EP2627171A1 - Composition comprising a pesticide and a polycarboxylate ether - Google Patents

Composition comprising a pesticide and a polycarboxylate ether

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Publication number
EP2627171A1
EP2627171A1 EP11764184.5A EP11764184A EP2627171A1 EP 2627171 A1 EP2627171 A1 EP 2627171A1 EP 11764184 A EP11764184 A EP 11764184A EP 2627171 A1 EP2627171 A1 EP 2627171A1
Authority
EP
European Patent Office
Prior art keywords
composition
plants
pesticide
atoms
composition according
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Withdrawn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
EP11764184.5A
Other languages
German (de)
French (fr)
Inventor
Torsten Knieriem
Charles W. Finch
Claudia Klodwig
Silke Flakus
Gerhard Albrecht
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
Priority claimed from EP10188735A external-priority patent/EP2443923A1/en
Application filed by BASF SE filed Critical BASF SE
Priority to EP11764184.5A priority Critical patent/EP2627171A1/en
Publication of EP2627171A1 publication Critical patent/EP2627171A1/en
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants

Definitions

  • a composition comprising a pesticide and a polycarboxylate ether
  • the present invention is a composition
  • a composition comprising a pesticide having a solubility in water of at most 10 g / l and a polycarboxylate based on a) components of the formula Ia and / or Ib and / or Ic as defined below and b) assemblies of general formula II as defined below.
  • Another object is a method of making the composition by contacting the pesticide and the polycarboxylate ether.
  • the invention further relates to a method for controlling phytopathogenic fungi and / or undesired plant growth and / or unwanted insect or mite infestation and / or for regulating the growth of plants, wherein the composition of the respective pests, their habitat or before the respective Pest to be protected plants, the soil and / or undesirable plants and / or the crops and / or their habitat act. Furthermore, the invention relates to seed containing the composition. Combinations of preferred features with other preferred features are encompassed by the present invention.
  • WO 2006/000592 discloses the use of amphiphilic polyether group-containing polymers as solubilizers, the polymers containing a hydrophobic monomer (such as styrene), an allyl alcohol alkoxylate, and optionally ethylenically unsaturated mono- or dicarboxylic acids.
  • a hydrophobic monomer such as styrene
  • an allyl alcohol alkoxylate such as styrene
  • optionally ethylenically unsaturated mono- or dicarboxylic acids optionally ethylenically unsaturated mono- or dicarboxylic acids.
  • WO 2009/007328 discloses the use of copolymers based on
  • a disadvantage of the known polymers is that allyl ethers can be copolymerized poorly as comonomers and that high molar masses of the polymers are difficult to achieve.
  • dispersant should also stabilize highly concentrated solid formulations after dilution with water.
  • suspensions especially suspension concentrates
  • low levels of addition of dispersant reduce serum formation and increase storage stability.
  • the dispersants should be readily available.
  • the dispersant can also be used in the treatment of seed with pesticides, for example, to achieve a high loading of the stain with active ingredient.
  • composition comprising a pesticide having a solubility in water of not more than 10 g / l and a polycarboxylate ether based on a) structural groups of the formula Ia and / or Ib and / or Ic as defined below and b) structural groups of the general Formula II as defined below.
  • Suitable polycarboxylate ethers are polymers based on
  • R 1 hydrogen or an aliphatic hydrocarbon radical having 1 to 20
  • M hydrogen, a monovalent or divalent metal cation, ammonium ion, an organic amine radical,
  • R 2 hydrogen, an aliphatic hydrocarbon radical having 1 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, an optionally substituted aryl radical having 6 to 14 C atoms,
  • n 0 to 200
  • ⁇ ', ⁇ " independently from 0 to 200
  • n + n 1 to 200
  • Hydrogen an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 carbon atoms, an optionally substituted aryl radical having 6 to 14 carbon atoms, mean.
  • copolymers according to the present invention contain at least 2 components a), and b).
  • additional components c) and d) may be present.
  • the first component a) is a mono- or dicarboxylic acid derivative having the general formula Ia, Ib or Ic.
  • R 1 is hydrogen or an aliphatic hydrocarbon radical having 1 to 20 C atoms, preferably a methyl group
  • X in the structures Ia and Ib is - O a M and / or - O - (cmH 2 mO) n - R 2 or - NH - (cmH 2 mO) n - R 2 with the following meaning for M, a, m, n and R 2 :
  • M is preferably hydrogen, a monovalent or divalent metal cation, or ammonium.
  • Substituted ammonium groups which are derived from primary, secondary or tertiary C 1-20 -alkylamines, C 1-20 -alkanolamines, C 3-8 -cycloalkylamines and C 8-14 -arylamines are preferably used as organic amine radicals.
  • R 2 is hydrogen, an aliphatic hydrocarbon radical having 1 to 20 C
  • the aliphatic hydrocarbons may hereby be linear or branched and saturated or unsaturated.
  • Preferred cycloalkyl radicals are cyclopentyl or cyclohexyl radicals
  • the preferred aryl radicals are phenyl or naphthyl radicals, which may in particular be substituted by hydroxyl, carboxyl or sulfonic acid radicals.
  • the second component b) corresponds to formula II and is derived from oxyalkylene glycol alkenyl ethers.
  • R 3 in turn represents hydrogen or an aliphatic hydrocarbon radical having 1 to 5 C atoms, which may also be linear or branched or unsaturated, p may assume values between 0 and 3.
  • the sum n '+ n" is preferably 3 to 150, in particular 5 to 100.
  • m 2 and / or 3, so that they are polyalkylene oxide groups which are derived from polyethylene oxide and / or polypropylene oxide.
  • p in formula II is 0 or 1, d. H. it is vinyl and / or alkyl cyano I koxy I ate.
  • the PCEs usually contain 50 to 95 mol% of the structural units of the formula Ia and / or Ib and / or Ic, and 5 to 50 mol% of the formula II, and optionally up to 20% by weight of comonomers.
  • These polymers preferably contain 55 to 75 mol% of structural groups of the formula Ia and / or Ib, 19.5 to 39.5 mol% of structural groups of the formula II, and optionally up to 20 mol% of comonomers.
  • the copolymers according to the invention additionally contain up to 50 mol%, in particular up to 20 mol% based on the sum of the components a) and b), optional comonomers.
  • Optional comonomers may be any copolymerizable ethylenically unsaturated monomers.
  • Examples are vinyl or (meth) acrylic acid derivatives such as styrene, ⁇ -methylstyrene, vinyl acetate, vinyl propionate, ethylene, propylene, isobutene, hydroxyalkyl (meth) acrylates, acrylamide, methacrylamide, N-vinylpyrrolidone, allylsulfonic acid, methallylsulfonic acid , Vinylsulfonic acid, vinylphosphonic acid, AMPS, methyl methacrylate, methyl acrylate, butyl acrylate, or allyl hexyl acrylate.
  • vinyl or (meth) acrylic acid derivatives such as styrene, ⁇ -methylstyrene, vinyl acetate, vinyl propionate, ethylene, propylene, isobutene, hydroxyalkyl (meth) acrylates, acrylamide, methacrylamide, N-vinylpyrrolidone, allylsulfonic acid, meth
  • Preferred optional comonomers are styrene, ⁇ -methylstyrene, vinyl acetate, vinyl propionate, ethylene, propylene, isobutene, N-vinylpryrrolidone, allylsulfonic acid, methallylsulfonic acid, vinylsulfonic acid or vinylphosphonic acid.
  • Particularly preferred optional comonomers are vinyl acetate, vinyl propionate, ethylene, propylene, isobutene, N-vinylpryrrolidone, allylsulfonic acid, methallylsulfonic acid, vinylsulfonic acid or vinylphosphonic acid.
  • optional comonomers are vinyl acetate, vinyl propionate, ethylene, propylene, isobutene, hydroxyalkyl (meth) acrylates, acrylamide, methacrylamide, N-vinylpyrrolidone, allylsulfonic acid, methallylsulfonic acid, vinylsulfonic acid, vinylphosphonic acid, AMPS, methyl methacrylate, methyl acrylate, butyl acrylate , or allylhexyl acrylate.
  • the PCE contains at most 5 mol%, particularly preferably at most 1 mol% and in particular at most 0.1 mol% of vinylaromatic monomers, such as those of the formula III
  • R a and R b are each independently H, methyl, or ethyl, R c is methyl or ethyl, and k is an integer from 0 to 2.
  • the PCE is free of vinyl aromatic monomers.
  • the number of repeating structural units in the copolymers is not limited. However, it has proven to be particularly advantageous to set average molecular weights of from 1,000 to 100,000 g / mol.
  • unsaturated mono- or dicarboxylic acid derivatives which form the subunits a) of the formulas Ia, Ib or Ic it is preferred to use: acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, itaconic acid imide and itaconic acid monoamide.
  • acrylic acid methacrylic acid, itaconic acid and itaconic monoamide
  • monovalent or divalent metal salts preferably sodium, potassium, calcium or ammonium salts.
  • the preferred substituents on the aryl radical are -OH, -COO " or -SO 3 ⁇ groups.
  • the unsaturated monocarboxylic acid derivatives can only be present as monoesters, while diester derivatives are also possible in the case of the dicarboxylic acid itaconic acid.
  • the derivatives of the formulas Ia, Ib and Ic can also be present as a mixture of esterified and free acids and are used in an amount of preferably 55 to 75 mol%.
  • the second component essential to the invention for the preparation of the copolymers according to the invention is an oxyalkylene glycol alkenyl ether, which is preferably used in an amount of 19.5 to 39.5 mol%.
  • the copolymers according to the present invention can be prepared by the usual methods, for example as described in WO 2005/075529, EP 0 736 553, EP 0 894 81 1, or WO 2000/77058.
  • the composition may contain from 0.001% to 20% PCE by weight.
  • agrochemical active ingredients 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, especially insecticides.
  • 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, 15th Ed. (2009), The British Crop Protection Council, London.
  • Suitable insecticides are insecticides of the class of carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosines, avermectins, milbemycins, juvenile hormone analogs, alkylhalides, organotin compounds, nereistoxin analogs, benzoylureas, diacylhydrazines, M ETI acaricides, as well as insecticides such as chloropicrin, pymetrozine, flonicamide, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, Chlorfenapyr, DNOC, buprofezine, cyromazine, amitraz, hydramethylnone, acequinocyl, fluacrypyrim, rotenone, or their derivatives.
  • Suitable fungicides are fungicides of the classes dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzylcarbamates, carbamates, carboxamides, carboxylic acid amides, chloronitriles, cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides , Dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy (2-amino) pyrimidines, hydroxyanilides, imidazoles, imidazolinones, in
  • 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, phosphoroamides, phosphorodithioates, phthalamates,
  • the pesticide is soluble in water at 20 ° C at most 10 g / l, preferably at most 0.5 g / l and more preferably at most 0.1 g / l.
  • pyraclostrobin is 1, 9 mg / l
  • prochloraz is 34 mg / l
  • metrafenone is 0.5 mg / l water-soluble.
  • the pesticide usually has a melting point above 30 ° C, preferably above 40 ° C and especially above 45 ° C.
  • pyraclostrobin has a melting point of 64 ° C, prochloraz of 47 ° C, and metrafenone of 100 ° C.
  • the composition according to the invention usually comprises 0.1 to 70% by weight of pesticide, preferably 1 to 50% by weight, in particular 3 to 30% by weight, based on the composition.
  • the pesticide is preferably present in suspended form in the composition, i. in the form of crystalline or amorphous particles which are solid at 20 ° C.
  • the suspended pesticide usually has a particle size distribution with an xso value of 0.1 to 10 ⁇ , preferably from 0.2 ⁇ to 5 ⁇ and more preferably from 0.5 ⁇ to 2 ⁇ .
  • the particle size distribution can be determined by laser light diffraction of an aqueous suspension comprising the particles.
  • Sample preparation for example dilution to measurement concentration, depends in this measurement method inter alia on the fineness and concentration of the active ingredients in the suspension sample and on the measuring instrument used (for example Malvern Mastersizer). The procedure must be worked out for the respective system and is known to the person skilled in the art.
  • compositions according to the invention may furthermore also comprise auxiliaries customary for agrochemical formulations, the choice of auxiliaries being directed to the specific application form, the type of formulation or the active ingredient.
  • auxiliaries are solvents, solid carriers, surface-active substances (such as surfactants, solubilizers, protective colloids, wetting agents and adhesives), organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, if appropriate adhesives (for example for seed treatment) or customary auxiliaries for bait formulation (eg attractants, feeds, bitter substances).
  • the solvents used are water or organic solvents, such as mineral oil fractions of medium to high boiling point, such as kerosene and diesel oil, and also hydrocarbons.
  • tar oils and oils of vegetable or animal origin aliphatic, cyclic and aromatic hydrocarbons, for example paraffins, tetrahydronaphthalene, alkylated naphthalene and derivatives thereof, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, glycols, ketones such as Cyclohexanone, gamma-butyrolactone, dimethyl fatty acid amides, 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 composition contains water.
  • Solid carriers are mineral soils such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • the formulation preferably does not contain solid carriers.
  • surfactants are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, eg. B. of lignin (Borresperse ® grades, Borregaard, Norway), phenol, naphthalene (Morwet ® types, Akzo Nobel, USA) and dibutyl (nekal ® types, BASF, Germany), and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulf
  • Suitable thickeners are compounds which impart a modified flow behavior to the formulation, ie a high viscosity at rest and low viscosity in an agitated state. Examples are polysaccharides, proteins (such as casein or gelatin), synthetic polymers, or inorganic layer minerals. Such thickeners are commercially available, such as Xanthan Gum (Kelzan ®, CP Kelco, USA), Rhodopol ® 23 (Rhodia, France) or Veegum ® (RT Vanderbilt, USA) or Attac lay ® (Engelhard Corp., NJ, USA).
  • the content of thickener in the formulation depends on the effectiveness of the thickener. One skilled in the art will select a level to obtain the desired viscosity of the formulation. The content will usually be 0.01 to 10 wt.%.
  • Bactericides may be added to stabilize the composition.
  • bactericides are those based on dichlorophen and benzyl alcohol formal and isothiazolinone derivatives such as alkylisothiazolinones and Benzisothiazolino- nen (Acetide ® MBS from Thor Chemie).
  • suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin.
  • defoamers are silicone emulsions (such as, for example, silicone ® SRE, Wacker, Germany or Rhodorsil ®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds and mixtures thereof.
  • Suitable adhesives are all customary binders which can be used in pickling agents.
  • polyvinylpyrrolidone polyvinyl acetate, polyvinyl alcohol and Tylose.
  • the composition according to the invention may contain at least 5% by weight of inorganic salts, preferably at least 10% by weight and in particular at least 15% by weight.
  • Suitable inorganic salts are inorganic compounds which comprise anions and catalines and dissolve in water to at least 10 g / l, preferably to at least 50 g / l and in particular to at least 150 g / l at 20 ° C.
  • the composition is an aqueous suspension in which at least one pesticide is in particulate form or in encapsulated form.
  • the suspension preferably contains from 0.0001 to 10% by weight, particularly preferably from 0.0001 to 1% by weight, and in particular from 0.001 to 0.5% by weight, of polycarboxylate ether.
  • the aqueous suspension may contain at least 5% by weight of inorganic salts, preferably at least 10% by weight and in particular at least 15% by weight.
  • the composition is an agrochemical formulation in the form of a suspension concentrate (SC).
  • SC usually contains at least 10% by weight of water, preferably from 20 to 80% by weight.
  • the content of PCE may be 0.01 to 10% by weight, preferably 0.05 to 2% by weight, and more preferably 0.05 to 0.8% by weight.
  • At least one pesticide is in suspended form.
  • the composition is an agrochemical formulation in the form of a suspoemulsion (SE).
  • SE usually contains at least 10% by weight of water, preferably from 20 to 80% by weight.
  • PCE may be 0.01 to 10% by weight, preferably 0.05 to 2% by weight, and more preferably 0.05 to 0.8% by weight.
  • At least one pesticide may be in suspended form and another pesticide may be in emulsified form.
  • the composition is an agrochemical formulation in the form of a capsule suspension (CS).
  • the CS usually contains at least 10% by weight of water, preferably from 20 to 80% by weight.
  • the content of PCE may be 0.01 to 10% by weight, preferably 0.05 to 2% by weight, and more preferably 0.05 to 0.8% by weight.
  • At least one pesticide may be in encapsulated form.
  • the composition is a solid composition.
  • the solid composition preferably contains from 0.01 to 20% by weight, preferably from 0.05 to 5% by weight, and in particular from 0.1 to 1.0% by weight, of polycarboxylate ether.
  • the composition is an agrochemical formulation in the form of a water-dispersible granule (WG).
  • WG water-dispersible granule
  • the WG is usually a solid.
  • the content of PCE may be 0.01 to 20% by weight, preferably 0.05 to 5% by weight, and more preferably 0.1 to 1.0% by weight.
  • At least one pesticide may be in the form of solid particles.
  • the present invention further relates to a process for the preparation of the composition according to the invention by bringing the pesticide and the polycarboxylate tether in contact.
  • Conventional processes for the preparation of agrochemical formulations are suitable.
  • the composition of the invention is usually diluted before use to produce the so-called tank mix. Dilution is carried out with mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, coal tar oils and oils of plant or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration. Preferably, water is used.
  • the diluted composition is usually applied by spraying or atomizing.
  • the content of PCE in the tank mix is usually less than 0.1% by weight, preferably less than 0.01% by weight, and especially less than 0.001% by
  • wetting agents, adjuvants, herbicides, bactericides, fungicides can be added immediately before use (tank mix). These agents can be added to the compositions according to the invention by weight. Ratio 1: 100 to 100: 1, preferably 1: 10 to 10: 1 are admixed.
