EP2378868A2 - Dispersion aqueuse contenant des particules de pesticides et un amphiphile - Google Patents

Dispersion aqueuse contenant des particules de pesticides et un amphiphile

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Publication number
EP2378868A2
EP2378868A2 EP09765128A EP09765128A EP2378868A2 EP 2378868 A2 EP2378868 A2 EP 2378868A2 EP 09765128 A EP09765128 A EP 09765128A EP 09765128 A EP09765128 A EP 09765128A EP 2378868 A2 EP2378868 A2 EP 2378868A2
Authority
EP
European Patent Office
Prior art keywords
dispersion
amphiphile
active ingredient
solid composition
acid
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Withdrawn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
EP09765128A
Other languages
German (de)
English (en)
Inventor
Sebastian Koltzenburg
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 EP09765128A priority Critical patent/EP2378868A2/fr
Publication of EP2378868A2 publication Critical patent/EP2378868A2/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • A01N25/30—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 characterised by the surfactants
    • 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 amphiphile
  • the present invention is an aqueous dispersion comprising solid drug particles having a particle size of up to 10 microns and an amphiphile. Furthermore, the invention relates to a process for the preparation of the dispersion by bringing a drug and an amphiphile in contact. Furthermore, the invention relates to a solid composition comprising active ingredient particles having a particle size of up to 10 microns and an amphiphile, obtained by drying the aqueous dispersion.
  • the invention further relates to the use of the dispersion or the solid composition 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 the dispersion or the solid composition on the particular pests, their habitat and / or the plants to be protected from the respective pest, the soil and / or on undesirable plants and / or crops and / or their habitat, and the use of the dispersion or the solid composition for Control of undesirable insect or mite infestation on plants and / or for controlling phytopathogenic fungi and / or for controlling undesired plant growth by treating crop seeds with the dispersion or solid composition.
  • the invention 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 oligo- mers. But also higher molecular aids such as colloids and amphiphilic polymers give the ability to stabilize drug particles in a smaller dimension.
  • very finely divided dispersions can be stabilized by osmotically adding Ostwald ripening by the addition of extremely poorly water-soluble substances such as hexadecane.
  • Aqueous dispersions comprising active ingredient particles having a particle size of less than 10 ⁇ m and an amphiphile are generally known:
  • WO 1995/25504 discloses a pharmaceutical composition comprising a stable emulsion of a drug entrapped in a hydrohobic emulsion of a long-chain carboxylic acid, which may be, for example, erucic acid.
  • WO 2008/002485 discloses nanoparticles comprising an amorphous drug core and a stabilizer absorbed on the surface of the core.
  • a stabilizer stearic acid or sodium dodecyl sulfate may be mentioned.
  • WO 2004/006959 discloses nanoparticle-containing liquid compositions comprising particles having a size of less than 2000 nm, stabilizer and osmotically active crystallization inhibitor.
  • the stabilizer is, for example, stearic acid or phosphates.
  • WO 2008/100896 discloses a composition comprising acid, emulsifier, co-emulsifier and water.
  • the composition may additionally comprise erucic acid.
  • WO 1998/04761 discloses a microemulsion comprising not less than 40% by weight of water, organic solvent and anionic surfactant selected from aliphatic carboxylic acids having 14 to 23 carbon atoms.
  • WO 2003/059063 discloses a fungicidal composition
  • a fungicidal composition comprising a fatty acid having from 5 to 22 carbon atoms and a selected organic acid.
  • the fatty acid may be, for example, erucic acid.
  • EP 0 388 239 discloses an aqueous suspension comprising a surfactant and particles a sparingly soluble agrochemical active ingredient.
  • a disadvantage of the prior art inter alia, that insufficient stabilization of the particles is achieved against particle growth, so that additional crystallization inhibitors, co-emulsifiers, or other organic acids must be added.
  • the object of the present invention was to identify new possibilities for the stable formulation of pesticide particles having a particle size of less than 10 ⁇ m.
  • the method should manage with low-cost, technically available substances that are also good for the environment.
  • the object was achieved by an aqueous dispersion comprising active ingredient particles having a particle size of up to 10 ⁇ m and an amphiphile, the amphiphile being soluble in water at 20 ° C. to not more than 10% by weight.
  • an amphiphile is understood as meaning a substance or a mixture of substances of at least one hydrophilic and at least one hydrophobic building block.
  • Hydrophobic building blocks usually have an extremely low water solubility. This is understood to mean a water solubility of ⁇ 1 g / L, preferably ⁇ 0.1 g / L, particularly preferably ⁇ 0.01 g / L and in particular ⁇ 0.001 g / L. Examples are long chain alkanes, fused aromatic ring systems, silicones and perfluorinated compounds.
  • the hydrophilic building block is polar and enters energetically favorable interactions with water.
  • These may be acid groups such as carboxylic acid, sulfonic acid, phosphoric acid, phosphonic acid or neutralized embodiments of these groups, for example with alkali metal or ammonium ions as genion such as sodium, lithium, potassium, ammonium or tetraalkylammonium, such as tetrabutylammonium act.
