EP1677605A1 - Nouvelles formulations contenant du cuivre - Google Patents

Nouvelles formulations contenant du cuivre

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Publication number
EP1677605A1
EP1677605A1 EP04790441A EP04790441A EP1677605A1 EP 1677605 A1 EP1677605 A1 EP 1677605A1 EP 04790441 A EP04790441 A EP 04790441A EP 04790441 A EP04790441 A EP 04790441A EP 1677605 A1 EP1677605 A1 EP 1677605A1
Authority
EP
European Patent Office
Prior art keywords
copper
polylysine
composition according
copper salt
formulation
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Withdrawn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
EP04790441A
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German (de)
English (en)
Inventor
Thomas Pfeiffer
Maximilian Angel
Adolf Parg
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
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1677605A1 publication Critical patent/EP1677605A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00—Purpose of the treatment
    • B27K2240/20—Removing fungi, molds or insects

Definitions

  • the present invention relates to fungicidal agrochemical compositions comprising a) at least one copper salt and b) polylysine, and / or c) at least one polylysine derivative,
  • polylysine, polylysine derivatives or a combination of polylysine and polylysine derivatives in copper-containing fungicidal formulations are examples of polylysine, polylysine derivatives or a combination of polylysine and polylysine derivatives in copper-containing fungicidal formulations.
  • Copper salts have long been used in agriculture to control phytopathogenic fungi on crops.
  • inorganic copper salts which are difficult or insoluble in water, such as copper oxychloride, are mostly used for this.
  • EP-A 39 788 describes copper amine salts of organic mono-, di- or polycarboxylic acids, it being possible to use water-soluble acidic copolymers based on acrylic acid or methacrylic acid and acrylic acid or methacrylic acid esters as polycarboxylic acids.
  • EP-A 237 946 discloses copper amine salts of organic water-soluble, acidic copolymers based on acrylic acid or methacrylic acid and acrylic acid or methacrylic acid esters.
  • WO 02/083599 discloses fungicidal fertilizers which contain a combination of alkali and alkaline earth metal hydroxides, hydrolyzed peptides and copper salts, such as copper hydroxide. It has now surprisingly been found that the use of polylysine and / or polylysine derivatives in copper-containing fungicidal formulations improves the fungicidal action or produces a constant fungicidal action with a reduced amount of copper or copper salt.
  • a further increase in the action and thus a further reduction in the application rate is achieved by admixing one or more fungicidal active ingredients. In many cases, a synergistic increase in effectiveness is observed.
  • the present invention therefore relates to fungicidal agrochemical compositions comprising
  • the invention further relates to the use of polylysine, polylysine derivatives or a combination of polylysine and polylysine derivatives in copper-containing fungicidal formulations to improve the effectiveness.
  • copper salts a) are to be understood as mono- or, preferably, divalent copper salts of inorganic and organic acids, for example copper oxychloride, copper octanoate, copper ammonium carbonate, copper arsenate, copper oxysulfate, copper formate, copper propionate, copper oxyacetate, copper citrate, copper chloride, copper diammonium chloride, copper nitrate Copper carbonate, copper carbonate basic, copper pyrophosphate, copper phosphate, EDTA disodium copper salt, EDTA diammonium copper salt, copper oxalate, copper tartrate, copper gluconate, copper glycinate, copper glutamate, copper aspartate, copper glutonate, copper adipate, copper canmitate, copper stecateate, copper stylate, copper stylate, copper stecateate, copper stecateate, copper stylate, copper stecateate, copper stylate, copper stecate, copper stylate, copper stecate, copper stecate
  • Copper naphthenate, copper-8-quinolates and tricopper dichloride-dimethyldithiocarbamate used particularly preferably copper acetate, copper carbonate, copper oxychloride, copper hydroxide, copper oxide, copper oxychloride sulfate, copper sulfate, copper sulfate basic, oxine copper, copper bis- (3- ( phenylsalicylate), copper dihydrazinium disulfate, copper chloride trihydroxide, copper octanoate, copper ammonium carbonate, copper arsenate, copper oxysulfate, copper phthalate, copper 8-quinolate and copper trichloride dimethyldithiocarbamate.
  • Powdered or granulated formulations are preferably used copper salts which are largely insoluble in water, such as copper oxychloride or copper hydroxide.
  • soluble copper salts such as e.g. Copper sulfate used.
