EP2378869A2 - Dispersion aqueuse contenant des particules de pesticides et un saccharide en solution - Google Patents

Dispersion aqueuse contenant des particules de pesticides et un saccharide en solution

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Publication number
EP2378869A2
EP2378869A2 EP09795382A EP09795382A EP2378869A2 EP 2378869 A2 EP2378869 A2 EP 2378869A2 EP 09795382 A EP09795382 A EP 09795382A EP 09795382 A EP09795382 A EP 09795382A EP 2378869 A2 EP2378869 A2 EP 2378869A2
Authority
EP
European Patent Office
Prior art keywords
dispersion
saccharide
pesticide
disaccharide
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09795382A
Other languages
German (de)
English (en)
Inventor
Sebastian Koltzenburg
Andreas Bauder
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP09795382A priority Critical patent/EP2378869A2/fr
Publication of EP2378869A2 publication Critical patent/EP2378869A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • A01N25/02—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 liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof

Definitions

  • Aqueous dispersion comprising pesticide particles and dissolved saccharide
  • the present invention relates to an aqueous dispersion comprising solid pesticide particles having a particle size of less than 10 ⁇ m and a saccharide dissolved in the aqueous phase. Furthermore, the invention relates to a process for preparing a dispersion according to the invention by bringing into contact a pesticide and a saccharide which is a monosaccharide, a disaccharide or a mixture of mono- and disaccharide.
  • a further subject matter relates to the use of a saccharide for slowing down the particle growth of pesticide particles having a particle size of up to 10 ⁇ m in aqueous dispersion, the use of the dispersion or the solid composition for controlling phytopathogenic fungi and / or undesired plant growth and / or or undesired insect or mite infestation and / or for regulating the growth of plants, by applying the dispersion or the solid composition to the respective pests, their habitat and / or the plants to be protected from the respective pest, the soil and / or and the use of the dispersion or the solid composition for controlling unwanted insect or mite infestation on plants and / or for controlling phytopathogenic fungi and / or for controlling unwanted plant growth by ma n seeds of crops treated with the dispersion or the solid composition.
  • the present invention also relates to seed treated with the dispersion or the solid composition. Combinations of preferred features with other preferred features are encompassed by the present invention.
  • Typical stabilizers are low molecular weight surfactants or oligomers. But also higher molecular aids such as colloids and amphiphilic polymers give the ability to stabilize drug particles in a smaller dimension. Similarly, finely divided dispersions can be stabilized by the addition of extremely poorly water-soluble substances such as hexadecane osmotically against Ostwaldreifung.
  • US Pat. No. 6,426,028 B1 discloses an aqueous suspension of a microencapsulated pesticide, wherein the suspension may contain from 3 to 30% by weight of a monosaccharide.
  • WO 2004/047516 discloses an aqueous seed treatment composition which may contain fertilizers, binders and 0 to 25% by weight of sugar. In addition to the water-soluble fertilizer, a pesticide may be added.
  • EP 0 031 454 discloses a liquid fungicidal formulation in which dimethylformamide and / or N-methylpyrrolidone are used as the solvent, and stabilizing additives of from 1 to 40% by weight of saccharides.
  • Aqueous dispersions comprising pesticide particles having a particle size of less than 10 microns and a saccharide dissolved in the aqueous phase are well known:
  • WO 2005/046328 discloses active substance formulations comprising at least one active substance and at least one random copolymer prepared by free-radical polymerization and composed of selected monomers.
  • the particle diameter of the pesticide is less than 1 ⁇ m.
  • the formulation may contain, as plasticizer, glucose or sucrose.
  • WO 1997/13503 discloses a method of producing nanoparticles comprising combining an agent, e.g. As pesticide, with a matrix material, for. B. sucrose and spray-drying the mixture of solution.
  • an agent e.g. As pesticide
  • a matrix material for. B. sucrose