  • the hydrophilic building block may be an ON-goether such as oligoethylene oxide.
  • the linking of the building blocks takes place either directly or by other chemical linkers known to the person skilled in the art, for example an ester or amide bond.
  • amphiphiles have a Krafftddling of at least 25 ° C, preferably at least 40 0 C and more preferably at least 60 0 C. At temperatures below the Krafftrios there are no micelles, and the material appears water insoluble. There is a low residual molecular solubility which is less than 1 g / L, preferably ⁇ 0.1 g / L, more preferably ⁇ 0.01 g / L and especially ⁇ 0.001 g / L.
  • the amphiphile is soluble in water at 20 ° C. to at most 10% by weight, preferably to at most 1% by weight, more preferably to at most 0.1% by weight, especially to at most 0.01% by weight.
  • the amphiphile is an aliphatic acid or salt thereof, wherein the aliphatic acid in water at 20 0 C for at most 10.% Is soluble.
  • the aliphatic acid is present in water at 20 0 C for at most 10.%, Bvorzugt than 1 wt.%, Particularly preferably at most 0.1 wt.% By weight, especially not more than 0.01.% Soluble.
  • the amphiphile is the salt of an aliphatic acid, the aliphatic acid is commonly used to determine water solubility.
  • the aliphatic acid usually contains a linear or branched, saturated or unsaturated aliphatic group, and also an acid group, such as a carboxylic acid group, sulfonic acid group or phosphoric acid groups, preferably a carboxylic acid group.
  • Suitable salts of the aliphatic acid are, for example, alkali metal, alkaline earth metal or ammonium salts of the aliphatic acid. Mixtures of the aforementioned aliphatic acid, their salts or of aliphatic acid with salts aliphatic acids are e- b décor possible.
  • the aliphatic acid is preferably a fatty acid having at least 20 carbon atoms.
  • the fatty acid contains 22 to 36 carbon atoms. It can be linear or branched, saturated or unsaturated.
  • Suitable fatty acids are, for example, arachidonic acid (C20), behenic acid (C22), erucic acid (C22), lignoceric acid (C24), cerotic acid (C26) or melissic acid (C30), preferably erucic acid and behenic acid, in particular erucic acid.
  • Erucic acid (cis-13-docosenoic acid) is a monounsaturated fatty acid found in abundance in the seeds of some rape varieties and sea kale species, especially in the Abyssinian cabbage (Crambus abyssinica).
  • Most of the dispersion according to the invention contains at most 40% by weight, preferably at most 35% by weight, particularly preferably at most 30% by weight, of the amphiphile, based on the active ingredient used.
  • the dispersion usually contains at least 1% by weight, preferably at least 3% by weight, more preferably at least 5% by weight and especially at least 15% by weight of the amphiphile, based on the active ingredient used.
  • An aqueous dispersion may be an aqueous emulsion or aqueous suspension, preferably it is an aqueous suspension.
  • the term "suspension” is understood in particular also to mean dispersions of particles from supercooled melts which contain particles which are below their equilibrium melting point.
  • An aqueous dispersion usually comprises water as the continuous phase and solid particles as the disperse phase. Most of the dispersion of the invention contains 30 to 98 wt.%, Preferably 40 to 90 wt.%, Particularly preferably 50 to 80 wt.% Water.
  • the active ingredient particles usually comprise at least 80% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight of active ingredient.
  • the active ingredient particles preferably consist of active ingredient.
  • the content of active ingredient particles having a particle size of less than 10 ⁇ m in the aqueous suspension can vary within wide ranges, such as from 0.001 to 50% by weight, preferably from 0.01 to 40% by weight.
  • the particle size of the active ingredient 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. Pieces (dynamic light scattering), for example with a Brookhoven Instruments BI90 instrument.
  • 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 device 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 drug particles may be crystalline or amorphous, preferably amorphous.
  • A-morph means that the molecular building blocks of a homogeneous solid are not arranged in crystal lattices.
  • Amorphous active ingredient particles means that the particles are substantially free of crystalline active substance, wherein preferably from 80 to 100 wt.%, In particular from 90 to 100 wt.% Of the material amorphous.
  • Amorphous forms can be distinguished from crystalline forms by various methods, for example by microscopic examination in polarized light, differential scanning calorimetry (DSC), X-ray diffraction or solubility comparisons, preferably by DSC.
  • Suitable active ingredients are, for example, colorants, cosmetic active ingredients, pharmaceutical active substances, pesticides, fertilizers, additives for food or animal feed, auxiliaries for polymers, paper, textile, leather or detergents and cleaners. Likewise, mixtures of the above active substances are suitable. In general, active ingredients which are soluble in water in water at most at 10 g / l, preferably at most 1 g / l, particularly preferably at most 0.1 g / l and especially at most 0.01 g / at 20 ° C., are very suitable.
  • the dispersion of the invention usually contains 1 to 60 wt.%, Preferably 5 to 50 wt.% Active ingredient particles based on the dispersion. Usually, it contains at most 40% by weight, preferably at most 30% by weight, of amphiphile, based on the active substance. It usually contains at least 0.1% by weight, preferably at least 1% by weight, more preferably at least 5% by weight, of amphiphile, based on the active substance.
