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EP2378868A2 - Aqueous dispersion comprising pesticide particles and an amphiphile - Google Patents

Aqueous dispersion comprising pesticide particles and an amphiphile

Info

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Withdrawn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)
French (fr)
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/en
Publication of EP2378868A2 publication Critical patent/EP2378868A2/en
Withdrawn legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/02Biocides, 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
    • A01N25/04Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/30Biocides, 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
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647Triazoles; Hydrogenated triazoles
    • A01N43/6531,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N47/00Biocides, 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
    • A01N47/08Biocides, 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
    • A01N47/10Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N47/00Biocides, 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
    • A01N47/08Biocides, 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
    • A01N47/28Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38Ureas 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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Abstract

The invention relates to an aqueous dispersion comprising solid pesticide particles having a particle size of up to 10 μm and an amphiphile. The invention further relates to a method for producing said dispersion by contacting an active substance and an amphiphile. The invention also relates to a solid composition containing active substance particles having a particle size of up to 10 μm 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 unwanted plant growth and/or unwanted infestation with insects and/or acarides and/or for controlling the growth of plants. The invention finally relates to seeds which are treated with the dispersion or the solid composition.

Description

Wässrige Dispersion umfassend Pestizidpartikel und Amphiphil Aqueous dispersion comprising pesticide particles and amphiphile
Gegenstand der vorliegenden Erfindung ist eine wässrige Dispersion umfassend feste Wirkstoff partikel mit einer Partikelgröße von bis zu 10 μm und ein Amphiphil. Weiterhin betrifft die Erfindung ein Verfahren zur Herstellung der Dispersion, indem man einen Wirkstoff und ein Amphiphil in Kontakt bringt. Ferner betrifft die Erfindung eine feste Zusammensetzung umfassend Wirkstoffpartikel mit einer Partikelgröße von bis zu 10 μm und einem Amphiphil, erhalten durch Trocknen der wässrigen Dispersion. Die Erfindung betrifft außerdem die Verwendung der Dispersion oder der festen Zusammen- Setzung zur Bekämpfung von phytopathogenen Pilzen und/oder unerwünschtem Pflanzenwuchs und/oder unerwünschtem Insekten- oder Milbenbefall und/oder zur Regulation des Wachstums von Pflanzen, indem man die Dispersion oder die feste Zusammensetzung auf die jeweiligen Schädlinge, deren Lebensraum und/oder die vor dem jeweiligen Schädling zu schützenden Pflanzen, den Boden und/oder auf unerwünschte Pflanzen und/oder die Nutzpflanzen und/oder deren Lebensraum einwirken lässt, sowie die Verwendung der Dispersion oder der festen Zusammensetzung zur Bekämpfung von unerwünschtem Insekten- oder Milbenbefall auf Pflanzen und/oder zur Bekämpfung von phytopathogenen Pilzen und/oder zur Bekämpfung unerwünschten Pflanzenwuchses, indem man Saatgüter von Nutzpflanzen mit der Dispersion oder der festen Zusammensetzung behandelt. Schließlich betrifft die Erfindung Saatgut, behandelt mit der Dispersion oder der festen Zusammensetzung. Kombinationen bevorzugter Merkmale mit anderen bevorzugten Merkmalen werden von der vorliegenden Erfindung umfasst.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. Finally, 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.
Viele Wirkstoffe, beispielsweise Pestizide, werden idealerweise in Form von wässrigen Systemen bereitgestellt. Dies erschwert naturgemäß eine effektive Anwendung von in Wasser nicht löslichen Wirkstoffen, da die in der wässrigen Lösung verfügbare Konzentration und damit die biologische Aktivität gering sind. Es ist bekannt, dass Löslichkeit, Dispergierbarkeit und Bioverfügbarkeit von Wirkstoffpartikeln durch Vergrößerung der Partikeloberfläche, das heißt durch Verkleinerung der Partikelgröße bei gleicher Gesamtmenge, erhöht werden kann. Beispielsweise ist die Penetration biologischer Membranen bei kleinerer Partikelgröße vereinfacht. Ebenso erhöhen sich die Lösungsgeschwindigkeit und die apparente Löslichkeit der Partikel, siehe auch Müller RH, Benita S, Böhm BHL, eds. Stuttgart, Germany: Medpharm Scientific Publishers; 1998. Das bedeutet gleichzeitig, dass gegenüber der Anwendung des Wirkstoffs in Form größerer Partikel die benötigten Wirkstoffmengen bei Verwendung von Partikeln im Größenbereich weniger Mikrometer, bevorzugt unterhalb von einem Mikrometer, zur Erzielung des gleichen Effektes kleiner sind.Many agents, such as pesticides, are ideally provided in the form of aqueous systems. This, of course, complicates the effective use of water-insoluble drugs because the concentration available in the aqueous solution, and thus the biological activity, is low. It is known that the solubility, dispersibility and bioavailability of active ingredient particles can be increased by enlarging the particle surface, that is to say by reducing the particle size while maintaining the same total amount. For example, the penetration of biological membranes is simplified with smaller particle size. Likewise, the dissolution rate and the apparent solubility of the particles increase, see also Müller RH, Benita S, Böhm BHL, eds. Stuttgart, Germany: Medpharm Scientific Publishers; 1998. This means at the same time that compared with the use of the active ingredient in the form of larger particles, the required amounts of active ingredient are smaller when using particles in the size range less micrometers, preferably below one micrometer, to achieve the same effect.
Zur kolloidalen Stabilisierung von Systemen mit Teilchengrößen unter zehn Mikrometer werden häufig oberflächenaktive Substanzen eingesetzt, die die Agglomeration der Partikel inhibieren. Typische Stabilisatoren sind niedermolekulare Tenside oder Oligo- mere. Aber auch höhermolekulare Hilfsmittel wie beispielsweise Kolloide und amphiphile Polymere geben die Möglichkeit, Wirkstoffteilchen in kleiner Dimension zu stabilisieren. Ebenso können feinstteilige Dispersionen durch den Zusatz extrem schwer wasserlöslicher Substanzen wie z.B. Hexadecan osmotisch gegen Ostwaldrei- fung stabilisiert werden.For colloidal stabilization of systems with particle sizes below ten micrometers surface-active substances are frequently used, which inhibit the agglomeration of the particles. 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. Likewise, very finely divided dispersions can be stabilized by osmotically adding Ostwald ripening by the addition of extremely poorly water-soluble substances such as hexadecane.
Wässrige Dispersionen umfassend Wirkstoffpartikel mit einer Partikelgröße von unter 10 μm und ein Amphiphil sind allgemein bekannt:Aqueous dispersions comprising active ingredient particles having a particle size of less than 10 μm and an amphiphile are generally known:
WO 1995/25504 offenbart eine pharmazeutisches Mittel umfassend eine stabile Emulsion eines Arzneimittels eingeschlossen in eine hydrohobe Emulsion einer langketigen Carbonsäure, welche beispielsweise Erucasäure sein kann.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 offenbart Nanopartikel umfassend einen amorphen Arzneimittel-Kern und ein Stabilisator absorbiert auf der Oberfläche des Kerns. Als Stabilisator sind Stearinsäure oder Natriumdodecylsulfat genannt.WO 2008/002485 discloses nanoparticles comprising an amorphous drug core and a stabilizer absorbed on the surface of the core. As a stabilizer stearic acid or sodium dodecyl sulfate may be mentioned.
WO 2004/006959 offenbart Nanopartikel-haltige flüssige Zusammensetzungen umfassend Partikel mit einer Größe von unter 2000 nm, Stabilisator und osmotisch aktiven Kristallisationsinhibitor. Der Stabilisator ist beispielsweise Stearinsäure oder Phosphate.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 offenbart eine Zusammensetzung umfassend Säure, Emulgator, Co- Emulgator und Wasser. Die Zusammensetzung kann zusätzlich Erucasäure umfassen.WO 2008/100896 discloses a composition comprising acid, emulsifier, co-emulsifier and water. The composition may additionally comprise erucic acid.