  • the pesticide concentration in the tank mix can be varied in larger areas. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%. Depending on the type of desired effect, the application rates in crop protection range from 0.01 to 2.0 kg of active ingredient per ha.
  • the present invention further relates to a method for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired insect or mite infestation and / or for regulating the growth of plants, wherein the composition according to the invention on the respective pests, their habitat 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 present invention further relates to seed containing the composition according to the invention.
  • the present invention further relates to the use of the polycarboxylate ether for dispersing pesticides having a solubility in water of at most 10 g / l in aqueous compositions.
  • the pesticide is preferably in suspended form in the aqueous composition, i. in the form of crystalline or amorphous particles which are solid at 20 ° C.
  • the content of PCE in the aqueous composition is usually less than 0.1% by weight, preferably less than 0.01% by weight, and especially less than 0.001% by weight.
  • the method for pickling seeds wherein
  • step (b) optionally drying the seed obtained in step (a)
  • the polycarboxylate ether can be used as described above or in the form of the composition according to the invention.
  • the composition of the invention or the polycarboxylate before application to the seed with a solvent, preferably water are diluted.
  • This seed pretreated in this way can subsequently be treated with an agrochemical suspension formulation comprising at least one agrochemical active substance suitable for dressing seed, the active substance being present in solid particles having a size between 0.1 ⁇ m and 10 ⁇ m.
  • agrochemical formulations are suspension formulations of one (or more) agrochemical active (eg, SC, OD, FS), which must have the above particle sizes.
  • SC, OD, FS agrochemical active
  • the active substance suspension can also be prepared from a (optionally also commercially available) solid formulation of an active ingredient by dispersing in a solvent, preferably water (see above).
  • a solvent preferably water
  • seed includes seeds of all kinds, e.g. Grains, seeds, fruits, tubers, cuttings and similar forms.
  • seed preferably describes grains and seeds here.
  • Suitable seeds are cereals seed crops, root crops, oilseeds, vegetable seeds, spice seed, ornamental plant seed, e.g. Seeds of durum wheat, wheat, barley, oats, rye, maize (fodder corn and sweetcorn), soya, oilseeds, cruciferous vegetables, cotton, sunflowers, bananas, rice, oilseed rape, beets, sugar beets, fodder beet, egg plants, potatoes, grass, (ornamental -) Lawn, forage grass, tomatoes, leeks, squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, brassica species, melons, beans, peas, garlic, onions, carrots, sugarcane, tobacco, grapes, petunia and geraniums, pansies , Balsam.
  • the term seed here describes cereals and soybeans.
  • compositions according to the invention can be used for pickling seeds by plants obtained by conventional culture methods and for pickling seeds of transgenic plants.
  • seed can be used that is tolerant to herbicides, e.g. plants resistant to sulfonylureas, imidazolinones or glufonate or glyphosate (see, e.g., EP-A-0242236, EP-A-242246) (WO 92/00377) (EP-A-0257993, U.S. Pat No. 5,013,659) or transgenic plant seeds, e.g.
  • seed of plants can be used which have modified properties in comparison with conventional plants.
  • modified starch synthesis for example WO 92/1 1376, WO 92/14827, WO 91/19806) or fatty acid compositions (WO 91/13972).
  • plants also includes those plants which have been modified by breeding, mutagenesis or genetic engineering methods including those on the market or biotechnological agricultural products under development.
  • Genetically modified plants are plants whose genetic material has been altered in a way that does not occur under natural conditions by crossing, mutations or natural recombination (ie recomposition of genetic information).
  • one or more genes are integrated into the genome of the plant in order to improve the properties of the plant.
  • Such genetic engineering modifications also include post-translational modifications of proteins, oligo- or polypeptides, for example by means of glycolsylation or binding of polymers such as prenylated, acetylated or farnelysed residues or PEG residues.
  • auxin herbicides such as auxin herbicides such.
  • B. Dicamba or 2,4-D bleaching herbicides such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors or phytoene desaturase (PDS) inhibitors, acetolactate synthase (ALS) inhibitors such.
  • HPPD hydroxyphenylpyruvate dioxygenase
  • PDS phytoene desaturase
  • ALS acetolactate synthase
  • EPSPS Enolpyruvylshikimat-3-phosphate synthase
  • Glyphosate glutamine synthetase (GS) -
  • Inhibitors such. As glufosinate, lipid biosynthesis inhibitors such. Acetyl-CoA carboxylase (ACCase) inhibitors, or oxynil herbicides (eg, bromoxynil or loxynil). Furthermore, plants have been produced which are resistant to several classes of herbicides by several genetic engineering measures, eg resistant to glyphosate and glufosinate, or to glyphosate and a herbicide of another class, such as, for example, ALS inhibitors, HPPD inhibitors, auxin herbicides and ACCase inhibitors. These herbicide resistance technologies are e.g. As described in Pest Managers. Be.
  • Glyphosate or glufosinate are produced under the trade name Roundup Ready ® (glyphosate-resistant, Monsanto, USA) Cultivance ® (imidazolinone resistant, BASF SE, Germany) and Liberty Link ® (glufosinate-resistant, Bayer CropScience, Germany ) are available.
  • toxins eg. B. those from the bacterial strain Bacillus produce.
  • Toxins produced by such genetically engineered plants include e.g. B. Insecticidal proteins of Bacillus spp., In particular of B. thuringiensis, such as the endotoxins CrylAb, CrylAc, CrylF, Cry1Fe2, Cry2Ab, Cry3A, Cry3Bb1, Cry9c, Cry34Ab1 or Cry35Ab1; or vegetative insecticidal proteins (VIPs), e.g.
  • VIPs vegetative insecticidal proteins
  • VIP1, VIP2, VIP3, or VIP3A Insecticidal proteins from nematode-colonizing bacteria en, z. B. Photorhabdus spp. or Xenorhabdus spp .; Toxins from animal organisms, eg. B. Wepsen, spider or scorpion toxins; fungal toxins, e.g. Eg from Streptomyces; herbal lectins, e.g. From pea or barley; agglutinins; Proteinase inhibitors, e.g. Trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; Ribosome Inactivating Proteins (RIPs), e.g.
  • RIPs Ribosome Inactivating Proteins
  • Steroid metabolizing enzymes e.g. 3-hydroxy steroid oxidase, ecdysteroid IDP glycosyltransferase, cholesterol oxidase, ecdysone inhibitors, or HMG-CoA reductase
  • ion channel blocker
  • toxins can also be produced in the plants as proteoxins, hybrid proteins, truncated or otherwise modified proteins.
  • Hybrid proteins are characterized by a novel combination of different protein domains (see, for example, WO 2002/015701).
  • Further examples of such toxins or genetically modified plants which produce these toxins are described in EP-A 374 753, WO 93/07278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03 / 18810 and WO 03/52073.
  • the methods for producing these genetically modified plants are known in the art and z. As set forth in the publications mentioned above. Many of the aforementioned toxins confer on the plants producing them tolerance to pests of all taxonomic arthropod classes, in particular to beetles (Coeleropta), diptera (Diptera) and
  • YieldGard ® (corn cultivars producing the toxin CrylAb), YieldGard ® Plus (corn cultivars producing the toxins CrylAb and Cry3Bb1), StarLink ® (corn cultivars producing the toxin Cry9c), Herculex ® RW (corn cultivars toxins which Cry34Ab1, Cry35Ab1 and the enzyme phosphinothricin N-acetyltransferase [PAT] produce); NuCOTN ® 33B (cotton cultivars producing the Cry1 Ac toxin), Bollgard ® I (cotton cultivars producing the Cry1 Ac toxin), Bollgard ® II (cotton cultivars producing the toxins CrylAc and Cry2Ab2); VIP COT ® (cotton cultivars producing a VIP-toxin); NewLeaf ® (potato cultivars producing the Cry3A toxin); Bt Xtra ®, NatureGard® ®, KnockOut ®
  • plants which produce by genetic engineering measures one or more proteins that cause increased resistance or resistance to bacterial, viral or fungal pathogens, such as.
  • proteins that cause increased resistance or resistance to bacterial, viral or fungal pathogens
  • pathogenesis-related proteins PR proteins, see EP-A 0 392 225
  • resistance proteins for example potato varieties which produce two resistance genes against Phytophthora infestans from the Mexican wild potato Solanum bulbocastanum
  • T4 lyso - zym eg, potato varieties that are resistant to bacteria such as Erwinia amylvora due to the production of this protein.
  • plants are included whose productivity has been improved by genetic engineering methods by z.
  • the productivity eg biomass, grain yield, starch, oil or protein content
  • the tolerance to drought, salt or other limiting environmental factors or the resistance to pests and fungal, bacterial and viral pathogens is increased
  • plants are included whose ingredients have been modified in particular to improve the human or animal diet using genetic engineering methods by z.
  • oil plants can produce health-promoting long-chain omega-3 fatty acids or monounsaturated omega-9 fatty acids (eg Nexera ® rapeseed, DOW Agro Sciences, Canada).
  • plants are included, which have been modified for the improved production of raw materials by means of genetic engineering methods by z.
  • the amylopectin content of potatoes (Amflora ® potato, BASF SE, Germany) was increased.
  • seed is also claimed which contains a composition according to the invention.
  • the application rates are generally between 0.1 g-10 kg of active ingredient per 100 kg of seed, preferably 1 g to 5 kg, more preferably from 1 g to 2.5 kg. For special seeds such as salad, the application rates may be higher. For soya, amounts of 0.1-10 kg are used.
  • Seed treatment may be carried out by spraying the seed with the formulation or mixing of the seed with the formulation, optionally followed by drying the seed before sowing and germination by methods known to those skilled in the art.
  • the present invention comprises a method for regulating the
  • the invention preferably comprises methods for controlling undesirable insect or mite infestation on plants and / or for controlling phytopathogenic fungi, characterized in that seed of crop plants having a pesticide having a solubility in water of not more than 10 g / l and Treated polycarboxylate treated.
  • the polycarboxalate ether can be used as described above or in the form of the composition according to the invention.
  • the advantages of the invention are that even a high dispersion stability can be achieved with smaller amounts of the dispersant according to the invention. This is especially true for formulations containing high levels of pesticide.
  • the dispersants according to the invention also stabilize highly concentrated solid formulations after dilution with water. With suspensions (in particular suspension concentrates) serum formation is reduced by small amounts of addition of dispersant according to the invention, and the storage stability is increased.
  • a further advantage is that with lower amounts of the dispersant according to the invention already a high dispersion stability can be achieved, especially for Formiitechniken (v.a. aqueous formulations) with high salt content.
  • Flexity® An aqueous suspension concentrate containing 25.2 wt% metrafenone and additives such as alkyl polysaccharide and sodium alkylnaphthalenesulfonate-formaldeyde condensate, pH about 7, surface tension 31 mN / m (20 ° C), dynamic viscosity 616 mPa.s (20 ° C) C, 100 1 / s), commercially available from BASF SE.
  • Glenium® ACE 430 polycarboxylate ether according to the invention, liquid with solids content about 30% by weight, pH 5.5 +/- 1 at 20 ° C, commercially available from BASF Construction Polymers GmbH.
  • Glenium® B233 polycarboxylate ether according to the invention, water-soluble liquid with solids content> 30% by weight, pH about 7 at 20 ° C, commercially available from BASF Construction Polymers GmbH.
  • Glenium® 3400 NV Polycarboxylate ether according to the invention, water-soluble liquid with solids content> 30% by weight, pH about 7.8 at 20 ° C., commercially available from BASF Construction Polymers GmbH.
  • Glenium® ACE 30 Polycarboxylate ether according to the invention, water-soluble liquid with solids content about 30% by weight, pH 6.5 +/- 1.5 at 20 ° C., commercially available from BASF Construction Polymers GmbH.
  • Example 1 Dispersion stability
  • SC suspension concentrate
  • PCE Polycarboxiylatether
  • the dispersion stability was determined according to CIPAC MT180 in a graduated tip cylinder in which 100 ml of water (19.2 ° dH) is introduced. After addition of 1 ml of suspension concentrate, the mixture is brought to complete dispersion and then allowed to stand. The sediment volume is read after 120 min (Table 1).
  • Example 2 Dispersion stability of granules after dispersion
  • a granulate formulation containing 75% by weight of tritosulfuron was admixed with 0.25% by weight (2.5 g / kg) of polycarboxylate ether.
  • the sediment volume was determined in a graduated cylinder, in which 100 ml of water (19.2 ° dH) is submitted. After addition of 0.2 g or 2 g of granules, the mixture is brought to complete dispersion and then allowed to stand. The sediment volume is read after 30 min. As a control, a formulation without Polycarboxiylatether was stored. The results are summarized in Tables 2 and 3.
  • Glenium® ACE 430 20 g / l 0.05 g / l 0.6 ml 0.65 ml
  • Glenium® ACE 30 20 g / l 0.05 g / l 0.75 ml 0.6 ml
  • the suspension concentrate Flexity® was mixed with 1 g / l Polycarboxiylatether or stored for control without Polycarboxiylatether.
  • the storage stability with respect to sedimentation was determined after storage at 54 ° C. for 14 days.
  • the supernatant (serum formation) was determined by visual assessment (Table 4).
  • the suspension 1 according to Table 5 was in equal parts (1: 1: 1) with the commercially available seed treatment product Rubin® TT (aqueous suspension concentrate containing 42 g / l pyrimethanil, 25 g / l triticonazole and 38.6 g / l prochloraz, he - available from BASF SE) and mixed with water. 6 mL of this mixture was applied to 1 kg of wheat in a commercially available Rotitz brand laboratory teat.
  • An aqueous suspension concentrate (SC) containing 300 g / l mepiquat chloride, 50 g / l prohexadione calcium, 200 g / l ammonium nitrate, 150 g / l nonionic surfactant and other auxiliaries (such as thickener, defoamer) was prepared in accordance with Reference Example 2 in EP1339284B1 , The SC was mixed with 5, 10, 25 or 50 g / l Polycarboxiylatether (PCE) or stored for control without Polycarboxiylatether. Glenium® B233, Glenium® 3400 NV, Glenium® ACE 30, or Glenium® ACE 430 were used as PCE.
  • the dispersion stability (as a 2.0% dispersion) was determined after 14 days storage at 10 ° C as described in Example 1.
  • the control sample without PCE found 0.5 ml of sediment. All samples in which a PCE was added at one of the above concentrations showed less than 0.05 ml of sediment. Even at high salt concentrations, the stability of the storage of the dispersion could be achieved thanks to the PCE.
  • SC aqueous suspension concentrate
  • 29 wt.% Pyraclostrobin containing 29 wt.% Pyraclostrobin, 3.5 wt.% Dispersant, 3.5 wt.% Polyalkylenoxidblockcopolymer, 0.3 wt.% Xanthan gum and further auxiliaries was two weeks at -10 ° C or at Stored at 50 ° C. Particle size was measured and the increase calculated from storage at -10 ° C.
  • the dispersants used were Glenium.RTM. B233, Glenium.RTM. 3400 NV, Glenium.RTM. ACE 30, or Glenium.RTM. ACE 430, as well as for the control of Atlox.RTM. 4913 (commercially available from Uniqema, which contains a reaction product of methyl methacrylate, methacrylic acid and methoxy PEG). methacrylate) or Soprophor® BSU (commercially available from Rhodia, containing ethoxylated (16 EO) tristyrylphenol, CAS 99734-09-5).

Abstract

The subject matter of the present invention is a composition containing a pesticide with a solubility in water of no more than 10 g/l and a polycarboxylate ether based on a) groups of formula Ia and/or Ib and/or Ic as defined below and b) groups of general formula II as defined below. The subject matter also includes a method for producing the composition by bringing the pesticide and polycarboxylate ether into contact. The invention further relates to a method for combating phytopathogenic fungi and/or undesirable plant growth and/or undesirable insect or mite infestation and/or for regulating the growth of plants, wherein the composition is allowed to act on the respective pests, the habitat thereof or the plants to be protected from the respective pest, the soil and/or on undesirable plants and/or the useful plants and/or the habitat thereof. The invention further relates to seeds containing the composition.

Description

Zusammensetzung umfassend ein Pestizid und ein Polycarboxylatether  A composition comprising a pesticide and a polycarboxylate ether
Gegenstand der vorliegenden Erfindung ist eine Zusammensetzung enthaltend ein Pestizid mit einer Löslichkeit in Wasser von höchstens 10 g/l und ein Polycarboxyla- tether auf Basis von a) Baugruppen der Formel la und/oder Ib und/oder Ic wie nachstehend definiert und b) Baugruppen der allgemeinen Formel II wie nachstehend definiert. Weiterer Gegenstand ist ein Verfahren zur Herstellung der Zusammensetzung indem man das Pestizid und den Polycarboxylatether in Kontakt bringt. Die Erfindung betrifft weiterhin ein Verfahren zur Bekämpfung von phytopathogenen Pilzen und/oder unerwünschtem Pflanzenwuchs und/oder unerwünschtem Insekten- oder Milbenbefall und/oder zur Regulation des Wachstums von Pflanzen, wobei man die Zusammensetzung auf die jeweiligen Schädlinge, deren Lebensraum 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. Ferner betrifft die Erfindung Saatgut enthaltend die Zusammensetzung. Kombinationen bevorzugter Merkmale mit anderen bevorzugten Merkmalen werden von der vorliegenden Erfindung umfasst. The present invention is a composition comprising a pesticide having a solubility in water of at most 10 g / l and a polycarboxylate based on a) components of the formula Ia and / or Ib and / or Ic as defined below and b) assemblies of general formula II as defined below. Another object is a method of making the composition by contacting the pesticide and the polycarboxylate ether. The invention further relates to a method for controlling phytopathogenic fungi and / or undesired plant growth and / or unwanted insect or mite infestation and / or for regulating the growth of plants, wherein the composition of the respective pests, their habitat or before the respective Pest to be protected plants, the soil and / or undesirable plants and / or the crops and / or their habitat act. Furthermore, the invention relates to seed containing the composition. Combinations of preferred features with other preferred features are encompassed by the present invention.
