WO2024126118A1

WO2024126118A1 - Agrochemical formulations of high density pesticides

Info

Publication number: WO2024126118A1
Application number: PCT/EP2023/084040
Authority: WO
Inventors: Yongqing Lan; Thomas Kroehl; Brigitte ZBORON; Sarah ROHR
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2022-12-13
Filing date: 2023-12-04
Publication date: 2024-06-20
Anticipated expiration: 2025-06-13

Abstract

A liquid formulation comprising a) a pesticide with a density above 2.5 g/cm³ and in form of particles, which are suspended in an aqueous phase, b) a polyalkylene oxide block copolymer, c) a phenolsulfonic acid condensation product, d) and a silica thickener.

Description

Agrochemical formulations of high density pesticides

This invention relates to liquid formulations comprising a pesticide with a density of 2.5 g/cm³ or above and in form of particles, which are suspended in an aqueous phase, a polyalkylene oxide block copolymer, a phenolsulfonic acid condensation product and a silica thickener. It also relates to a method for the preparation of such formulations. Further embodiments are directed to the methods for controlling pests.

Agrochemical formulations in form of aqueous suspensions are known and contain suspended pesticide particles in an aqueous liquid phase. Such suspension concentrates are particularly suitable if the suspended particles have a low solubility in water. Suspension concentrates have many benefits. For example, they provide good safety and user convenience due to their liquid character. However, these formulation types have various drawbacks, e.g. they often show long term stability issues if these formulations are highly loaded with suspended particles. Especially suspension concentrates comprising particles with high densities like metal pesticides, in particular copper pesticides, show stability issues in form of undesired sedimentation due to the high density of the metal compounds. The object of the present invention was to overcome these and other drawbacks.

The objective has been achieved by a liquid formulation comprising a) a pesticide with a density of 2.5 g/cm³ or above in form of particles, which are suspended in an aqueous phase, b) a polyalkylene oxide block copolymer, c) a phenolsulfonic acid condensation product, d) and a silica thickener.

The terms “composition” and “formulation” are herein used synonymously.

Formulations of the invention are liquid at 20 °C. Formulations of the invention comprise a liquid phase and a suspended solid phase. The liquid phase is preferably an aqueous phase. “Aqueous phase” as used herein means that the liquid phase contains at least 30 wt% of water, preferably at least 40 wt%, more preferably at least 50 wt%, most preferably at least 40 wt%, especially preferably at least 60 wt%, such as at least 80 wt%, in particular at least 90 wt%, each time based on the total weight of the liquid phase.

The liquid phase may in addition to water further comprise one or more water miscible solvents. “Water miscible” as used herein means that a liquid has a solubility in water at 20°C of at least 10 g/l, preferablyof at 50 g/l. Suitable water miscible solvents and liquid carriers include alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols like ethylene glycol and propylene glycol DMSO; ketones, e.g. acetone, methyl ethyl ketone, diethyl ketone, tert-butyl methyl ketone, cyclohexanone; esters, e.g. lactates, gamma-butyrolactone; phosphonates; amines; amides, e.g. N-methylpyrrol- idone; nitriles such as acetonitrile and propionitrile; N,N-dialkyl lactamides like N,N-dimethyl lactamide; tetrahydrofuran; dimethylformamide; N,N-dimethylacetamide; N-alkyl pyrrolidone (especially N-methyl pyrrolidone, N-(n-butyl) pyrrolidone, N-(t-butyl) pyrrolidone or N-(sek-butyl) pyrrolidone), N-butyl-2-pyrrolidone, proglyme, 1 ,3 dimethyl-2-imidazolidinone, popylene carbonate; and mixtures thereof.

The solid phase comprises solid particles which are suspended in the liquid phase. The solid phase comprises pesticide particles.

Formulations of the invention contain a pesticide with a density of 2.5 g/cm³ or above. According to the invention such pesticides are water insoluble and are present as solid particles suspended in the liquid phase. The term “water insoluble” as used herein means that such pesticides have a water-solubility at 20°C and at pH 6.6 below 1 g/l, preferably below 100 mg/l. In one embodiment, the pesticide, especially the copper pesticide has a water-solubility at 20°C and at pH 7 of up to 10 g/l, preferably of up to 1 g/l, more preferably of up to 0.1 g/l and even more preferably up to 0.01 g/l.

Formulations of the invention contain a pesticide with a density of at least 2.5 g/cm³, preferably of at least 2.8 g/cm³, more preferably of at least 3.0 g/cm³, most preferably of at least 3.3 g/cm³. In one embodiment, such pesticide is a metal compound, typically a metal salt. In one embodiment, such pesticide is a copper compound, typically a copper salt. The density value may be determined by the OECD method 109.

When reference is made herein to “metal pesticides” or “copper pesticides”, this shall mean a pesticide that is a metal compound, especially a copper compound, that is water insoluble and that has a density of at least 2.5 g/cm³, preferably of at least 2.8 g/cm³, more preferably of at least 3.0 g/cm³, most preferably of at least 3.3 g/cm³.