WO 1998/04761 offenbart eine Microemulsion umfassend nicht weniger als 40 Gew.% Wasser, organisches Lösungsmittel und anionisches Tensid, welches ausgewählt ist aus aliphatischen Carbonsäuren mit 14 bis 23 Kohlenstoffatomen.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 offenbart eine fungizide Zusammensetzung umfassend eine Fettsäure mit 5 bis 22 Kohlenstoffatomen und eine ausgewählte organische Säure. Die Fettsäure kann beispielsweise Erucasäure sein.WO 2003/059063 discloses 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 offenbart eine wässrige Suspension umfassend ein Tensid und Partikel eine schwerlöslichen agrochemischen Wirkstoffs.EP 0 388 239 discloses an aqueous suspension comprising a surfactant and particles a sparingly soluble agrochemical active ingredient.
Nachteilig an Stand der Technik ist unter anderem, dass eine nicht ausreichende Stabilisierung der Partikel gegen Partikelwachstum erreicht wird, so dass zusätzliche Kristallisationsinhibitoren, Coemulgatoren, oder weitere organische Säuren zugesetzt werden müssen. Aufgabe der vorliegenden Erfindung war es, neue Möglichkeiten zur stabilen Formulierung von Pestizidpartikeln mit einer Partikelgröße von unter 10 μm zu identifizieren. Insbesondere sollte die Methode mit kostengünstigen, technisch verfügbaren Substanzen auskommen, die auch gut umweltverträglich sind.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 μm. In particular, the method should manage with low-cost, technically available substances that are also good for the environment.
Die Aufgabe wurde gelöst duch eine wässrige Dispersion umfassend Wirkstoffpartikel mit einer Partikelgröße von bis zu 10 μm und ein Amphiphil, wobei das Amphiphil in Wasser bei 20 0C zu höchstens 10 Gew.% löslich ist.The object was achieved by an aqueous dispersion comprising active ingredient particles having a particle size of up to 10 μm and an amphiphile, the amphiphile being soluble in water at 20 ° C. to not more than 10% by weight.
Allgemein wird unter einem Amphiphil eine Substanz oder eine Mischung von Substanzen aus mindestens einem hydrophilen und mindestens einem hydrophoben Baustein verstanden. Hydrophobe Bausteine weisen meist eine extrem niedrige Wasserlöslichkeit auf. Hierunter wird eine Wasserlöslichkeit von < 1 g/L, bevorzugt < 0,1 g/L, besonders bevorzugt <0,01 g/L und insbesondere < 0,001 g/L verstanden. Beispiele sind langkettige Alkane, kondensierten aromatische Ringsysteme, Silikone und perfluorierten Verbindungen. Der hydrophile Baustein ist polar und geht energetisch günstige Wechselwirkungen mit Wasser ein. Hierbei kann es sich um Säuregruppen wie z.B. Carbonsäure, Sulfonsäure, Phosphorsäure, Phosphonsäure oder neutralisierte Ausführungsformen dieser Gruppen, beispielsweise mit Alkali- oder Ammoniumionen als Ge- genion wie z.B. Natrium, Lithium, Kalium, Ammonium oder Tetraalkylammonium, wie z.B. Tetrabutylammonium, handeln. Ebenso kann der hydrophile Baustein ein ON- goether wie z.B. Oligoethylenoxid sein. Die Verknüpfung der Bausteine erfolgt entweder direkt oder durch sonstige, dem Fachmann bekannte chemische Linker wie z.B. eine Ester- oder Amidbindung. In einer Ausführungsform haben Amphiphile einen Krafftpunkt von mindestens 25°C, bevorzugt mindestens 400C und besonders bevorzugt mindestens 600C. Bei Temperaturen unterhalb des Krafftpunkts liegen keine Mizellen vor, und das Material erscheint wasserunlöslich. Es liegt eine geringe molekulare Restlöslichkeit vor, die unter 1 g/L, bevorzugt < 0,1 g/L, besonders bevorzugt <0,01 g/L und insbesondere < 0,001 g/L liegt. In einer bevorzugten Ausführungsform ist das Amphiphil in Wasser bei 20 °C zu höchstens 10 Gew.%, bevorzugt zu höchstens 1 Gew.%, besonders bevorzugt zu höchstens 0,1 Gew.%, speziell zu höchstens 0,01 Gew.% löslich.Generally, 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. Likewise, 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. In one embodiment, amphiphiles have a Krafftpunkt of at least 25 ° C, preferably at least 40 0 C and more preferably at least 60 0 C. At temperatures below the Krafftpunkts 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. In a preferred embodiment, 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.
Bevorzugt ist das Amphiphil eine aliphatische Säure oder deren Salz, wobei die alipha- tische Säure in Wasser bei 20 0C zu höchstens 10 Gew.% löslich ist. Die aliphatische Säure ist in Wasser bei 20 0C zu höchstens 10 Gew.%, bvorzugt höchstens 1 Gew.%, besonders bevorzugt höchstens 0,1 Gew.%, speziell höchstens 0,01 Gew.% löslich. Wenn das Amphiphil das Salz einer aliphatische Säure ist, so wird üblicherweise zur Bestimmung der Wasserlöslichkeit die aliphatische Säure verwendet. Die aliphatische Säure enthält übicherweise eine lineare oder verzweigte, gesättigten oder ungesättigten aliphatische Gruppe, sowie eine Säuregruppe, wie eine Carbonsäuregruppe, SuI- fonsäuregruppe oder Phosphorsäuregruppen, bevorzugt eine Carbonsäuregruppe. Geeignete Salze der aliphatischen Säure sind beispielsweise Alkali-, Erdalkali-, oder Ammoniumsalze der aliphatischen Säure. Mischungen vorgenannter aliphatische Säure, deren Salzen oder von aliphatische Säure mit Salzen aliphatische Säuren sind e- benfalls möglich.Preferably, 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. When 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- benfalls possible.
Die aliphatische Säure ist bevorzugt eine Fettsäure mit mindestens 20 Kohlenstoffatome. Bevorzugt enthält die Fettsäure 22 bis 36 Kohlenstoffatome. Sie kann linear oder verzweigt, gesättigt oder ungesättigt sein. Geeignete Fettsäuren sind beispielsweise Arachidonsäure (C20), Behensäure (C22), Erucasäure (C22), Lignocerinsäure (C24), Cerotinsäure (C26) oder Melissinsäure (C30), bevorzugt Erucasäure und Behensäure, insbesonder Erucasäure. Erucasäure (cis-13-Docosensäure) ist eine einfach ungesättigte Fettsäure, die sich in großer Menge im Samen von einigen Rapssorten und Meerkohlarten, vor allem im Abessinischen Meerkohl (Crambus abyssinica), findet.The aliphatic acid is preferably a fatty acid having at least 20 carbon atoms. Preferably, 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).
Meist enthält die erfindungsgemäße Dispersion höchstens 40 Gew.%, bevorzugt höchstens 35 Gew.%, besonders bevorzugt höchstens 30 Gew.% des Amphiphils bezogen auf den eingesetzten Wirkstoff. Die Dispersion enthält üblicherweise mindestens 1 Gew.%, bevorzugt mindestens 3 Gew.%, besonders bevorzugt mindestens 5 Gew.% und speziell mindestens 15 Gew.% des Amphiphils bezogen auf den eingesetzten Wirkstoff.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.
Eine wässrige Dispersion kann eine wässrige Emulsion oder wässrige Suspension sein, bevorzugt ist sie eine wässrige Suspension. Unter dem Begriff „Suspension" werden in diesem Zusammenhang insbesondere auch Dispersionen von Partikeln aus unterkühlten Schmelzen verstanden, die Partikel enthalten, die sich unterhalb ihres Gleichgewichtsschmelzpunktes befinden.An aqueous dispersion may be an aqueous emulsion or aqueous suspension, preferably it is an aqueous suspension. In this context, 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.
Eine wässrige Dispersion umfasst üblicherweise Wasser als kontinuierliche Phase und feste Partikel als disperse Phase. Meist enthält die erfindungsgemäße Dispersion 30 bis 98 Gew.%, bevorzugt 40 bis 90 Gew.%, besonders bevorzugt 50 bis 80 Gew.% Wasser.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.