Agrochemische Formulierungen enthaltend Vinylether sind allgemein bekannt: Agrochemical formulations containing vinyl ethers are well known:
WO 2006/000592 offenbart die Verwendung von amphiphilen Polyethergruppen enthaltenden Polymeren als Lösungsvermittler, wobei die Polymere ein hydrophobes Monomer (wie Styrol), ein Allylalkoholalkoxylat, und optional ethylenisch ungesättigte Mono- oder Dicarbonsäuren enthalten. WO 2006/000592 discloses the use of amphiphilic polyether group-containing polymers as solubilizers, the polymers containing a hydrophobic monomer (such as styrene), an allyl alcohol alkoxylate, and optionally ethylenically unsaturated mono- or dicarboxylic acids.
WO 2009/007328 offenbart die Verwendung von Copolymeren auf Basis von WO 2009/007328 discloses the use of copolymers based on
(Meth)Acrylsäure und nichtionischen Monomeren (wie Vinylether) zur Stabilisierung von in Wasser schlecht löslichen Wirkstoffen. WO 2003/043420 offenbart die Verwendung eines Copolymers auf Basis eines Olefine und/oder eines Vinylethers sowie einer ethylenisch ungesättigten Dicarbonsäure, als Adjuvans bei der Behandlung von Pflanzen. (Meth) acrylic acid and nonionic monomers (such as vinyl ethers) for the stabilization of poorly water-soluble active ingredients. WO 2003/043420 discloses the use of a copolymer based on an olefin and / or a vinyl ether and an ethylenically unsaturated dicarboxylic acid as an adjuvant in the treatment of plants.
Nachteilig an den bekannten Polymere ist, dass sich Allylether als Comonomere schlecht einpolymerisieren lassen und hohe Molmassen der Polymere schwer zu erreichen sind. A disadvantage of the known polymers is that allyl ethers can be copolymerized poorly as comonomers and that high molar masses of the polymers are difficult to achieve.
Aufgabe der Erfindung war eine Möglichkeit zu finden um mit geringeren Mengen Dispergiermittel bereits eine hohe Dispersionsstabiliät erreicht werden kann. Dies gilt insbesondere bei Formulierungen, die hohe Konzentrationen von Pestizid enthalten. Die Dispergiermittel sollten auch hochkonzentrierte Festformulierungen nach Verdünnung mit Wasser stabilisieren. Bei Suspensionen (v.a. Suspensionskonzentraten) soll durch geringe Mengen Zusatz von Dispergiermittel die Serumbildung verringert, und die Lagerstabilität erhöht werden. Außerdem sollten die Dispergiermittel leicht zugänglich sein. Weitere Aufgabe war, dass das Dispergiermittel auch bei der Beizung von Saatgut mit Pestiziden benutzt werden kann, beispielsweise um eine hohe Beladung der Beize mit Wirkstoff zu erreichen. It was an object of the invention to find a way to achieve a high dispersion stability even with smaller amounts of dispersant. This is especially true for formulations containing high levels of pesticide. The dispersants should also stabilize highly concentrated solid formulations after dilution with water. For suspensions (especially suspension concentrates) should low levels of addition of dispersant reduce serum formation and increase storage stability. In addition, the dispersants should be readily available. Another object was that the dispersant can also be used in the treatment of seed with pesticides, for example, to achieve a high loading of the stain with active ingredient.
Die Aufgabe wurde gelöst durch eine Zusammensetzung enthaltend ein Pestizid mit einer Löslichkeit in Wasser von höchstens 10 g/l und ein Polycarboxylatether auf Basis von a) Baugruppen der Formel la und/oder Ib und/oder Ic wie nachstehend definiert und b) Baugruppen der allgemeinen Formel II wie nachstehend definiert. The object has been achieved by a composition comprising a pesticide having a solubility in water of not more than 10 g / l and a polycarboxylate ether based on a) structural groups of the formula Ia and / or Ib and / or Ic as defined below and b) structural groups of the general Formula II as defined below.
Geeignete Polycarboxylatether (im folgenden auch "PCE") sind Polymere auf Basis von Suitable polycarboxylate ethers (hereinafter also "PCE") are polymers based on
a) Baugruppen der Formel la und/oder Ib und/oder Ic a) assemblies of the formula Ia and / or Ib and / or Ic
cox  cox
- CH2 - CR1 - _ CH2 - C - _ CH2 - C - CH2 - CH 2 - CR 1 - _ CH 2 - C - _ CH 2 - C - CH 2
COX CH2 0 = C C = 0 COX CH 2 0 = CC = 0
\ /  \ /
COX Y  COX Y
la Ib ,c la Ib, c
wobei R1 = Wasserstoff oder ein aliphatischer Kohlenwasserstoffrest mit 1 bis 20 wherein R 1 = hydrogen or an aliphatic hydrocarbon radical having 1 to 20
C-Atomen,  C-atoms,
X = -OMa, -0-(CmH2mO)n-R2, -N H-(CmH2mO)nR2' X = -OM a , -O- (C m H 2 m O) n -R 2 , -N H- (C m H 2 mO) n R 2 '
M = Wasserstoff, ein ein- oder zweiwertiges Metallkation, Ammoniumion, ein organischer Aminrest, M = hydrogen, a monovalent or divalent metal cation, ammonium ion, an organic amine radical,
R2 = Wasserstoff, ein aliphatischer Kohlenwasserstoffrest mit 1 bis 20 C- Atomen, ein cycloaliphatischer Kohlenwasserstoffrest mit 5 bis 8 C- Atomen, ein ggf. substituierter Arylrest mit 6 bis 14 C-Atomen, R 2 = hydrogen, an aliphatic hydrocarbon radical having 1 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, an optionally substituted aryl radical having 6 to 14 C atoms,
Y = O, N R2, Y = O, NR 2 ,
m = 2 bis 4, und  m = 2 to 4, and
n = 0 bis 200  n = 0 to 200
bedeuten, und mean, and
b) Baugruppen der allgemeinen Formel I I b) assemblies of the general formula I I
— CH2— CR3— - CH 2 - CR 3 -
(CH2)P— O— (Cm H2mO)n.— (Cm..H2m..O)n..— R4 wobei R3 = Wasserstoff oder einen aliphatischen Kohlenwasserstoffrest mit 1 bis 5 (CH 2) P - O- (C m H 2m O) n .- (C m ..H ..O 2m) n ..- R 4 wherein R 3 = hydrogen or an aliphatic hydrocarbon radical having from 1 to 5
C-Atomen,  C-atoms,
η',η" = unabhängig voneinander 0 bis 200,  η ', η "= independently from 0 to 200,
m',m" = unabhängig voneinander 2 bis 4, n + n = 1 bis 200, m ', m "= independently of one another 2 to 4, n + n = 1 to 200,
0 bis 3, bedeuten und  0 to 3, mean and
Wasserstoff, ein aliphatischer Kohlenwasserstoffrest mit 1 bis 20 C- Atomen, ein cycloaliphatischer Kohlenwasserstoffrest mit 5 bis 8 C- Atomen, ein ggf. substituierter Arylrest mit 6 bis 14 C-Atomen, bedeuten.  Hydrogen, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 carbon atoms, an optionally substituted aryl radical having 6 to 14 carbon atoms, mean.
Die Copolymere entsprechend der vorliegenden Erfindung enthalten mindestens 2 Baugruppen a), und b). Optional können zusätzlich die Baugruppen c) und d) vorhan- den sein. The copolymers according to the present invention contain at least 2 components a), and b). Optionally, additional components c) and d) may be present.
Die erste Baugruppe a) stellt ein Mono- oder Dicarbonsäure-Derivat mit der allgemeinen Forme la, Ib oder Ic dar. Beim Monocarbonsäure-Derivat la bedeutet R1 Wasserstoff oder einen aliphatischen Kohlenwasserstoffrest mit 1 bis 20 C-Atomen, vorzugs- weise eine Methylgruppe. X in den Strukturen la und Ib steht für - OaM und/oder - O - (CmH2mO)n - R2 bzw. - N H - (CmH2mO)n - R2 mit folgender Bedeutung für M, a, m, n und R2: The first component a) is a mono- or dicarboxylic acid derivative having the general formula Ia, Ib or Ic. In the monocarboxylic acid derivative Ia, R 1 is hydrogen or an aliphatic hydrocarbon radical having 1 to 20 C atoms, preferably a methyl group , X in the structures Ia and Ib is - O a M and / or - O - (cmH 2 mO) n - R 2 or - NH - (cmH 2 mO) n - R 2 with the following meaning for M, a, m, n and R 2 :
M bedeutet Wasserstoff, ein ein- oder zweiwertiges Metallkation, Ammonium, ein orga- nischer Aminrest sowie a = Vi oder 1 , je nachdem, ob es sich bei M um ein ein- oder zweiwertiges Kation handelt. M bedeutet bevorzugt Wasserstoff, ein ein- oder zweiwertiges Metallkation, oder Ammonium. Als organische Aminreste werden vorzugsweise substituierte Ammonium-Gruppen eingesetzt, die sich ableiten von primären, sekundären oder tertiären Ci-20-Alkylaminen, Ci-20-Alkanolaminen, Cs-e-Cycloalkylaminen und C8-14-Arylaminen. Beispiele für die entsprechenden Amine sind Methylamin, Dimethy- lamin, Trimethylamin, Ethanolamin, Diethanolamin, Triethanolamin, Methyldiethanola- min, Cyclohexylamin, Dicyclohexylamin, Phenylamin, Diphenylamin in der protonierten (Ammonium)Form. R2 bedeutet Wasserstoff, ein aliphatischer Kohlenwasserstoffrest mit 1 bis 20 C-M is hydrogen, a monovalent or divalent metal cation, ammonium, an organic amine radical and a = Vi or 1, depending on whether M is a monovalent or divalent cation. M is preferably hydrogen, a monovalent or divalent metal cation, or ammonium. Substituted ammonium groups which are derived from primary, secondary or tertiary C 1-20 -alkylamines, C 1-20 -alkanolamines, C 3-8 -cycloalkylamines and C 8-14 -arylamines are preferably used as organic amine radicals. Examples of the corresponding amines are methylamine, dimethylamine, trimethylamine, ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, cyclohexylamine, dicyclohexylamine, phenylamine, diphenylamine in the protonated (ammonium) form. R 2 is hydrogen, an aliphatic hydrocarbon radical having 1 to 20 C
Atomen, ein cycloaliphatischer Kohlenwasserstoffrest mit 5 bis 8 C-Atomen, ein Arylrest mit 6 bis 14 C-Atomen, der ggf. noch substituiert sein kann, m = 2 bis 4 sowie n = 0 bis 200 sein kann. Die aliphatischen Kohlenwasserstoffe können hierbei linear oder verzweigt sowie gesättigt oder ungesättigt sein. Als bevorzugte Cycloalkylreste sind Cyclopentyl- oder Cyclohexylreste, als bevorzugte Arylreste Phenyl- oder Naphthyl- reste anzusehen, die insbesondere noch durch Hydroxyl-, Carboxyl- oder Sulfonsäu- regruppen substituiert sein können. Atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 carbon atoms, an aryl radical having 6 to 14 carbon atoms, which may optionally be substituted, m = 2 to 4 and n = 0 to 200 may be. The aliphatic hydrocarbons may hereby be linear or branched and saturated or unsaturated. Preferred cycloalkyl radicals are cyclopentyl or cyclohexyl radicals, and the preferred aryl radicals are phenyl or naphthyl radicals, which may in particular be substituted by hydroxyl, carboxyl or sulfonic acid radicals.
Anstelle des oder neben dem Dicarbonsäure-Derivat gemäß Formel Ib kann die Bau- gruppe a) (Mono- oder Dicarbonsäure-Derivat) auch in cyclischer Form entsprechend Formel Ic vorliegen, wobei Y = O (Säureanhydrid) oder N R2 (Säureimid) darstellen kann mit der oben bezeichneten Bedeutung für R2. Die zweite Baugruppe b) entspricht Formel II und leitet sich von Oxyalkylenglykol- Alkenylethern ab. R3 bedeutet wiederum Wasserstoff oder einen aliphatischen Kohlenwasserstoffrest mit 1 bis 5 C-Atomen, der ebenfalls linear oder verzweigt bzw. auch ungesättigt sein kann, p kann Werte zwischen 0 und 3 annehmen. Vorzugsweise wird als Baugruppen der Formel II ein Polyethylenglykolmonovinylether mit p = 0 und m" = 2 verwendet. Die Summe n' + n" ist bevorzugt 3 bis 150, insbesondere 5 bis 100. Instead of or in addition to the dicarboxylic acid derivative according to formula Ib, the group a) (mono- or dicarboxylic acid derivative) may also be present in cyclic form according to formula Ic, where Y = O (acid anhydride) or NR 2 (acid imide) with the meaning given above for R 2 . The second component b) corresponds to formula II and is derived from oxyalkylene glycol alkenyl ethers. R 3 in turn represents hydrogen or an aliphatic hydrocarbon radical having 1 to 5 C atoms, which may also be linear or branched or unsaturated, p may assume values between 0 and 3. The components of the formula II used are preferably a polyethylene glycol monovinyl ether with p = 0 and m "= 2. The sum n '+ n" is preferably 3 to 150, in particular 5 to 100.
Gemäß den bevorzugten Ausführungsformen bedeuten in den Formeln la und Ib m = 2 und/oder 3, so daß es sich um Polyalkylenoxid-Gruppen handelt, die sich von Poly- ethylenoxid und/oder Polypropylenoxid ableiten. In einer weiteren bevorzugten Ausführungsform bedeutet p in Formel II 0 oder 1 , d. h. es handelt sich um Vinyl- und/oder AI ky I po lya I koxy I ate . Die PCE enthalten üblicherweise 50 bis 95 Mol-% Baugruppen der Formel la und/oder Ib und/oder Ic, und 5 bis 50 Mol-% Baugruppen der Formel II, und optional bis zu 20 Gew.% Comonomere. According to the preferred embodiments, in the formulas Ia and Ib, m = 2 and / or 3, so that they are polyalkylene oxide groups which are derived from polyethylene oxide and / or polypropylene oxide. In a further preferred embodiment, p in formula II is 0 or 1, d. H. it is vinyl and / or alkyl cyano I koxy I ate. The PCEs usually contain 50 to 95 mol% of the structural units of the formula Ia and / or Ib and / or Ic, and 5 to 50 mol% of the formula II, and optionally up to 20% by weight of comonomers.
Vorzugsweise enthalten diese Polymere 55 bis 75 Mol-% Baugruppen der Formel la und/oder Ib, 19,5 bis 39,5 Mol-% Baugruppen der Formel II, und optional bis zu 20 Mol% Comonomere. These polymers preferably contain 55 to 75 mol% of structural groups of the formula Ia and / or Ib, 19.5 to 39.5 mol% of structural groups of the formula II, and optionally up to 20 mol% of comonomers.
Gemäß einer bevorzugten Ausführungsform enthalten die erfindungsgemäßen Copo- lymere zusätzlich noch bis zu 50 Mol-%, insbesondere bis zu 20 Mol-% bezogen auf die Summe der Baugruppen a) und b), optionale Comonomere. Optionale Comonomere können beliebige copolymerisierbare ethylenisch ungesättigte Monomere sein. Beispiele sind Vinyl- oder (Meth-) Acrylsäure-Derivaten wie Styrol, α-Methylstyrol, Vinyl- acetat, Vinylpropionat, Ethylen, Propylen, Isobuten, Hydroxyalkyl(meth)acrylate, Acry- lamid, Methacrylamid, N-Vinylpyrrolidon, Allylsulfonsäure, Methallylsulfonsäure, Vinyl- sulfonsäure, Vinylphosphonsäure, AMPS, Methylmethacrylat, Methylacrylat, Butylacry- lat, oder Allylhexylacrylat. Bevorzugte optionale Comonomere sind Styrol, a-Methyl- styrol, Vinylacetat, Vinylpropionat, Ethylen, Propylen, Isobuten, N-Vinylpryrrolidon, Allylsulfonsäure, Methallylsulfonsäure, Vinylsulfonsäure oder Vinylphosphonsäure. Besonders bevorzugte optionale Comonomere sind Vinylacetat, Vinylpropionat, Ethylen, Propylen, Isobuten, N-Vinylpryrrolidon, Allylsulfonsäure, Methallylsulfonsäure, Vinylsulfonsäure oder Vinylphosphonsäure. In einer weiteren besonders bevorzugten Aus- fürhungsform sind optionale Comonomere Vinylacetat, Vinylpropionat, Ethylen, Propylen, Isobuten, Hydroxyalkyl(meth)acrylate, Acrylamid, Methacrylamid, N-Vinylpyrrolidon, Allylsulfonsäure, Methallylsulfonsäure, Vinylsulfonsäure, Vinylphosphonsäure, AMPS, Methylmethacrylat, Methylacrylat, Butylacrylat, oder Allylhexylacrylat. Bevorzugt enthält der PCE höchstens 5 mol%, besonders bevorzugt höchstens 1 mol% und insbesondere höchstens 0,1 mol% vinylaromatische Monomere, wie solche der Formel III According to a preferred embodiment, the copolymers according to the invention additionally contain up to 50 mol%, in particular up to 20 mol% based on the sum of the components a) and b), optional comonomers. Optional comonomers may be any copolymerizable ethylenically unsaturated monomers. Examples are vinyl or (meth) acrylic acid derivatives such as styrene, α-methylstyrene, vinyl acetate, vinyl propionate, ethylene, propylene, isobutene, hydroxyalkyl (meth) acrylates, acrylamide, methacrylamide, N-vinylpyrrolidone, allylsulfonic acid, methallylsulfonic acid , Vinylsulfonic acid, vinylphosphonic acid, AMPS, methyl methacrylate, methyl acrylate, butyl acrylate, or allyl hexyl acrylate. Preferred optional comonomers are styrene, α-methylstyrene, vinyl acetate, vinyl propionate, ethylene, propylene, isobutene, N-vinylpryrrolidone, allylsulfonic acid, methallylsulfonic acid, vinylsulfonic acid or vinylphosphonic acid. Particularly preferred optional comonomers are vinyl acetate, vinyl propionate, ethylene, propylene, isobutene, N-vinylpryrrolidone, allylsulfonic acid, methallylsulfonic acid, vinylsulfonic acid or vinylphosphonic acid. In a further particularly preferred embodiment, optional comonomers are vinyl acetate, vinyl propionate, ethylene, propylene, isobutene, hydroxyalkyl (meth) acrylates, acrylamide, methacrylamide, N-vinylpyrrolidone, allylsulfonic acid, methallylsulfonic acid, vinylsulfonic acid, vinylphosphonic acid, AMPS, methyl methacrylate, methyl acrylate, butyl acrylate , or allylhexyl acrylate. Preferably, the PCE contains at most 5 mol%, particularly preferably at most 1 mol% and in particular at most 0.1 mol% of vinylaromatic monomers, such as those of the formula III
Wobei Ra und Rb unabhängig voneinander jeweils für H, Methyl, oder Ethyl stehen, Rc Methyl oder Ethyl bedeutet und k eine ganze Zahl von 0 bis 2 ist. Speziell ist der PCE frei von vinylaromatischen Monomeren. Wherein R a and R b are each independently H, methyl, or ethyl, R c is methyl or ethyl, and k is an integer from 0 to 2. Specifically, the PCE is free of vinyl aromatic monomers.
