active ingredient in a concentration of typically 10 to 90 wt%, preferably 15 to 60 wt%, more preferably 20 to 50 wt%, based on the total weight of the pesticide composition.

[0035] The pesticide composition is typically prepared by contacting triethylammonium chloride, particles containing dinpropylidaz, and water. The triethylammonium chloride, particles, and water can be contacted in any order, for example, in a first step, the particles can be contacted with water, and then triethylammonium chloride can be added.

[0036] The pesticide compositions can be prepared by known methods, for example as described in 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.

[0037] Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners, moisturizing agents, repellents, attractants, feeding stimulants, compatibilizers, bactericides, antifreeze agents, antifoaming agents, colorants, tackifiers and binders.

[0038] Suitable solvents and liquid carriers are water and organic solvents, such as medium to high boiling mineral oil fractions, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, paraffins, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactate esters, carbonate esters, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.

[0039] Suitable solid carriers or fillers are mineral earths, such as silicates, silica gel, talc, kaolin, limestone, lime, chalk, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, such as cellulose, starch; fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; products of plant origin, such as cereal meal, bark meal, wood meal, nut shell meal and mixtures thereof.

[0040] Suitable surfactants are surface active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof.Such surfactants can be used as emulsifiers, dispersants, solubilizers, wetters, 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 Edition or North American Edition).

[0041] Suitable anionic surfactants are the alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates and mixtures thereof.Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefinsulfonates, ligninsulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.Examples of sulfates are sulfates of fatty acids and oils, ethoxylated alkylphenols, alcohols, ethoxylated alcohols or fatty acid esters.Examples of phosphates are phosphoric acid esters.Examples of carboxylates are alkyl carboxylates, and carboxylated alcohols or alkylphenol ethoxylates.

[0042] Suitable nonionic surfactants are 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 alkoxylated with 1 to 50 equivalents. Ethylene oxide and / or propylene oxide, preferably ethylene oxide, can be used for the alkoxylation. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitan, ethoxylated sorbitan, sucrose esters and glucose esters or alkyl polyglucosides. Examples of polymeric surfactants are homopolymers or copolymers of vinylpyrrolidone, vinyl alcohol or vinyl acetate.

[0043] Suitable cationic surfactants are quaternary surfactants, such as 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, including blocks of polyethylene oxide and polypropylene oxide, or ABC type, including blocks of alkanol, polyethylene oxide and polypropylene oxide.Suitable polyelectrolytes are polyacids or polybases.Examples of polyacids are polyacrylic acid or alkali salts of polyacid comb polymers.Examples of polybases are polyvinylamines or polyethyleneamines.

[0044] Suitable adjuvants are compounds that have negligible or no pesticidal activity of their own and improve the biological performance of compound I against the target. Examples are surfactants, mineral or vegetable oils, and other auxiliary agents. Further examples are listed in Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, Chapter 5.

[0045] Suitable thickening agents are polysaccharides (eg xanthan gum, carboxymethylcellulose), organoclays (organically modified or unmodified), polycarboxylates and silicates.

[0046] Suitable bactericides are bronopol and isothiazolinone derivatives, such as alkylisothiazolinones and benzoisothiazolinones.

[0047] Suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin.

[0048] Suitable antifoaming agents are silicones, long chain alcohols and salts of fatty acids.

[0049] Suitable colorants (e.g. red, blue or green) are pigments with low water solubility and water soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin, azo and phthalocyanine colorants).

[0050] Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylates, biological or synthetic waxes, and cellulose ethers.

[0051] Solutions for seed treamtents (LS), suspoemulsions (SE) and flowable concentrates (FS) are usually applied for the purpose of treating plant propagation material, especially seeds. The compositions in question, after 2-10-fold dilution, give active substance concentrations of 0.01-60% by weight, preferably 0.1-40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods of applying the pesticide compositions to the plant propagation material, especially to the seeds, include dressing, coating, pelleting, dusting, immersion and in-furrow application methods on the propagation material. Preferably, the pesticide compositions are applied to the plant propagation material by methods that do not induce germination, for example by dressing, pelleting, coating and dusting on the seeds.