Die Wirkstoffpartikel umfassen meist mindestens 80 Gew.%, bevorzugt mindestens 90 Gew.%, besonders bevorzugt mindestens 95 Gew.% Wirkstoff. Bevorzugt bestehen die Wirkstoffpartikel aus Wirkstoff. Der Gehalt an Wirkstoffpartikel mit einer Partikelgröße von unter 10 μm in der wässrigen Suspension kann in weiten Bereichen variieren, wie von 0,001 bis 50 Gew.%, bevorzugt von 0,01 bis 40 Gew.%.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 μm 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.
Die Partikelgröße der Wirkstoffpartikel bezeichnet üblicherweise die zahlenmittlere Par- tikelgröße. Sie liegt unter 10 μm, bevorzugt unter 2 μm, besonders bevorzugt unter 1 μm. Die Partikelgröße liegt meist über 5 nm, bevorzugt über 20 nm, besonders bevorzugt über 50 nm. Die Partikelgröße wird meist mittels Photonenkorrelationsspektrosko- pie (dynamische Lichtstreuung), beispielsweise mit einem Gerät der Marke Brookha- ven Instruments BI90, bestimmt. Die Probenvorbereitung, beispielsweise die Verdünnung auf Messkonzentration, hängt bei diesem Messverfahren unter anderem von der Feinheit und Konzentration der Wirkstoffe in der Dispersionssprobe sowie vom ver- wendeten Messgerät ab. Die Vorgehensweise muss für das jeweilige System ausgearbeitet werden und ist dem Fachmann bekannt.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.
Die festen Wirkstoffpartikel können kristallin oder amorph, bevorzugt amorph sein. A- morph bedeutet, dass die molekularen Bausteine eines homogenen Festkörpers nicht in Kristallgittern angeordnet sind. Amorphe Wirkstoffpartikel bedeutet, dass die Partikel weitgehend frei von kristallinem Wirkstoff sind, wobei bevorzugt von 80 bis 100 Gew.%, insbesondere von 90 bis 100 Gew.% des Materials amorph vorliegen. Amorphe Formen können von kristallinen Formen unterschieden werden durch verschiedene Methoden, beispielsweise durch mikroskopische Untersuchung in polarisiertem Licht, Dif- ferential Scanning Kalorimetrie (DSC), Röntgenbeugung oder Löslichkeitsvergleiche, bevorzugt durch DSC.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.
Geeignete Wirkstoffe sind beispielsweise Farbmittel, Kosmetikwirkstoffe, Pharmawirk- stoffe, Pestizide, , Düngemittel, Zusatzstoffe für Lebensmittel oder Tierfutter, Hilfsmittel für Polymere, Papier, Textil, Leder oder Wasch- und Reinigungsmittel. Ebenso sind Mischungen vorstehender Wirkstoffe geeignet. Im Allgemeinen sind Wirkstoffe gut geeignet, die in Wasser in Wasser höchstens zu 10 g/l, bevorzugt höchstens 1 g/l, besonders bevorzugt höchstens 0,1 g/l und speziell höchstens 0,01 g/ bei 20 0C löslich sind.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.
Die erfindungsgemäße Dispersion enthält meist 1 bis 60 Gew.%, bevorzugt 5 bis 50 Gew.% Wirkstoffpartikel bezogen auf die Dispersion. Üblicherweise enthält sie höchstens 40 Gew.%, bevorzugt höchstens 30 Gew.% Amphiphil bezogen auf den Wirkstoff enthalten sind. Üblicherweise enthält sie mindestens 0,1 Gew.%, bevorzugt mindes- tens 1 Gew.%, besonders bevorzugt mindestens 5 Gew. % Amphiphil bezogen auf den Wirkstoff enthalten sind.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.
Beispiele für Farbmittel sind Farbstoffe, Drucktinten, Pigmente, UV Absorber, optische Aufheller oder IR-Farbstoffe. Während organische Farbstoffe ein Absorptionsmaximum im Wellenlängenbereich von 400 bis 850 nm besitzen, haben optische Aufheller ein oder mehrere Absorptionsmaxima im Bereich von 250 bis 400 nm. Optische Aufheller emittieren bekanntlich beim Bestrahlen mit UV-Licht eine Fluoreszenzstrahlung im sichtbaren Bereich. Beispiele für optische Aufheller sind Verbindungen aus den Klassen der Bisstyrylbenzole, Stilbene, Benzoxazole, Cumarine, Pyrene und Naphthaline. Geeignet sind auch Markierungsstoffe für Flüssigkeiten, beispielsweise Mineralölmar- ker. Unter UV-Absorbern werden im Allgemeinen UV-Strahlen absorbierende Verbindungen verstanden, die die absorbierte Strahlung strahlungslos deaktivieren. Solche Verbindungen werden beispielsweise in Sonnenschutzmitteln und zur Stabilisierung von organischen Polymeren eingesetzt.Examples of 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.
Weitere geeignete Wirkstoffe sind Kosmetikwirkstoffe. Kosmetika sind Stoffe oder Zu- bereitungen aus Stoffen, die ausschließlich oder überwiegend dazu bestimmt sind, äußerlich am Körper des Menschen oder in seiner Mundhöhle zur Reinigung, Pflege, zum Schutz, zur Erhaltung eines guten Zustandes, zur Parfümierung, zur Veränderung des Aussehens oder dazu angewendet zu werden, den Körpergeruch zu beeinflussen.Other suitable active ingredients are cosmetic ingredients. 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.
Geeignet sind beispielsweise auch Antiinsektenmittel, wie Icaridin oder N,N-Diethyl- meta-toluamid (DEET).Also suitable are, for example, anti-insect agents, such as icaridine or N, N-diethyl-meta-toluamide (DEET).
Als Wirkstoffe können außerdem alle Pharmawirkstoffe eingesetzt werden.In addition, all active pharmaceutical ingredients can be used as active ingredients.
Weitere geeignete Wirkstoffe sind Zusatzstoffe für Lebensmittel oder Tierfutter, wie Lebensmittelfarbstoffe, Aminosäuren, Vitamine, Konservierungsmittel, Antioxidantien, Geruchs- oder Geschmackstoffe.Other suitable active ingredients are additives for food or animal feed, such as food dyes, amino acids, vitamins, preservatives, antioxidants, odors or flavors.
Als Wirkstoffe können auch Pestizide und Düngemittel verwendet werden, bevorzugt Pestizide.Pesticides and fertilizers may also be used as active ingredients, preferably pesticides.
Besonders bevorzugte Wirkstoffe sind Pestizide. Der Begriff Pestizid bezeichnet mindestens einen Wirkstoff ausgewählt aus der Gruppe der Fungizide, Insektizide, Nema- tizide, Herbizide, Safener und/oder Wachstumsregulatoren. Bevorzugte Pestizide sind Fungizide, Insektizide und Herbizide. Auch Mischungen von Pestiziden aus zwei oder mehr der vorgenannten Klassen können verwendet werden. Der Fachmann ist vertraut mit solchen Pestiziden, die beispielsweise in Pesticide Manual, 14th Ed. (2006), The British Crop Protection Council, London, gefunden werden können.Particularly preferred agents are pesticides. The term pesticide 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. Also, 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.
Geeignete Insektizide sind Insektizide der Klasse der Carbamate, Organophophate, Organochlor-Insektizide, Phenylpyrazole, Pyrethroide, Neonicotinoide, Spinosine, A- vermectine, Milbemycine, Juvenil Hormon Analoga, Alkylhalide, Organozinn-Suitable insecticides are insecticides of the class of carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosines, A-vermectins, milbemycins, juvenile hormone analogs, alkylhalides, organotin
Verbindungen, Nereistoxin-Analoga, Benzoylharnstoffe, Diacylhydrazine, METI Akari- zide, sowie Insektizide wie Chloropicrin, Pymetrozin, Flonicamid, Clofentezin, Hexythi- azox, Etoxazol, Diafenthiuron, Propargit, Tetradifon, Chlorfenapyr, DNOC, Buprofezin, Cyromazin, Amitraz, Hydramethylnon, Acequinocyl, Fluacrypyrim, Rotenon, oder derenCompounds, nereistoxin analogues, benzoylureas, diacylhydrazines, METI acaricides, and insecticides such as chloropicrin, pymetrozine, flonicamide, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifone, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnone, Acequinocyl, Fluacrypyrim, Rotenone, or their
Derivate.Derivatives.