  • a disadvantage of the prior art is, inter alia, that complex synthesized polymers must be added, or that the particle formation process takes place during the drying process and therefore is difficult to control.
  • the object of the present invention was to find new possibilities for the stable formulation of pesticide particles having a particle size of less than 10 ⁇ m.
  • the method should make do with cheap, readily available resources that are also good for the environment.
  • aqueous dispersion comprising solid pesticide particles with a particle size of less than 10 ⁇ m and a solution dissolved in the aqueous phase.
  • saccharide wherein the saccharide is a monosaccharide, a disaccharide or a mixture of mono- and disaccharide, and the total content of mono- and disaccharide is at least 15% by weight based on the aqueous dispersion, wherein the pesticide is insoluble in water and wherein the pesticide particles are amorphous.
  • An aqueous dispersion usually comprises water as the continuous phase and solid or liquid particles as the disperse phase.
  • the dispersion is preferably a suspension whose disperse phase comprises solid particles.
  • the dispersion contains at least 5% by weight, preferably at least 15% by weight, particularly preferably at least 20% by weight of water.
  • the dispersion contains from 1 to 85% by weight, preferably from 5 to 80% by weight, particularly preferably from 10 to 60% by weight, of water.
  • the dispersion of the invention typically has a viscosity of at least 100 mPas, preferably at least 200, more preferably at least 300 mPas, and especially at least 500 mPas at 20 0 C.
  • the viscosity is usually at most 10,000 mPas, preferably not more than 5000 mPas and particularly not more than 2000 mPas at 20 ° C.
  • the viscosity can be determined according to Brookfield.
  • the pesticide particles usually comprise at least 80% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight and in particular at least 99% by weight of solid pesticide.
  • the pesticide particles are pesticide.
  • the pesticide particles are usually free of a polymeric coating layer.
  • Polymeric shell layers contain, for example, polymers such as polyurethane, polyamide, polyacrylate, melamine, gelatin, albumin, chitosan, urea-formaldehyde resins, melamine-formaldehyde resins. These polymers encapsulate the pesticide with a polymeric layer.
  • the particle size of the pesticide particles usually denotes the number average particle size. It is less than 10 microns, preferably less than 2 microns, more preferably less than 1 micron.
  • the particle size is usually above 5 nm, preferably above 20 nm, particularly preferably above 50 nm.
  • the particle size is usually determined by means of photon correlation spectroscopy (dynamic light scattering), for example using a device of the Brookhoven Instruments BI90 brand.
  • the sample preparation for example the dilution to measurement concentration, depends among other things on the fineness and concentration of the active ingredients in the dispersion sample and on the measuring instrument used in this measurement method. The procedure must be worked out for the respective system and is known to the person skilled in the art.
  • the solid pesticide particles can be amorphous.
  • Amorphous means that the molecular building blocks of a homogeneous solid are not arranged in crystal lattices.
  • Amorphous drug particles means that the particles are largely free of crystalline
  • Active ingredient wherein preferably from 80 to 100 wt.%, In particular from 90 to 100 % By weight of the material amorphous.
  • Amorphous forms can be distinguished from crystalline forms by various methods, such as microscopic examination in polarized light, differential scanning calorimetry (DSC), X-ray diffraction, or solubility comparisons, preferably by DSC.
  • the saccharide is a monosaccharide, a disaccharide or a mixture of mono- and disaccharide. This means that at least one monosaccharide, at least one disaccharide or a mixture of at least one mono- and at least one disaccharide can be present.
  • the saccharide is preferably a disaccacharide, in particular sucrose.
  • Suitable monosaccharides are, for example, pentoses and pentuloses, as well as the hexoses and hexuloses.
  • Suitable pentoses are, for. B. d-ribose, d-xylose and i-arabinose.
  • Suitable hexoses are, for example, d-glucose, d-mannose and d-galactose.
  • Suitable hexuloses are e.g. d-fructose and sorbose.