[0052] When used for plant protection, the amount of active ingredient applied is, depending on the type of effect desired, 0.001 to 2 kg / ha, preferably 0.005 to 2 kg / ha, more preferably 0.05 to 0.9 kg / ha, in particular 0.1 to 0.75 kg / ha.

[0053] In the treatment of plant propagation material, such as seeds, for example by dusting, coating or drenching the seeds, an amount of active ingredient of 0.1 to 1000 g, preferably 1 to 1000 g, more preferably 1 to 100 g, most preferably 5 to 100 g per 100 kilograms of plant propagation material (preferably seeds) is generally required.

[0054] When used in the protection of materials or stored products, the amount of active ingredient applied depends on the type of application area and the desired effect. Amounts customarily applied in the protection of materials are from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg, of active substance per cubic meter of treated material.

[0055] Various types of oils, wetters, adjuvants, fertilizers or micronutrients, and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) can be added to the pesticide composition as a premix or, if appropriate, only immediately before use (tank mix). These agents can be mixed into the composition according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

[0056] The user usually applies the composition according to the invention from a pre-dosing device, a knapsack sprayer, a spray tank, a spray plane or an irrigation system. Usually, the pesticide composition is adjusted to the desired application concentration with water, buffers and / or further auxiliaries and a ready-to-use spray liquid or a pesticide composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters of ready-to-use spray liquid are applied per hectare of agriculturally useful area.

[0057] According to one embodiment, the individual components of the composition according to the invention, for example parts of a kit or parts of a binary or ternary mixture, may be mixed by the user himself in a spray tank, where appropriate further auxiliaries may be added.

[0058] The present invention also relates to the use of triethylammonium chloride to inhibit crystal growth of zincpropyridaz 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, compared to a pesticide composition that does not contain triethylammonium chloride. Typically, the two compositions are incubated at 40° C. for four weeks, and the particle size is measured, for example, by laser diffraction.

[0059] The present invention further relates to a method of treating plant propagation material comprising the step of contacting the plant propagation material with a pesticide composition.

[0060] A further object is a method of treating or protecting an animal from infestation or infestation by an invertebrate pest comprising contacting the animal with a pesticidally effective amount of the pesticide composition.

[0061] A further object is a method for combating or controlling an invertebrate pest comprising contacting said pest, or its food supply, habitat, or breeding grounds, with a pesticidally effective amount of a pesticidal composition as defined in any of the claims.

[0062] A further object is a method for protecting growing plants from attack or infestation by invertebrate pests comprising contacting the plants, or the soil or water in which the plants are growing, with a pesticidally effective amount of the pesticide composition.

[0063] The pesticide compositions are suitable for use to protect agricultural crops, plants, plant propagation materials such as seeds, or the soil or water in which plants are growing, from attack or infestation by animal pests.

[0064] The pesticide compositions are effective both via contact and ingestion. Furthermore, the pesticide compositions can be applied to any and all developmental stages, including eggs, larvae, pupae and adults.

[0065] Application can be carried out both before and after the infestation of the crop, plant, plant propagation material, such as seeds, soil or area, material or environment by the pest.

[0066] Suitable application methods include, among others, soil treatment, seed treatment, in-furrow application and foliar application. Soil treatment methods include soil irrigation, drip irrigation (drip application to soil), root, tuber or bulb impregnation, or soil injection. Seed treatment techniques include seed dressing, seed coating, seed dusting, seed soaking, and seed pelleting. In-furrow application typically includes the steps of making furrows in cultivated land, sowing seeds in the furrows, applying the pesticide composition to the furrows, and closing the furrows. Foliar application refers to applying the pesticide composition to the leaves of plants, for example through a spraying device. For foliar application, it may be advantageous to use pheromones in combination with the pesticide composition to modify the behavior of pests. Suitable pheromones for particular crops and pests are known to those of skill in the art and are publicly available from pheromone and semiochemical databases, such as http: / / www.pherobase.com.

[0067] As used herein, the term "contacting" includes both direct contact (application of the pesticide composition directly to the animal pest or plant, typically to the foliage, stem or roots of the plant) and indirect contact (application of the pesticide composition to the locus, i.e., the habitat, breeding ground, plant, seed, soil, area, material or environment of the animal pest or plant in which the pest is growing or may grow).