  • polylysine chosen for component b) denotes crosslinked and uncrosslinked polymers or oligomers of lysine with an average molar mass (weight average) of 300 to 2,000,000 g / mol. Polylysine with average molecular weights of 500 to 100,000 g / mol is preferably used. Polylysine with average molecular weights of 1000 to 50,000 g / mol is particularly preferred.
  • the amino groups of the lysine units can be linked via the ⁇ and / or ⁇ position.
  • polymer chains particularly in the case of higher molecular weight polylysine, can be crosslinked by lysine in that both amino groups of a lysine unit react, the second amino group being condensed with a further polylysine chain.
  • Cross-links of this type can take place depending on the reaction conditions during the production of the polylysine.
  • polylysine is known and can be carried out, for example, according to the procedure described in JP 97-33122 or EP-A 256 423. While linking the Ly- Sin units can be biocatalyzed selectively via the ⁇ -amino groups, the condensation can also take place thermally, for example at temperatures above 100 ° C. via the ⁇ - and ⁇ -amino groups, the ⁇ -amino groups reacting preferentially.
  • uncrosslinked polylysine (component b) is used.
  • polylysine derivative chosen for component c) denotes crosslinked and uncrosslinked copolymers or cooligomers of lysine with further monomers which are capable of reacting with lysine.
  • the monomers include amines and diamines, carboxylic acids, dicarboxylic acids, alkyldiketenes, lactones, lactams and amino acids (US 6111057 and US 6034204), and derivatives of carboxylic and dicarboxylic acids in the form of their acid esters, amides, chlorides and anhydrides, several of the listed monomers can also be condensed as mixtures with lysine. Isocyanates and diisocyanates are also suitable as monomers.
  • Polylysine derivatives with an average molecular weight (weight average) of 300 to 2,000,000 g / mol are used. Polylysine derivatives with a molecular weight of 500 to 100,000 g / mol are preferably used. Polylysine derivatives with a molecular weight of 1000 to 50,000 g / mol are particularly preferably used.
  • the lysine units contained can be linked via the amino groups in the ⁇ and / or ⁇ position.
  • the polymer chains can be crosslinked, in particular in the case of higher molecular weight polylysene derivatives, by lysine and / or by the additionally contained monomers, in that when crosslinked via a lysine unit, both amino groups of the lysine (analogously to polylysine a) react and / or in the case of crosslinking the second functional group of the monomer reacts with an additional chain of a polylysine derivative via an additionally contained monomer unit.
  • Cross-links of this type can take place depending on the reaction conditions during the preparation of the polylysine derivative.
  • Non-crosslinked polylysine is preferably used.
  • Polylysine b) and polylysine derivatives c) can also be alkoxylated (cf. WO 00/71601) and crosslinked (cf. WO 00/71600). In contrast to a possible crosslinking during the polymerization with, for example, lysine, this crosslinking takes place in a targeted manner and after the polymerization.
  • Suitable crosslinkers are the compounds mentioned in WO 00/71600, such as, for example, bisglycidyl ether of polyethylene glycol.
  • the choice of the crosslinking agent can also influence the film properties (eg elongation, tensile strength, modulus of elasticity, stickiness, solubility) of the compositions according to the invention containing copper salts. This is particularly advantageous because it releases the copper ions and the adhesion the mixtures or complexes or their films can be controlled on surfaces.
  • compositions according to the invention crosslinked polylysine, in particular that obtainable by the processes described in WO 00/71600, is used.
  • Polylysine or polylysine derivatives can be prepared from lysine in enantiomerically pure form, in particular from the L-enantiomer, or from the D, L-racemate or a mixture thereof.
  • the thermal condensation can take place according to WO 00/71600.
  • compositions according to the invention preferably contain 0.01 to 95% by weight, in particular 0.01 to 50% by weight, of polylysine and / or polylysine derivative.
  • Copper salts preferably make up 0.01 to 80% by weight, in particular 0.01 to 50% by weight, based on copper.
  • the weight ratio of copper to polylysine and / or polylysine derivative is usually 1: 100 to 20: 1 parts by weight, in particular 1:20 to 20: 1, preferably 1: 7 to 10: 1, preferably 1: 5 to 3: 1 parts by weight, particularly preferably 1: 3 to 1: 1 parts by weight.