Die Anzahl der sich wiederholenden Struktureinheiten in den Copolymeren ist nicht eingeschränkt. Als besonders vorteilhaft hat es sich jedoch erwiesen, mittlere Molekulargewichte von 1 000 bis 100 000 g/Mol einzustellen. The number of repeating structural units in the copolymers is not limited. However, it has proven to be particularly advantageous to set average molecular weights of from 1,000 to 100,000 g / mol.
Als ungesättigte Mono- oder Dicarbonsäure-Derivate, welche die Baugruppen a) der Formel la, Ib bzw. Ic bilden, werden vorzugsweise eingesetzt: Acrylsäure, Methacryl- säure, Itaconsäure, Itaconsäureanhydrid, Itaconsäureimid und Itaconsäuremonoamid. As unsaturated mono- or dicarboxylic acid derivatives which form the subunits a) of the formulas Ia, Ib or Ic it is preferred to use: acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, itaconic acid imide and itaconic acid monoamide.
Anstelle von Acrylsäure, Methacrylsäure, Itaconsäure und Itaconsäuremonoamid können auch deren ein- oder zweiwertige Metallsalze, vorzugsweise Natrium-, Kalium-, Calcium- oder Ammoniumsalze, verwendet werden. Instead of acrylic acid, methacrylic acid, itaconic acid and itaconic monoamide, it is also possible to use their monovalent or divalent metal salts, preferably sodium, potassium, calcium or ammonium salts.
Als Acryl-, Methacryl- oder Itaconsäureester werden vor allem Derivate verwendet, deren alkoholische Komponente ein Polyalkylenglykol der allgemeinen Formel HO - (CmH2mO)n - R2 mit R2 = H, aliphatischer Kohlenwasserstoffrest mit 1 bis 20 C-Atomen, cycloaliphatischer Kohlenwasserstoffrest mit 5 bis 8 C-Atomen, ggf. substituierter Aryl- rest mit 6 bis 14 C-Atomen sowie m = 2 bis 4 und n = 0 bis 200. As acrylic, methacrylic or itaconic acid esters, especially derivatives are used, the alcoholic component of a polyalkylene glycol of the general formula HO - (C m H2mO) n - R 2 with R 2 = H, aliphatic hydrocarbon radical having 1 to 20 carbon atoms, cycloaliphatic Hydrocarbon radical having 5 to 8 C atoms, optionally substituted aryl radical having 6 to 14 C atoms and m = 2 to 4 and n = 0 to 200.
Die bevorzugten Substituenten am Arylrest sind -OH -, -COO" - oder -S03 ~-Gruppen. The preferred substituents on the aryl radical are -OH, -COO " or -SO 3 ~ groups.
Die ungesättigten Monocarbonsäure-Derivate können nur als Monoester vorliegen, während im Falle der Dicarbonsäure Itaconsäure auch Diesterderivate möglich sind. The unsaturated monocarboxylic acid derivatives can only be present as monoesters, while diester derivatives are also possible in the case of the dicarboxylic acid itaconic acid.
Die Derivate der Formel la, Ib und Ic können auch als Mischung von veresterten und freien Säuren vorliegen und werden in einer Menge von vorzugsweise 55 bis 75 Mol-% verwendet. The derivatives of the formulas Ia, Ib and Ic can also be present as a mixture of esterified and free acids and are used in an amount of preferably 55 to 75 mol%.
Die zweite erfindungswesentliche Komponente zur Herstellung der erfindungsgemäßen Copolymeren stellt ein Oxyalkylenglykol-Alkenylether dar, der vorzugsweise in einer Menge von 19,5 bis 39,5 Mol-% eingesetzt wird. Die Copolymere entsprechend der vorliegenden Erfindung können nach den üblichen Methoden hergestellt werden, beispielsweise wie in WO 2005/075529, EP 0 736 553, EP 0 894 81 1 , oder WO 2000/77058 beschrieben. The second component essential to the invention for the preparation of the copolymers according to the invention is an oxyalkylene glycol alkenyl ether, which is preferably used in an amount of 19.5 to 39.5 mol%. The copolymers according to the present invention can be prepared by the usual methods, for example as described in WO 2005/075529, EP 0 736 553, EP 0 894 81 1, or WO 2000/77058.
Die Zusammensetzung kann von 0,001 bis 20 Gew% PCE enthalten. The composition may contain from 0.001% to 20% PCE by weight.
Der Begriff agrochemische Wirkstoffe (im folgenden auch Pestizide genannt) bezeichnet mindestens einen Wirkstoff ausgewählt aus der Gruppe der Fungizide, Insektizide, Nematizide, Herbizide, Safener und/oder Wachstumsregulatoren. Bevorzugte Pestizide sind Fungizide, Insektizide und Herbizide, insbesondere Insektizide. 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, 15th Ed. (2009), The British Crop Protection Council, London, gefunden wer- den können. Geeignete Insektizide sind Insektizide der Klasse der Carbamate, Orga- nophophate, Organochlor-Insektizide, Phenylpyrazole, Pyrethroide, Neonicotinoide, Spinosine, Avermectine, Milbemycine, Juvenil Hormon Analoga, Alkylhalide, Organo- zinn-Verbindungen, Nereistoxin-Analoga, Benzoylharnstoffe, Diacylhydrazine, M ETI Akarizide, sowie Insektizide wie Chloropicrin, Pymetrozin, Flonicamid, Clofentezin, He- xythiazox, Etoxazol, Diafenthiuron, Propargit, Tetradifon, Chlorfenapyr, DNOC, Bupro- fezin, Cyromazin, Amitraz, Hydramethylnon, Acequinocyl, Fluacrypyrim, Rotenon, oder deren Derivate. Geeignete Fungizide sind Fungizide der Klassen Dinitroaniline, Allyla- mine, Anilinopyrimidine, Antibiotica, aromatische Kohlenwasserstoffe, Benzenesulfo- namide, Benzimidazole, Benzisothiazole, Benzophenone, Benzothiadiazole, Benzotria- zine, Benzylcarbamate, Carbamates, Carboxamide, Carbonsäureamdide, Chloronitrile, Cyanoacetamideoxime, Cyanoimidazole, Cyclopropanecarboxamide, Dicarboximide, Dihydrodioxazine, Dinitrophenylcrotonate, Dithiocarbamate, Dithiolane, Ethylphospho- nate, Ethylaminothiazolcarboxamide, Guanidines, Hydroxy-(2-amino-)pyrimidine, Hydroxyanilides, Imidazole, Imidazolinone, Anorganika, Isobenzofuranone, Methoxyac- rylate, Methoxycarbamates, Morpholines, N-Phenylcarbamate, Oxazolidinedione, Oxi- minoacetate, Oximinoacetamide, Peptidylpyrimidinnucleoside, Phenylacetamide, Phe- nylamide, Phenylpyrrole, Phenylharnstoffe, Phosphonate, Phosphorothiolate, Phtha- lamsäuren, Phthalimide, Piperazine, Piperidine, Propionamide, Pyridazinone, Pyridine, Pyridinylmethylbenzamide, Pyrimidinamine, Pyrimidine, Pyrimidinonehydrazone, Pyrro- loquinolinone, Quinazolinone, Chinoline, Chinone, Sulfamide, Sulfamoyltriazole, Thia- zolecarboxamide, Thiocarbamate, Thiophanate, Thiophenecarboxamide, Toluamide, Triphenylzinn Verbindungen, Triazine, Triazole. Geeignete Herbizide sind Herbizide der Klassen der Acetamide, Amide, Aryloxyphenoxypropionate, Benzamide, Benzofuran, Benzoesäuren, Benzothiadiazinone, Bipyridylium, Carbamate, Chloroacetamide, Chlorcarbonsäuren, Cyclohexanedione, Dinitroaniline, Dinitrophenol, Diphenylether, Glycine, Imidazolinone, Isoxazole, Isoxazolidinone, Nitrile, N-phenylphthalimide, Oxa- diazole, Oxazolidinedione, Oxyacetamide, Phenoxycarbonsäuren, Phenylcarbamate, Phenylpyrazole, Phenylpyrazoline, Phenylpyridazine, Phosphinsäuren, Phosphoroami- date, Phosphorodithioate, Phthalamate, Pyrazole, Pyridazinone, Pyridine, Pyridincar- bonsäuren, Pyridinecarboxamide, Pyrimidindione, Pyrimidinyl(thio)benzoate, Chinolin- carbonsäuren, Semicarbazone, Sulfonylaminocarbonylt azolinone, Sulfonylharnstoffe, Tetrazolinone, Thiadiazole, Thiocarbamate, Triazine, Triazinone, T azole, Triazolino- ne, Triazolocarboxamide, Triazolopy midine, Triketone, Uracile, Harnstoffe. The term agrochemical active ingredients (also referred to below as 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, especially insecticides. 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, 15th Ed. (2009), The British Crop Protection Council, London. Suitable insecticides are insecticides of the class of carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosines, avermectins, milbemycins, juvenile hormone analogs, alkylhalides, organotin compounds, nereistoxin analogs, benzoylureas, diacylhydrazines, M ETI acaricides, as well as insecticides such as chloropicrin, pymetrozine, flonicamide, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, Chlorfenapyr, DNOC, buprofezine, cyromazine, amitraz, hydramethylnone, acequinocyl, fluacrypyrim, rotenone, or their derivatives. Suitable fungicides are fungicides of the classes dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzylcarbamates, carbamates, carboxamides, carboxylic acid amides, chloronitriles, cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides , Dicarboximides, dihydrodioxazines, 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, pyridinylmethylbenzamines de, pyrimidinamines, pyrimidines, Pyrimidinonehydrazone, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles, thiazolecarboxamides, thiocarbamates, thiophanates, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines, triazoles. 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, phosphoroamides, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl (thio) benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltinolinones, sulfonylureas, tetrazolinones, thiadiazoles , Thiocarbamates, triazines, triazinones, tazoles, triazolinos, triazolocarboxamides, triazolopy- midine, triketones, uracils, ureas.
Das Pestizid ist in Wasser bei 20 °C höchstens zu 10 g/l löslich, bevorzugt zu höchstens 0,5 g/l und besonders bevorzugt zu höchstens 0,1 g/l. Pyraclostrobin ist bei- spielsweise zu 1 ,9 mg/l, Prochloraz zu 34 mg/L, und Metrafenon zu 0,5 mg/l wasserlöslich. The pesticide is soluble in water at 20 ° C at most 10 g / l, preferably at most 0.5 g / l and more preferably at most 0.1 g / l. For example, pyraclostrobin is 1, 9 mg / l, prochloraz is 34 mg / l, and metrafenone is 0.5 mg / l water-soluble.
Das Pestizid hat üblicherweise einen Schmelzpunkt von über 30 °C, bevorzugt über 40 °C und speziell über 45 °C. Pyraclostrobin hat beispielsweise eine Schmelzpunkt von 64 °C, Prochloraz von 47 °C, und Metrafenon von 100 °C. The pesticide usually has a melting point above 30 ° C, preferably above 40 ° C and especially above 45 ° C. For example, pyraclostrobin has a melting point of 64 ° C, prochloraz of 47 ° C, and metrafenone of 100 ° C.
Die erfindungsgemäße Zusammensetzung umfasst üblicherweise 0.1 bis 70 Gew.% Pestizid, bevorzugt 1 bis 50 Gew. %, insbesondere 3 bis 30 Gew.%, bezogen auf die Zusammensetzung. The composition according to the invention usually comprises 0.1 to 70% by weight of pesticide, preferably 1 to 50% by weight, in particular 3 to 30% by weight, based on the composition.
Das Pestizid liegt bevorzugt in suspendierter Form in der Zusammensetzung vor, d.h. in Form kristalliner oder amorpher Partikel, die bei 20 °C fest sind. Das suspendierte Pestizid weist meist eine Partikelgrößenverteilung mit einem xso-Wert von 0,1 bis 10 μιη auf, bevorzugt von 0,2 μιτι bis 5 μιη und besonders bevorzugt von 0,5 μιη bis 2 μιτι. Die Partikelgrößenverteilung kann durch Laserlichtbeugung einer wässerigen Suspension umfassend die Partikel bestimmt werden. Die Probenvorbereitung, beispielsweise die Verdünnung auf Messkonzentration, hängt bei diesem Messverfahren unter anderem von der Feinheit und Konzentration der Wirkstoffe in der Suspensionsprobe sowie vom verwendeten Messgerät (z.B. Malvern Mastersizer) ab. Die Vorgehensweise muss für das jeweilige System ausgearbeitet werden und ist dem Fachmann bekannt. The pesticide is preferably present in suspended form in the composition, i. in the form of crystalline or amorphous particles which are solid at 20 ° C. The suspended pesticide usually has a particle size distribution with an xso value of 0.1 to 10 μιη, preferably from 0.2 μιτι to 5 μιη and more preferably from 0.5 μιη to 2 μιτι. The particle size distribution can be determined by laser light diffraction of an aqueous suspension comprising the particles. Sample preparation, for example dilution to measurement concentration, depends in this measurement method inter alia on the fineness and concentration of the active ingredients in the suspension sample and on the measuring instrument used (for example Malvern Mastersizer). The procedure must be worked out for the respective system and is known to the person skilled in the art.
Die erfindungsgemäßen Zusammensetzungen können weiterhin auch für agrochemische Formulierungen übliche Hilfsmittel enthalten, wobei sich die Wahl der Hilfsmittel nach der konkreten Anwendungsform, dem Formulierungstyp bzw. dem Wirkstoff rich- tet. Beispiele für geeignete Hilfsmittel sind Lösungsmittel, feste Trägerstoffe, oberflächenaktive Stoffe (wie Tenside, Solubilisatoren, Schutzkolloide, Netzmittel und Haftmittel), organische und anorganische Verdicker, Bakterizide, Frostschutzmittel, Entschäumer, ggf. Kleber (z. B. für Saatgutbehandlung) oder übliche Hilfsmittel für Köderformulierung (z. B. Lockstoffe, Futtermittel, Bitterstoffe). The compositions according to the invention may furthermore also comprise auxiliaries customary for agrochemical formulations, the choice of auxiliaries being directed to the specific application form, the type of formulation or the active ingredient. Examples of suitable auxiliaries are solvents, solid carriers, surface-active substances (such as surfactants, solubilizers, protective colloids, wetting agents and adhesives), organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, if appropriate adhesives (for example for seed treatment) or customary auxiliaries for bait formulation (eg attractants, feeds, bitter substances).
Als Lösungsmittel kommen Wasser oder organische Lösungsmittel wie Mineralölfraktionen von mittlerem bis hohem Siedepunkt wie Kerosin und Dieselöl, ferner Kohlen- teeröle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Paraffine, Tetrahydronaphthalin, alkylierte Naph- thaline und deren Derivate, alkylierte Benzole und deren Derivate, Alkohole wie Methanol, Ethanol, Propanol, Butanol und Cyclohexanol, Gykole, Ketone wie Cyclohexa- non, 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 enthält die Zusammensetzung Wasser. The solvents used are water or organic solvents, such as mineral oil fractions of medium to high boiling point, such as kerosene and diesel oil, and also hydrocarbons. tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example paraffins, tetrahydronaphthalene, alkylated naphthalene and derivatives thereof, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, glycols, ketones such as Cyclohexanone, gamma-butyrolactone, dimethyl fatty acid amides, 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 composition contains water.
Feste Trägerstoffe sind Mineralerden wie Kieselsäuren, Kieselgele, Silikate, Talkum, Kaolin, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel, wie Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pflanzliche Pro- dukte wie Getreidemehl, Baumrinden-, Holz- und Nußschalenmehl, Cellulosepulver oder andere feste Trägerstoffe. Die Formulierung enthält bevorzugt keine festen Träge rstoffe. Solid carriers are mineral soils such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers. The formulation preferably does not contain solid carriers.