Geeignete Fungizide sind Fungizide der Klassen Dinitroaniline, Allylamine, Anilinopy- rimidine, Antibiotica, aromatische Kohlenwasserstoffe, Benzenesulfonamide, Benzimi- dazole, Benzisothiazole, Benzophenone, Benzothiadiazole, Benzotriazine, Benzylcar- bamate, Carbamates, Carboxamide, Carbonsäureamdide, Chloronitrile, Cyano- acetamideoxime, Cyanoimidazole, Cyclopropanecarboxamide, Dicarboximide, Di- hydrodioxazine, Dinitrophenylcrotonate, Dithiocarbamate, Dithiolane, Ethylphosphona- te, Ethylaminothiazolcarboxamide, Guanidines, Hydroxy-(2-amino-)pyrimidine, Hydro- xyanilides, Imidazole, Imidazolinone, Anorganika, Isobenzofuranone, Methoxyacrylate, Methoxycarbamates, Morpholines, N-Phenylcarbamate, Oxazolidinedione, Oximinoa- cetate, Oximinoacetamide, Peptidylpyrimidinnucleoside, Phenylacetamide, Phenylami- de, Phenylpyrrole, Phenylharnstoffe, Phosphonate, Phosphorothiolate, Phthalamsäu- ren, Phthalimide, Piperazine, Piperidine, Propionamide, Pyridazinone, Pyridine, Pyridi- nylmethylbenzamide, Pyrimidinamine, Pyrimidine, Pyrimidinonehydrazone, Pyrroloqui- nolinone, Quinazolinone, Chinoline, Chinone, Sulfamide, Sulfamoyltriazole, Thiazole- carboxamide, Thiocarbamate, Thiocarbamate, Thiophanate, Thiophenecarboxamide, Toluamide, Triphenylzinn Verbindungen, Triazine, Triazole.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, inorganics, isobenzofuranones, methoxyacrylates, methoxycarbamates, morpholines, N-phenylcarbamates, oxazolidinediones, Oximinoacetates, oximinoacetamides, peptidylpyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles, phenylureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamides, pyrimidinamines, pyrimidines, pyrimidinonehydrazones, pyrroloquimers nolinone, quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles, thiazole-carboxamides, thiocarbamates, thiocarbamates, thiophanates, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines, triazoles.
Geeignete Herbizide sind Herbizide der Klassen der Acetamide, Amide, Aryloxypheno- xypropionate, Benzamide, Benzofuran, Benzoesäuren, Benzothiadiazinone, Bipyridyli- um, Carbamate, Chloroacetamide, Chlorcarbonsäuren, Cyclohexanedione, Dinitroanili- ne, Dinitrophenol, Diphenylether, Glycine, Imidazolinone, Isoxazole, Isoxazolidinone, Nitrile, N-phenylphthalimide, Oxadiazole, Oxazolidinedione, Oxyacetamide, Phenoxy- carbonsäuren, Phenylcarbamate, Phenylpyrazole, Phenylpyrazoline, Phenylpyridazine, Phosphinsäuren, Phosphoroamidate, Phosphorodithioate, Phthalamate, Pyrazole, Py- ridazinone, Pyridine, Pyridincarbonsäuren, Pyridinecarboxamide, Pyrimidindione, Pyri- midinyl(thio)benzoate, Chinolincarbonsäuren, Semicarbazone, Sulfonylaminocarbo- nyltriazolinone, Sulfonylharnstoffe, Tetrazolinone, Thiadiazole, Thiocarbamate, Triazine, Triazinone, Triazole, Triazolinone, Triazolinone, Triazolocarboxamide, Triazolopy- rimidine, Triketone, Uracile, Harnstoffe.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, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl (thio) benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolinones, triazolocarboxamides, triazolopyridines, triketones, uracils, ureas.
Bevorzugt werden Pestizide, die in Wasser unlöslich sind. Geeignete unlösliche Pestizide sind solche, die bei 20 0C in Wasser höchstens 3 Gew.%, bevorzugt höchstens 1 Gew.%, besonders bevorzugt höchstens 0,1 Gew. % und ganz speziell höchstens 0,01 % löslich sind. Geeignete unlösliche Pestizide sind beispielsweise (Löslichkeit in Was- ser bei 20 0C jeweils in Klammer) Pyraclostrobin (1 ,9 mg/l), Epoxiconazol (6,6 mg/l), Prochloraz (34 mg/l), bevorzugt Pyraclostrobin.Preference is given to pesticides which are insoluble in water. 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.
Die eingesetzten Pestizide sind oft Feststoffe bei 20 0C. Der Schmelzpunkt liegt bevorzugt bei mindestens 30 0C und bevorzugt bei mindestens 40 0C.The pesticides used are often solids at 20 ° C. The melting point is preferably at least 30 ° C. and preferably at least 40 ° C.
Die Erfindung betrifft auch ein Verfahren zur Herstellung der erfindungsgemäßen Dispersion indem man ein Wirkstoff und ein Amphiphil, wobei das Amphiphil in Wasser bei 20 0C zu höchstens 10 Gew.% löslich ist, in Kontakt bringt. Man kann den dispergierten Wirkstoff in Kontakt mit dem Amphiphil bringen oder nach dem in Kontakt bringen von Wirkstoff und Amphiphil dispergieren. Dem Fachmann sind verschiedenste Verfahren zur Dispergierung von Wirkstoffen wie Pestiziden allgemein bekannt. Geeignete Verfahren sind beispielsweise Fällungsverfahren, Emulgierverfahren, Evaporationsverfah- ren, Schmelzemulgierung oder Mahlverfahren, bevorzugt Fällungsverfahren. Bevorzugt wird der Wirkstoff und das Amphiphil in einem wässrigen System in Kontakt gebracht und dispergiert. Besonders bevorzugt wird das Amphiphil in einem organischen Lösungsmittel eingesetzt, speziell in dem gleichen Lösungsmittelsystem wie der Wirkstoff. Geeignete Wirkstoffe sind die vorgehend beschriebene. Üblicherweise ist das Wirkstoff in Wasser unlöslich. Bevorzugt ist der Wirkstoff ein Pestizid ist, das in Wasser unlöslich ist. Geeignete Amphiphile sind die vorgehend beschriebenen Amphiphile. Bevorzugt ist das Amphiphil ist eine Fettsäure, die mindestens 20, bevorzugt 22 bis 36, Kohlenstoffatome enthält.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. The person skilled in various methods for the dispersion of active substances such as pesticides are well known. Suitable processes are, for example, precipitation processes, emulsification processes, evaporation processes. ren, melt emulsification or milling process, preferably precipitation method. Preferably, the drug and the amphiphile are contacted and dispersed in an aqueous system. Particularly preferably, 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. Usually, the active ingredient is insoluble in water. Preferably, the active ingredient is a pesticide which is insoluble in water. Suitable amphiphiles are the amphiphiles described above. Preferably, the amphiphile is a fatty acid containing at least 20, preferably 22 to 36, carbon atoms.
Besonders bevorzugte Verfahren erfolgen dergestalt, dass man das eine wässrige Lösung bereitstellt, daen Wirkstoff und das Amphiphil in einem mit Wasser mischbaren organischen Lösungsmittel löst, und die beiden Lösungen turbulent mischt (Fällungsverfahren); den Wirkstoff und das Amphiphil in einem mit Wasser nicht mischbaren organischen Lösungsmittel löst, mit einer wässrigen Lösung turbulent mischt, und optional das organische Lösungsmittel entfernt (Emulgierverfahren, optional mit Evaporation); eine Schmelze enthaltend geschmolzenen Wirkstoff und das Amphiphil mit einer wässerigen Lösung mischt und abkühlt (Schmelzemulgierung); oder den Wirkstoff in Gegenwart des Amphiphil mahlt (Mahlverfahren).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).
