WO2022248294A1 - Nouvelles formulations agrochimiques ayant une résistance à la pluie améliorée - Google Patents

Nouvelles formulations agrochimiques ayant une résistance à la pluie améliorée Download PDF

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Publication number
WO2022248294A1
WO2022248294A1 PCT/EP2022/063368 EP2022063368W WO2022248294A1 WO 2022248294 A1 WO2022248294 A1 WO 2022248294A1 EP 2022063368 W EP2022063368 W EP 2022063368W WO 2022248294 A1 WO2022248294 A1 WO 2022248294A1
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polyurethane
formulation
polymer
formulation according
formulations
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PCT/EP2022/063368
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English (en)
Inventor
Markus FIESS
Dieter Strobel
Christian Sowa
Simon Nord
Matthias Bratz
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Basf Se
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Priority to EP22729241.4A priority Critical patent/EP4346407A1/fr
Publication of WO2022248294A1 publication Critical patent/WO2022248294A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/02—Sulfur; Selenium; Tellurium; Compounds thereof

Definitions

  • the present invention is directed to agrochemical formulations comprising one or more pesti cides P and dispersed particles of a biodegradable polymer A, wherein polymer A has a glass transition temperature below 20 °C.
  • US20180332846 discloses agricultural spray composition, comprising a vinyl ester-based poly mer dispersion; a plasticizer; and an active.
  • US20110071228A1 discloses agricultural compositions comprising polyacrylate polymer disper sions.
  • the objective was achieved by agrochemical formulations comprising one or more pesticides P and dispersed particles of a biodegradable polymer A, wherein polymer A has a glass transition temperature below 20 °C.
  • the objective was achieved by agrochemical formulations comprising one or more pesticides P and a dispersion of a biodegradable polymer A, in particular of a biode gradable polyurethane dispersion PD, where said polyurethane dispersion PD comprises dis persed particles of a biodegradable polyurethane A.
  • the objective was achieved by agrochemical formulations comprising one or more pesticides P and dispersed particles of a polymer A, where polymer A is biodegradable.
  • the objective was achieved by agrochemical formulations comprising one or more pesticides P and dispersed particles of a polyurethane A, where polyurethane A is biodegrada ble.
  • polymer A in particular polyurethane A, has a glass transition tem perature below 20 °C.
  • polyurethane A has no melting point above 20°C or wherein polyurethane A has a melting point above 20 °C with an enthalpy of fusion lower than 10 J/g.
  • Formulations of the invention comprise one or more pesticides P.
  • pesticide refers to at least one active substance selected from the group of the fungi cides, insecticides, nematicides, herbicides, safeners, biopesticides and/or growth regulators.
  • Preferred pesticides P are fungicides, insecticides, herbicides and growth regulators.
  • In one em bodiment pesticides P are selected from fungicides, insecticides and herbicides.
  • Especially pre ferred pesticides P are fungicides. Mixtures of pesticides of two or more of the abovementioned classes may also be used.
  • Suitable insecti cides include 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, benzo- ylureas, diacylhydrazines, METI acarizides, and insecticides such as chloropicrin, pymetrozin, flonicamid, clofentezin, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorofenapyr, DNOC, buprofezine, cyroma
  • Suitable fungicides include fungicides from the clas ses of dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, ben- zenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, ben- zotriazines, benzyl carbamates, carbamates, carboxamides, carboxylic acid diamides, chloroni- triles cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy-(2-amino)pyrimidines, hydroxyanilides, imidazoles
  • Suitable herbicides include herbicides from the classes of the acetamides, amides, aryloxyphe- noxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dini- trophenol, diphenyl ether, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N- phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithi
  • Pesticides P are insoluble in water, meaning that pesticide P have a solubility in water of less than 10 g/l at 20 °C.
  • pesticides P have a solubility in water of less thanl g/l, and in particular less than 0.5 g/l, in each case at 20 °C.
  • pesticide P is a non-systemic fungicide. Such fungicides are sometimes also referred to as contact fungicides.
  • pesticide P is selected from captan, chloroneb, chlorothalonil, mancozeb, sulfur, copper oxy chloride, thiram, methiram, maneb, zineb, ametoctradin, mefentri- fluconazole, metyltetraprole, fluxapyroxad, flufenoxadiazam, epoxiconazole, pyraclostrobin or mixtures thereof.