Als oberflächenaktive Stoffe (Adjuvanten, Netz-, Haft-, Dispergier- oder Emulgiermittel) kommen die Alkali-, Erdalkali-, Ammoniumsalze von aromatischen Sulfonsäuren, z. B. von Lignin-(Borresperse®-Typen, Borregaard, Norwegen), Phenol-, Naphthalin- (Morwet®-Typen, Akzo Nobel, USA) und Dibutylnaphthalinsulfonsäure (Nekal®-Typen, BASF, Deutschland), sowie von Fettsäuren, Alkyl- und Alkylarylsulfonaten, Alkyl-, Lau- rylether- und Fettalkoholsulfaten, sowie Salze sulfatierter Hexa-, Hepta- und Octade- canole sowie von Fettalkoholglykolethern, Kondensationsprodukte von sulfoniertem Naphthalin und seiner Derivate mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphthalinsulfonsäuren mit Phenol und Formaldehyd, Polyoxyethyle- noctylphenolether, ethoxyliertes Isooctyl-, Octyl- oder Nonylphenol, Alkylphenyl-, Tribu- tylphenylpolyglykolether, Alkylarylpolyetheralkohole, Isotridecylalkohol, Fettalkoholethy- lenoxid-Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylen- oder Polyoxypropylenal- kylether, Laurylalkoholpolyglykoletheracetat, Sorbitester, Lignin-Sulfitablaugen sowie Proteine, denaturierte Proteine, Polysaccharide (z.B. Methylcellulose), hydrophob modifizierte Stärken, Polyvinylalkohol (Mowiol®-Typen, Clariant, Schweiz), Polycarboxyla- te (Sokalan®-Typen, BASF, Deutschland), Polyalkoxylate, Polyvinylamin (Lupamin®- Typen, BASF, Deutschland), Polyethylenimin (Lupasol®-Typen, BASF, Deutschland), Polyvinylpyrrolidon und deren Copolymere in Betracht. As surfactants (adjuvants, wetting agents, adhesives, dispersants or emulsifiers) are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, eg. B. of lignin (Borresperse ® grades, Borregaard, Norway), phenol, naphthalene (Morwet ® types, Akzo Nobel, USA) and dibutyl (nekal ® types, BASF, Germany), and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and Formaldehyde, polyoxyethylene noctylphenol ethers, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylphenyl polyglycol ethers, alkylarylpolyether alcohols, isotridecylalcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin sulphite liquors and Proteins, denatured proteins, polysaccharides (eg methylc ellulose), hydrophobically modified starches, polyvinyl alcohol (Mowiol ® types, Clariant, Switzerland), Polycarboxyla- te (Sokalan ® types, BASF, Germany), polyalkoxylates, polyvinylamine (Lupamin ® - types, BASF, Germany), polyethyleneimine (Lupasol ® types, BASF, Germany), polyvinylpyrrolidone and copolymers thereof.
Geeignete Verdicker sind Verbindungen, die der Formulierung ein modifiziertes Fließverhalten verleihen, d. h. eine hohe Viskosität im Ruhezustand und niedrige Viskosität im bewegten Zustand. Beispiele sind Polysaccharide, Proteine (wie Casein oder gelati- ne), synthetische Polymere, oder anorganische Schichtmineralien. Solche Verdicker sind kommerziell erhältlich, beispielsweise Xanthan Gum (Kelzan®, CP Kelco, USA), Rhodopol® 23 (Rhodia, Frankreich) oder Veegum® (R.T. Vanderbilt, USA) oder Attac- lay® (Engelhard Corp., NJ, USA). Der Gehalt an Verdicker in der Formulierung richtet sich nach der Wirksamkeit des Verdickers. Der Fachmann wird einen Gehalt wählen, um die gewünschte Viskosität der Formulierung zu erhalten. Der Gehalt wird meist 0,01 bis 10 Gew.% betragen. Suitable thickeners are compounds which impart a modified flow behavior to the formulation, ie a high viscosity at rest and low viscosity in an agitated state. Examples are polysaccharides, proteins (such as casein or gelatin), synthetic polymers, or inorganic layer minerals. Such thickeners are commercially available, such as Xanthan Gum (Kelzan ®, CP Kelco, USA), Rhodopol ® 23 (Rhodia, France) or Veegum ® (RT Vanderbilt, USA) or Attac lay ® (Engelhard Corp., NJ, USA). The content of thickener in the formulation depends on the effectiveness of the thickener. One skilled in the art will select a level to obtain the desired viscosity of the formulation. The content will usually be 0.01 to 10 wt.%.
Bakterizide können zur Stabilisierung der Zusammensetzung zugesetzt werden. Beispiele für Bakterizide sind solche basierend auf Diclorophen und Benzylalkoholhemi- formal sowie Isothiazolinonderivaten wie Alkylisothiazolinonen und Benzisothiazolino- nen (Acticide® MBS der Fa. Thor Chemie). Beispiele für geeignete Frostschutzmittel sind Ethylenglycol, Propylenglycol, Harnstoff und Glycerin. Beispiele für Entschäumer sind Silikonemulsionen (wie z. B. Silikon® SRE, Wacker, Deutschland oder Rhodorsil®, Rhodia, Frankreich), langkettige Alkohole, Fettsäuren, Salze von Fettsäuren, fluororganische Verbindungen und deren Gemische. Bactericides may be added to stabilize the composition. Examples of bactericides are those based on dichlorophen and benzyl alcohol formal and isothiazolinone derivatives such as alkylisothiazolinones and Benzisothiazolino- nen (Acetide ® MBS from Thor Chemie).. Examples of suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin. Examples of defoamers are silicone emulsions (such as, for example, silicone ® SRE, Wacker, Germany or Rhodorsil ®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds and mixtures thereof.
Als Kleber kommen alle üblichen in Beizmitteln einsetzbaren Bindemittel in Frage. Vorzugsweise genannt seien Polyvinylpyrrolidon, Polyvinylacetat, Polyvinylalkohol und Tylose. Die erfindungsgemäße Zusammensetzung kann mindestens 5 Gew.% anorganische Salze enthalten, bevorzugt mindestens 10 Gew.% und insbesondere mindestens 15 Gew.%. Geeignete anorganische Salze sind anorganische Verbindungen, die Anionen und Katioinen umfassen und sich in Wasser zu mindestens 10 g/l, bevorzugt zu mindestens 50 g/l und insbesondere zu mindestens 150 g/l lösen bei 20 °C. Suitable adhesives are all customary binders which can be used in pickling agents. Preferably mentioned are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose. The composition according to the invention may contain at least 5% by weight of inorganic salts, preferably at least 10% by weight and in particular at least 15% by weight. Suitable inorganic salts are inorganic compounds which comprise anions and catalines and dissolve in water to at least 10 g / l, preferably to at least 50 g / l and in particular to at least 150 g / l at 20 ° C.
In eine bevorzugten Ausführungsform ist die Zusammensetzung eine wässrige Suspension, in der mindestens ein Pestizid in partikulärer Form oder in verkapselter Form vorliegt. Bevorzugt enthält die Suspension 0,0001 bis 10 Gew.%, besonders bevorzugt 0,0001 bis 1 Gew.%, und insbesondere 0,001 bis 0,5 Gew.% Polycarboxylatether. Die wässrige Suspension kann mindestens 5 Gew.% anorganische Salze enthalten, bevorzugt mindestens 10 Gew.% und insbesondere mindestens 15 Gew.%. In a preferred embodiment, the composition is an aqueous suspension in which at least one pesticide is in particulate form or in encapsulated form. The suspension preferably contains from 0.0001 to 10% by weight, particularly preferably from 0.0001 to 1% by weight, and in particular from 0.001 to 0.5% by weight, of polycarboxylate ether. The aqueous suspension may contain at least 5% by weight of inorganic salts, preferably at least 10% by weight and in particular at least 15% by weight.
In einer besonders bevorzugten Ausführungsform ist die Zusammensetzung eine agrochemische Formulierung in Form eines Suspensionskonzentrat (SC). Das SC enthält üblicherweise mindestens 10 Gew.% Wasser, bevorzugt von 20 bis 80 Gew.%. Der Gehalt an PCE kann bei 0,01 bis 10 Gew.%, bevorzugt bei 0,05 bis 2 Gew%, und insbesondere bei 0,05 bis 0,8 Gew%, liegen. Mindestens ein Pestizid liegt in suspendierter Form vor. In a particularly preferred embodiment, the composition is an agrochemical formulation in the form of a suspension concentrate (SC). The SC usually contains at least 10% by weight of water, preferably from 20 to 80% by weight. The content of PCE may be 0.01 to 10% by weight, preferably 0.05 to 2% by weight, and more preferably 0.05 to 0.8% by weight. At least one pesticide is in suspended form.
In einer weiteren besonders bevorzugten Ausführungsform ist die Zusammensetzung eine agrochemische Formulierung in Form einer Suspoemulsion (SE). Die SE enthält üblicherweise mindestens 10 Gew.% Wasser, bevorzugt von 20 bis 80 Gew.%. Der Gehalt an PCE kann bei 0,01 bis 10 Gew.%, bevorzugt bei 0,05 bis 2 Gew%, und insbesondere bei 0,05 bis 0,8 Gew%, liegen. Mindestens ein Pestizid kann in suspendierter Form vorliegen, und ein weiteres Pestizid kann in emulgierter Form vorliegen. In einer weiteren besonders bevorzugten Ausführungsform ist die Zusammensetzung eine agrochemische Formulierung in Form einer Kapselsuspension (CS). Die CS enthält üblicherweise mindestens 10 Gew.% Wasser, bevorzugt von 20 bis 80 Gew.%. Der Gehalt an PCE kann bei 0,01 bis 10 Gew.%, bevorzugt bei 0,05 bis 2 Gew%, und insbesondere bei 0,05 bis 0,8 Gew%, liegen. Mindestens ein Pestizid kann in verkap- seiter Form vorliegen. In a further particularly preferred embodiment, the composition is an agrochemical formulation in the form of a suspoemulsion (SE). The SE usually contains at least 10% by weight of water, preferably from 20 to 80% by weight. Of the Content of PCE may be 0.01 to 10% by weight, preferably 0.05 to 2% by weight, and more preferably 0.05 to 0.8% by weight. At least one pesticide may be in suspended form and another pesticide may be in emulsified form. In a further particularly preferred embodiment, the composition is an agrochemical formulation in the form of a capsule suspension (CS). The CS usually contains at least 10% by weight of water, preferably from 20 to 80% by weight. The content of PCE may be 0.01 to 10% by weight, preferably 0.05 to 2% by weight, and more preferably 0.05 to 0.8% by weight. At least one pesticide may be in encapsulated form.
In einer weiteren bevorzugten Ausführungsform ist die Zusammensetzung eine feste Zusammensetzung ist. Bevorzugt enthält die feste Zusammensetzung 0,01 bis 20 Gew.%, bevorzugt 0,05 bis 5 Gew%, und insbesondere 0,1 bis 1 ,0 Gew%, Polycar- boxylatether. In another preferred embodiment, the composition is a solid composition. The solid composition preferably contains from 0.01 to 20% by weight, preferably from 0.05 to 5% by weight, and in particular from 0.1 to 1.0% by weight, of polycarboxylate ether.
In einer besonders bevorzugten Ausführungsform ist die Zusammensetzung eine agrochemische Formulierung in Form einer wasserdispergierbaren Granulats (WG). Das WG ist meist ein Feststoff. Der Gehalt an PCE kann bei 0,01 bis 20 Gew.%, bevorzugt bei 0,05 bis 5 Gew%, und insbesondere 0,1 bis 1 ,0 Gew%, liegen. Mindestens ein Pestizid kann in Form fester Teilchen vorliegen. In a particularly preferred embodiment, the composition is an agrochemical formulation in the form of a water-dispersible granule (WG). The WG is usually a solid. The content of PCE may be 0.01 to 20% by weight, preferably 0.05 to 5% by weight, and more preferably 0.1 to 1.0% by weight. At least one pesticide may be in the form of solid particles.
Die vorliegende Erfindung betrifft weiterhin ein Verfahren zur Herstellung der erfindungsgemäßen Zusammensetzung indem man das Pestizid und den Polycarboxyla- tether in Kontakt bringt. Übliche Verfahren zur Herstellung von agrochemischen Formulierungen sind dafür geeignet. The present invention further relates to a process for the preparation of the composition according to the invention by bringing the pesticide and the polycarboxylate tether in contact. Conventional processes for the preparation of agrochemical formulations are suitable.
Die erfindungsgemäße Zusammensetzung wird meist vor der Anwendung verdünnt um den sog. Tankmix herzustellen. Zur Verdünnung kommen Mineralölfraktionen von mitt- lerem bis hohem Siedepunkt, wie Kerosin oder Dieselöl, ferner Kohlenteeröle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Toluol, Xylol, Paraffin, Tetrahydronaphthalin, alkylierte Naph- thaline oder deren Derivate, Methanol, Ethanol, Propanol, Butanol, Cyclohexanol, Cyc- lohexanon, Isophoron, stark polare Lösungsmittel, z.B. Dimethylsulfoxid, N-Methyl- pyrrolidon oder Wasser in Betracht. Bevorzugt wird Wasser verwendet. Die verdünnte Zusammensetzung wird üblicherweise durch Versprühen oder Vernebeln angewendet. Der Gehalt an PCE im Tankmix liegt meist bei unter 0,1 Gew.%, bevorzugt bei unter 0,01 Gew.%, und unsbesondere bei unter 0,001 Gew.%. The composition of the invention is usually diluted before use to produce the so-called tank mix. Dilution is carried out with mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, coal tar oils and oils of plant or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration. Preferably, water is used. The diluted composition is usually applied by spraying or atomizing. The content of PCE in the tank mix is usually less than 0.1% by weight, preferably less than 0.01% by weight, and especially less than 0.001% by weight.
Zu dem Tankmix können Öle verschiedenen Typs, Netzmittel, Adjuvante, Herbizide, Bakterizide, Fungizide unmittelbar vor der Anwendung (Tankmix) zugesetzt werden. Diese Mittel können zu den erfindungsgemäßen Zusammensetzungen im Gewichts- Verhältnis 1 :100 bis 100:1 , bevorzugt 1 :10 bis 10:1 zugemischt werden. Die Pestizid- konzentration im Tankmix kann in größeren Bereichen variiert werden. Im Allgemeinen liegen sie zwischen 0,0001 und 10%, vorzugsweise zwischen 0,01 und 1 %. Die Aufwandmengen liegen bei der Anwendung im Pflanzenschutz je nach Art des gewünsch- ten Effektes zwischen 0,01 und 2,0 kg Wirkstoff pro ha. To the tank mix oils of various types, wetting agents, adjuvants, herbicides, bactericides, fungicides can be added immediately before use (tank mix). These agents can be added to the compositions according to the invention by weight. Ratio 1: 100 to 100: 1, preferably 1: 10 to 10: 1 are admixed. The pesticide concentration in the tank mix can be varied in larger areas. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%. Depending on the type of desired effect, the application rates in crop protection range from 0.01 to 2.0 kg of active ingredient per ha.
Die vorliegende Erfindung betrifft weiterhin ein Verfahren zur Bekämpfung von phyto- pathogenen Pilzen und/oder unerwünschtem Pflanzenwuchs und/oder unerwünschtem Insekten- oder Milbenbefall und/oder zur Regulation des Wachstums von Pflanzen, wobei man die erfindungsgemäße Zusammensetzung auf die jeweiligen Schädlinge, deren Lebensraum 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. Die vorliegende Erfindung betrifft weiterhin Saatgut enthaltend die erfindungsgemäße Zusammensetzung. The present invention further relates to a method for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired insect or mite infestation and / or for regulating the growth of plants, wherein the composition according to the invention on the respective pests, their habitat 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 present invention further relates to seed containing the composition according to the invention.
Die vorliegende Erfindung betrifft weiterhin die Verwendung des Polycarboxylatethers zur Dispergierung von Pestiziden mit einer Löslichkeit in Wasser von höchstens 10 g/l in wässrigen Zusammensetzungen. Das Pestizid liegt bevorzugt in suspendierter Form in der wässrigen Zusammensetzung vor, d.h. in Form kristalliner oder amorpher Partikel, die bei 20 °C fest sind. Der Gehalt an PCE in der wässrigen Zusammensetzung liegt meist bei unter 0,1 Gew.%, bevorzugt bei unter 0,01 Gew.%, und unsbesondere bei unter 0,001 Gew.%. The present invention further relates to the use of the polycarboxylate ether for dispersing pesticides having a solubility in water of at most 10 g / l in aqueous compositions. The pesticide is preferably in suspended form in the aqueous composition, i. in the form of crystalline or amorphous particles which are solid at 20 ° C. The content of PCE in the aqueous composition is usually less than 0.1% by weight, preferably less than 0.01% by weight, and especially less than 0.001% by weight.
In einer Ausführungsform der vorliegenden Erfindung ist das Verfahren zum Beizen von Saatgut, wobei man In one embodiment of the present invention, the method for pickling seeds, wherein
(a) Saatgut mit einem Pestizid mit einer Löslichkeit in Wasser von höchstens 10 g/l und dem Polycarboxylatether behandelt; und  (a) treating seed with a pesticide having a solubility in water of not more than 10 g / l and the polycarboxylate ether; and
(b) das in Schritt (a) erhaltene Saatgut gegebenenfalls trocknet (b) optionally drying the seed obtained in step (a)
Der Polycarboxylatether kann wie vorstehend beschrieben eingesetzt werden oder in Form der erfindungsgemäßen Zusammensetzung. Hierbei kann -falls gewünscht- die erfindungsgemäße Zusammensetzung oder der Polycarboxylatether vor Applikation auf das Saatgut mit einem Lösungsmittel, vorzugsweise Wasser verdünnt werden. The polycarboxylate ether can be used as described above or in the form of the composition according to the invention. Here, if desired, the composition of the invention or the polycarboxylate before application to the seed with a solvent, preferably water are diluted.