Speziell geeignet ist ein Verfahren, indem man eine wässrige Lösung bereitstellt, den Wirkstoff und das Amphiphil in einem mit Wasser mischbaren organischen Lösungsmittel löst, und die beiden Lösungen turbulent mischt (Fällungsverfahren);Specifically, 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);
Die Lösung des Wirkstoff und des Amphiphils in einem mit Wasser mischbaren organischen Lösungsmittel enthält meist ein mit Wasser mischbares organisches Lösungsmittel. Mischbar mit Wasser bedeutet in diesem Zusammenhang, dass die organischen Lösungsmittel bei 20 0C ohne Phasenseparation zu mindestens 10 Gew.-%, bevorzugt zu 15 Gew.%, besonders bevorzugt zu 20 Gew.-% mit Wasser mischbar sind. Die Lösung kann optional weitere Formulierungshilfsmittel umfassen, beispielsweise Dispergiermittel. Die Lösung kann bei Bedarf bei erhöhter Temperatur hergestellt werden. Geeignete Lösungsmittel sind d-Cβ-Alkylalkohole wie Methanol, Ethanol, Propanol, Isopropanol, 1-Butanol, 2-Butanol, tert-Butanol, Ester, Ketone wie Aceton, Methylethyl- keton, Methylisopropylketon, Methylisobutylketon, Acetale, Ether, cyclische Ether wie Tetrahydrofuran, aliphatische Carbonsäuren wie Ameisensäure, Essigsäure, Propionsäure, N-substituierte oder N,N-disubstituierte-Carbonsäureamide wie Acetamid, Carbonsäureester wie beispielsweise Essigester und Lactone wie beispielsweise Butyro- lacton, Dimethylformamid (DMF) und Dimethylpropionamid, aliphatische und aromati- sehe Chlorkohlenwasserstoffe wie Methylenchlorid, Chloroform, 1 ,2-Dichlorethan oder Chlorbenzol, N-Lactame, Glykole wie Ethylenglykol oder Propylenglykol sowie Mischungen genannter Lösungsmittel. Bevorzugte Lösungsmittel sind Glykole, Methanol, Ethanol, Isopropanol, Dimethylformamid, N-Methylpyrrolidon, Methylenchlorid, Chloroform, 1 ,2-Dichlorethan, Chlorbenzol, Aceton, Methylethylketon, Methylisopropylketon, Methylisobutylketon, Tetrahydrofuran sowie Mischungen genannter Lösungsmittel. Besonders bevorzugte Lösungsmittel sind Propylenglykol, Methanol, Ethanol, Isopro- panol, Dimethylformamid und Tetrahydrofuran, insbesondere Propylenglykol.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 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 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, chloroform, 1, 2-dichloroethane or chlorobenzene, N-lactams, glycols such as ethylene glycol or propylene glycol and mixtures of said solvents. 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.
Die wässrige Lösung enthält Wasser und optional weitere Formulierungshilfsmittel, beispielsweise Dispergiermittel.The aqueous solution contains water and optionally further formulation auxiliaries, for example dispersants.
Zum turbulenten Mischen sind dem Fachmann allgemein bekannte Verfahren bekannt. Der Prozessschritt kann diskontinuierlich, beispielsweise in einem Rührbehälter, oder kontinuierlich durchgeführt werden. Kontinuierlich arbeitende Maschinen und Apparaturen zur Emulgierung sind beispielsweise sind Kolloidmühlen, Zahnkranzdispergierma- schinen und andere Bauformen dynamischer Mischer, weiterhin Hochdruckhomogeni- satoren, Pumpen mit nachgeschalteten Düsen, Ventilen, Membranen oder sonstigen engen Spaltgeometrien, statische Mischer, In-Iine Mischer nach dem Rotor-Stator- Prinzip (Ultra-Turrax, Inline Dissolver), Mikromischsysteme sowie Ultraschall- Emulgiersysteme. Bevorzugt werden Zahnkranzdispergiermaschinen oder Hochdruckhomogenisatoren eingesetzt. Die Temperatur der eingesetzten Lösungen kann von 20 bis 200 0C, bevorzugt bei 50 bis 150 0C betragen. In einer weiteren bevorzugten Ausführungsform kann das turbulente Mischen in einer Mischkammer erfolgen.For turbulent mixing, methods well known to those skilled in the art are known. 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. In a further preferred embodiment, the turbulent mixing can take place in a mixing chamber.
Die durch das erfindungsgemäße Verfahren hergestellte Dispersion kann verdünnt werden oder so wie sie sind weiter verwendet werden. Außerdem ist es möglich die wässrige Dispersion einzuengen.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.
Bei dem erfindungsgemäßen Verfahren wird üblicherweise ein Wirkstoff wie vorbeschrieben eingesetzt. Bevorzugt wird ein Pestizid eingesetzt, das in Wasser unlöslich ist. Als Amphiphil werden bei dem Verfahren meist die vorbeschriebenen aliphatischen Säuren eingesetzt, insbesondere eine Fettsäure, die mindestens 20, bevorzugt 22 bis 36, Kohlenstoffatome enthält.In the method according to the invention is usually an active ingredient as described above. Preferably, a pesticide is used which is insoluble in water. As 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.
Optional können weitere Formulierungshilfmittel vor, während oder nach dem Verfahren zugesetzt werden. Formulierungshilfsmittel sind beispielsweise Lösungsmittel, Tenside, anorganischen Emulgatoren (sog. Pickering-Emulgatoren), Antischäumungs- mittel, Verdicker, Frostschutzmittel, sowie Bakterizide. Für die Saatgutbeize gedachte Formulierungen können zusätzlich noch Kleber sowie gegebenenfalls Pigmente enthalten.Optionally, further formulation auxiliaries may be added before, during or after the process. Formulation aids are, for example, solvents, surfactants, inorganic emulsifiers (so-called Pickering emulsifiers), antifoaming agents, thickeners, antifreeze agents, and also bactericides. For seed dressing intended formulations may additionally contain adhesives and optionally pigments.
Als Lösungsmittel kommen Wasser, organische Lösungsmittel wie Mineralölfraktionen von mittlerem bis hohem Siedepunkt wie Kerosin und Dieselöl, ferner Kohlenteeröle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromati- sehe Kohlenwasserstoffe, z.B. Paraffine, Tetrahydronaphthalin, alkylierte Naphthaline und deren Derivate, alkylierte Benzole und deren Derivate, Alkohole wie Methanol, Ethanol, Propanol, Butanol und Cyclohexanol, Gykole, Ketone wie Cyclohexanon, gamma-Butyrolacton, Dimethylfettsäureamide, Fettsäuren und Fettsäureester und stark polare Lösungsmittel, z.B. Amine wie N-Methylpyrrolidon, in Betracht. Grundsätzlich können auch Lösungsmittelgemische verwendet werden sowie Gemische aus den vorstehend genannten Lösungsmitteln und Wasser. Bevorzugt werden die vorgenannten Lösungsmittel erst nach dem Verfahren zugesetzt, wenn eine Dispersion des Wirkstoffs entstanden ist.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, Dimethylfettsäureamide, fatty acids and fatty acid esters and highly polar Solvents, for example amines such as N-methylpyrrolidone, into consideration. In principle, solvent mixtures and mixtures of the abovementioned solvents and water can also be used. Preferably, the abovementioned solvents are added only after the process when a dispersion of the active ingredient has formed.
Meist enthält die erfindungsgemäße wässrige Dispersion höchstens 30 Gew.%, bevorzugt höchsten 20 Gew.%, insbesondere höchstens 10 Gew.% organisches Lösungsmittel.In most cases, 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.