  • Other suitable monosaccharides are e.g. the 6-deoxy sugars, such as I-fucose and I-rhamnose. Mixtures of the above monosaccharides are also suitable.
  • Preferred monosaccharides are d-glucose and d-fructose.
  • Suitable disaccharides are, for example, sucrose, maltose, lactose, trehalose, cellobiose, gentiobiose, isomaltose, lactulose, maltulose, melibiose, neohesperidosis, neotrehalose, nigerose, palatinose, rutinose, sophorose, or mixtures of the above disaccharides.
  • Preferred disaccharides are sucrose, maltose and lactose, especially sucrose.
  • Suitable mixtures of mono- and disaccharides are, for example, mixtures of the abovementioned monosaccharides and disaccharides.
  • the total content of mono- and disaccharide in the aqueous dispersion is at least 15% by weight, preferably at least 20% by weight, particularly preferably at least 25% by weight, based on the aqueous dispersion.
  • the total content is usually at most 90% by weight, preferably at most 70% by weight, particularly preferably at most 60% by weight, based on the aqueous dispersion.
  • pesticide denotes at least one active ingredient selected from the group of fungicides, insecticides, nematicides, herbicides, safeners and / or growth regulators.
  • Preferred pesticides are fungicides, insecticides and herbicides.
  • mixtures of pesticides of two or more of the above classes may be used.
  • the person skilled in the art is familiar with such pesticides which are described, for example, in Pesticides Manual, 14th Ed. (2006), The British Crop Protection Council, London.
  • Suitable insecticides are insecticides of the class of carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosines, A-vermectins, milbemycins, juvenile hormone analogs, alkylhalides, organotin compounds, nereistoxin analogs, benzoylureas, diacylhydrazines, METI antibodies.
  • insecticides such as chloropicrin, pymetrozine, flonicamide, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnone, acequinocyl, fluacrypyrim, rotenone, or their derivatives.
  • insecticides such as chloropicrin, pymetrozine, flonicamide, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnone, acequinocyl, fluacrypyrim, rotenone, or their derivatives.
  • Suitable fungicides are fungicides of the classes dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzylcarbamates, carbamates, carboxamides, carboxylic acid amides, chloronitriles, cyanoacetamide oximes, cyanoimidazoles , Cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenylcrotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy (2-amino) pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorgan
  • Suitable herbicides are herbicides of the classes of acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ethers, glycines, imidazolinones, isoxazoles, isoxazolidinones , Nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates,
  • Suitable insoluble pesticides are those which at 20 ° C. in water have at most 3% by weight, preferably at most 1% by weight, more preferably at most 0.1% by weight and very particularly at most 0.01 % are soluble.
  • suitable insoluble pesticides are (solubility in water at 20 ° C. in each case in brackets) pyraclostrobin (1.9 mg / l), epoxiconazole (66 mg / l), prochloraz (34 mg / l), preferably pyraclostrobin.
  • the pesticides used are often solids at 20 ° C.
  • the melting point of the active compounds is preferably at least 30 ° C. and preferably at least 40 ° C.
  • the invention also relates to a process for the preparation of the dispersion according to the invention by bringing into contact a pesticide and a saccharide which is a monosaccharide, a disaccharide or a mixture of mono- and disaccharide.
  • the dispersed pesticide may be brought into contact with the saccharide or dispersed after contacting the drug and saccharide.
  • Suitable methods are, for example, precipitation methods, emulsification methods, evacuation methods, melt emulsification or milling methods, preferably precipitation methods.
  • the pesticide and the saccharide are contacted and dispersed in an aqueous system.
  • the saccharide is particularly preferably used in aqueous solution.
  • Suitable pesticides are the pesticides described above.
  • the pesticide is insoluble in water.
  • Suitable saccharides are the previously described saccharides.
  • the saccharide is sucrose.