Dieses so vorbehandelte Saatgut kann anschliessend mit einer agrochemischen Suspensionsformulierung enthaltend mindestens einen, zur Beizung von Saatgut geeigneten agrochemischen Wirkstoff, wobei der Wirkstoff in festen Partikeln vorliegt, welche eine Größe zwischen 0,1 μιη und 10μιη haben, behandelt werden. Diese agrochemischen Formulierungen sind Suspensionsformulierungen eines (oder mehrerer) agrochemischen Wirkstoffes sein (zBsp. SC, OD, FS), wobei der Wirkstoff die oben angeführten Teilchengrößen aufweisen muß. Die Herstellung von Suspensionsformulierungen ist dem Fachmann bekannt, und ist weiter oben erläutert. This seed pretreated in this way can subsequently be treated with an agrochemical suspension formulation comprising at least one agrochemical active substance suitable for dressing seed, the active substance being present in solid particles having a size between 0.1 μm and 10 μm. These agrochemical formulations are suspension formulations of one (or more) agrochemical active (eg, SC, OD, FS), which must have the above particle sizes. The preparation of suspension formulations is known to the person skilled in the art and is explained above.
Alternativ kann die Wirkstoffsuspension auch aus einer (ggf. auch kommerziell erhältlichen) Festformulierung eines Wirkstoffes durch Dispergieren in einem Lösungsmittel, vorzugsweise Wasser, hergestellt werden (s.o.). Der Begriff Saatgut umfasst Saatgut aller Arten, wie z.B. Körner, Samen, Früchte, Knollen, Stecklinge und ähnliche Formen. Bevorzugt beschreibt der Begriff Saatgut hier Körner und Samen. Alternatively, the active substance suspension can also be prepared from a (optionally also commercially available) solid formulation of an active ingredient by dispersing in a solvent, preferably water (see above). The term seed includes seeds of all kinds, e.g. Grains, seeds, fruits, tubers, cuttings and similar forms. The term seed preferably describes grains and seeds here.
Geeignetes Saatgut sind Getreidesaaten Halmfruchtsaaten, Hackfruchtsaaten, Ölsaa- ten, Gemüsesaaten, Gewürzsaatgut, Zierpflanzensaatgut, z.B. Saatgut von Hartweizen, Weizen, Gerste, Hafer, Roggen, Mais (Futtermais und Zuckermais), Soja , Ölsaaten, Kreuzblütler, Baumwolle, Sonnenblumen, Bananen, Reis, Raps, Rüben, , Zuckerrüben, Futterrüben, Eierpflanzen, Kartoffeln, Gras, (Zier-)Rasen, Futtergras, Tomaten, Lauch, Kürbis, Kohl, Eisbergsalat, Pfeffer, Gurken, Melonen, Brassica species, Melo- nen, Bohnen, Erbsen, Knoblauch, Zwiebeln, Karotten, Zuckerrohr, Tabak, Weintrauben, Petunien und Geranien, Stiefmütterchen, Springkraut. Bevorzugt beschreibt der Begriff Saatgut hier Getreide und Soja. Suitable seeds are cereals seed crops, root crops, oilseeds, vegetable seeds, spice seed, ornamental plant seed, e.g. Seeds of durum wheat, wheat, barley, oats, rye, maize (fodder corn and sweetcorn), soya, oilseeds, cruciferous vegetables, cotton, sunflowers, bananas, rice, oilseed rape, beets, sugar beets, fodder beet, egg plants, potatoes, grass, (ornamental -) Lawn, forage grass, tomatoes, leeks, squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, brassica species, melons, beans, peas, garlic, onions, carrots, sugarcane, tobacco, grapes, petunia and geraniums, pansies , Balsam. Preferably, the term seed here describes cereals and soybeans.
Die erfindungsgemäßen Zusammensetzungen können zum Beizen von Saatgut durch herkömmliche Züchtungsmethoden erhaltener Pflanzen sowie zum Beizen von Saatgut transgener Pflanzen eingesetzt werden. The compositions according to the invention can be used for pickling seeds by plants obtained by conventional culture methods and for pickling seeds of transgenic plants.
Wie bereits erwähnt kann Saatgut eingesetzt werden, das gegenüber Herbiziden tolerant ist, z.B. gegenüber Sulfonylharnstoffen, Imidazolinonen oder Glufonsinat oder Glyphosate resistenen Pflanzen (s. z.B. EP-A-0242236, EP-A-242246) (WO 92/00377) (EP-A-0257993, U.S. Pat. No. 5,013,659) oder Saatgut transgener Pflanzen, z.B. As already mentioned, seed can be used that is tolerant to herbicides, e.g. plants resistant to sulfonylureas, imidazolinones or glufonate or glyphosate (see, e.g., EP-A-0242236, EP-A-242246) (WO 92/00377) (EP-A-0257993, U.S. Pat No. 5,013,659) or transgenic plant seeds, e.g.
Baumwolle, die Bacillus thuringiensis toxin (Bt toxins) produzieren und dadurch gegenüber bestimmten Schadorganismen gegenüber resistent sind (EP-A-0142924, EP-A- 0193259). Cotton producing Bacillus thuringiensis toxin (Bt toxins) and thereby resistant to certain harmful organisms (EP-A-0142924, EP-A-0193259).
Weiterhin kann auch Saatgut von Pflanzen eingesetzt werden, die im Vergleich mit herkömmlichen Pflanzen modifizierte Eigenschaften aufweisen. Beispiele hierfür sind geänderte Stärkesynthese (e.g. WO 92/1 1376, WO 92/14827, WO 91/19806) oder Fettsäurezusammensetzungen (WO 91/13972). Furthermore, seed of plants can be used which have modified properties in comparison with conventional plants. Examples of these are modified starch synthesis (for example WO 92/1 1376, WO 92/14827, WO 91/19806) or fatty acid compositions (WO 91/13972).
Der Begriff Pflanzen schließt auch solche Pflanzen ein, die durch Züchtung, Mutage- nese oder gentechnische Methoden verändert wurden einschließlich der auf dem Markt oder in Entwicklung befindlichen biotechnologischen Agrarprodukte. Gentechnisch veränderte Pflanzen sind Pflanzen, deren genetisches Material in einer Weise verändert worden ist, wie sie unter natürlichen Bedingungen durch Kreuzen, Mutationen oder natürliche Rekombination (d.h. Neuzusammenstellung der Erbinformation) nicht vor- kommt. Dabei werden in der Regel ein oder mehrere Gene in das Erbgut der Pflanze integriert, um die Eigenschaften der Pflanze zu verbessern. Derartige gentechnische Veränderungen umfassen auch posttranslationale Modifikationen von Proteinen, Oligo- oder Polypeptiden z.B. mittels Glykolsylierung oder Bindung von Polymeren wie z.B. prenylierter, acetylierter oder farnelysierter Reste oder PEG-Reste. The term plants also includes those plants which have been modified by breeding, mutagenesis or genetic engineering methods including those on the market or biotechnological agricultural products under development. Genetically modified plants are plants whose genetic material has been altered in a way that does not occur under natural conditions by crossing, mutations or natural recombination (ie recomposition of genetic information). As a rule, one or more genes are integrated into the genome of the plant in order to improve the properties of the plant. Such genetic engineering modifications also include post-translational modifications of proteins, oligo- or polypeptides, for example by means of glycolsylation or binding of polymers such as prenylated, acetylated or farnelysed residues or PEG residues.
Beispielhaft seien Pflanzen genannt, die durch züchterische und gentechnische Maßnahmen eine Toleranz gegen bestimmter Herbizidklassen, wie Auxinherbizide wie z. B. Dicamba oder 2,4-D, Ausbleichungsherbizide wie Hydroxyphenylpyruvat-Dioxygenase (HPPD)-Inhibitoren oder Phytoendesaturase (PDS)-Inhibitoren, Acetolactat-Synthase (ALS)-Inhibitoren wie z. B. Sulfonylharnstoffe, Enolpyruvylshikimat-3-Phosphat- Synthase (EPSPS)-lnhibitoren wie z. B. Glyphosat, Glutaminsynthetase (GS)-By way of example plants are mentioned, which by breeding and genetic engineering measures a tolerance against certain herbicide classes, such as auxin herbicides such. B. Dicamba or 2,4-D, bleaching herbicides such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors or phytoene desaturase (PDS) inhibitors, acetolactate synthase (ALS) inhibitors such. As sulfonylureas, Enolpyruvylshikimat-3-phosphate synthase (EPSPS) inhibitors such. Glyphosate, glutamine synthetase (GS) -
Inhibitoren wie z. B. Glufosinat, Lipidbiosynthese-Inhibitoren wie z. B. Acetyl-CoA- Carboxylase (ACCase)-lnhibitoren, oder Oxynil-Herbizide (z. B. Bromoxynil oder loxy- nil) erworben haben. Weiterhin wurden Pflanzen erzeugt, die durch mehrere gentechnische Maßnahmen resistent gegenüber mehreren Herbizidklassen sind, z B. resistent gegen Glyphosat und Glufosinat, oder gegen Glyphosat und einer Herbizid einer anderen Klasse wie z. B. ALS-Inhibitoren, HPPD-Inhibitoren, Auxinherbizide und ACCase- Inhibitoren. Diese Herbizidresistenztechnologien sind z. B. beschrieben in Pest Managern. Sei. 61 , 2005, 246; 61 , 2005, 258; 61 , 2005, 277; 61 , 2005, 269; 61 , 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sei. 57, 2009, 108; Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1 185; und darin zitierten Referenzen. Durch Züchtung und Mutagenese wurde z. B. Clearfield®-Raps (BASF SE, Deutschland) erzeugt, der eine Toleranz gegen Imidazolinone, z. B. Imazamox, hat, oder ExpressSun®- Sonnenblumen (DuPont, USA), die eine Toleranz gegen Sulfonylharnstoffherbizide, wie z. B. Tribenuron, haben. Mit Hilfe gentechnischer Methoden wurden Kulturpflan- zen, wie Soja, Baumwolle, Mais, Rüben und Raps, erzeugt, die resistent gegenInhibitors such. As glufosinate, lipid biosynthesis inhibitors such. Acetyl-CoA carboxylase (ACCase) inhibitors, or oxynil herbicides (eg, bromoxynil or loxynil). Furthermore, plants have been produced which are resistant to several classes of herbicides by several genetic engineering measures, eg resistant to glyphosate and glufosinate, or to glyphosate and a herbicide of another class, such as, for example, ALS inhibitors, HPPD inhibitors, auxin herbicides and ACCase inhibitors. These herbicide resistance technologies are e.g. As described in Pest Managers. Be. 61, 2005, 246; 61, 2005, 258; 61, 2005, 277; 61, 2005, 269; 61, 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed. 57, 2009, 108; Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1 185; and references cited therein. By breeding and mutagenesis z. B. Clearfield ® rapeseed (BASF SE, Germany) produced, the tolerance to imidazolinones, z. B. imazamox, has, or Express- ® - sunflowers (DuPont, USA), the tolerance to sulfonylurea herbicides such. Tribenuron. Using genetic engineering methods, crops such as soybeans, cotton, corn, beets and oilseed rape were produced, which were resistant to
Glyphosat oder Glufosinat sind, erzeugt, welche unter den Handelsnamen Roundup- Ready® (Glyphosat-resistent, Monsanto, U.S.A.), Cultivance® (Imidazolinon-resistent, BASF SE, Deutschland) und Liberty Link® (Glufosinat-resistent, Bayer CropScience, Deutschland) erhältlich sind. Glyphosate or glufosinate are produced under the trade name Roundup Ready ® (glyphosate-resistant, Monsanto, USA) Cultivance ® (imidazolinone resistant, BASF SE, Germany) and Liberty Link ® (glufosinate-resistant, Bayer CropScience, Germany ) are available.
Weiterhin sind auch Pflanzen umfasst, die mit Hilfe gentechnischer Maßnahmen ein oder mehrere Toxine, z. B. solche aus dem Bakterienstamm Bacillus, produzieren. Toxine, die durch solche gentechnisch veränderten Pflanzen hergestellt werden, umfassen z. B. Insektizide Proteine von Bacillus spp., insbesondere von B. thuringiensis, wie die Endotoxine CrylAb, Cryl Ac, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 , Cry9c, Cry34Ab1 oder Cry35Ab1 ; oder vegetative Insektizide Proteine (VIPs), z. B. VIP1 , VIP2, VIP3, oder VIP3A; Insektizide Proteine von Nematoden-kolonisierenden Bakteri- en, z. B. Photorhabdus spp. oder Xenorhabdus spp.; Toxine aus tierischen Organismen, z. B. Wepsen,-, Spinnen- oder Skorpionstoxine; pilzliche Toxine, z. B. aus Strep- tomyceten; pflanzliche Lektine, z. B. aus Erbse oder Gerste; Agglutinine; Proteinase- Inhibitoren, z. B. Trypsin-Inhibitoren, Serinprotease-Inhibitoren, Patatin, Cystatin oder Papain-Inhibitoren; Ribosomen-inaktivierende Proteine (RIPs), z. B. Ricin, Mais-RIP, Abrin, Luffin, Saporin oder Bryodin; Steroid-metabolisierende Enzyme, z. B. 3-Hydroxy- steroid-Oxidase, Ecdysteroid-IDP-Glycosyl-Transferase, Cholesterinoxidase, Ecdyson- Inhibitoren oder HMG-CoA-Reduktase; lonenkanalblocker, z. B. Inhibitoren von Natrium- oder Calziumkanälen; Juvenilhormon-Esterase; Rezeptoren für das diuretischen Hormon (Helicokininrezeptoren); Stilbensynthase, Bibenzylsynthase, Chitinasen und Glucanasen. Diese Toxine können in den Pflanzen auch als Prätoxine, Hybridproteine, verkürzte oder anderweitig modfizierte Proteine produziert werden. Hybridproteine zeichnen sich durch eine neue Kombination von verschiedenen Proteindomänen aus (siehe z. B. WO 2002/015701 ). Weitere Besipiele für derartige Toxine oder gentech- nisch veränderte Pflanzen, die diese Toxine produzieren, sind in EP-A 374 753, WO 93/07278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073 offenbart. Die Methoden zur Herstellung dieser gentechnisch veränderten Pflanzen sind dem Fachmann bekannt und z. B. in den oben erwähnten Publikationen dargelegt. Zahlreiche der zuvor genannten Toxine verleihen den Pflanzen, die die- se produzieren, eine Toleranz gegen Schädlinge aus allen taxonomischen Arthropo- denklassen, insbesondere gegen Käfer (Coeleropta), Zweiflügler (Diptera) und Furthermore, plants are included which, with the aid of genetic engineering measures one or more toxins, eg. B. those from the bacterial strain Bacillus produce. Toxins produced by such genetically engineered plants include e.g. B. Insecticidal proteins of Bacillus spp., In particular of B. thuringiensis, such as the endotoxins CrylAb, CrylAc, CrylF, Cry1Fe2, Cry2Ab, Cry3A, Cry3Bb1, Cry9c, Cry34Ab1 or Cry35Ab1; or vegetative insecticidal proteins (VIPs), e.g. VIP1, VIP2, VIP3, or VIP3A; Insecticidal proteins from nematode-colonizing bacteria en, z. B. Photorhabdus spp. or Xenorhabdus spp .; Toxins from animal organisms, eg. B. Wepsen, spider or scorpion toxins; fungal toxins, e.g. Eg from Streptomyces; herbal lectins, e.g. From pea or barley; agglutinins; Proteinase inhibitors, e.g. Trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; Ribosome Inactivating Proteins (RIPs), e.g. Ricin, corn RIP, abrin, luffin, saporin or bryodin; Steroid metabolizing enzymes, e.g. 3-hydroxy steroid oxidase, ecdysteroid IDP glycosyltransferase, cholesterol oxidase, ecdysone inhibitors, or HMG-CoA reductase; ion channel blocker, e.g. B. inhibitors of sodium or calcium channels; Juvenile hormone esterase; Receptors for the diuretic hormone (helicokinin receptors); Stilbene synthase, bibenzyl synthase, chitinases and glucanases. These toxins can also be produced in the plants as proteoxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a novel combination of different protein domains (see, for example, WO 2002/015701). Further examples of such toxins or genetically modified plants which produce these toxins are described in EP-A 374 753, WO 93/07278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03 / 18810 and WO 03/52073. The methods for producing these genetically modified plants are known in the art and z. As set forth in the publications mentioned above. Many of the aforementioned toxins confer on the plants producing them tolerance to pests of all taxonomic arthropod classes, in particular to beetles (Coeleropta), diptera (Diptera) and