[0068] The term "effective amount" refers to an amount of active ingredient that is sufficient to control harmful fungi on cultivated plants or to protect the material, without causing substantial damage to the plants being treated. Such an amount can vary widely and depends on various factors, such as the pest species being controlled, the cultivated plants or materials being treated, the climatic conditions and the specific active ingredient being used.

[0069] The term "invertebrate pests" includes arthropods, gastropods and nematodes. Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, especially insects. Insects that are particularly associated with agricultural crops are typically referred to as crop pests.

[0070] The term "plant" refers to cereals, such as durum wheat and other wheats, rye, barley, triticale, oats, rice or corn (feed corn and sugar maize). maize) / sweet corn and field corn); beets, for example sugar beet or fodder beet; fruits, for example pome fruits, stone fruits or soft fruits, for example apple, pear, plum, peach, nectarine, almond, cherry, papaya, strawberry, raspberry, blackberry or gooseberry; legumes, for example beans, lentils, peas, alfalfa or soybean; oil plants, for example rapeseed (oilseed), turnip rape, mustard, olive, sunflower, coconut, cocoa bean, castor oil plant, oil palm, peanut or soybean; cucurbits, for example squash, pumpkin, cucumber or melon; fibre plants, for example cotton, flax, hemp or jute; citrus fruits, for example orange, lemon, grapefruit or mandarin; vegetables, for example eggplant, spinach, lettuce (e.g. iceberg lettuce), chicory, cabbage, asparagus, cabbage, carrot, onion, garlic, leek, tomato, potato, cucurbits or sweet pepper; lauraceae plants, for example avocado, cinnamon or camphor; energy and raw materials plants, for example corn, soybean, rapeseed, sugar cane or oil palm; tobacco; nuts, for example walnuts; pistachios; coffee; tea; bananas; vines (table grapes and grape juice vines); hops; sweet leaf (also called stevia); rubber plants or ornamental and forestry plants, for example flowers (e.g. carnation, petunia, geranium / pelargonium, pansy and impatiens), shrubs, broad-leaved trees (e.g. poplar) or evergreen trees, for example conifers; eucalyptus; turf; lawn; pasture, for example pasture for animal feed or ornamental use. Preferred plants include potato, sugar beet, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybean, rapeseed, legumes, sunflower, coffee or sugarcane; fruits; vines, ornamentals; or vegetables, such as cucumber, tomato, bean or squash. The term "plant" also includes cultivated plants.

[0071] The term "cultivated plant" should be understood to include plants that have been modified by mutagenesis or genetic engineering to provide the plant with new traits or to modify traits that are already present.

[0072] Advantages: The pesticide compositions are characterized by very high storage stability, reduced particle growth (eg, crystal growth), reduced settling, reduced gelling, favorable rheological profile, and high biological effectiveness.

[0073] The following examples illustrate the invention.

[0074] [Example] The following ingredients were used to prepare the example pesticide compositions: Insecticide A: 1-[(1RS)-1,2-dimethylpropyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-1H-pyrazole-4-carboxamide. Wetting agent: Ethoxylated castor oil, polymerized with an average of 40 ethylene oxide units per molecule, saponification number 58-66 (according to ISO 3657). Polymeric additive: Sulfomethylated lignosulfonate, organic sulfur content approximately 9 wt%, mass average molecular weight 20-50 kDa. Defoamer: Emulsion of dimethylsiloxane on silica particles, defoamer content 20wt%. Biocide A: A glycol-based solution of benzoisothiazolinone. Biocide B: An aqueous composition of benzisothiazolinone and 5-chloro-2-methylisothiazolin-3-one. Additive A: Hydrophobic fumed silica particles, surface modified with dimethyldichlorosilane, surface area 130 m 2 / g. Stabilizer A: Polyarylphenyl ether sulfate, ammonium salt, viscous liquid at 20°C.