  • Particularly preferred processes are carried out by dissolving the saccharide in aqueous solution, dissolving the pesticide in a water-miscible organic solvent, and turbulently mixing the solutions of the saccharide and the pesticide (precipitation method); the pesticide is dissolved in a water-immiscible organic solvent, mixed turbulently with an aqueous solution of the saccharide, and optionally the organic solvent is removed (emulsification process, optionally with evaporation); a melt containing molten pesticide in an aqueous solution containing the saccharide mixed and cooled (melt emulsification); or the pesticide is milled in the presence of the saccharide (milling method).
  • a method is to bring the saccharide into aqueous solution, dissolve the pesticide in a water-miscible organic solvent, and turbulently mix the solutions of the saccharide and the pesticide (precipitation method).
  • the solution of a pesticide in a water-miscible organic solvent usually contains a water-miscible organic solvent.
  • Miscible with water in this context means that the organic solvents are miscible with water at 20 ° C. without phase separation to at least 10% by weight, preferably to 15% by weight, particularly preferably to 20% by weight.
  • the solution can be optimally Onal further formulation aids include, for example, dispersants.
  • the solution can be prepared at elevated temperature as needed.
  • Suitable solvents are C 1 -C 6 -alkyl alcohols, such as methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol, tert-butanol, esters, ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, acetals, ethers, cyclic ethers, such as Tetrahydrofuran, aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, N-substituted or N, N-disubstituted carboxylic acid amides such as acetamide, carboxylic acid esters such as ethyl acetate and lactones such as butyrolactone, dimethylformamide (DMF) and dimethylpropionamide, aliphatic and aromatic chlorinated hydrocarbons such as methylene chloride , Chlor
  • Preferred solvents are glycols, methanol, ethanol, isopropanol, dimethylformamide, N-methylpyrrolidone, methylene chloride, chloroform, 1, 2-dichloroethane, chlorobenzene, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, tetrahydrofuran and mixtures of said solvents.
  • Particularly preferred solvents are propylene glycol, methanol, ethanol, isopropanol, dimethylformamide and tetrahydrofuran, in particular propylene glycol.
  • the aqueous solution of the saccharide usually contains at least one monosaccharide, at least one disaccharide or a mixture of mono- and disaccharides.
  • the total content of mono- and disaccharide is at least 15% by weight, preferably at least 20% by weight, particularly preferably at least 25% by weight, based on the aqueous solution.
  • the solution may optionally comprise other formulation auxiliaries, for example dispersants.
  • the process step can be carried out batchwise, for example in a stirred tank, or continuously.
  • Continuous machines and apparatuses for emulsification are, for example, colloid mills, sprocket dispersing machines and other types of dynamic mixers, furthermore high-pressure homogenizers, pumps with downstream nozzles, valves, membranes or other narrow gap geometries, static mixers, in-line mixers after the rotor-stator Principle (Ultra-Turrax, Inline Dissolver), micromixing systems and ultrasonic emulsification systems.
  • Spreader dispersing machines or high-pressure homogenizers are preferably used.
  • the turbulent mixing can take place in a mixing chamber.
  • the temperature of the solutions used can be from 20 to 200 0 C., preferably at 50 to 150 0 C.
  • the dispersion prepared by the process of the invention may be diluted or used as is. It is also possible to concentrate or dry the aqueous dispersion. In a preferred embodiment, the aqueous dispersion is dried. The drying can, for example done by spray drying.
  • the water content of the solid composition thus obtained is often at most 10% by weight, preferably at most 3% by weight, especially 0.5% by weight.
  • the method according to the invention usually uses a pesticide as described above.
  • a pesticide is used which is insoluble in water.
  • a saccharide in the process usually the above-described saccharides are used, in particular sucrose.
  • Formulation aids are, for example, solvents, surfactants, inorganic emulsifiers (so-called Pickering emulsifiers), antifoaming agents, thickeners, antifreeze agents, and also bactericides.