Schmetterlinge (Lepidoptera) und gegen Nematoden (Nematoda). Gentechnisch veränderte Pflanzen, die ein oder mehrere Gene, die für Insektizide Toxine kodieren, produzieren sind z. B. in den oben erwähnten Publikationen beschrieben und zum Teil kommerziell erhältlich, wie z. B. YieldGard® (Maissorten, die das Toxin CrylAb produzieren), YieldGard® Plus (Maissorten, die die Toxine CrylAb und Cry3Bb1 produzieren), Starlink® (Maissorten, die das Toxin Cry9c produzieren), Herculex® RW (Maissorten, die die Toxine Cry34Ab1 , Cry35Ab1 und das Enzym Phosphinothricin-N-Acetyl- transferase [PAT] produzieren); NuCOTN® 33B (Baumwollsorten, die das Toxin Cry1 Ac produzieren), Bollgard® I (Baumwollsorten, die das Toxin Cry1 Ac produzieren), Bollgard® II (Baumwollsorten, die die Toxine CrylAc und Cry2Ab2 produzieren); VIP- COT® (Baumwollsorten, die ein VIP-Toxin produzieren); NewLeaf® (Kartoffelsorten, die das Toxin Cry3A produzieren); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protec- ta®, Bt1 1 (z. B. Agrisure® CB) und Bt176 von Syngenta Seeds SAS, Frankreich, (Mais- Sorten, die das Toxin Cryl Ab und das PAT-Enyzm produzieren), MIR604 von Syngenta Seeds SAS, Frankreich (Maissorten, die ein modifizierte Version des Toxins Cry3A produzieren, siehe hierzu WO 03/018810), MON 863 von Monsanto Europe S.A., Belgien (Maissorten, die das Toxin Cry3Bb1 produzieren), IPC 531 von Monsanto Europe S.A., Belgien (Baumwollsorten, die eine modifizierte Version des Toxins Cryl Ac produ- zieren) und 1507 von Pioneer Overseas Corporation, Belgien (Maissorten, die das Toxin Cry1 F und das PAT-Enyzm produzieren). Weiterhin sind auch Pflanzen umfasst, die mit Hilfe gentechnische Maßnahmen ein oder mehrere Proteine produzieren, die eine erhöhte Resistenz oder Widerstandfähigkeit gegen bakterielle, virale oder pilzliche Pathogene bewirken, wie z. B. sogenannte Pathogenesis-related-Proteine (PR-Proteine, siehe EP-A O 392 225), Resistenzprotei- ne (z. B. Kartoffelsorten, die zwei Resistenzgene gegen Phytophthora infestans aus der mexikanischen Wildkartoffel Solanum bulbocastanum produzieren) oder T4-Lyso- zym (z. B. Kartoffelsorten, die durch die Produktion diese Proteins resistent gegen Bakterien wie Erwinia amylvora ist). Weiterhin sind auch Pflanzen umfasst, deren Produktivität mit Hilfe gentechnischer Methoden verbessert wurde, indem z. B. die Ertragsfä- higkeit (z. B. Biomasse, Kornertrag, Stärke-, Öl- oder Proteingehalt), die Toleranz gegenüber Trockenheit, Salz oder anderen begrenzenden Umweltfaktoren oder die Widerstandsfähigkeit gegenüber Schädlingen und pilzlichen, bakteriellen und viralen Pa- thogenen gesteigert wird. Weiterhin sind auch Pflanzen umfasst, deren Inhaltsstoffe insbesondere zur Verbesserung der menschlichen oder tierischen Ernährung mit Hilfe gentechnischer Methoden verändert wurden, indem z. B. Ölpflanzen gesundheitsfördernde langkettige Omega-3-Fettsäuren oder einfach ungesättigte Omega-9- Fettsäuren (z. B. Nexera®-Raps, DOW Agro Sciences, Kanada) produzieren. Weiterhin sind auch Pflanzen umfasst, die zur verbesserten Produktion von Rohstoffen mit Hilfe gentechnischer Methoden verändert wurden, indem z. B. der Amylopektin-Gehalt von Kartoffeln (Amflora®-Kartoffel, BASF SE, Deutschland) erhöht wurde. Butterflies (Lepidoptera) and nematodes (Nematoda). Genetically engineered plants that produce one or more genes encoding insecticidal toxins, e.g. As described in the publications mentioned above and partly commercially available, such as. B. YieldGard ® (corn cultivars producing the toxin CrylAb), YieldGard ® Plus (corn cultivars producing the toxins CrylAb and Cry3Bb1), StarLink ® (corn cultivars producing the toxin Cry9c), Herculex ® RW (corn cultivars toxins which Cry34Ab1, Cry35Ab1 and the enzyme phosphinothricin N-acetyltransferase [PAT] produce); NuCOTN ® 33B (cotton cultivars producing the Cry1 Ac toxin), Bollgard ® I (cotton cultivars producing the Cry1 Ac toxin), Bollgard ® II (cotton cultivars producing the toxins CrylAc and Cry2Ab2); VIP COT ® (cotton cultivars producing a VIP-toxin); NewLeaf ® (potato cultivars producing the Cry3A toxin); Bt Xtra ®, NatureGard® ®, KnockOut ®, BiteGard ®, Protec ta ®, Bt1 1 (z. B. Agrisure ® CB) and Bt176 from Syngenta Seeds SAS, France (corn varieties that the toxin Cryl Ab and producing the PAT enzyme), MIR604 from Syngenta Seeds SAS, France (maize varieties producing a modified version of the toxin Cry3A, see WO 03/018810), MON 863 from Monsanto Europe SA, Belgium (maize varieties producing the toxin Cry3Bb1 ), IPC 531 from Monsanto Europe SA, Belgium (cotton varieties producing a modified version of the toxin Cryl Ac) and 1507 from Pioneer Overseas Corporation, Belgium (maize varieties producing the toxin Cry1 F and the PAT enzyme). Furthermore, plants are included, which produce by genetic engineering measures one or more proteins that cause increased resistance or resistance to bacterial, viral or fungal pathogens, such as. For example, so-called pathogenesis-related proteins (PR proteins, see EP-A 0 392 225), resistance proteins (for example potato varieties which produce two resistance genes against Phytophthora infestans from the Mexican wild potato Solanum bulbocastanum) or T4 lyso - zym (eg, potato varieties that are resistant to bacteria such as Erwinia amylvora due to the production of this protein). Furthermore, plants are included whose productivity has been improved by genetic engineering methods by z. For example, the productivity (eg biomass, grain yield, starch, oil or protein content), the tolerance to drought, salt or other limiting environmental factors or the resistance to pests and fungal, bacterial and viral pathogens is increased , Furthermore, plants are included whose ingredients have been modified in particular to improve the human or animal diet using genetic engineering methods by z. For example, oil plants can produce health-promoting long-chain omega-3 fatty acids or monounsaturated omega-9 fatty acids (eg Nexera ® rapeseed, DOW Agro Sciences, Canada). Furthermore, plants are included, which have been modified for the improved production of raw materials by means of genetic engineering methods by z. B. the amylopectin content of potatoes (Amflora ® potato, BASF SE, Germany) was increased.
Im Rahmen der vorliegenden Erfindung wird auch Saatgut beansprucht, das eine erfindungsgemäße Zusammensetzung enthält. Die Aufwandmengen liegen im allgemeinen zwischen 0,1 g-10kg Wirkstoff pro 100kg Saatgut, vorzugsweise 1 g bis 5kg, besonders bevorzugt von 1 g - 2,5kg. Für spezielles Saatgut wie Salat können die Aufwandmengen auch höher sein. Für Soja werden Auwandmengen von 0,1 - 10 kg verwendet. Die Saatgutbehandlung kann durch Besprühung des Saatgutes mit der Formulierung oder Vermischen des Saatgutes mit der Formulierung ggf. gefolgt von Trocknen des Saatgutes vor dem Säen und vor Keimung nach dem Fachmann bekannten Methoden durchgeführt werden. Des weiteren umfasst die vorliegende Erfindung ein Verfahren zur Regulation desIn the context of the present invention, seed is also claimed which contains a composition according to the invention. The application rates are generally between 0.1 g-10 kg of active ingredient per 100 kg of seed, preferably 1 g to 5 kg, more preferably from 1 g to 2.5 kg. For special seeds such as salad, the application rates may be higher. For soya, amounts of 0.1-10 kg are used. Seed treatment may be carried out by spraying the seed with the formulation or mixing of the seed with the formulation, optionally followed by drying the seed before sowing and germination by methods known to those skilled in the art. Furthermore, the present invention comprises a method for regulating the
Wachstums von Pflanzen und/oder zur Bekämpfung unerwünschten Pflanzenwuchses und /oder zur Bekämpfung von unerwünschtem Insekten- oder Milbenbefall auf Pflanzen und/oder zur Bekämpfung von phytopathogenen Pilzen, dadurch gekennzeichnet, dass man Saatgüter von Nutzpflanzen mit einem Pestizid mit einer Löslichkeit in Was- ser von höchstens 10 g/l und dem Polycarboxylatether behandelt behandelt. Vorzugsweise umfasst die Erfindung Verfahren zur Bekämpfung von unerwünschtem Insekten- oder Milbenbefall auf Pflanzen und/oder zur Bekämpfung von phytopathoge- nen Pilzen, dadurch gekennzeichnet, dass man Saatgüter von Nutzpflanzen mit einem Pestizid mit einer Löslichkeit in Wasser von höchstens 10 g/l und dem Polycarboxyla- tether behandelt behandelt. Der Polycarboxalatether kann wie vorstehend beschrieben oder in Form der erfindungsgemäßen Zusammensetzung eingesetzt werden. Growth of plants and / or for controlling undesired plant growth and / or for controlling undesirable insect or mite infestation on plants and / or for controlling phytopathogenic fungi, characterized in that seed of crop plants with a pesticide having a solubility in water of not more than 10 g / l and treated with the polycarboxylate ether. The invention preferably comprises methods for controlling undesirable insect or mite infestation on plants and / or for controlling phytopathogenic fungi, characterized in that seed of crop plants having a pesticide having a solubility in water of not more than 10 g / l and Treated polycarboxylate treated. The polycarboxalate ether can be used as described above or in the form of the composition according to the invention.
Die Vorteile der Erfindung sind dass mit geringeren Mengen des erfindungsgemäßen Dispergiermittel bereits eine hohe Dispersionsstabiliät erreicht werden kann. Dies gilt insbesondere bei Formulierungen, die hohe Konzentrationen von Pestizid enthalten. Die erfindungsgemäßen Dispergiermittel stabilisieren auch hochkonzentrierte Festformulierungen nach Verdünnung mit Wasser. Bei Suspensionen (v.a. Suspensionskonzentraten) wird durch geringe Mengen Zusatz von erfindungsgemäßen Dispergiermittel die Serumbildung verringert, und die Lagerstabilität erhöht. Weiterer Vorteil ist, dass mit geringeren Mengen des erfindungsgemäßen Dispergiermittel bereits eine hohe Dispersionsstabiliät erreicht werden kann, besonders auch für Formiiierungen (v.a. wässerige Formulierungen) mit hohem Salzgehalt. The advantages of the invention are that even a high dispersion stability can be achieved with smaller amounts of the dispersant according to the invention. This is especially true for formulations containing high levels of pesticide. The dispersants according to the invention also stabilize highly concentrated solid formulations after dilution with water. With suspensions (in particular suspension concentrates) serum formation is reduced by small amounts of addition of dispersant according to the invention, and the storage stability is increased. A further advantage is that with lower amounts of the dispersant according to the invention already a high dispersion stability can be achieved, especially for Formiiierungen (v.a. aqueous formulations) with high salt content.
Nachfolgende Beispiele erläutern die Erfindung ohne sie einzuschränken. The following examples illustrate the invention without limiting it.
Beispiele Examples
Flexity®: Ein wässriges Suspensionskonzentrat enthaltend 25,2 Gew.% Metrafenon und Additive, wie Alkylpolysaccharid und Natriumalkylnaphthalinsulfonat- Formaldeyd-Kondensat, pH etwa 7, Oberflächenspannung 31 mN/m (20 °C), dynamische Viskosität 616 mPa.s (20 °C, 100 1/s), kommerziell erhältlich von BASF SE. Flexity®: An aqueous suspension concentrate containing 25.2 wt% metrafenone and additives such as alkyl polysaccharide and sodium alkylnaphthalenesulfonate-formaldeyde condensate, pH about 7, surface tension 31 mN / m (20 ° C), dynamic viscosity 616 mPa.s (20 ° C) C, 100 1 / s), commercially available from BASF SE.
Glenium® ACE 430: erfindungsgemäßer Polycarboxylatether, Flüssigkeit mit Feststoffgehalt etwa 30 Gew.%, pH 5,5+/- 1 bei 20 °C, kommerziell erhältlich von BASF Construction Polymers GmbH.  Glenium® ACE 430: polycarboxylate ether according to the invention, liquid with solids content about 30% by weight, pH 5.5 +/- 1 at 20 ° C, commercially available from BASF Construction Polymers GmbH.
Glenium® B233: erfindungsgemäßer Polycarboxylatether, wasserlösliche Flüssigkeit mit Feststoffgehalt >30 Gew.%, pH etwa 7 bei 20 °C, kommerziell erhältlich von BASF Construction Polymers GmbH.  Glenium® B233: polycarboxylate ether according to the invention, water-soluble liquid with solids content> 30% by weight, pH about 7 at 20 ° C, commercially available from BASF Construction Polymers GmbH.
Glenium® 3400 NV: erfindungsgemäßer Polycarboxylatether, wasserlösliche Flüssig- keit mit Feststoffgehalt >30 Gew.%, pH etwa 7,8 bei 20 °C, kommerziell erhältlich von BASF Construction Polymers GmbH.  Glenium® 3400 NV: Polycarboxylate ether according to the invention, water-soluble liquid with solids content> 30% by weight, pH about 7.8 at 20 ° C., commercially available from BASF Construction Polymers GmbH.
Glenium® ACE 30: erfindungsgemäßer Polycarboxylatether, wasserlösliche Flüssigkeit mit Feststoffgehalt etwa 30 Gew.%, pH 6,5+/- 1 ,5 bei 20 °C, kommerziell erhältlich von BASF Construction Polymers GmbH.  Glenium® ACE 30: Polycarboxylate ether according to the invention, water-soluble liquid with solids content about 30% by weight, pH 6.5 +/- 1.5 at 20 ° C., commercially available from BASF Construction Polymers GmbH.
Beispiel 1 - Dispersionsstabilität Das Suspensionskonzentrat (SC) Flexity® wurde mit 1 , 10 oder 25 g/l Polycarboxiylatether (PCE) versetzt bzw. zur Kontrolle ohne Polycarboxiylatether gelagert. Die Dispersionsstabilität wurde direkt nach Zugabe („Initial") des Polycarboxiylatether und nach 14 tägiger Lagerung bei 54 °C („gelagert") bestimmt. Example 1 - Dispersion stability The suspension concentrate (SC) Flexity® was mixed with 1, 10 or 25 g / l Polycarboxiylatether (PCE) or stored for control without Polycarboxiylatether. The dispersion stability was determined directly after addition ("initial") of the Polycarboxiylatether and after 14 days of storage at 54 ° C ("stored").
Die Dispersionsstabilität wurde nach CIPAC MT180 bestimmt in einem graduierten Spitzzylinder, in den 100 ml Wasser (19,2 ° dH) vorgelegt wird. Nach Zugabe von 1 ml Suspensionskonzentrat wird die Mischung zur vollständigen Dispersion gebracht und dann stehen gelassen. Das Sedimentvolumen wird nach 120 min abgelesen (Tabelle 1 ). The dispersion stability was determined according to CIPAC MT180 in a graduated tip cylinder in which 100 ml of water (19.2 ° dH) is introduced. After addition of 1 ml of suspension concentrate, the mixture is brought to complete dispersion and then allowed to stand. The sediment volume is read after 120 min (Table 1).
Tabelle V. Table V.
Beispiel 2 - Dispersionsstabilität von Granulaten nach Dispergieren Example 2 - Dispersion stability of granules after dispersion
Eine Granulat-Formulierung enthaltend 75 Gew.% Tritosulfuron wurde mit 0,25 Gew.% (2,5 g/kg) Polycarboxiylatether versetzt.  A granulate formulation containing 75% by weight of tritosulfuron was admixed with 0.25% by weight (2.5 g / kg) of polycarboxylate ether.
Die Sedimentvolumen wurde bestimmt in einem graduierten Spitzzylinder, in den 100 ml Wasser (19,2 ° dH) vorgelegt wird. Nach Zugabe von 0,2 g bzw. 2 g Granulat wird die Mischung zur vollständigen Dispersion gebracht und dann stehen gelassen. Das Sedimentvolumen wird nach 30 min abgelesen. Zur Kontrolle wurde auch eine Rezeptur ohne Polycarboxiylatether gelagert. Die Ergebnisse sind in Tabelle 2 und 3 zusam- mengefasst. The sediment volume was determined in a graduated cylinder, in which 100 ml of water (19.2 ° dH) is submitted. After addition of 0.2 g or 2 g of granules, the mixture is brought to complete dispersion and then allowed to stand. The sediment volume is read after 30 min. As a control, a formulation without Polycarboxiylatether was stored. The results are summarized in Tables 2 and 3.
Tabelle 2: Dispersionsstabilität Table 2: Dispersion stability
PCE Granulat in PCE in Sediment Sediment  PCE granules in PCE in sediment sediment
Dispersion Dispersion [ml] Initial [ml] Gelagert Dispersion Dispersion [ml] Initial [ml] Stored
Ohne 2 g/l - 0,2 ml < 0,25mlWithout 2 g / l - 0.2 ml <0.25ml
Glenium® ACE 430 2 g/l 0,005 g/l <0,05 ml < 0,15mlGlenium® ACE 430 2 g / l 0.005 g / l <0.05 ml <0.15 ml
Glenium® ACE 30 2 g/l 0,005 g/l 0,15 ml < 0,2mlGlenium® ACE 30 2 g / l 0.005 g / l 0.15 ml <0.2 ml
Ohne 20 g/l - 2 ml 5 mlWithout 20 g / l - 2 ml 5 ml
Glenium® ACE 430 20 g/l 0,05 g/l 0,6 ml 0,65 ml Glenium® ACE 30 20 g/l 0,05 g/l 0,75 ml 0,6 ml Glenium® ACE 430 20 g / l 0.05 g / l 0.6 ml 0.65 ml Glenium® ACE 30 20 g / l 0.05 g / l 0.75 ml 0.6 ml
Tabelle 3: Table 3:
Beispiel 3 - Lagerstabilität von Suspensionskonzentraten Example 3 - Storage stability of suspension concentrates
Das Suspensionskonzentrat Flexity® wurde mit 1 g/l Polycarboxiylatether versetzt bzw. zur Kontrolle ohne Polycarboxiylatether gelagert. Die Lagerstabilität hinsichtlich Sedimentation wurde nach 14 tägiger Lagerung bei 54 °C bestimmt. Die überstehende Flüssigkeit (Serumbildung) wurde durch visuelle Beurteilung bestimmt (Tabelle 4).  The suspension concentrate Flexity® was mixed with 1 g / l Polycarboxiylatether or stored for control without Polycarboxiylatether. The storage stability with respect to sedimentation was determined after storage at 54 ° C. for 14 days. The supernatant (serum formation) was determined by visual assessment (Table 4).