  • colorants are dyes, printing inks, pigments, UV absorbers, optical brighteners or IR dyes. While organic dyes have an absorption maximum in the wavelength range from 400 to 850 nm, optical brighteners have one or more absorption maxima in the range from 250 to 400 nm. Optical brighteners emit fluorescence radiation in the visible range when irradiated with UV light. Examples of optical brighteners are compounds from the classes of bisstyrylbenzenes, stilbenes, benzoxazoles, coumarins, pyrenes and naphthalenes. Also suitable are markers for liquids, for example mineral oil markers. UV absorbers are generally UV-absorbing compounds which deactivate the absorbed radiation without radiation. Such Compounds are used for example in sunscreens and for the stabilization of organic polymers.
  • Cosmetics are substances or preparations of substances that are exclusively or predominantly intended, externally on the human body or in the oral cavity for cleaning, care, protection, maintenance of a good condition, perfuming, changing the appearance or to to be applied, to influence the body odor.
  • anti-insect agents such as icaridine or N, N-diethyl-meta-toluamide (DEET).
  • active pharmaceutical ingredients can be used as active ingredients.
  • Suitable active ingredients are additives for food or animal feed, such as food dyes, amino acids, vitamins, preservatives, antioxidants, odors or flavors.
  • Pesticides and fertilizers may also be used as active ingredients, preferably pesticides.
  • pesticides denotes at least one active substance 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.
  • One skilled in the art will be familiar with such pesticides as described, for example, in Pesticide 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
  • 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 , Cyclopropane-carboxamides, dicarboximides, di- hydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy (2-amino) pyrimidines, hydroxyanilides, imidazoles, imidazolinones,
  • 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 are soluble at 20 ° C. in water 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%.
  • Suitable insoluble pesticides are, for example, (solubility in water at 20 0 C ser each in brackets) pyraclostrobin (1, 9 mg / l), epoxiconazole (6.6 mg / l), prochloraz (34 mg / l), preferably pyraclostrobin.
  • the pesticides used are often solids at 20 ° C.
  • the melting point 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 an active ingredient and an amphiphile, wherein the amphiphile in water at 20 0 C to at most 10 wt.% Is soluble, brings into contact.
  • the dispersed drug may be brought into contact with the amphiphile or dispersed after contacting drug and amphiphile.
  • Suitable processes are, for example, precipitation processes, emulsification processes, evaporation processes. ren, melt emulsification or milling process, preferably precipitation method.
  • the drug and the amphiphile are contacted and dispersed in an aqueous system.
  • the amphiphile is used in an organic solvent, especially in the same solvent system as the active ingredient.
  • Suitable active ingredients are those described above.
  • the active ingredient is insoluble in water.
  • the active ingredient is a pesticide which is insoluble in water.
  • Suitable amphiphiles are the amphiphiles described above.
  • the amphiphile is a fatty acid containing at least 20, preferably 22 to 36, carbon atoms.
  • Particularly preferred methods are to provide the one aqueous solution, dissolve the active ingredient and the amphiphile in a water-miscible organic solvent, and mix the two solutions turbulently (precipitation method); dissolves the active substance and the amphiphile in a water-immiscible organic solvent, mixes turbulently with an aqueous solution, and optionally removes the organic solvent (emulsification process, optionally with evaporation); a melt containing molten agent and the amphiphile is mixed with an aqueous solution and cooled (melt emulsification); or grinding the active ingredient in the presence of the amphiphile (milling method).
  • a method is to provide an aqueous solution, dissolve the active ingredient and the amphiphile in a water-miscible organic solvent, and mix the two solutions turbulently (precipitation method);
  • the solution of the active ingredient and the amphiphile in a water-miscible organic solvent usually contains a water-miscible organic solvent.
  • Miscible with water 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 may optionally comprise other formulation auxiliaries, 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 see chlorinated hydrocarbons such as methylene chloride, chloro
  • 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 contains water and optionally further 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, toothed disc 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 downstream of the rotor Stator principle (Ultra-Turrax, Inline Dissolver), micromixing systems and ultrasonic emulsification systems.
  • Sprocket dispersing machines or high-pressure homogenizers are preferably used.
  • the temperature of the solutions used can be from 20 to 200 0 C., preferably at 50 to 150 0 C.
  • the turbulent mixing can take place in a mixing chamber.
  • the dispersion prepared by the process of the invention may be diluted or used as is. In addition, it is possible to narrow the aqueous dispersion.
  • an active ingredient as described above.
  • a pesticide is used which is insoluble in water.
  • amphiphile in the process usually the above-described aliphatic acids are used, in particular a fatty acid containing at least 20, preferably 22 to 36, carbon atoms.
  • 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.
  • the solvents used include water, organic solvents such as mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons. see hydrocarbons, for example paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, gycols, ketones such as cyclohexanone, gamma-butyrolactone, Dimethylfettklaamide, fatty acids and fatty acid esters and highly polar Solvents, for example amines such as N-methylpyrrolidone, into consideration.