  • pesticide P is selected from captan, chloroneb, chlorothalonil, mancozeb, sulfur, copper oxy chloride, thiram, methiram, maneb, zineb, ametoctradin or mix tures thereof.
  • Formulations of the invention normally comprise a pesticidally effective amount of a pesticide.
  • effective amount denotes an amount of the composition or of the pesticide, which is sufficient for controlling harmful pests on or around cultivated plants or in the protection of mate rials and which does not result in a substantial damage to the treated plants upon use and, if applicable after dilution with water. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific pesticide used.
  • Pesticides P are preferably present as solid particles.
  • the solid particles of pesticide P are dispersed in the formulation.
  • the solid particles of pesticide P have an average particle size d50 from 0.1 to 10 pm, preferably 0.2 pm to 5 pm and especially preferably 0.5 pm to 2.5 pm (as determined by laser diffraction according to ISO 1332).
  • formulations of the invention comprise 0.01 to 700 g/l of one or more pesti cides P.
  • formulations of the invention comprise 0.1 to 700 g/l of one or more pesti cides P.
  • formulations of the invention comprise 10 to 500 g/l of one or more pesti cides P.
  • formulations of the invention comprise 0.01 to 20 grams of one or more pesticides P, preferably 0.1 to 15 g/l.
  • Polymer A is preferably a polyurethane, herein referred to as polyurethane A.
  • Polyurethane A is a polymeric material comprising a polyurethane polymer.
  • polyurethane A comprises only one type of polyurethane and has a monomodal mass dis tribution.
  • polyurethane A comprises a mixture or two or more polyure thanes, resulting in a bimodal or oligomodal mass distribution of the polymer.
  • Polyurethane A is biodegradable.
  • Biodegradability is the ability of organic substances to be broken down by micro-organisms in the presence of oxygen (aerobic) to carbon dioxide, water, biomass and mineral salts or other elements that are present (mineralization).
  • Composting is the aerobic degradation of organic matter to make compost.
  • Home compost is the product of privately generated organic waste, such as food, garden and paper product waste, which has been subjected to composting, and which product is applied to private property soils.
  • Biodegradable when used in this application, shall mean that a polymeric material is “biode gradable” according to at least one of the methods defined by the European Chemicals Agency (ECHA) in the “Background Document to RAC and SEAC Opinions on Intentionally Added Mi croplastics” of 11 June 2020, section 2.2.1.6, table 22.
  • ECHA European Chemicals Agency
  • polyurethane A is biodegradable in the sense that the carbon of the mate rial is mineralized to CO2 by 90% (absolute or relative to the degradation of micro-crystalline cel lulose powder) within 24 months in soil at 25 °C, as determined according to EN ISO 17556:2019.
  • polyurethane A is biodegradable in the sense that the carbon of a film of polyurethane A decomposes under home composting conditions to more than 90% by weight into C02 within 360 days, as determined by aerobic degradation according to ISO 14855-1 (2012) in a controlled composting test but at ambient temperature (25 ⁇ 5 °C) to simulate home composting conditions instead of the prescribed temperature of 58 °C, typical to simulate com posting conditions in industrial composting facilities.
  • Polyurethane A is biodegradable and has a glass transition temperature below 20 °C.
  • Glass transition temperatures are determined by Differential Scanning Calorimetry (ASTM D 3418-08, ’’midpoint temperature” of second heating curve, heating rate 20 K/min).
  • polyurethane A is characterized in that either it has no melting point above 20°C or in that polyurethane A has a melting point above 20 °C with an enthalpy of fusion lower than 10 J/g.
  • polyurethane A is composed of (a) at least one diisocyanate,
  • polyurethane A is composed of
  • polyurethane A has a glass transition temperature below 20 °C, characterized in that the polyurethane either has no melting point above 20°C or wherein polyurethane A has a melting point above 20 °C with an enthalpy of fusion lower than 10 J/g.
  • At least 60 % by weight of polyurethane A is composed of
  • At least 80 % by weight of the polyurethane A is composed of at least one aliphatic polyesterdiol (b).
  • At least 80 % by weight of the at least one polyesterdiol (b) is composed of at least one aliphatic dicarboxylic acid and of at least one aliphatic diol.