  • intended formulations may additionally contain adhesives and optionally pigments.
  • Suitable solvents include water, organic solvents such as medium to high boiling point mineral oil fractions such as kerosene and diesel oil, coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g.
  • solvent mixtures and mixtures of the abovementioned solvents and water can also be used.
  • the aforementioned solvents are added only after the process when a dispersion of the pesticide has formed.
  • the aqueous dispersion according to the invention contains at most 30% by weight, preferably at most 20% by weight, in particular at most 10% by weight, of organic solvent.
  • anionic, cationic and / or nonionic surfactants are added.
  • Common nonionic surfactants are, for example, ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation from 3 to 50, alkyl radical: C 4 to C 12) and ethoxylated fatty alcohols (degree of ethoxylation from 3 to 80, alkyl radical: Cs to C 36).
  • Lutensol® A grades C12 to Cu fatty alcohol ethoxylates, ethoxylation degree from 3 to 8
  • Lutensol® AO grades C13 to cis oxo alcohol ethoxylates, degree of ethoxylation from 3 to 30
  • Lutensol® AT- Trademarks C16 to Cis fatty alcohol ethoxylates, degree of ethoxylation from 1 1 to 80
  • Lutensol® ON grades Cao-oxo alcohol ethoxylates, degree of ethoxylation from 3 to 11
  • Lutensol® TO grades C13 oxo alcohol ethoxylates, degree of ethoxylation from 3 to 20) from BASF SE.
  • amphiphilic polymers for example as described in EP 1 756 188 B1, paragraph [0012] to [0068], or in DE 10 2006 001 529 A1, paragraph [0025] to [0055], or based on the monomers Acrylic acid, butyl methacrylate, methyl methacrylate, hydroxyethyl methacrylate and / or iso-butyl methacrylate.
  • amphiphilic block polymers in particular based on ethylene oxide-propylene oxide. Examples are Pluronic® PE grades (EO-PO-EO triblock polymers, EO: ethylene oxide, PO: propylene oxide).
  • comb polymers especially based on alkoxypolyoxyalkyl (meth) acrylates, such as comb polymers of methyl methacrylate, methacrylic acid and (methoxypolyethylene glycol) methacrylate (commercially available as Atlox® 4913 from Uniqema).
  • polysaccharides and their derivatives preferably polysaccharides based on inulin, for example Inutec® SP1 (inulin from chicory with grafted-on alkyl groups).
  • Typical anionic surfactants are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C8 to C12), for example sodium dodecyl sulfate, of sulfuric monoesters of ethoxylated alkanols (degree of ethoxylation from 4 to 30, alkyl radical: C12 to C18) and ethoxylated alkylphenols (degree of ethoxylation from 3 to 50 , Alkyl radical: C 4 to C 12), of alkylsulfonic acids (alkyl radical: C 12 to C 18) and of alkylarylsulfonic acids (alkyl radical: Cg to Cis). Further anionic surfactants further compounds of the general formula (I)
  • R 1 and R 2 are H atoms or C 4 - to C 24 -alkyl and are not simultaneously H atoms, and M 1 and M 2 may be alkali metal ions and / or ammonium ions proved.
  • R 1 and R 2 are preferably linear or branched alkyl radicals having 6 to 18 C atoms, in particular having 6, 12 and 16 C atoms or hydrogen, where R 1 and R 2 are not both simultaneously H and Atoms are.
  • M 1 and M 2 are preferably sodium, potassium or ammonium, with sodium being particularly preferred.
  • Particularly advantageous compounds (I) are those in which M 1 and M 2 are sodium, R 1 is a branched alkyl radical having 12 C atoms and R 2 is an H atom or R 1 .
  • technical mixtures are used which have a proportion of 50 to 90% by weight of the monoalkylated product, such as, for example, Dowfax® 2A1 (trademark of the Dow Chemical Company).
  • salts of dialkyl sulphosuccinates such as sodium dioctyl sulphosuccinate (commercially available as Lutensit® A-BO from BASF SE).
  • arylphenol alkoxylates or their sulfated or phosphated derivatives especially ethoxylated di- and tristryrylphenols or their sulfated or phosphated derivatives, such as Soprophor® from Rhodia (ammonium salt of the ethoxylated tristyrylphenol sulfate having about 16 ethylene oxide groups per molecule).
  • Soprophor® from Rhodia
  • partially neutralized alkali metal salts of (meth) acrylic acid-maleic acid copolymers for example the Sokalan® grades from BASF, in particular Sokalan CP45 (acrylic acid-maleic acid copolymer, sodium salt, partially neutralized).