  • solvent mixtures and mixtures of the abovementioned solvents and water can also be used.
  • the abovementioned solvents are added only after the
  • 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 to 80
  • Lutensol® ON grades Cao-oxoalcohol ethoxylates, degree of ethoxylation from 3 to 1 l
  • Lutensol® TO grades cis-oxo alcohol ethoxylates, degree of ethoxylation from 3 to 20) of 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 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 acid halides of ethoxylated alkanols (degree of ethoxylation of from 4 to 30, alkyl radical: C12 to Cis) and ethoxylated alkylphenols (degree of ethoxylation of 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 radicals) rest: Cg to de).
  • 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 usually a Ce- to Cis-alkyl-, alkylaryl or heterocyclic radical-containing cationic salts, 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.
  • a Ce- to Cis-alkyl-, alkylaryl or heterocyclic radical-containing cationic salts for example primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts,
  • 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-trimethlyammonium sulfate, N, N-distearyl-N, N-dimethylammonium sulfate and the gemini-surfactant N, N '- (lauryl-dimethyl) ethylenediamine disulfate, ethoxylated tallow fatty alkyl N-methylammonium sulfate and
  • the anionic counter groups are as low as possible nucleophilic, such as, for example, perchlorate, sulfate, phosphate, nitrate and carbonylates, such as acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and conjugated anions of organosulfonic acids, such as methylsulfonate, trifluoromethylsulfonate and para-toluenesulfonate, furthermore tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate.
  • nucleophilic such as, for example, perchlorate, sulfate,
  • concentration of the added surfactant or its mixture can vary within wide ranges. Usually, concentrations of 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 impart a pseudo-plastic rheology to the formulation, i.e. high-level high 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.
  • adhesives which may be present in seed dressing formulations
  • all conventional binders which can be used in pickling agents are suitable.
  • polyvinylpyrrolidone polyvinyl acetate
  • polyvinyl alcohol polyvinyl alcohol
  • Tylose polyvinyl alcohol
  • dyes 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 furthermore relates to a solid composition comprising active ingredient particles having a particle size of up to 10 ⁇ m and an amphiphile, obtained by drying the dispersion according to 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 one of an amphiphile, for example an aliphatic acid or its salt, wherein the aliphatic acid is soluble in water at 20 ° C. to at most 10% by weight in order to slow down the growth of active ingredient particles having a particle size of up to 10 ⁇ m in aqueous dispersion.
  • the slowdown in particle growth is understood to mean that, after storage of the dispersion at 20 ° C. for 24 h, the particle size has increased less than in the case of a comparison solution without amphiphile.
  • the dispersion or solid composition of the present invention can be used to control phytopathogenic fungi and / or undesired plant growth and / or undesirable insect or morbid infestation and / or to regulate the growth of plants by treating the dispersion or solid composition the respective pests, their habitat and / or the plants to be protected from the respective pest, the soil and / or undesirable plants and / or the crops and / or their habitat.
  • the dispersion according to the invention or the solid composition according to the invention can be used for controlling undesirable insect or mite infestation on plants and / or for controlling phytopathogenic fungi and / or for controlling undesired plant growth by cultivating seeds of crops with the dispersion or the solid composition treated.
  • the invention further relates to seed treated with the dispersion of the invention or the solid composition according to the invention.
  • the term "treated” generally means stained.
  • the dispersion according to the invention usually remains on the seed.
  • the seed preferably contains the dispersion according to the invention or the solid composition according to the invention.
  • the advantage of the present invention is that the aqueous dispersion of active ingredient particles having a particle size of less than 10 ⁇ m has a slower particle growth (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, for example, a fatty acid.
  • the method according to the invention has the advantage that it can be carried out with existing systems. Furthermore, stable aqueous dispersions of drug particles are accessible.
  • the solution thus obtained was moved to a second mixing nozzle and mixed with water (precooled to 5 0 C) with a pumping rate of 16 kg / h turbulent. In the mixture, particle formation of pyraclostrobin takes place. The resulting amorphous precipitate of pyraclostrobin was discharged and analyzed.
  • the aqueous suspension contained 0.42% by weight of pyraclostrobin and 0 / 0.025 / 0.05 / 0.11% by weight of erucic acid.
  • the particle sizes of pyraclostrobin were determined by means of laser diffraction (Maillvern Mastersizer S) and laser scattering (Brookhaven Instruments BI90) for 24 h (Tables 1 and 2).
  • the experiment was repeated replacing erucic acid with 4 g of sodium dodecane sulfate (SDS).
  • SDS sodium dodecane sulfate
  • the aqueous suspension thus obtained contained 0.42% by weight of pyraclostrobin and 0.1% by weight of SDS.