  • polyesterdiol (b) is made of at least 10 mol%, preferably at least 20 mol% based on the sum of diols used for making the polyesterdiol of branched aliphatic diols, prefera bly neopentyl glycol.
  • At least 60 wt% of polyurethane A is composed of a) at least one diisocyanate, b) at least one diol, where, of these, bi ) from 10 to 100 mol%, based on the total amount of the diols (b), are polyester- diols with a molar mass of from 500 to 5000 g/mol, b2 ) from 0 to 90 mol%, based on the total amount of the diols (b), have a molar mass of from 60 to 500 g/mol, c) at least one bifunctional carboxylic acid selected from dihydroxycarboxylic acids and diaminocarboxylic acids, d) optionally other polyfunctional compounds which differ from the monomers (a) to (c) and which have reactive groups, where these are alcoholic hydroxy groups, primary or secondary amino groups, or isocyanate groups, and e) optionally monofunctional compounds which differ from the monomers (a) to (d) and which have a reactive group
  • the dispersed particles of polymer A preferably polyurethane A
  • polymer A especially polyurethane A
  • formulations of the invention in amounts of 5 to 500 gram per liter, preferably 20 to 200 g/l.
  • Such formulations are also referred to as “concentrated formulations” comprising the polyurethane A as built-in rain fastness additive.
  • formulations of the invention comprise 5 to 500 g/l of polyurethane A, more preferably 20 to 200 g/l of polyurethane A.
  • polymer A especially polyurethane A
  • formulations of the invention in amounts of 0.02 to 20 gram per liter, preferably 0.1 to 10 g/l.
  • Such formulations are also referred to as “diluted formulations” comprising the polyurethane A as spray solution rain fastness additive.
  • Formulations of the invention typically contain one or more aqueous solvents S.
  • aqueous as used herein in the context of formulations or aqueous solvents means that a homogenous solvent mixture contains at least 50 wt%, preferably at least 70 wt%, more preferably at least 90 wt%, especially preferably at least 95 wt% and particularly preferably at least 99 wt% of water.
  • solvent S consists of water.
  • formulations of the invention are concentrated aqueous formulations that contain pesticide P as dispersed solid particles in an amount of 0.1 to 700 g/l as well as polyure thane A in an amount of 5 to 500 g/l.
  • pesticide P as dispersed solid particles in an amount of 0.1 to 700 g/l as well as polyure thane A in an amount of 5 to 500 g/l.
  • Such concentrated formulations can be diluted with water and then applied in the field.
  • Typical examples of such formulations are suspension concen trates (SC), and a suspoemulsions (SE).
  • formulations of the invention comprise
  • formulations of the invention comprise
  • formulations of the invention comprise
  • Such agrochemical formulations are often prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, Lon don, 2005.
  • the farmer dilutes concentrated pesticide formulations prior to the applica tion on the crop to obtain the “spray solution”.
  • Such spray solutions typically comprise pesticides P in an amount of 0.01 to 20 grams of pesticides P per liter, preferably 0.1 to 15 g/l.
  • Such spray solutions are herein also referred to as diluted formulations or diluted mixtures.
  • the farmer adds 50-200 liter of water to 0.5-5.0 liter of the concentrated formulation to obtain the spray solution.
  • such spray solutions are prepared and applied such that 40 to 2000 grams of pesticide are applied per hectare, preferably 50 to 1000 g/ha.
  • such spray solution is obtained by diluting a concentrated pesticide formu lation that also contains polymer A, especially polyurethane A, in the concentrated formulation with water (“built-in adjuvant”).
  • such spray solution is obtained by mixing a concentrated pesticide formula tion (that typically does not comprise polymer A), a polymer dispersion PD, especially polyure thane dispersion PD, and water.
  • a concentrated pesticide formula tion that typically does not comprise polymer A
  • a polymer dispersion PD especially polyure thane dispersion PD
  • water water
  • the concentrated pesticide formula tion and polymer A are added to the spray solution as different components.
  • polymer A, especially polyurethane A, and concentrated formulation are only mixed at the spray solution stage, the nature of the agrochemical formulation is in principle not decisive.
  • pesticide P is present in the spray solution in particulate, suspended form.
  • solid particles of pesticide P are formed during or after application on the crop.