In one embodiment, formulations of the invention contain a copper pesticide. In one embodiment, formulations of the invention comprise one or more of copper pesticides selected from the group consisting of copper oxychloride, copper ammonium carbonate, copper octanoate, copper oxide and copper hydroxide. In one embodiment, formulations of the invention comprise copper oxychloride, also referred to as dicopper chloride trihydroxide.

Typically, formulations of the invention comprise from 10 to 600 g/l, preferably from 100 to 500 g/l, and in particular from 200 to 400 g/l of metal pesticide, especially copper pesticide, especially copper oxychloride.

Metal pesticides, especially copper pesticides, have a high density as compared to other non- metal pesticides. The density of the copper pesticide typically ranges from 2.5 to 4 g/cm³, more preferably from 3.2 to 3.8 g/cm³ and most preferably from 3.4 to 3.6 g/cm³.

This is contrasted by other types of pesticides like organic compounds comprising no high density metals that typically have a density of 1 to 1.8 g/cm³.

Typically, the D50 particle size of metal pesticides in formulations of the invention, especially of copper pesticides, range from 0.01 to 30pm, more preferably 0.1 to 20pm and most preferably from 1 to 10pm. The particles typically have an D50 value of at least 0.75 pm, preferably at least 1 pm. The particles may be characterized by their size distribution, which can be determined by dynamic light scattering techniques. Suitable dynamic light scattering measurement units are inter alia produced under the trade name Malvern Mastersizer 3000. The particles may be characterized by their median diameter, which is usually abbreviated as D50 value. The D50 value refers to a particular particle diameter, wherein half of the particle population by volume is smaller than this diameter. The D50 value is typically determined according to ISO 13320:2009.

When reference is made herein to an “agrochemical active”, “further agrochemical active” or a “further pesticide”, this shall mean an agrochemical active or pesticide different from pesticides having a density of 2.5 g/cm³ or above, especially metal pesticides or copper pesticides.

Formulations of the invention may contain one or more further agrochemical actives. The term “agrochemical active” refers to a substance that confers a desirable biological activity to the formulation. Typically, the further agrochemical active is a pesticide. Further agrochemical actives are typically selected from fungicides, insecticides, nematicides, herbicides, safeners, nitrification inhibitors, urease inhibitors, plant growth regulators, micronutrients, biopesticides and/or growth regulators. In one embodiment, the further agrochemical active is an insecticide. In one embodiment, the further agrochemical active is a herbicide. In another embodiment, the further agrochemical active is a fungicide. In one embodiment the formulation of the invention comprises one or more water soluble further pesticides or one or more water insoluble further pesticides or both. In one embodiment the formulation of the invention comprises one or more water soluble further pesticides and no water insoluble further pesticide. In one embodiment, the formulation of the invention comprises one or more water soluble further pesticides and one or more water insoluble further pesticides. In one embodiment, the formulation of the invention comprises no water soluble further pesticides and one or more water insoluble further pesticides.

“Water insoluble” pesticides typically have a water-solubility at 20°C and at pH 7 of up to 10 g/l, preferably of up to 1 g/l, more preferably of up to 0.1 g/l and even more preferably up to 0.01 g/l.