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

Abstract

L'invention concerne une dispersion aqueuse contenant des particules solides de substance active d'une taille maximale de 10 μm et un amphiphile. L'invention concerne en outre un procédé pour produire ladite dispersion, procédé selon lequel on met en contact une substance active et un amphiphile. L'invention concerne également une composition solide contenant des particules de substance active d'une taille maximale de 10 μm et un amphiphile, obtenue par séchage de la dispersion aqueuse. L'invention concerne par ailleurs 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.
EP09765128A 2008-12-18 2009-12-10 Dispersion aqueuse contenant des particules de pesticides et un amphiphile Withdrawn EP2378868A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09765128A EP2378868A2 (fr) 2008-12-18 2009-12-10 Dispersion aqueuse contenant des particules de pesticides et un amphiphile

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08172206 2008-12-18
EP09765128A EP2378868A2 (fr) 2008-12-18 2009-12-10 Dispersion aqueuse contenant des particules de pesticides et un amphiphile
PCT/EP2009/066837 WO2010079037A2 (fr) 2008-12-18 2009-12-10 Dispersion aqueuse contenant des particules de pesticides et un amphiphile

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EP2378868A2 true EP2378868A2 (fr) 2011-10-26

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US (1) US20110263422A1 (fr)
EP (1) EP2378868A2 (fr)
JP (1) JP5568093B2 (fr)
CN (1) CN102316726A (fr)
BR (1) BRPI0917771A2 (fr)
WO (1) WO2010079037A2 (fr)

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BR112013026574A8 (pt) * 2011-06-10 2018-01-23 Huntsman Corporation Australia Pty Ltd formulação de suspensão à base de óleo agrícola, composição de pré-mistura, e, métodos para preparar uma composição de pré-mistura, uma formulação de suspensão à base de óleo e uma formulação de od
JP2013095739A (ja) * 2011-11-04 2013-05-20 Kyoyu Agri Kk 有害節足動物防除組成物

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Also Published As

Publication number Publication date
BRPI0917771A2 (pt) 2015-08-04
JP5568093B2 (ja) 2014-08-06
JP2012512825A (ja) 2012-06-07
WO2010079037A3 (fr) 2011-05-12
WO2010079037A2 (fr) 2010-07-15
US20110263422A1 (en) 2011-10-27
CN102316726A (zh) 2012-01-11

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