  • the concentrated formulations of pesticides P that are used to prepare such di luted formulations of the invention can be aqueous or non-aqueous.
  • such diluted formulations according to the invention are obtained by adding polymer A, especially polyurethane A, preferably as an aqueous polyurethane dispersion PD, to such di luted aqueous formulation of pesticides P.
  • formulations of the invention are obtained by mixing 5 to 1000 g, preferably 20 to 200 g of polymer A, especially polyurethane A, as a polymer dispersion PD, especially polyurethane dispersion PD, 0.5 to 5.0 liter of a concentrated pesticide formulation and 50 to 300 liter of water.
  • the resulting spray solution is typically suitable to be sprayed on 1 hectare of agricultural land.
  • the concentrated pesticide formulation therefore can be for example be a sus pension concentrate (SC), suspoemulsion (SE), emulsifiable concentrate (EC), dispersable con centrate (DC), oil dispersion (OD), soluble liquid (SL), oil in water emulsion (EW), capsule sus pension (CS), wettable granule (WG) or wettable powder (WP).
  • SC sus pension concentrate
  • SE suspoemulsion
  • EC emulsifiable concentrate
  • DC dispersable con centrate
  • OD oil dispersion
  • SL oil in water emulsion
  • EW capsule sus pension
  • WG wettable granule
  • WP wettable powder
  • formulations of the invention comprise
  • formulations of the invention comprise
  • formulations of the invention comprise
  • formulations of the invention comprise
  • Formulations of the invention may comprise auxiliaries as they customarily used in agrochemi cal formulations.
  • auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, further adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, col orants and tackifiers.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil frac tions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkyl ated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; gly cols; DMSO; ketones, e.g. cyclohexanone; esters, e.g.
  • mineral oil frac tions of medium to high boiling point e.g. kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e. g. toluene, paraffin, tetrahydronaphthal
  • lactates carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, lime stone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammo nium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • mineral earths e.g. silicates, silica gels, talc, kaolins, lime stone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharide powders e.g.
  • 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 emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective col loid, or adjuvant. Examples of surfactants are listed in McCutcheon’s, Vol.1 : Emulsifiers & De tergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • 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 con densed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, 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 are alkoxylate surfactants, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylate surfactants are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equiva lents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
  • polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or poly- ethyleneamines.
  • Suitable further adjuvants are compounds, which have a neglectable or even no pesticidal ac tivity themselves, and which improve the biological performance of the pesticide 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 thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazoli- nones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants are pigments of low water solubility and water- soluble dyes.
  • examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
  • the agrochemical compositions typically comprise between 0.01 and 95 wt%, preferably be tween 0.1 and 90 wt%, and most preferably between 0.5 and 75 wt% of pesticide, based on the composition.
  • Another aspect of the present invention are processes for making agrochemical formulations comprising mixing of at least one pesticide P, at least one aqueous solvent and optionally formulation auxiliaries with a polymer dispersion PD, especially polyurethane dispersion PD, said polymer dispersion PD, especially polyurethane dispersion PD, being an aqueous disper sion of polymer A, especially polyurethane A.
  • Another aspect of the present invention are agrochemical formulations obtainable by processes that comprise mixing of at least one pesticide P, at least one aqueous solvent and optionally for mulation auxiliaries with a polymer dispersion PD, said polymer dispersion PD being an aque ous dispersion of polymer A.
  • Another aspect of the present invention are agrochemical formulations obtainable by processes that comprise mixing of at least one pesticide P, at least one aqueous solvent and optionally for mulation auxiliaries with a polyurethane dispersion PD, said polyurethane dispersion PD being an aqueous dispersion of polyurethane A.
  • polyurethane dispersions PD are secondary dispersions that are obtained by dispersing a readily obtained polyurethane in water.
  • a solution of a polyurethane A in a non-aqueous solvent e.g. acetone, is mixed with water and from the resulting mixture, the non-aqueous solvent is removed by distillation.
  • polyu rethane A is precipitated from a solution in an organic solvent by addition of water.
  • Polymer dispersions PD especially polyurethane dispersions PD, typically contain dispersed polymer particles having an average particle size d90 of 20 nm to 1000 nm, preferably of 40 nm to 500 nm. (as determined by ultracentrifugation).