  • Suitable cationic surfactants are generally cationic salts containing C ⁇ - to Cis-alkyl, -alkylaryl or heterocyclic radicals, for example primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and salts of amine oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts.
  • dodecylammonium acetate or the corresponding sulfate examples which may be mentioned are dodecylammonium acetate or the corresponding sulfate, the sulfates or acetates of the various 2- (N, N, N-trimethylammonium) ethyl paraffins, N-cetylpyridinium sulfate, N-laurylpyridinium sulfate and N-cetyl-N, N, N-trimethylammonium sulfate, N-dodecyl-N, N, N-trimethylammonium sulfate, N-octyl-N, N, N-trimethylammonium sulfate, N, N-distearyl-N, N-dimethylammonium sulfate and the gemini-surfactant N, N '- (lauryl-dimethyl) ethylenediamine disulfate, ethoxylated t
  • the anionic counter groups are as low as possible nucleophilic, such as perchlorate, sulfate, phosphate, nitrate and Carboxylates, such as acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and conjugated anions of organosulfonic acids, such as Methyl sulfonate, trifluoromethyl sulfonate and para-toluenesulfonate, furthermore tetrafluoroborate, tetraphenyl borate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate.
  • nucleophilic such as perchlorate, sulfate, phosphate
  • concentration of the added surfactant or its mixture can vary within wide ranges. Usually, concentrations of from 0.1 to 30% by weight, based on the aqueous dispersion, are used.
  • inorganic emulsifiers are metal salts, such as salts, oxides and hydroxides of calcium, magnesium, iron, zinc, nickel, titanium, aluminum, silicon, barium or manganese. Mention may be made of magnesium hydroxide, magnesium carbonate, magnesium oxide, calcium oxalate, calcium carbonate, barium carbonate, barium sulfate, titanium dioxide, aluminum oxide, aluminum hydroxide and zinc sulfide. Silicates, bentonite, hydroxyapatite and hydrotalcites are also mentioned.
  • thickeners compounds which give the formulation a pseudo-plastic flow behavior, ie high-level viscosity and low viscosity in the agitated state
  • thickeners are, for example, polysaccharides, such as xanthan gum, or organic layer minerals.
  • Suitable antifoams are, for example, silicone emulsions, long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.
  • Bactericides may be added to stabilize the aqueous formulation.
  • Suitable bactericides which may be present in the formulations according to the invention are all bactericides customary for the formulation of agrochemical active compounds, for example diclorophene and benzyl alcohol hemiformal.
  • Suitable antifreeze agents are, for example, polyhydric alcohols, such as ethylene glycol, propylene glycol or glycerol, preferably glycerol. Usually, from 0 to 30% by weight, preferably from 10 to 20% by weight, based on the aqueous solution, is added.
  • Suitable adhesives which may be present in seed dressing formulations are all customary binders which can be used in pickling agents.
  • Preferably mentioned are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose.
  • dyes are added to the formulations according to the invention. All dyes customary for such purposes are suitable, for example Cl. Pigment Red 48: 2. Both water-insoluble pigments and water-soluble dyes are useful in this case.
  • Crystallization inhibitors generally do not need to be added. At most 5% by weight, more preferably at most 1% by weight and especially no crystallization inhibitors are preferably added.
  • the present invention further relates to a solid composition obtained by drying the dispersion of the invention.
  • the drying can be done for example by spray drying.
  • the water content of the solid composition is often at most 10% by weight, preferably at most 3% by weight, especially 0.5% by weight.
  • the invention further relates to the use of a saccharide which is a monosaccharide, a disaccharide or a mixture of mono- and disaccharide, for slowing the particle growth of pesticide particles having a particle size of up to 1 ⁇ m in aqueous dispersion.
  • a saccharide which is a monosaccharide, a disaccharide or a mixture of mono- and disaccharide, for slowing the particle growth of pesticide particles having a particle size of up to 1 ⁇ m in aqueous dispersion. Comparable under the suppression of particle growth is one that less increased the particle size after 24 h storage of the dispersion at 20 0 C has weight as in a comparative solution having less than 15.% Saccharide, preferably without saccharide.