Tabelle 4: Table 4:
Beispiel 4 -Hochkonzentrierer Suspensionen für Saatgutbehandlung Example 4 - High Concentrate Suspensions for Seed Treatment
Es wurde zu 200 mL Wasser jeweils 5 g des zu testenden Dispergiermittels gegeben und darin jeweils 800 g festes Calciumcarbonat eingerührt (Tabelle 5). Der Vergleichsversuch mit dem kommerziellen Dispergiermittel Ufoxan 3A (ein Natriumlignosulfonat CAS 8061 -51 -6, von Borregard Lignoech) führte zu einer nicht fliessfägien Konsistenz. Tabelle 5:  In each case, 5 g of the dispersant to be tested were added to 200 ml of water and in each case 800 g of solid calcium carbonate were stirred into it (Table 5). The comparative experiment with the commercial dispersant Ufoxan 3A (a sodium lignosulfonate CAS 8061 -51 -6, from Borregard Lignoech) resulted in a non-flowable consistency. Table 5:
Die Suspension 1 gemäß Tabelle 5 wurde in gleichen Teilen (1 :1 :1 ) mit dem kommerziell verfügbaren Saatgutbehandlungsprodukt Rubin® TT (wässriges Suspensionkonzentrat enthaltend 42 g/l Pyrimethanil, 25 g/l Triticonazol und 38,6 g/l Prochloraz, er- hältlich von BASF SE) sowie mit Wasser gemischt. Von dieser Mischung wurden in einem handelsüblichen Laborbeizer der Marke Rotostat 6 mL auf 1 kg Weizen aufgebracht. Beispiel 5 - Dispersionsstabilität bei hoher Salzkonzentration The suspension 1 according to Table 5 was in equal parts (1: 1: 1) with the commercially available seed treatment product Rubin® TT (aqueous suspension concentrate containing 42 g / l pyrimethanil, 25 g / l triticonazole and 38.6 g / l prochloraz, he - available from BASF SE) and mixed with water. 6 mL of this mixture was applied to 1 kg of wheat in a commercially available Rotitz brand laboratory teat. Example 5 - Dispersion stability at high salt concentration
Ein wässriges Suspensionskonzentrat (SC) enthaltend 300 g/l Mepiquatchlorid, 50 g/l Prohexadion-Calcium, 200 g/l Ammoniumnitrat, 150 g/l nichtionisches Tensid, sowie weitere Hilfsstoffe (wie Verdicker, Entschäumer) wurde analog Referenzbeispiel 2 in EP1339284B1 hergestellt. Das SC wurde mit 5, 10, 25 oder 50 g/l Polycarboxiylatether (PCE) versetzt bzw. zur Kontrolle ohne Polycarboxiylatether gelagert. Als PCE wurden Glenium® B233, Glenium® 3400 NV, Glenium® ACE 30, oder Glenium® ACE 430 verwendet.  An aqueous suspension concentrate (SC) containing 300 g / l mepiquat chloride, 50 g / l prohexadione calcium, 200 g / l ammonium nitrate, 150 g / l nonionic surfactant and other auxiliaries (such as thickener, defoamer) was prepared in accordance with Reference Example 2 in EP1339284B1 , The SC was mixed with 5, 10, 25 or 50 g / l Polycarboxiylatether (PCE) or stored for control without Polycarboxiylatether. Glenium® B233, Glenium® 3400 NV, Glenium® ACE 30, or Glenium® ACE 430 were used as PCE.
Die Dispersionsstabilität (als 2,0 % Dispersion) wurde nach 14 tägiger Lagerung bei 10 °C bestimmt wie unter Beispiel 1 beschrieben. Bei der Kontrollprobe ohne PCE fand man 0,5 ml Sediment. Alle Proben, bei denen ein PCE in einer der genannten Konzent- rationen zugesetzt wurde, zeigten unter 0,05 ml Sediment. Selbst bei hohen Salzkonzentrationen konnten dank der PCE die eine höhere Stabilität bei der Lagerung der Dispersion erreicht werden. The dispersion stability (as a 2.0% dispersion) was determined after 14 days storage at 10 ° C as described in Example 1. The control sample without PCE found 0.5 ml of sediment. All samples in which a PCE was added at one of the above concentrations showed less than 0.05 ml of sediment. Even at high salt concentrations, the stability of the storage of the dispersion could be achieved thanks to the PCE.
Beispiel 6 - Dispersionsstabilität Example 6 - Dispersion stability
Ein wässriges Suspensionskonzentrat (SC) enthaltend 29 Gew.% Pyraclostrobin, 3,5 Gew.% Dispergiermittel, 3,5 Gew.% Polyalkylenoxidblockcopolymer, 0,3 Gew.% Xanthangum und weiter Hilfsstoffe wurde zwei Wochen bei -10 °C bzw. bei 50 °C gelagert. Die Partikelgröße wurde gemessen und die Zunahme berechnet ausgehend von der Lagerung bei -10 °C.  An aqueous suspension concentrate (SC) containing 29 wt.% Pyraclostrobin, 3.5 wt.% Dispersant, 3.5 wt.% Polyalkylenoxidblockcopolymer, 0.3 wt.% Xanthan gum and further auxiliaries was two weeks at -10 ° C or at Stored at 50 ° C. Particle size was measured and the increase calculated from storage at -10 ° C.
Als Dispergiermittel wurden Glenium® B233, Glenium® 3400 NV, Glenium® ACE 30, oder Glenium® ACE 430 verwendet, sowie zur Kontrolle Atlox® 4913 (kommerzell erhältlich von Uniqema; enthält ein Reaktionsprodukt von Methylmethacrylat, Methacryl- säure und Methoxy-PEG-methacrylat) oder Soprophor® BSU (kommerzell erhältlich von Rhodia; enthält ethoxyliertes (16 EO) Tristyrylphenol, CAS 99734-09-5). The dispersants used were Glenium.RTM. B233, Glenium.RTM. 3400 NV, Glenium.RTM. ACE 30, or Glenium.RTM. ACE 430, as well as for the control of Atlox.RTM. 4913 (commercially available from Uniqema, which contains a reaction product of methyl methacrylate, methacrylic acid and methoxy PEG). methacrylate) or Soprophor® BSU (commercially available from Rhodia, containing ethoxylated (16 EO) tristyrylphenol, CAS 99734-09-5).
Tabelle 7: Table 7:
+ 50 °C 2,88 59% + 50 ° C 2.88 59%
Glenium® ACE 30 - 10 °C 1 ,89 0% Glenium® ACE 30 - 10 ° C 1, 89 0%
+ 50 °C 2,93 55% + 50 ° C 2.93 55%
Glenium® B233 - 10 °C 1 ,79 0% Glenium® B233 - 10 ° C 1, 79 0%
+ 50 °C 2,84 59% a) nicht erfindungsgemäß  + 50 ° C 2.84 59% a) not according to the invention

Claims

Patentansprüche claims
1 . Zusammensetzung enthaltend ein Pestizid mit einer Löslichkeit in Wasser von höchstens 10 g/l und ein Polycarboxylatether auf Basis von a) Baugruppen der Formel la und/oder Ib und/oder Ic 1 . Composition comprising a pesticide having a solubility in water of not more than 10 g / l and a polycarboxylate ether based on a) subunits of the formulas Ia and / or Ib and / or Ic
cox  cox
CH2 CR1 CH 2 CR 1
CH2 C C CH 2 CC
\ /  \ /
COX Y  COX Y
la Ib Ic  la Ib Ic
wobei R 1 - Wasserstoff oder ein aliphatischer Kohlenwasserstoffrest mit 1 bis 20 C-Atomen,  where R 1 is hydrogen or an aliphatic hydrocarbon radical having 1 to 20 C atoms,
X -OMa, -0-(CmH2mO)n-R2, -N H-(CmH2mO)nR2' X -OM a , -O- (C m H 2 m O) n -R 2 , -N H- (C m H 2 mO) n R 2 '
M Wasserstoff, ein ein- oder zweiwertiges Metallkation,  M is hydrogen, a monovalent or divalent metal cation,
Ammoniumion, ein organischer Aminrest, Ammonium ion, an organic amine radical,
R2 Wasserstoff, ein aliphatischer Kohlenwasserstoffrest mit 1 bis 20 R 2 is hydrogen, an aliphatic hydrocarbon radical having 1 to 20
C-Atomen, ein cycloaliphatischer Kohlenwasserstoffrest mit 5 bis C atoms, a cycloaliphatic hydrocarbon radical with 5 bis
8 C-Atomen, ein ggf. substituierter Arylrest mit 6 bis 14 C-8 C atoms, an optionally substituted aryl radical having 6 to 14 C
Atomen, atoms,
Y O, N R2, YO, NR 2 ,
m 2 bis 4, und  m 2 to 4, and
n 0 bis 200  n 0 to 200
b) Baugruppen der allgemeinen Formel I I b) assemblies of the general formula I I
— CH2— CR3— - CH 2 - CR 3 -
(CH2)P— O— (Cm H2mO)n.— (Cm..H2m..O)n..— R wobei R3 = Wasserstoff oder einen aliphatischen Kohlenwasserstoffrest mit 1 bis 5 C-Atomen, (CH 2) P - O- (C m H 2m O) n .- (C m ..H ..O 2m) n ..- R where R 3 = hydrogen or an aliphatic hydrocarbon radical having 1 to 5 carbon atoms .
η',η" = unabhängig voneinander 0 bis 200,  η ', η "= independently from 0 to 200,
m',m" = unabhängig voneinander 2 bis 4,  m ', m "= independently of one another 2 to 4,
n' + n" = 1 bis 200,  n '+ n "= 1 to 200,
p = 0 bis 3, bedeuten und  p = 0 to 3, mean and
R4 = Wasserstoff, ein aliphatischer Kohlenwasserstoffrest mit 1 bis 20 R 4 = hydrogen, an aliphatic hydrocarbon radical having 1 to 20
C-Atomen, ein cycloaliphatischer Kohlenwasserstoffrest mit 5 bis 8 C-Atomen, ein ggf. substituierter Arylrest mit 6 bis 14 C- Atomen, bedeuten. C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, an optionally substituted aryl radical having 6 to 14 C atoms, mean.
2. Zusammensetzung nach Anspruch 1 , wobei der Polycarboxylatether 55 bis 75 Mol- To Baugruppen der Formel la und/oder Ib, und 19,5 bis 39,5 Mol-% Baugruppen der Formel II enthält. 2. The composition of claim 1, wherein the polycarboxylate ether contains 55 to 75 mol-To assemblies of the formula Ia and / or Ib, and 19.5 to 39.5 mol% of the formula II.
3. Zusammensetzung nach Anspruch 1 oder 2, wobei der Polycarboxylatether bis zu 50 Mol-% Comonomere enthält bezogen auf die Summe der Baugruppen a) und b), und wobei die Comonomere ausgewählt sind aus Vinyl- oder (Meth-) 3. Composition according to claim 1 or 2, wherein the polycarboxylate ether contains up to 50 mol% of comonomers based on the sum of the components a) and b), and wherein the comonomers are selected from vinyl or (meth)
Acrylsäure-Derivaten wie Styrol, α-Methylstyrol, Vinylacetat, Vinylpropionat, Ethylen, Propylen, Isobuten, Hydroxyalkyl(meth)acrylate, Acrylamid,  Acrylic acid derivatives such as styrene, α-methylstyrene, vinyl acetate, vinyl propionate, ethylene, propylene, isobutene, hydroxyalkyl (meth) acrylates, acrylamide,
Methacrylamid, N-Vinylpyrrolidon, Allylsulfonsäure, Methallylsulfonsäure,  Methacrylamide, N-vinylpyrrolidone, allylsulfonic acid, methallylsulfonic acid,
Vinylsulfonsäure, Vinylphosphonsäure, AM PS, Methylmethacrylat, Methylacrylat, Butylacrylat, oder Allylhexylacrylat.  Vinyl sulfonic acid, vinyl phosphonic acid, AM PS, methyl methacrylate, methyl acrylate, butyl acrylate, or allyl hexyl acrylate.
4. Zusammensetzung nach einem der Ansprüche 1 bis 3, wobei die 4. The composition according to any one of claims 1 to 3, wherein the
Zusammensetzung mindestens 5 Gew.% anorganische Salze enthält.  Composition contains at least 5 wt.% Of inorganic salts.
5. Zusammensetzung nach einem der Ansprüche 1 bis 4, wobei der 5. The composition according to any one of claims 1 to 4, wherein the
Polycarboxylatether frei von vinylaromatischen Monomeren ist.  Polycarboxylatether is free of vinyl aromatic monomers.
6. Zusammensetzung nach einem der Ansprüche 1 bis 5, wobei die 6. The composition according to any one of claims 1 to 5, wherein the
Zusammensetzung eine wässrige Suspension ist, in der mindestens ein Pestizid in partikulärer Form oder in verkapselter Form vorliegt.  Composition is an aqueous suspension in which at least one pesticide is in particulate form or in encapsulated form.
7. Zusammensetzung nach einem der Ansprüche 1 bis 6, wobei die 7. The composition according to any one of claims 1 to 6, wherein the
Zusammensetzung eine wässrige Suspension ist, die 0,001 bis 10 Gew.%  Composition is an aqueous suspension containing 0.001 to 10% by weight.
Polycarboxylatether enthält.  Contains polycarboxylate ether.
8. Zusammensetzung nach einem der Ansprüche 1 bis 7, wobei die 8. The composition according to any one of claims 1 to 7, wherein the
Zusammensetzung eine feste Zusammensetzung ist.  Composition is a solid composition.
9. Zusammensetzung nach einem der Ansprüche 1 bis 8, wobei die A composition according to any one of claims 1 to 8, wherein the
Zusammensetzung eine feste Zusammensetzung ist, die 1 ,0 bis 5,0 Gew.% Polycarboxylatether enthält.  Composition is a solid composition containing 1, 0 to 5.0 wt.% Polycarboxylatether.
10. Verfahren zur Herstellung der Zusammensetzung gemäß einem der Ansprüche 1 bis 8 indem man das Pestizid und den Polycarboxylatether in Kontakt bringt. 10. A process for the preparation of the composition according to any one of claims 1 to 8 by bringing the pesticide and the polycarboxylate ether in contact.
1 1 . Verwendung des Polycarboxylatethers gemäß einem der Ansprüche 1 bis 8 zur Dispergierung von Pestiziden mit einer Löslichkeit in Wasser von höchstens 10 g/l in wässrigen Zusammensetzungen. 1 1. Use of the polycarboxylate ether according to any one of claims 1 to 8 for the dispersion of pesticides having a solubility in water of not more than 10 g / l in aqueous compositions.
12. Verfahren zur Bekämpfung von phytopathogenen Pilzen und/oder unerwünschtem Pflanzenwuchs und/oder unerwünschtem Insekten- oder Milbenbefall und/oder zur Regulation des Wachstums von Pflanzen, wobei man die Zusammensetzung gemäß einem der Ansprüche 1 bis 9 auf die jeweiligen Schädlinge, deren 12. A method for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired insect or mite infestation and / or for regulating the growth of plants, wherein the composition according to any one of claims 1 to 9 to the respective pests whose
Lebensraum 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.  Habitat or plants to be protected from the particular pest, soil and / or undesirable plants and / or crops and / or their habitat.
13. Saatgut enthaltend die Zusammensetzung gemäß einem der Ansprüche 1 bis 9. 13. Seed containing the composition according to any one of claims 1 to 9.
14. Verfahren zum Beizen von Saatgut, wobei man 14. A method for pickling seeds, wherein
(a) das Saatgut mit einem Pestizid mit einer Löslichkeit in Wasser von höchstens 10 g/l und dem Polycarboxylatether gemäß einem der Ansprüche 1 bis 9 behandelt; und  (a) treating the seed with a pesticide having a solubility in water of not more than 10 g / l and the polycarboxylate ether according to any one of claims 1 to 9; and
(b) das in Schritt (a) erhaltene Saatgut gegebenenfalls trocknet.  (b) optionally drying the seed obtained in step (a).
15. Verfahren zur Bekämpfung von unerwünschtem Insekten- oder Milbenbefall auf Pflanzen und/oder zur Bekämpfung von phytopathogenen Pilzen, wobei man Saatgüter von Nutzpflanzen mit einem Pestizid mit einer Löslichkeit in Wasser von höchstens 10 g/l und dem Polycarboxylatether gemäß einem der Ansprüche 1 bis 9 behandelt. 15. A method for controlling unwanted insect or mite infestation on plants and / or for controlling phytopathogenic fungi, wherein seed of crops with a pesticide having a solubility in water of at most 10 g / l and the polycarboxylate according to one of claims 1 to 9 treated.
EP11764184.5A 2010-10-11 2011-10-04 Composition comprising a pesticide and a polycarboxylate ether Withdrawn EP2627171A1 (en)

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