  • polymer dispersions PD especially polyurethane dispersions PD, have a solid con tent of 5 wt% to 45 wt %, preferably 10 to 40 wt%.
  • Formulations of the invention or prepared according to processes of the invention are suitable for agrochemical application. They are especially suitable for crop protection applications. In particular, they are suitable for foliar crop protection applications.
  • 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 ap ples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, currants or goose berries; 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 tange rines; vegetable plants, for example spinach, lettuce, asparagus, cabbages, carrots, onions, to matoes, potatoes, pumpkin/squash or capsicums; plants of the laurel family, for example
  • Another aspect of the present invention are methods 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 formulations of the invention are 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.
  • these methods of the invention comprise the following steps:
  • these methods of the invention comprise the following steps:
  • step B Preparing a mixture of the agrochemical formulation of step A with a polymer dispersion PD, especially a polyurethane dispersion PD, and water.
  • step B Allowing the formulation obtained in step B to act on the respective pests, their environ ment 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.
  • these methods of the invention comprise the following steps:
  • step B adding a polyurethane dispersion PD containing polyurethane A to the formulation of step A,
  • step D Allowing the formulation obtained in step C to act on the respective pests, their environ ment 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. It is possible that step A (providing an agrochemical formulation comprising one or more pesti cides P) and step B (adding a polyurethane dispersion PD containing polyurethane A) are com bined in step.
  • the invention related to a method for producing the formulation of the inven tion which comprises mixing one or more pesticide P, at least one aqueous solvent and option ally formulation auxiliaries with a polymer dispersion PD, said polymer dispersion PD being an aqueous dispersion of polymer A.
  • the invention related to a method for producing the formulation of the inven tion which comprises mixing one or more pesticide P, at least one aqueous solvent and option ally formulation auxiliaries with a polyurethane dispersion PD, said polyurethane dispersion PD being an aqueous dispersion of polyurethane A.
  • these methods of the invention comprise the following steps:
  • step C adding a polyurethane dispersion containing polyurethane A to the aqueous, diluted mix ture obtained in step B,
  • step C Allowing the formulation obtained in step C to act on the respective pests, their environ ment 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.
  • the dilution of an agrochemical formulation with water in steps B and C is also referred to as the preparation of a spray solution.
  • Another aspect of the present invention is the use of polyurethanes A in agrochemical applica tions, where polyurethane A is biodegradable and has a glass transition temperature below 20 °C.
  • Another aspect of the present invention is the use of polyurethanes A in agrochemical applica tions, where polymer A is biodegradable and has a glass transition temperature below 20 °C.
  • polyurethanes A are used in crop protection applications- In one embodiment, polyurethanes A are used in foliar applications of agrochemical formula tions.
  • polyurethanes A are used for improving the rain fastness of pesticides.
  • polyurethane dispersion PD is an aqueous dispersion of polyurethane A, in agrochemical applica tions.
  • polyurethane dispersions PD are used in crop protection applications- In one embodiment, polyurethane dispersions PD are used in foliar applications of agrochemical formulations. In one embodiment, polyurethane dispersions PD are used for improving the rain fastness of pesticides.
  • Formulations of the invention are easy and economical to make.
  • Formulations of the invention have a high efficacy in controlling pests.
  • Formulations of the invention show high rain fastness.
  • Formulations of the invention are environmentally friendly. Formulations of the invention are bio degradable.
  • Polyurethanes A and polyurethane dispersions PD increase the efficacy of agricultural formula tions for controlling pests.
  • Polyurethanes A and polyurethane dispersions PD increase the rain fastness of agricultural for mulations while maintaining the biodegradability of the formulations.
  • Glass transition temperatures are determined by Differential Scanning Calorimetry (ASTM D 3418-08, ’’midpoint temperature” of second heating curve, heating rate 20 K/min).
  • the biodegradability was determined by determining the amount of carbon of the polymer that was mineralized to CO2 (absolute or relative to the degradation of micro-crystalline cellulose powder) within 24 months in soil at 25 °C according to EN ISO 17556:2019.
  • the amount of mineralized carbon needs to be at least 90 %.