The skilled worker 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 are insecticides from the class of the carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosins, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin compounds nereistoxin analogs, benzoylureas, diacylhydrazines, METI acarizides, and insecticides such as chloropicrin, pymetrozin, flonicamid, clofentezin, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorofenapyr, DNOC, buprofezine, cyromazine, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, rotenone, or their derivatives. Suitable fungicides are fungicides from the classes of dinitroanilines, allylamines, ani- linopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, ben- zisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzyl carbamates, carbamates, carboxamides, carboxylic acid diamides, chloronitriles cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenyl croto- nates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy-(2-amino)pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganic substances, isobenzofuranones, methoxyacrylates, methoxycarbamates, morpholines, N-phenylcarbamates, oxazolidinediones, oximinoacetates, oximinoacetamides, peptidylpyrimi- dine nucleosides, phenylacetamides, phenylamides, phenylpyrroles, phenylureas, phospho- nates, phosphorothiolates, phthalamic acids, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamides, pyrimidinamines, pyrimidines, pyrimidinonehydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles, thiazolecarboxamides, thiocarbamates, thiophanates, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines, triazoles. Suitable herbicides are herbicides from the classes of the acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridinium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ether, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phe- nylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, 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, tria- zolopyrimidines, triketones, uracils, ureas. Suitable plant growth regulators are antiauxins, auxins, cytokinins, defoliants, ethylene modulators, ethylene releasers, gibberellins, growth inhibitors, morphactins, growth retardants, growth stimulators, and further unclassified plant growth regulators. Suitable micronutrients are compounds comprising boron, zinc, iron, copper, manganese, chlorine, and molybdenum. Suitable nitrification inhibitors are linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl) propionate (MHPP), Karanjin, brachialacton, p-benzoquinone sorgoleone, 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N- serve), dicyandiamide (DCD, DIDIN), 3,4-dimethyl pyrazole phosphate (DMPP, ENTEC), 4- amino-1 ,2,4-triazole hydrochloride (ATC), 1-amido-2-thiourea (ASU), 2-amino-4-chloro-6- methylpyrimidine (AM), 2-mercapto-benzothiazole (MBT), 5-ethoxy-3-trichloromethyl-1 ,2,4-thi- odiazole (terrazole, etridiazole), 2-sulfanilamidothiazole (ST), ammoniumthiosulfate (ATU), 3- methylpyrazol (3-MP), 3,5-dimethylpyrazole (DMP), 1 ,2,4-triazol thiourea (Til), N-(1 H-pyrazolyl- methyl)acetamides such as N-((3(5)-methyl-1 H-pyrazole-1-yl)methyl)acetamide, and N-(1 H-py- razolyl-methyl)formamides such as N-((3(5)-methyl-1 H-pyrazole-1-yl)methyl formamide, N-(4- chloro-3(5)-methyl-pyrazole-1-ylmethyl)-formamide, N-(3(5),4-dimethyl-pyrazole-1-ylmethyl)- formamide, neem, products based on ingredients of neem, cyan amide, melamine, zeolite powder, catechol, benzoquinone, sodium tetraborate , zinc sulfate, 2-(3,4-dimethyl-1 H-pyrazol-1- yl)succinic acid (referred to as “DMPSA1” in the following) and/or 2-(4,5-dimethyl-1 H-pyrazol-1- yl)succinic acid (referred to as “DMPSA2” in the following), and/or a derivative thereof, and/or a salt thereof; glycolic acid addition salt of 3,4-dimethyl pyrazole (3,4-dimethyl pyrazolium glycolate, referred to as “DMPG” in the following), and/or an isomer thereof, and/or a derivative thereof; citric acid addition salt of 3,4-dimethyl pyrazole (3,4-dimethyl pyrazolium citrate, referred to as “DMPC” in the following), and/or an isomer thereof, and/or a derivative thereof; lactic acid addition salt of 3,4-dimethyl pyrazole (3,4-dimethyl pyrazolium lactate, referred to as “DMPL” in the following), and/or an isomer thereof, and/or a derivative thereof; mandelic acid addition salt of 3,4- dimethyl pyrazole (3,4-dimethyl pyrazolium mandelate, referred to as “DM PM” in the following), and/or an isomer thereof, and/or a derivative thereof; 1 ,2,4-triazole (referred to as „TZ“ in the following), and/or a derivative thereof, and/or a salt thereof; 4-Chloro-3-methylpyrazole (referred to as „CIMP” in the following), and/or an isomer thereof, and/or a derivative thereof, and/or a salt thereof; a reaction adduct of dicyandiamide, urea and formaldehyde, or a triazonyl-formaldehyde- dicyandiamide adduct; 2-cyano-1-((4-oxo-1 ,3,5-triazinan-1-yl)methyl)guanidine, 1-((2-cy- anoguanidino)methyl)urea; 2-cyano-1-((2-cyanoguanidino)methyl)guanidine; 3,4-dimethyl pyra- zole phosphate; allylthiourea, and chlorate salts. Examples of envisaged urease inhibitors include N-(n-butyl) thiophosphoric acid triamide (NBPT, Agrotain), N-(n-propyl) thiophosphoric acid triamide (NPPT), 2-nitrophenyl phosphoric triamide (2-NPT), further NXPTs known to the skilled person, phenylphosphorodiamidate (PPD/PPDA), hydroquinone, ammonium thiosulfate, and mixtures of NBPT and NPPT (see e.g. US 8,075,659). Such mixtures of NBPT and NPPT may comprise NBPT in amounts of from 40 to 95% wt.-% and preferably of 60 to 80% wt.-% based on the total amount of active substances. Such mixtures are marketed as LIMUS, which is a composition comprising about 16.9 wt.-% NBPT and about 5.6 wt.-% NPPT and about 77.5 wt.-% of other ingredients including solvents and adjuvants.

In one embodiment, the further pesticides are selected from one or more of the group consisting of azole or oxadiazole pesticides. In one embodiment the agrochemical active is Mefentriflucon- azole or Flufenoxadiazam or a mixture thereof. In one embodiment, formulations of the invention contain the agrochemical actives Mefentrifluconazole and Flufenoxadiazam.

In one embodiment, the further pesticide is present in the form of suspended particles in the formulation. The particles may be characterized by their size distribution, which can be determined by dynamic light scattering techniques. Suitable dynamic light scattering measurement units are inter alia produced under the trade name Malvern Mastersizer 3000. The particles may be characterized by their median diameter, which is usually abbreviated as D50 value. The D50 value refers to a particular particle diameter, wherein half of the particle population by volume is smaller than this diameter. The D50 value is typically determined according to ISO 13320:2009.

The particles of further pesticides typically have an D50 value from 0.01 pm to 30 pm, preferably from 0.1 pm to 20 pm, more preferably from 0.5 to 20 pm, most preferably from 0.5 pm to 15 pm, especially preferably from 0.5 pm to 10 pm. The particles typically have an D50 value of at least 0.75 pm, preferably at least 1 pm. The suspended particles may be present in the form of crystalline or amorphous particles which are solid at 20°C.