[0075] Example 1: Preparation of Suspension Concentrate Suspension concentrates were prepared containing the ingredients in Table A. The suspension concentrates differed in the type and concentration of stabilizer used. For each type of stabilizer, suspension concentrates were produced having 0.0 wt%, 0.1 wt%, 0.2 wt%, 0.4 wt%, 0.6 wt%, 0.8 wt%, and 1 wt% of each stabilizer. The stabilizers tested were triethylammonium chloride, sodium chloride, ammonium chloride, ammonium sulfate, triethylammonium bromide, Stabilizer A, and tetraethylammonium iodide.

[0076] In the first step, a premix containing 3 wt% xanthan gum was made by adding xanthan gum, a portion of Biocide A, and a portion of Biocide B to water. The premix was mixed with a cowles blade until the xanthan gum was fully hydrated and the premix was homogenous.

[0077] In a second step, stabilizer solutions containing 10 wt % of a given stabilizer listed in Table B were prepared by diluting each stabilizer with water under stirring.

[0078] In the third step, the millbase was prepared by adding Biocide A, 50% portion of the wetting agent, the polymeric additive, the defoamer, 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 milled in a bead mill until an average particle size of 2-3 micrometers was reached.

[0079] After the millbase reached particle size it was mixed with the remaining wetting agent and premix to produce the final suspension concentrate.

[0080] After the final suspension concentrate was prepared, the volume of the suspension concentrate was divided into several subsamples and each stabilizer solution and water was added and mixed until homogenous.

[0081] [Table 1]

[0082] [Example 2] Evaluation of stability All suspension concentrates prepared in Example 1 were placed in a -10°C / 30°C cycling chamber (temperature cycled every 24 hours). After 8 or 16 weeks of storage, samples were evaluated microscopically for crystal growth. The results are summarized in Table B.

[0083] [Table 2]

Claims

1. a) Suspended particles containing zincpropylidaz and b) Triethylammonium chloride Including, The concentration of triethylammonium chloride is at least 0.3 wt. % based on the total weight of the pesticide composition; Aqueous pesticide compositions.

2. 2. The pesticide composition according to claim 1, wherein the suspended particles a) have a D50 value of 1 to 5 μm.

3. 3. A pesticide composition according to claim 1 or 2, wherein the concentration of triethylammonium chloride is up to 2 wt%.

4. 4. A pesticide composition according to any one of claims 1 to 3, wherein the suspended particles are suspended crystalline particles.

5. 5. A pesticide composition according to any one of claims 1 to 4, wherein the weight ratio of suspended particles a) to triethylammonium chloride is up to 70:

1.

6. a) 40 to 95 wt% water, b) 5-40 wt% suspended particles; c) 0.3 to 2 wt % of triethylammonium chloride, 6. The pesticide composition according to any one of claims 1 to 5, each containing based on the total weight of the pesticide composition.

7. 7. A pesticide composition according to any one of claims 1 to 6, wherein triethylammonium chloride is present in dissolved form.

8. 8. A pesticide composition according to any one of claims 1 to 7, comprising a further pesticidal active ingredient.

9. 9. A method for producing the pesticide composition of any one of claims 1 to 8, comprising contacting triethylammonium chloride, particles comprising dinpropylidaz, and water.

10. Use of triethylammonium chloride to inhibit crystal growth of zincpropyridaz particles suspended in an aqueous pesticide composition.

11. 9. A method of treating plant propagation material comprising the step of contacting the plant propagation material with a pesticide composition according to any one of claims 1 to 8.

12. 10. A method for treating or protecting a non-human animal from infestation or infection by an invertebrate pest, comprising contacting the non-human animal with a pesticidally effective amount of the pesticide composition of any one of claims 1 to 8.

13. 10. A method for combating or controlling an invertebrate pest comprising contacting the pest, or its habitat, or breeding grounds, with a pesticidally effective amount of the pesticide composition of any one of claims 1 to 8.

14. 10. A method for protecting growing plants from attack or infestation by invertebrate pests comprising contacting the plants, or the soil or water in which the plants are growing, with a pesticidally effective amount of the pesticide composition of any one of claims 1 to 8.

15. A pesticide composition according to any one of claims 1 to 8 for treating or protecting an animal from infestation or infection by an invertebrate pest.

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