Im Allgemeinen werden anionische, kationische und/oder nichtionische Tenside zugesetzt. Gebräuchliche nichtionische Tenside sind beispielsweise ethoxylierte Mono-, Di- und Tri-Alkylphenole (Ethoxilierungsgrad von 3 bis 50, Alkylrest: C4 bis C12) sowie e- thoxylierte Fettalkohole (Ethoxilierungsgrad von 3 bis 80; Alkylrest: Cs bis C36). Beispiele hierfür sind die Lutensol® A-Marken (C12 bis Cu-fettalkoholethoxylate, Ethoxilie- rungsgrad von 3 bis 8), Lutensol® AO-Marken (C13 bis Cis-Oxoalkoholethoxylate, E- thoxilierungsgrad von 3 bis 30), Lutensol® AT-Marken (C16 bis Cis-Fettalkohol- ethoxylate, Ethoxilierungsgrad von 1 1 bis 80), Lutensol® ON-Marken (Cio-Oxoalkohol- ethoxylate, Ethoxilierungsgrad von 3 bis 1 1 ) und die Lutensol® TO-Marken (Cis- Oxoalkoholethoxylate, Ethoxilierungsgrad von 3 bis 20) der BASF SE. Weiterhin ge- eignet sind amphiphile Polymere, beispielsweise wie in EP 1 756 188 B1 , Absatz [0012] bis [0068], oder in DE 10 2006 001 529 A1 , Absatz [0025] bis [0055], beschrieben oder auf Basis der Monomeren Acrylsäure, Butylmethacrylat, Methylmethacrylat, Hydroxyethylmethacrylat und/oder iso-Butylmethacrylat. Geeignet sind auch amphiphile Blockpolymere, insbesondere auf Basis Ethylenoxid-Propylenoxid. Beispiele sind Pluronic® PE Marken (EO-PO-EO Triblockpolymere; EO: Ethylenoxid, PO: Propyleno- xid). Geeignet sind auch Kammpolymere, besonders auf Basis von Alkoxypolyoxyalky- len(meth)acrylaten, wie Kammpolmyere aus Methylmethacrylat, Methacrylsäure und (Methoxypolyethylenglykol)methacrylat (kommerziell erhältlich als Atlox® 4913 von Uniqema). Gebräuchlich sind auch Polysaccharide und deren Derivate, bevorzugt Po- lysaccharide auf Basis Inulin, beispielsweise Inutec® SP1 (Inulin aus Chicoree mit aufgepfropften Alkylgruppen).In general, 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). Examples are the 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 (Cio-oxoalcohol ethoxylates, degree of ethoxylation from 3 to 1 l) and the Lutensol® TO grades (cis-oxo alcohol ethoxylates, degree of ethoxylation from 3 to 20) of BASF SE. Also suitable are 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. Also suitable are 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). Also suitable are 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). Also common are polysaccharides and their derivatives, preferably polysaccharides based on inulin, for example Inutec® SP1 (inulin from chicory with grafted alkyl groups).
Übliche anionische Tenside sind z.B. Alkalimetall- und Ammoniumsalze von Alkylsulfa- ten (Alkylrest: C8 bis C12), beispielsweise Natriumdodecylsulfat, von Schwefelsäure- halbestern ethoxylierter Alkanole (Ethoxilierungsgrad von 4 bis 30, Alkylrest: C12 bis Cis) und ethoxylierter Alkylphenole (Ethoxilierungsgrad von 3 bis 50, Alkylrest: C4 bis C12), von Alkylsulfonsäuren (Alkylrest: C12 bis Ciβ) und von Alkylarylsulfonsäuren (Alkyl- rest: Cg bis de). Als weitere anionische Tenside haben sich ferner Verbindungen der allgemeinen Formel (I)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)
worin R1 und R2 H-Atome oder C4- bis C24-Alkyl bedeuten und nicht gleichzeitig H- Atome sind, und M1 und M2 Alkalimetallionen und/oder Ammoniumionen sein können, erwiesen. In der allgemeinen Formel (I) bedeuten R1 und R2 bevorzugt lineare oder verzweigte Alkylreste mit 6 bis 18 C-Atomen, insbesondere mit 6, 12 und 16 C-Atomen oder Wasserstoff, wobei R1 und R2 nicht beide gleichzeitig H-Atome sind. M1 und M2 sind bevorzugt Natrium, Kalium oder Ammonium, wobei Natrium besonders bevorzugt ist. Besonders vorteilhaft sind Verbindungen (I), in denen M1 und M2 Natrium, R1 ein verzweigter Alkylrest mit 12 C-Atomen und R2 ein H-Atom oder R1 ist. Häufig werden technische Gemische verwendet, die einen Anteil von 50 bis 90 Gew.-% des monoal- kylierten Produktes aufweisen, wie beispielsweise Dowfax® 2A1 (Marke der Dow Chemical Company). Geeignet sind auch Salze von Dialkylsulphosuccinaten, wie Natriumdioctylsulphosuccinat (kommerziell erhältlich als Lutensit® A-BO von BASF SE). Weiterhin geeignet sind Arylphenolalkoxylate oder deren sulfatierte oder phospha- tierte Derivate, besonders ethoxylierte Di- und Tristryrylphenole oder deren sulfatierte oder phosphatierte Derivate, wie Soprophor ® von Rhodia (Ammoniumsalz des ethoxy- lierten Tristyrylphenolsulfats mit etwa 16 Ethylenoxidgruppen pro Molekül). Ebenso geeignet sind teilneutralisierte Alkalisalze von (Meth)Acrylsäure-Maleinsäure- Copolymere, beispielsweise die Sokalan®-Marken der BASF, insbesondere Sokalan CP45 (Acrylsäure-Maleinsäure-Copolymerisat, Natriumsalz, teilweise neutralisiert). wherein 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. In the general formula (I), 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 . Frequently, 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). Also suitable are salts of dialkyl sulphosuccinates, such as sodium dioctyl sulphosuccinate (commercially available as Lutensit® A-BO from BASF SE). Also suitable are 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). Also suitable are 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).
Geeignete kationische Tenside sind in der Regel einen Ce- bis Cis-Alkyl-, -Alkylaryl- oder heterocyclischen Rest aufweisende kationische Salze, zum Beispiel primäre, sekundäre, tertiäre oder quartäre Ammoniumsalze, Alkanolammoniumsalze, Pyridinium- salze, Imidazoliniumsalze, Oxazoliniumsalze, Morpholiniumsalze, Thiazoliniumsalze sowie Salze von Aminoxiden, Chinoliniumsalze, Isochinoliniumsalze, Tropyliumsalze, Sulfoniumsalze und Phosphoniumsalze. Beispielhaft genannt seien Dodecylammoniu- macetat oder das entsprechende Sulfat, die Sulfate oder Acetate der verschiedenen 2- (N,N,N-Trimethylammonium)ethylparaffinsäureester, N-Cetylpyridiniumsulfat, N- Laurylpyridiniumsulfat sowie N-Cetyl-N,N,N-trimethylammoniumsulfat, N-Dodecyl- N,N,N-trimethylammoniumsulfat, N-Octyl-N,N,N-trimethlyammoniumsulfat, N, N- Distearyl-N,N-dimethylammoniumsulfat sowie das Gemini-Tensid N,N'-(Lauryl- dimethyl)ethylendiamindisulfat, ethoxyliertes Talgfettalkyl-N-methylammoniumsulfat und ethoxyliertes Oleylamin (beispielsweise Uniperol® AC der BASF SE, ca. 12 Ethy- lenoxideinheiten). Wesentlich ist, dass die anionischen Gegengruppen möglichst gering nucleophil sind, wie beispielsweise Perchlorat, Sulfat, Phosphat, Nitrat und Carbo- xylate, wie Acetat, Trifluoracetat, Trichloracetat, Propionat, Oxalat, Citrat, Benzoat, sowie konjugierte Anionen von Organosulfonsäuren, wie zum Beispiel Methylsulfonat, Trifluormethylsulfonat und para-Toluolsulfonat, weiterhin Tetrafluoroborat, Tetraphe- nylborat, Tetrakis(pentafluorophenyl)borat, Tetrakis[bis(3,5-trifluormethyl)phenyl]borat, Hexafluorophosphat, Hexafluoroarsenat oder Hexafluoroantimonat.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. 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 ethoxylated oleylamine (for example Uniperol® AC from BASF SE, about 12 ethylene oxide units). It is essential that 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.