Formulations of the invention comprise a polyalkylene oxide block copolymer. The block copolymer may be a diblock copolymer or a triblock copolymer, wherein the triblock copolymer is preferred. The blocks of the block polymer may be of the A-B or A-B-A type, where the A-B-A type is preferred. Typically, the block copolymer is a nonionic dispersant. The block copolymer is preferably an alkoxylate block copolymer, which preferably comprises blocks of polyethylene oxide and polypropylene oxide. The alkoxylate block copolymers comprise usually at least 20 wt%, preferably at least 30 wt% of polymerized ethylene oxide. In a preferred form the alkoxylate block copolymers comprise at least 10 wt%, preferably at least 15 wt% of polymerized ethylene oxide. The alkoxylate block copolymers are preferably a block polymer A- B-A type comprising blocks of polyethylene oxide (block "A") and polypropylene oxide (block "B"). The alkoxylate block copolymers are preferably terminated on both ends by hydroxyl groups.

Preferably, formulations of the invention comprise a block copolymer, wherein the polymer comprises blocks of polypropylene glycol and blocks of polyethylene glycol. Typically, the percentage of polyethylene glycol in the block copolymer is from 20 to 80%, preferably from 30 to 70%, most preferable from 40 to 60%. The ratio between the polypropylene glycol and polyethylene glycol may be determined by the NMR technique.

The molecular weight of the block copolymer may be from 1000 to 30000 g/mol, preferably from 1500 to 10000 g/mol, most preferable from 4000 to 8000 g/mol, as calculated from the hydroxy value. The hydroxy value may be determined by the method DIN EN ISO 4692-2.

Typically, the molecular weight of the propylene glycol block of the block copolymer is from 1000 to 20000 g/mol, preferably from 1000 to 8000 g/mol, most preferable from 2000 to 5000 g/mol, as calculated from the molecular weight of the block copolymer and the ratio between both blocks of polypropylene glycol and polyethylene glycol.

Typically, the block copolymer has a surface tension in a 1 g/L solution in water and at 23 °C from 10 to 70 nM/m, preferably from 20 to 60 nM/m, and most preferable from 30 to 50 nM/m. The surface tension may be determined by the method EN 14370, applying the Harkins-Jordan correction.

In one embodiment, formulations of the invention comprise a block copolymer with blocks of polypropylene glycol and blocks of polyethylene glycol of a ration from 40% to 60% and a molecular weight of the block polymer from 4000 to 8000 g/mol.

In one embodiment, formulations of the invention comprise a block copolymer with blocks of polypropylene glycol and blocks of polyethylene glycol and the percentage of polyethylene glycol ranges from 40% to 60%, and the molecular weight of the block polymer ranges from 4000 to 8000 g/mol and the surface tension of the block copolymer ranges from 30 to 50 nM/m. Typically, formulations of the invention comprise from 0.1 to 100 g/l, preferably from 1 to 50 g/l, and in particular from 5 to 20 g/l of polypropylene glycol and polyethylene glycol block copolymer.

Formulations of the invention comprise a hydroxybenzenesulfonic acid condensation product. Such condensation products are typically derived from both phenol and phenolsulfonic acid. When reference is made herein to a “phenolsulfonic acid” this shall mean a “hydroxybenzenesulfonic acid” or vice versa.

In one embodiment, formulations of the invention comprise a phenolsulfonic acid condensation product that is obtained by condensation with formaldehyde.

In one embodiment, the phenolsulfonic acid condensation product is the sodium salt of the polymer obtained through the condensation of phenolsulfonic acid with formaldehyde, urea and phenol. Typically, such phenolsulfonic acid condensation product comprises inorganic sodium salts such as sodium sulfate as impurities.

The phenolsulfonic acid condensates preferably have a mean molecular weight in the range from 500 to 1500 Da, more preferably from 600 to 1200 Da, determined by means of gel permeation chromatography. The proportion of condensates with molar masses above 10 000 Da is preferably less than 25% by weight, in particular less than 20% by weight, of the overall condensate.

The molar ratio of formaldehyde to phenolsulfonic acid is in the range from 1 :1 to 1 :2, preferably from 1 :1.3 to 1 :1.7.

Typically, formulations of the invention comprise from 0.5 to 200 g/l, preferably from 1 to 100 g/l, more preferably from 10 to 80 g/l and in particular from 30 to 70 g/l of hydroxybenzenesulfonic acid condensation product.

Formulations of the invention comprise a thickener. In one embodiment, the thickener is present in dispersed form in the aqueous phase. In another embodiment, the thickener may be present in the form of particles. Formulations of the invention typically comprise the thickener in a concentration of at least 0.1 wt%, preferably at least 0.5 wt% based on the liquid phase of the formulation. Formulations of the invention typically comprise the thickener in a concentration of up to 5 wt%, preferably up to 2 wt% based on the liquid phase of the formulation. In one embodiment, formulations of the invention comprise the thickener in a concentration range from 0.1 wt% to 10 wt%, preferably from 0.5 wt% to 5 wt%, more preferably from 0.8 wt% to 2 wt%, based on the liquid phase of the formulation. Formulations of the invention comprise a silica thickener, preferably from the group of precipitated silicas or fumed silica. In one embodiment the silica thickener is a precipitated silica. Precipitated silicas are typically produced by precipitation from a solution containing silicate salts, such as by the reaction of an alkaline silicate solution with a mineral acid. Preferably the precipitated silica particles are hydrophilic. Preferably the precipitated silica particles are not hydrophobized, for example by modification by treatment with a silane or a siloxane. Typically, such precipitated silicas thickeners include precipitated silica, aluminium and calcium silicates. In one embodiment the silica thickener is a fumed silica.