  • Formulation F1 formulation comprising 600 g/l of sulfur as dispersed particles dispersed in wa ter, average particle size d50: 2 pm (determined by laser diffraction),
  • the mixture is neutralized with 125.4 g of a 5% strength of aque ous sodium hydroxide solution and the mixture is dispersed using 1201 g of deionized water.
  • a solution of 9.08 g diethylenetriamine (DETA) in 110 g deionized water is added dropwise in 10 min.
  • the mixture is diluted with 127 g water and the acetone is removed by distillation in vacuo, and solids content is adjusted to 30%.
  • Example 4 10 droplets with a volume of 1 pl_ each of a spray solution containing 4 liter of Formulation F1, 200 liters of water and 300 g of Polyurethane Dispersion A were deposited on wheat leaves. 3 replicates of wheat leaves applied with 10 droplets each were prepared. All droplets of spray so lution stayed spatially separated on the wheat leaves during drying due to poor spreading of the spray solution on the wheat leaf surface. The total mass of applied sulfur was calculated from the total volume of applied spray solution and the concentration of sulfur in the spray solution. The dried spray solution was clearly visible for the naked eye due to the content of sulfur in the spray solution.

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention concerne une formulation agrochimique comprenant un ou plusieurs pesticides P et des particules dispersées d'un polymère biodégradable A, le polymère A ayant une température de transition vitreuse inférieure à 20° C.
PCT/EP2022/063368 2021-05-28 2022-05-18 Nouvelles formulations agrochimiques ayant une résistance à la pluie améliorée WO2022248294A1 (fr)

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Citations (4)

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US20110071228A1 (en) 2008-05-21 2011-03-24 Bayer Cropscience Ag Insecticidal formulations with improved long-term effect on surfaces
WO2012121413A1 (fr) * 2011-03-08 2012-09-13 Sumitomo Chemical Company, Limited Composition pesticide
WO2016091801A1 (fr) * 2014-12-09 2016-06-16 Basf Se Dispersion aqueuse de pesticide et de particules polymères contenant un tensioactif copolymérisable
US20180332846A1 (en) 2015-03-09 2018-11-22 Celanese International Corporation Agricultural adjuvants and processes for making and using same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110071228A1 (en) 2008-05-21 2011-03-24 Bayer Cropscience Ag Insecticidal formulations with improved long-term effect on surfaces
WO2012121413A1 (fr) * 2011-03-08 2012-09-13 Sumitomo Chemical Company, Limited Composition pesticide
WO2016091801A1 (fr) * 2014-12-09 2016-06-16 Basf Se Dispersion aqueuse de pesticide et de particules polymères contenant un tensioactif copolymérisable
US20180332846A1 (en) 2015-03-09 2018-11-22 Celanese International Corporation Agricultural adjuvants and processes for making and using same

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"Pesticide Manual", 2013, BRITISH CROP PROTECTION COUNCIL
BACKGROUND DOCUMENT TO RAC AND SEAC OPINIONS ON INTENTIONALLY ADDED MI-CROPLASTICS, 11 June 2020 (2020-06-11)
COTTERILL J V ET AL: "Improving the persistence of a formulation of the avian repellent cinnamamide, for the protection of autumn-sown oilseed rape", PEST MANAGEMENT SCIENCE, PUBLISHED FOR SCI BY WILEY, vol. 60, no. 10, 1 October 2004 (2004-10-01), pages 1019 - 1024, XP002432280, ISSN: 1526-498X, DOI: 10.1002/PS.911 *
KNOWLES: "New developments in crop protection product formulation", AGROW REPORTS DS243, T&F INFORMA, 2005
MCCUTCHEON: "Emulsifiers & Detergents, McCutcheon's Directories", 2008, GLEN ROCK
MOLLETGRUBEMANN: "Formulation technology", 2001, WILEY VCH, WEINHEIM
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ZHENG FENG ET AL: "Novel strategy with an eco-friendly polyurethane system to improve rainfastness of tea saponin for highly efficient rice blast control", JOURNAL OF CLEANER PRODUCTION, ELSEVIER, AMSTERDAM, NL, vol. 264, 16 April 2020 (2020-04-16), XP086164594, ISSN: 0959-6526, [retrieved on 20200416], DOI: 10.1016/J.JCLEPRO.2020.121685 *

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AR125995A1 (es) 2023-08-30
EP4346407A1 (fr) 2024-04-10

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