Die Konzentration des zugesetzten Tensids bzw. deren Mischung kann in weiten Bereichen variieren. Üblicherweise werden Konzentrationen von 0,1 bis 30 Gew.%, bezogen auf die wässerige Disperson verwendet.The 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.
Beispiele für anorganische Emulgatoren sind Metallsalze, wie Salze, Oxide und Hydroxide von Calcium, Magnesium, Eisen, Zink, Nickel, Titan, Aluminium, Silicium, Barium oder Mangan. Zu nennen sind Magnesiumhydroxid, Magnesiumcarbonat, Magnesiumoxid, Calciumoxalat, Calciumcarbonat, Bariumcarbonat, Bariumsulfat, Titandioxid, A- luminiumoxid, Aluminiumhydroxid und Zinksulfid. Silikate, Bentonit, Hydroxyapatit und Hydrotalcite seien ebenfalls genannt.Examples of 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.
Beispiele für Verdicker (Verbindungen, die der Formulierung ein pseudo-plastisches Fließverhalten verleihen, d.h. hohe Viskosität im Ruhezustand und niedrige Viskosität im bewegten Zustand) sind beispielsweise Polysaccharide, wie Xanthan Gum, oder organische Schichtmineralien.Examples of thickeners (compounds which impart a pseudo-plastic rheology to the formulation, i.e. high-level high viscosity and low viscosity in the agitated state) are, for example, polysaccharides such as xanthan gum or organic layer minerals.
Als Antischaummittel kommen beispielsweise Silikonemulsionen, langkettige Alkohole, Fettsäuren, fluororganische Verbindungen und deren Gemische in Betracht.Suitable antifoams are, for example, silicone emulsions, long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.
Bakterizide können zur Stabilisierung der wässrigen Formulierung zugesetzt werden. Als Bakterizide, die in den erfindungsgemäßen Formulierungen enthalten sein können, kommen alle zur Formulierung von agrochemischen Wirkstoffen üblichen Bakterizide in Betracht wie zum Beispiel Diclorophen und Benzylalkoholhemiformal.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.
Geeignete Frostschutzmittel sind beispielsweise mehrwertige Alkohole wie Ethylengly- col, Propylenglycol oder Glycerin, bevorzugt Glycerin. Üblicherweise werden 0 bis 30 Gew.%, bevorzugt 10 bis 20 Gew.% bezogen auf die wässerige Lösung zugesetzt.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.
Als Kleber, die in Beizmittel-Formulierungen enthalten sein können, kommen alle übli- chen in Beizmitteln einsetzbaren Bindemittel in Frage. Vorzugsweise genannt seien Polyvinylpyrrolidon, Polyvinylacetat, Polyvinylalkohol und Tylose.As adhesives which may be present in seed dressing formulations, all conventional binders which can be used in pickling agents are suitable. Preferably mentioned are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose.
Des weiteren können den erfindungsgemäßen Formulierungen optional auch Farbstoffe zugesetzt werden. Hierbei kommen alle für derartige Zwecke üblichen Farbstoffe in Betracht, beispielsweise Cl. Pigment Red 48:2. Dabei sind sowohl in Wasser wenig lösliche Pigmente als auch in Wasser lösliche Farbstoffe verwendbar. Kristallisationsinhibitoren brauchen im Allgemeinen nicht zugesetzt werden. Bevorzugt werden höchstens 5 Gew.%, besonders bevorzugt höchstens 1 Gew.% und speziell keine Kristallisationsinhibitoren zugesetzt.Furthermore, it is optionally also possible to add 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.
Die vorliegende Erfindung betrifft ferner eine feste Zusammensetzung umfassend Wirkstoffpartikel mit einer Partikelgröße von bis zu 10 μm und einem Amphiphil, erhalten durch Trocknung der erfindungsgemäßen Dispersion. Die Trocknung kann beispielsweise durch Sprühtrocknung erfolgen. Der Wasserhalt der festen Zusammensetzung beträgt oft höchstens 10 Gew.%, bevorzugt höchstens 3 Gew.%, insbesondere 0,5 Gew.%.The present invention furthermore relates to a solid composition comprising active ingredient particles having a particle size of up to 10 μm 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.
Die Erfindung betrifft ferner die Verwendung eines eines Amphiphils, beispielsweise einer aliphatische Säure oder deren Salz, wobei die aliphatische Säure in Wasser bei 20 0C zu höchstens 10 Gew.% löslich ist, zur Verlangsamung des Wachstums von Wirkstoffpartikeln mit einer Partikelgröße von bis zu 10 μm in wässriger Dispersion. Unter der Verlangsamung des Partikelwachstums versteht man, dass nach 24 h Lagerung der Dispersion bei 20 0C die Partikelgröße weniger zugenommen hat als bei einer Vergleichslösung ohne Amphiphil.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 μm 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.
Die erfindungsgemäße Dispersion oder die erfindungsgemäße feste Zusammensetzung kann verwendet werden zur Bekämpfung von phytopathogenen Pilzen und/oder unerwünschtem Pflanzenwuchs und/oder unerwünschtem Insekten- oder M üben befall und/oder zur Regulation des Wachstums von Pflanzen, indem man die Dispersion oder die feste Zusammensetzung auf die jeweiligen Schädlinge, deren Lebensraum und/oder die vor dem jeweiligen Schädling zu schützenden Pflanzen, den Boden und/oder auf unerwünschte Pflanzen und/oder die Nutzpflanzen und/oder deren Lebensraum einwirken lässt.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.
Die erfindungsgemäße Dispersion oder die erfindungsgemäße feste Zusammenset- zung kann verwendet werden zur Bekämpfung von unerwünschtem Insekten- oder Milbenbefall auf Pflanzen und/oder zur Bekämpfung von phytopathogenen Pilzen und/oder zur Bekämpfung unerwünschten Pflanzenwuchs indem man Saatgüter von Nutzpflanzen mit der Dispersion oder der festen Zusammensetzung behandelt.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.
Die Erfindung betrifft ferner Saatgut, behandelt mit der erfindungsgemäßen Dispersion oder der erfindungsgemäßen festen Zusammensetzung. Der Ausdruck "behandelt" bedeutet im Allgemeinen gebeizt. Durch das Beizen des Saatguts verbleibt die erfindungsgemäße Dispersion üblicherweise auf dem Saatgut. Bevorzugt enthält das Saatgut die erfindungsgemäßen Dispersion oder die erfindungsgemäßen feste Zusammen- setzung. Vorteil der vorliegenden Erfindung ist, dass die wässrigen Dispersion von Wirkstoffpar- tikel mit einer Partikelgröße von unter 10 μm ein verlangsamtes Partikel Wachstum (Ostwaldreifung) aufweist. Weiterer Vorteil ist, dass die Partikel sich langsamer absetzen und nicht oder langsamer auskristallisieren. Vorteilhaft ist auch, dass diese Stabili- sierung der Disperison mit Hilfe eines umweltverträglichen Mittels, nämlich beispielsweise einer Fettsäure, erreicht wurde. Das erfindungsgemäße Verfahren hat den Vorteil, dass es mit bestehenden Anlagen durchgeführt werden kann. Des weiteren sind stabile wässrige Dispersionen von Wirkstoffpartikeln zugänglich.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. By pickling the seed, 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 μm 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.
Nachfolgende Beispiele erläutern die Erfindung ohne sie einzuschränken.The following examples illustrate the invention without limiting it.
BeispieleExamples
Zunächst wurden 16g Pyraclostrobin und 0 / 1 / 2 / 4 g (0 / 6 / 1 1 / 25 Gew.% bezüglich Pyraclostrobin) Erucasäure in 144g Propylenglycol eine Stunde mit 3 mm Glaskugeln mit einer Schüttelmaschine (Red Devil) suspendiert. Die resultierende, noch grobteilige Suspension wurde mit einer Fließgeschwindigkeit von 1 kg/h durch eine Mischdüse einer Lösezelle zugefahren. Dort wurde Propylenglycol mit einer Temperatur von 200 0C mit einer Pumprate von 2kg/h zugefahren. In der Lösezelle wurden beiden Ströme turbulent gemischt und eine Lösung von Pyraclostrobin und Erucasäure erzeugt.First, 16 g of pyraclostrobin and 0/1/2/4 g (0/6/1 1/25 wt.% With respect to pyraclostrobin) of erucic acid 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 suspension 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 and erucic acid was produced.