In one embodiment, the silica thickener contains silica particles with a specific surface area in the range from 50 to 500 m²/g, preferably from 100 to 350 m²/g, and in particular from 170 to 230 m²/g. In another form the inorganic thickener contains silica particles with specific surface area in the range from 50 to 600 m²/g, preferably from 140 to 450 m²/g, and in particular from 170 to 350 m²/g. In another form the silica thickener contains silica particles with specific surface area of at least 50 m²/g, preferably at least 80 m²/g, and in particular at least 120 m²/g. The specific surface area may refer to the BET surface area. The specific surface area (N₂), Multipoint, may be determined according to DIN ISO 9277.

Typically, formulations of the invention comprise from 0.1 to 100 g/l, preferably from 1 to 50 g/l, and in particular from 5 to 20 g/l of precipitated silica, aluminium and calcium silicates.

In general, a distinction is made in the case of particles between the primary and the secondary particle diameter. A plurality of smaller particles, having a primary diameter, may agglomerate to form a larger particle, having a secondary particle diameter. The secondary particle diameter can therefore often also be designated as agglomerate size. Typically, the inorganic thickener contains silica particles with a primary particle diameter in the range from 0.1 to 500 pm, preferably from 1 to 100 pm, in particular from 7 to 20 pm. The particle diameter, D50, is preferably determined by laser diffraction following ISO 13320-1.

Typically, the pH value of an aqueous dispersion of the silica particles is in the range from 3.5 to 8.5, preferably in the range from 5.5 to 7.5, and in particular in the range from 6 to 7. The specific pH value may be determined according to DIN ISO 787-9. The pH value is usually determined as a 5 wt% dispersion of the silica particles in water.

In one embodiment, formulations of the invention comprise a mixture of naphthalenesulfonic acid and a phenolsulfonic acid condensation product instead of or in combination with hydroxybenzenesulfonic acid condensation product. Formulations of the invention may comprise one naphthalene sulfonate. The term one naphthalene sulfonate shall include mono naphthalene sulfonates as well as condensation products of naphthalene sulfonates with formaldehyde. In each case, the naphthalene moieties may contain further substituents such as alkyl groups on the aromatic moiety.

In one embodiment said naphthalene sulfonate is 1-naphthalene sulfonate, 2-naphthalene sulfonate or a mixture thereof. In one embodiment, said naphthalene sulfonate is the condensation product of a naphthalene sulfonate with formaldehyde. In one embodiment, said condensation product of a naphthalene sulfonate with formaldehyde comprises a number average of 1.5 to 10, preferably 2 to 3 naphthalene moieties per molecule.

Typically, formulations of the invention comprise from 0.01 to 30 wt%, preferably from 1 to 25 wt%, and in particular from 10 to 20 wt% of the naphthalene sulfonate, based on the liquid phase of the formulation.

Formulations of the invention may contain a wide variety of auxiliaries. Suitable auxiliaries include solvents, liquid carriers, solid carriers or fillers, further surfactants different from block polymers, dispersants, emulsifiers, wetters (also referred as wetting agents), adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.

Suitable further surfactants include surface-active compounds different from a polyethylene oxide block copolymer b) and phenolsulfonic acid condensation product c), such as anionic, cationic, non-ionic and amphoteric surfactants, polyelectrolytes, block polymers other than block polymers with a molecular weight from 1000 to 30000 g/mol and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon’s, Vol.1 : Emulsifiers & Detergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

Suitable anionic surfactants include alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignin sulfonates, 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 alkyl naphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

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 which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. 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 sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.

Suitable cationic surfactants include quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines.

Suitable adjuvants include compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.

Suitable bactericides include bronopol and isothiazolinone derivatives such as alkylisothiazoli- nones and benzisothiazolinones. Suitable anti-freezing agents include ethylene glycol, propylene glycol, urea and glycerin. Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids. Suitable colorants (e.g. in red, blue, or green) include pigments of low watersolubility 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). Suitable tackifiers or binders include polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

Formulations of the inventions have typically a pH value of 3 or higher, preferably of 4 or higher, more preferably of 5 or higher, for example a pH of 3 to 12, 4 to 11 or 5 to 10.

In one embodiment, formulations of the invention comprise a) 10 to 600 g/l of a pesticide with a density of 2.5 g/cm³ or above and in form of particles, which are suspended in the aqueous phase, b) 0.1 to 100 g/l of a polyalkylene oxide block copolymer, c) 0.5 to 200 g/l of a phenolsulfonic acid condensation product, d) and 0.1 to 100 g/l of a silica thickener.

In one embodiment, formulations of the invention comprise a) 100 to 500 g/l of a pesticide with a density of 2.5 g/cm³ or above and in form of particles, which are suspended in the aqueous phase, b) 1 to 50 g/l of a polyalkylene oxide block copolymer, c) 1 to 100 g/l of a phenolsulfonic acid condensation product, d) and 1 to 50 g/l of a silica thickener.