  • the dispersion according to the invention or the solid composition according to the invention can be used for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired insect or mite infestation and / or for regulating the growth of plants by mixing the dispersion or the solid composition is allowed to act on the respective pests, their habitat and / or the plants to be protected from the particular pest, the soil and / or undesirable plants and / or the crops and / or their habitat.
  • the dispersion or solid composition of the present invention may be used to control undesirable insect or mite infestation on plants and / or to control phytopathogenic fungi and / or to control undesired plant growth by treating seeds of crops with the dispersion or solid composition.
  • the invention further relates to seed treated, preferably pickled, with the dispersion according to the invention or the solid composition according to the invention.
  • the seed contains the dispersion according to the invention or the solid composition according to the invention.
  • Conventional pickling methods can be used to treat seed.
  • the seed thus treated usually contains the dispersion or solid composition.
  • the advantage of the present invention is that the aqueous dispersion of pesticide particles having a particle size of less than 10 ⁇ m has a slower particle growth, in particular due to Ostwald ripening. Another advantage is that the particles settle more slowly and do not crystallize out or slow down. It is also advantageous that this stabilization of the dispersion was achieved with the aid of an environmentally compatible agent, namely a saccharide.
  • the method according to the invention has the advantage that it can be carried out with existing systems.
  • the saccharide used is easy and safe to handle and easily accessible without complex synthesis.
  • stable aqueous dispersions of pesticide particles are accessible.
  • Example 1 First, 16 g of pyraclostrobin in 144 g of propylene glycol were suspended for one hour with 3 mm glass beads with a shaker (Red Devil). The resulting, still coarse dispersion was fed at a flow rate of 1 kg / h through a mixing nozzle of a release cell. There, propylene glycol was fed at a temperature of 200 0 C with a pumping rate of 2kg / h. In the dissolution cell, both streams were mixed turbulently and a solution of pyraclostrobin was produced.
  • the solution of pyraclostrobin thus obtained was moved to a second mixing nozzle and mixed turbulently with a sucrose solution of 500 g of sucrose with 1000 g of water (ie 33.3% by weight) at a pumping rate of 16 kg / h.
  • the sucrose solution was cooled in a cryostat at 5 0 C prior to down.
  • a particle formation of pyraclostrobin takes place.
  • the resulting amorphous precipitate of pyraclostrobin was discharged.
  • An aqueous dispersion of 0.42% by weight of amorphous pyrablostrobin containing 29.0% by weight of sucrose was obtained.
  • Particle sizes were determined by laser diffraction (Malvern Mastersizer S) and laser scattering (Brookhaven Instruments BI90) for 24 h (Tables 1 and 2).
  • the batch was repeated without addition of sucrose and analyzed.
  • the experiment was repeated for comparison, wherein no sucrose was occupied, but 4 g of sodium dodeculphate (SDS) was added to the mixture of pyraclostrobin and propylene glycol.
  • SDS sodium dodeculphate
  • Example 2 Powdered pyraclostrobin and powdered epoxiconazole were in a
  • a fine emulsion was obtained, which was cooled immediately after homogenization in an ice water bath with stirring at a cooling rate of 3.0 K / min to temperatures less than or equal to 20 ° C.
  • a suspension of solid, amorphous pesticide particles was obtained.
  • emulsifier A aqueous dispersion of an amphiphilic copolymer of the monomers acrylic acid, butyl methacrylate, methyl methacrylate, hydroxyethyl methacrylate and isobutyl methacrylate with solids content of 33% by weight and polymer particle size of about 10 to 60 nanometers
  • emulsifier B aqueous solution of polyacrylic acid sodium salt, solids content 45% by weight, average molar mass 1200 g / mol, commercially available as Sokalan® PA15 from BASF SE.
  • the product B according to the invention (with sucrose) was composed like product A, but the water was replaced by a mixture of sucrose / water in the weight ratio 8/1.