Die so erhaltene Lösung wurde in eine zweite Mischdüse gefahren und mit Wasser (vorgekühlt auf 5 0C) mit einer Pumprate von 16 kg/h turbulent gemischt. Bei der Mi- schung findet eine Partikelbildung von Pyraclostrobin statt. Das so entstandene amorphe Präzipitat von Pyraclostrobin wurde ausgetragen und analysiert. Die wässrige Suspension enthielt 0,42 Gew.% Pyraclostrobin und 0 / 0,025 / 0,05 / 0,11 Gew.% Erucasäure.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.
Die Partikelgrößen von Pyraclostrobin wurden währen 24 h mittels Laserbeugung (MaI- vern Mastersizer S) und Laserstreuung (Brookhaven Instruments BI90) bestimmt (Tabelle 1 und 2).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).
Zum Vergleich wurde der Versuch wiederholt, wobei Erucasäure durch 4 g Natriumdo- deculsulfat (SDS) ersetzt wurde. Die so erhaltene wässrige Suspension enthielt 0,42 Gew.% Pyraclostrobin und 0,1 Gew.% SDS.For comparison, the experiment was repeated replacing erucic acid with 4 g of sodium dodecane sulfate (SDS). The aqueous suspension thus obtained contained 0.42% by weight of pyraclostrobin and 0.1% by weight of SDS.
Der Versuch zeigte, dass die Formulierungen mit Erucasäure ein verlangsamtes Partikelwachstum im Vergleich Ansatz ohne Erucasäure aufweisen. Tabelle"! : Analytik der Partikelgröße von Pyraclostrobin (Anteil <1 μm in %) mit Laserbeugung The experiment showed that formulations containing erucic acid have slower particle growth compared with no erucic acid. Table "!: Analysis of the particle size of pyraclostrobin (proportion <1 μm in%) with laser diffraction
Tabelle 2: Analytik der Partikelgröße (D in nm) von Pyraclostrobin mit Laserstreuung Table 2: Analysis of the particle size (D in nm) of pyraclostrobin with laser scattering

Claims

Ansprüche claims
1. Wässrige Dispersion umfassend feste Wirkstoffpartikel mit einer Partikelgröße von bis zu 10 μm und ein Amphiphil, dadurch gekennzeichnet, dass das Amphiphil ei- ne aliphatische Säure oder deren Salz ist, wobei die aliphatische Säure eine Fettsäure mit mindestens 20 Kohlenstoffatomen ist, und in Wasser bei 20 0C zu höchstens 10 Gew.% löslich ist.1. Aqueous dispersion comprising solid drug particles having a particle size of up to 10 microns and an amphiphile, characterized in that the amphiphile is an aliphatic acid or its salt, wherein the aliphatic acid is a fatty acid having at least 20 carbon atoms, and in water at 20 0 C to not more than 10 wt.% Is soluble.
2. Dispersion nach Anspruch 1 , dadurch gekennzeichnet, dass die aliphatische Säu- re eine Fettsäure mit 22 bis 36 Kohlenstoffatomen ist.2. Dispersion according to claim 1, characterized in that the aliphatic acid is a fatty acid having 22 to 36 carbon atoms.
3. Dispersion nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass der Wirkstoff in Wasser höchstens zu 10 g/l bei 20 0C löslich ist.3. Dispersion according to one of claims 1 or 2, characterized in that the active ingredient in water at most 10 g / l at 20 0 C is soluble.
4. Dispersion nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Wirkstoff ein Pestizid ist.4. Dispersion according to one of claims 1 to 3, characterized in that the active ingredient is a pesticide.
5. Dispersion nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass höchstens 40 Gew.% Amphiphil bezogen auf den Wirkstoff enthalten sind.5. Dispersion according to one of claims 1 to 4, characterized in that at most 40 wt.% Amphiphile based on the active ingredient are included.
6. Dispersion nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass 1 bis 60 Gew.% Wirkstoffpartikel bezogen auf die Dispersion enthalten sind.6. Dispersion according to one of claims 1 to 5, characterized in that 1 to 60 wt.% Active ingredient particles are contained based on the dispersion.
7. Dispersion nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Wirkstoff partikel aus Wirkstoff bestehen.7. Dispersion according to one of claims 1 to 6, characterized in that the active ingredient particles consist of active ingredient.
8. Verfahren zur Herstellung einer Dispersion gemäß einem der Ansprüche 1 bis 7, indem man den Wirkstoff und das Amphiphil in Kontakt bringt.8. A process for the preparation of a dispersion according to any one of claims 1 to 7, by bringing the active ingredient and the amphiphile in contact.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass der Wirkstoff ein Pestizid ist, das in Wasser unlöslich ist.9. The method according to claim 8, characterized in that the active ingredient is a pesticide which is insoluble in water.
10. Feste Zusammensetzung umfassend Wirkstoff partikel mit einer Partikelgröße von bis zu 10 μm und einem Amphiphil, erhalten durch Trocknen der wässrigen Dis- persion gemäß einem der Ansprüche 1 bis 7.10. Solid composition comprising active ingredient particles having a particle size of up to 10 microns and an amphiphile obtained by drying the aqueous dispersion according to any one of claims 1 to 7.
1 1. Verwendung eines Amphiphil gemäß einem der Ansprüche 1 bis 7 zur Verlangsamung des Wachstums von Wirkstoffpartikeln mit einer Partikelgröße von bis zu 10 μm in wässrigen Dispersionen.1 1. Use of an amphiphile according to any one of claims 1 to 7 for slowing down the growth of active ingredient particles having a particle size of up to 10 microns in aqueous dispersions.
12. Verwendung der Dispersion gemäß einem der Ansprüche 1 bis 7 oder der festen Zusammensetzung gemäß Anspruch 10 zur Bekämpfung von phytopathogenen Pilzen und/oder unerwünschtem Pflanzenwuchs und/oder unerwünschtem Insekten- oder Milbenbefall und/oder zur Regulation des Wachstums von Pflanzen, indem man die Dispersion oder die feste Zusammensetzung auf die jeweiligen Schädlinge, deren Lebensraum und/oder die vor dem jeweiligen Schädling zu schützenden Pflanzen, den Boden und/oder auf unerwünschte Pflanzen und/oder die Nutzpflanzen und/oder deren Lebensraum einwirken lässt.12. Use of the dispersion according to any one of claims 1 to 7 or the solid composition according to claim 10 for controlling phytopathogenic Fungi and / or undesired plant growth and / or unwanted insect or mite infestation; and / or for regulating the growth of plants by applying the dispersion or solid composition to the respective pests, their habitat and / or the plants to be protected from the respective pest , the soil and / or on unwanted plants and / or the crops and / or their habitat act.
13. Verwendung der Dispersion gemäß einem der Ansprüche 1 bis 7 oder der festen Zusammensetzung gemäß Anspruch 10 zur Bekämpfung von unerwünschtem In- sekten- oder Milbenbefall auf Pflanzen und/oder zur Bekämpfung von phytopatho- genen Pilzen und/oder zur Bekämpfung unerwünschten Pflanzenwuchses, indem man Saatgüter von Nutzpflanzen mit der Dispersion oder der festen Zusammensetzung behandelt.13. Use of the dispersion according to any one of claims 1 to 7 or the solid composition according to claim 10 for controlling unwanted 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.
14. Saatgut, enthaltend die Dispersion gemäß einem der Ansprüche 1 bis 7 oder die feste Zusammensetzung gemäß Anspruch 10. 14. Seed containing the dispersion according to any one of claims 1 to 7 or the solid composition according to claim 10.
EP09765128A 2008-12-18 2009-12-10 Aqueous dispersion comprising pesticide particles and an amphiphile Withdrawn EP2378868A2 (en)

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JP5568093B2 (en) 2014-08-06
CN102316726A (en) 2012-01-11
WO2010079037A2 (en) 2010-07-15

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