In one embodiment, formulations of the invention comprise a) 200 to 400 g/l of a pesticide with a density of 2.5 g/cm³ or above and in form of particles, which are suspended in the aqueous phase, b) 5 to 20 g/l of a polyalkylene oxide block copolymer, c) 30 to 70 g/l of a phenolsulfonic acid condensation product, d) and 5 to 20 g/l of a silica thickener.

In one embodiment, formulations of the invention comprise a) 10 to 600 g/l of copper oxychloride in form of particles, which are suspended in the aqueous phase, b) 0.1 to 100 g/l of a polyalkylene oxide block copolymer, c) 0.5 to 200 g/l of a phenolsulfonic acid condensation product, d) and 0.1 to 100 g/l of a silica thickener.

In one embodiment, formulations of the invention comprise a) 100 to 500 g/l of copper oxychloride in form of particles, which are suspended in the aqueous phase, b) 1 to 50 g/l of a polyalkylene oxide block copolymer, c) 1 to 100 g/l of a phenolsulfonic acid condensation product, d) and 1 to 50 g/l of a silica thickener.

In one embodiment, formulations of the invention comprise a) 200 to 400 g/l of copper oxychloride in form of particles, which are suspended in the aqueous phase, b) 5 to 20 g/l of a polyalkylene oxide block copolymer, c) 30 to 70 g/l of a phenolsulfonic acid condensation product, d) and 5 to 20 g/l of a silica thickener.

In one embodiment, formulations of the invention comprise a) 200 to 400 g/l of copper oxychloride in form of particles, which are suspended in the aqueous phase, b) 5 to 20 g/l of a polyalkylene oxide block copolymer, c) 30 to 70 g/l of a phenolsulfonic acid condensation product, d) 5 to 20 g/l of a silica thickener, e) and 50 to 400 g/l of further pesticides.

In one embodiment, formulations of the invention comprise a) 200 to 400 g/l of copper oxychloride in form of particles, which are suspended in the aqueous phase, b) 5 to 20 g/l of a polyalkylene oxide block copolymer, c) 30 to 70 g/l of a phenolsulfonic acid condensation product, d) 5 to 20 g/l of a silica thickener, e) and 50 to 400 g/l of further pesticides, especially azole or oxadiazole pesticides.

In one embodiment, formulations of the invention comprise a) 200 to 400 g/l of copper oxychloride in form of particles, which are suspended in the aqueous phase, b) 5 to 20 g/l of a polyalkylene oxide block copolymer, c) 30 to 70 g/l of a phenolsulfonic acid condensation product, d) 5 to 20 g/l of a silica thickener, e) and 50 to 400 g/l of further pesticides, especially Flufenoxadiazam and Mefentri- fluconazole.

In one embodiment, formulations of the invention comprise a) 200 to 400 g/l of copper oxychloride in form of particles, which are suspended in the aqueous phase, b) 5 to 20 g/l of a polyalkylene oxide block copolymer, c) 30 to 70 g/l of a phenolsulfonic acid condensation product, d) 5 to 20 g/l of a silica thickener, e) and 50 to 100 g/l of further pesticides, especially Flufenoxadiazam and Mefentri- fluconazole.

The present invention also relates to the use of a combination of phenolsulfonic acid condensation products and silica thickeners for reducing sedimentation of solid particles having a density of at least 2.5 g/cm³ that are dispersed in a liquid formulation.

In one embodiment, the present invention relates to the use of a combination of phenolsulfonic acid condensation products and silica thickeners for reducing sedimentation of solid particles having a density of at least 2.5 g/cm³ that are dispersed in a liquid aqueous formulation

In one embodiment, the present invention relates to the use of a combination of phenolsulfonic acid condensation products and silica thickeners for reducing sedimentation of solid metal pesticide particles, especially copper pesticide particles having a density of at least 2.5 g/cm³ that are dispersed in a liquid aqueous formulation.

The inhibition of sedimentation of a formulation with a high density of the metal compounds can be measured by comparing a formulation to which a phenolsulfonic acid condensation product and a silica thickener has been added as compared to a formulation from the art. Typically the sedimentation of solid components in a liquid formulation is determined by visual inspection of the formulation after storage under varying conditions, for example after storage at 40°C for 4 weeks.

Another embodiment of the present invention are processes for making formulations of the invention. Typically, formulations of the invention prepared in a process wherein a pesticide with a density of 2.5 g/cm³ and above, a polyalkylene oxide block copolymer, a phenolsulfonic acid condensation product, a silica thickener and optionally one or more further pesticides are contacted. The contacting of the components can be done in any order.

In one embodiment, the solid particles are milled to obtain the desired particle size. In one embodiment, formulations of the invention diluted with water before application to obtain a spray liquid, also referred to as spray solution or tank mix.