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

Abstract

L'invention concerne une dispersion aqueuse contenant des particules solides de pesticides d'une taille inférieure à 10 μm et un saccharide dissous dans la phase aqueuse. L'invention concerne en outre un procédé pour produire une dispersion selon l'invention, procédé selon lequel on met en contact et on disperse un pesticide et un saccharide, se présentant sous la forme d'un monosaccharide, d'un disaccharide ou d'un mélange de ces derniers. L'invention concerne également l'utilisation d'un saccharide pour ralentir la croissance de particules de pesticides d'une taille maximale de 10 μm dans la dispersion aqueuse, l'utilisation de la dispersion ou de la composition solide pour lutter contre les champignons phytopathogènes et/ou la croissance indésirable de végétaux et/ou l'infestation indésirable d'insectes ou d'acariens et/ou pour réguler la croissance de végétaux. L'invention concerne enfin des semences traitées avec la dispersion ou la composition solide selon l'invention.
EP09795382A 2008-12-18 2009-12-10 Dispersion aqueuse contenant des particules de pesticides et un saccharide en solution Withdrawn EP2378869A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09795382A EP2378869A2 (fr) 2008-12-18 2009-12-10 Dispersion aqueuse contenant des particules de pesticides et un saccharide en solution

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08172198 2008-12-18
PCT/EP2009/066835 WO2010079036A2 (fr) 2008-12-18 2009-12-10 Dispersion aqueuse contenant des particules de pesticides et un saccharide en solution
EP09795382A EP2378869A2 (fr) 2008-12-18 2009-12-10 Dispersion aqueuse contenant des particules de pesticides et un saccharide en solution

Publications (1)

Publication Number Publication Date
EP2378869A2 true EP2378869A2 (fr) 2011-10-26

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Country Status (6)

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US (1) US8541012B2 (fr)
EP (1) EP2378869A2 (fr)
JP (1) JP2012512824A (fr)
CN (1) CN102316725B (fr)
BR (1) BRPI0918332A2 (fr)
WO (1) WO2010079036A2 (fr)

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BR122018001851B1 (pt) 2007-08-13 2019-08-20 Monsanto Technology Llc Método de controle de nematódeos parasitas de plantas
ES2754503T3 (es) 2009-02-10 2020-04-17 Monsanto Technology Llc Composiciones y procedimientos de lucha contra nematodos
US8551913B2 (en) 2011-02-11 2013-10-08 Becker Underwood, Inc. Methods and compositions for reducing seed bridging
AU2012298686A1 (en) * 2011-08-25 2014-03-13 Dow Agrosciences Llc Increasing particle size of pesticides to reduce movement in soil
UA118254C2 (uk) * 2012-12-04 2018-12-26 Монсанто Текнолоджи Ллс Нематоцидні водні композиції концентрату суспензії
CN115386208A (zh) * 2022-08-11 2022-11-25 长兴电子（苏州）有限公司 可降解微珠及其制备方法与应用

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Also Published As

Publication number Publication date
WO2010079036A2 (fr) 2010-07-15
US8541012B2 (en) 2013-09-24
WO2010079036A3 (fr) 2011-05-12
CN102316725B (zh) 2014-08-13
CN102316725A (zh) 2012-01-11
US20110257010A1 (en) 2011-10-20
JP2012512824A (ja) 2012-06-07
BRPI0918332A2 (pt) 2015-08-11

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