The tank mix comprises the formulation at a concentration of from 1 to 99.9 wt%, preferably of from 5 to 99 wt%, more preferably of from 5 to 95 wt%, most preferably of from 20 to 80 wt% based on the total weight of the tank mix. The tank mix may comprise at least 30 wt% of thefor- mulation, preferably at least 50 wt%, more preferably at least 90 wt% of the formulation based on the total weigh of the tank mix. The tank mix typically comprises up to 99.9 wt% of the formulation based on the total weight of the tank mix, preferably up to 95 wt%, more preferably up to 90 wt%.

In one embodiment the formulation is mixed with fertilizers in the tank mix. Such fertilizers are typically inorganic and are used to control plant growth.

The weight ratio of the agrochemical suspension to the inorganic fertilizer in the tank mix may vary in broad ranges, such as from 100:1 to 1 :100, preferably from 98:2 to 2:98, most preferably from 95:1 to 1 :95.

The tank mix may be prepared by contacting the formulation, and the inorganic fertilizer, and optionally water in any suitable order. The contacting is typically achieved by mixing the components in a tank.

The tank mix may further contain auxiliaries as specified above for the agrochemical suspension. Typically, the tank mix may also contain further agrochemical actives.

The invention further relates to a method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein the agrochemical suspension or the tank mix is allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment.

Examples of suitable crop plants are cereals, for example wheat, rye, barley, triticale, oats or rice; beet, for example sugar or fodder beet; pome fruit, stone fruit and soft fruit, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, currants or gooseberries; legumes, for example beans, lentils, peas, lucerne or soybeans; oil crops, for example oilseed rape, mustard, olives, sunflowers, coconut, cacao, castor beans, oil palm, peanuts or soybeans; cucurbits, for example pumpkins/squash, cucumbers or melons; fiber crops, for example cotton, flax, hemp or jute; citrus fruit, for example oranges, lemons, grapefruit or tangerines; vegetable plants, for example spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, pumpkin/squash or capsicums; plants of the laurel family, for example avocados, cinnamon or camphor; energy crops and industrial feedstock crops, for example maize, soybeans, wheat, oilseed rape, sugar cane or oil palm; maize; tobacco; nuts; coffee; tea; bananas; wine (dessert grapes and grapes for vinification); hops; grass, for example turf; sweetleaf (Stevia rebaudania rubber plants and forest plants, for example flowers, shrubs, deciduous trees and coniferous trees, and propagation material, for example seeds, and harvested produce of these plants. Formulations of the inventions are preferably used in crop plants like soybean, cotton or wheat.

Solutions for seed treatment are in one embodiment employed for the purposes of treatment of plant propagation materials, particularly seeds. The compositions in question give, after two-to- tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying the agrochemical suspension, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and infurrow application methods of the propagation material. Preferably, the agrochemical suspension is applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.

When employed in plant protection, the amounts of agrochemical active applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.

In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of agrochemical active of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.

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

The user applies the agrochemical suspension or the tank mix according to the invention usually from a pre-dosage device, a knapsack sprayer, a drone, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical suspension is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical suspension according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.

According to one embodiment, individual components of the agrochemical suspension or the tank mix according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.

In a further embodiment, either individual components of the composition according to the invention or partially premixed components may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.

In a further embodiment, either individual components of the composition according to the invention or partially premixed components can be applied jointly (e.g. after tank mix) or consecutively.

Advantages of the present invention are, inter alia, that formulations of the invention have a high storage stability, even at elevated temperatures or under alternating temperatures. The advantages of present invention include that a high storage stability is achieved even at high pesticide loadings and despite the fact that one or more pesticides have a density above 2.5 g/cm³.

Further advantages are the particle size growth of dispersed agrochemical active substances, especially of pesticides with a density of 2.5 g/cm³ or above, is slowed down or suppressed the agglomeration of dispersed particles of agrochemical substances, especially of pesticides with a density of 2.5 g/cm³ or above, is slowed down or suppressed the settling of dispersed particles of agrochemical substances, especially of pesticides with a density of 2.5 g/cm³ or above, is slowed down or suppressed the abovementioned advantages are also attained in the presence of high salt concentrations formulations of the invention are compatible with a plurality of metal pesticides and further pesticides and other agrochemical actives formulations of the invention are easy and economical to make formulations of the invention have high biological activity formulations of the invention are environmentally friendly formulations of the invention suppress pesticidal resistance formulations of the invention are sustainable formulations of the invention are easy to use.

The examples which follow illustrate the invention without imposing any limitation. Materials used:

Pesticide 1 : Flufenoxadiazam

Pesticide 2: Mefentrifluconazole

Pesticide 3: Copper oxychloride

Compound 1 : 1 ,2-Benzisothiazolin-3-one (biocide)

Compound 2: Mixture-product of chlor-methyl-isothiazolinone and methyl-isothiazolinone (biocide)

Compound 3: Silicone Antifoam Emulsions

Compound 4: 1 ,2 propylene glycol (antifreeze)

Dispersant 1 : Naphthalene sulphonate condensate

Dispersant 2: Sodium alkyl naphthalene sulfonate blend

Dispersant 3: Phenolsulfonic acid condensation product with have a mean molecular weight in the range from 600 to 1200 Da

Dispersant 4: Polyethylene oxide and polypropylene oxide block copolymer comprising blocks of polypropylene glycol and blocks of polyethylene glycol with a content of polyethylene glycol in the molecule of 40% to 60%, a molecular weight of the block copolymer from 4000 to 8000 g/mol and a surface tension of the block copolymer from 30 to 50 nM/m

Dispersant 5: Polyethylene oxide and polypropylene oxide block copolymer comprising blocks of polypropylene glycol and blocks of polyethylene glycol with a content of polyethylene glycol in the molecule of 15 to 25%, a molecular weight of the block copolymer from 1500 to 2000 g/mol and a surface tension of the block copolymer from 35 to 45 nM/m.

Dispersant 6: Nonionic alkoxylate

Rheology modifier 1 : Xanthan gum

Rheology modifier 2: Precipitated silica, aluminium and calcium silicates, with a specific surface area of at least 120 m²/g and with a primary particle diameter in the range from 7 to 20 pm.

Rheology modifier 3: Magnesium aluminium silicate clay

1 : Screening of rheoloqv modifiers for lonq-term stability for SC1 to SC5

Formulations SC 1 to SC5 were prepared with following steps. First the dispersants were dissolved in water, then the pesticides were added, and the system was mixed in by stirring. Afterwards, a part (about half of the amount) of the rheology modifier and, components 1 -4 were added and were well mixed. The suspension was then milled with a basket mill till 80% of the particles were <2 pm. The particle size is measured with Mastersizer 3000. First the milling slurry was diluted with deionized water. When the diluted slurry achieved 5-15% light shading in Mastersizer 3000 measurement channel, particle size distribution was measured. The suspension was then sieved with a 150 pm filter. Finally, the other part of the rheology modifier was added and mixed. The amounts of the components are given in Table A. The „zero-shear viscosity" qp at „zero“ shear stress of the formulation should be „high“ for good long-term-storage stability regarding phase separation/sedimentation. On the other hand, the „in- finite-shear viscosity" r[°° at ..infinite" shear stress should be „low“ for good pourability/pumpability of the formulation. The measurement is conducted under shear-controlled conditions, preferably at 20°C, in a range of shear stresses from preferably 0.1 to 500 Pa over a time period of preferably 30 min. The „zero-shear viscosity" and the Jnfinite-shear viscosity" are read from a plot of shear viscosity [Pa s] against Shear stress [Pa], The samples were examined for height of serum Hs developed over storage. The total height of formulation Hf in the vials was measured. Serum percentage level = Hs/ Hf *100%. The testing results of shear viscosity at zero shear stress qp [Pa s] and the visual inspection of the phase separation are summarized in Table A.

Table A: Ingredients of SC1 to SC5 and screening of rheology modifiers for long-term stability a> According to the invention. Example 2: Biology efficacy of SC3 and SC4

In a field trial, samples show the biology efficacy of SC3 and SC4 on two different pests on crop plants.

Table B: Biology efficacy results of visual inspection of two pests on crop plants in comparison between SC3 and SC4. ^a> According to the invention.

Claims

1. A liquid formulation comprising a) a pesticide with a density above 2.5 g/cm³ and in form of particles, which are suspended in an aqueous phase, b) a polyalkylene oxide block copolymer, c) a phenolsulfonic acid condensation product, d) and a silica thickener.

2. The formulation according to claim 1 , wherein said pesticide with a density above

2.5 g/cm³ is a copper pesticide.

3. The formulation according to claim 2, wherein the copper pesticide is selected from the group consisting of copper oxychloride, copper ammonium carbonate, copper octanoate, copper oxide and copper hydroxide.

4. The formulation according to any of claims 1 to 3, wherein said formulation comprises one or more further pesticides different from said pesticide with a density above 2.5 g/cm³.

5. The formulation according to claim 4, wherein said further pesticide comprises an Oxadiazole.

6. The formulation according to any of claims 1 to 5, wherein said formulation comprises Flufenoxadiazam.

7. The formulation according to any of claims 1 to 6, wherein said formulation comprises Mefentrifluconazole.

8. The formulation according to any of claims 1 to 7, wherein said phenolsulfonic acid condensation product is a polymer with formaldehyde and urea.

9. The formulation according to claim 8, wherein said phenolsulfonic acid condensation product has a mean molecular range from 500 to 1500 Da.

10. The formulation according to any of claims 1 to 9, wherein said silica thickener has a mean particle-size D50 from 7 to 20 pm.

11. A method for the preparation of the formulation as defined in any of claims 1 to 10, where a pesticide with a density of 2.5 g/cm³ and above, a polyalkylene oxide block copolymer, a phenolsulfonic acid condensation product, a silica thickener and optionally one or more pesticides are mixed.

A non-therapeutic method for controlling phytopathogenic fungi and/or undesired plant growth and/or undesired attack by insects or mites and regulating the growth of plants, where the formulation as defined in claims 1 to 11 is allowed to act on the particular pests, their habitat or the plants to be protected from the particular pest, the soil and/or on undesired plants and/or the useful plants and/or their habitat. Use of a combination of phenolsulfonic acid condensation products, a polyalkylene oxide block copolymer and silica thickeners for reducing sedimentation of solid particles having a density of at least 2.5 g/cm³ that are dispersed in a liquid formulation.