  • compositions according to the invention can contain at least one further fungicidal active ingredient (d) as further components; the following are particularly suitable for this:
  • acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl, • amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidine, guazatine, iminoctadine, spiroxamine, tridemorph • anilinopyrimidines such as pyrimethanil, mepanipyrimine, antibiotics, griminodimine, griminodimine, cyclin, antibiotics, graminodimine, cyclinophyne, pyridine, ciminodimine, cyclinophyne, pyrimethin, cyphinodimine, gramodin, cyphinodimine, grimodin, cyclin, such as griminodimine, cyclinophyne, or cyanodimine , Polyoxin, oxytetracycline or streptomycin • Azo
  • fungicidal active ingredients can be found in the Pesticide Manual, 12th Edition, London ⁇ 2000 or in the Compendium of Pesticide Common Names on the Internet at http://www.hclrss.demon.co.uk/index.html.
  • At least one of the above-mentioned group of possible fungicidal active ingredients is preferably used as the further active ingredient d).
  • the active ingredient is particularly preferably selected from the group consisting of the following active ingredients:
  • acylalanines such as benalaxyl, metalaxyl, ofurace or oxadixyl, • antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin, oxytetracycline or streptomycin, • amine derivatives such as guazatine or iminoctadine, • azoles such as bitertanol, bromoconazole, dyproconazole, dyproconazole, cyprozazolone, dypoloconazole, dyproconazole, dyproconazole, dyproconazole, dyproconazole, dyproconazole, dyproconazole, dyproconazole, dyproconazole, dyproconazole, cyproazolone , Fenbuconazole, fluquiconazole, flusiiazole
  • synergistic mixtures containing copper and other fungicidal active ingredients from the strobilurin class include disclosed in WO 97/15189 and WO 00/30450, these combinations of active substances are particularly preferred in the compositions according to the invention.
  • the ratio of the further fungicidal active ingredient to copper is preferably 50: 1 to 1: 1000, preferably 1: 1 to 1: 100, in particular 1: 3 to 1:10 (parts by weight of active ingredient :Copper).
  • Liquid formulations contain as a further component (e) a solvent, preferably 0.1 to 98% by weight.
  • suitable solvents are water, aromatic solvents (e.g. Solvesso products, xylene), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol, pentanol, benzyl alcohol), ketones (e.g. cyclohexanone, gamma-butryolactone), pyrrolidones (NMP , NOP), acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters.
  • solvent mixtures can also be used.
  • Preferred solvents are water, N-methylpyrrolidone (NMP), cyclohexanone and gamma-butyrolactone. Mixtures of different solvents can also be used.
  • compositions according to the invention can additionally contain, as further component f), one or more basic nitrogen compounds, usually in 0.1 to 80% by weight, such as ammonia (formation of copper amine complexes), primary and secondary amines such as, for example, ethylenediamine and propylenediamine and basic amino acids , these preferably as L-isomers, for example lysine, preferably ammonia.
  • the nitrogen compounds are preferably present in 1 to 10, particularly preferably 2 to 6, molar equivalents, based on copper.
  • the nitrogen compounds can also be present in 1 equivalent, in less than 1 equivalent or in an even smaller amount. Higher quantities, such as up to 50 equivalents, are also possible.
  • compositions according to the invention can optionally also contain other auxiliaries g) suitable for the formulation.
  • auxiliaries g suitable for the formulation. This includes the following classes of substances:
  • Surface-active substances such as wetting agents, adhesives or dispersants, anti-foaming agents, thickeners, carriers, anti-freeze agents and bactericides.
  • Carriers in particular in solid formulations, are usually present in 0.1 to 99% by weight, preferably in 10 to 80% by weight.
  • Other auxiliaries are usually contained in 0.1 to 40% by weight.
  • thickeners ie compounds which impart a pseudoplastic flow behavior to the formulation, ie high viscosity at rest and low viscosity in the moving state
  • thickeners are, for example, polysaccharides or organic layered minerals such as xanthan gum (Kelzan® from Kelco), Rhodopol® 23 ( Rhone Poulenc) or Veegum® (company RT Vanderbilt) or Attaclay® (company Engelhardt).
  • Suitable anti-foaming agents are silicone emulsions (such as, for example, Silicon® SRE, from Wacker or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.
  • Bactericides can be added to stabilize the aqueous fungicide formulation.
  • Suitable bactericides are, for example, Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas.
  • Suitable antifreeze agents are e.g. Ethylene glycol, propylene glycol or glycerin.
  • Examples of carriers are natural rock flour (e.g. kaolins, clays, talc, chalk) and synthetic rock powder (e.g. highly disperse silica, silicates), examples of emulsifiers are nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants tel as mentioned below.
  • natural rock flour e.g. kaolins, clays, talc, chalk
  • synthetic rock powder e.g. highly disperse silica, silicates
  • examples of emulsifiers are nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants tel as mentioned below.
  • surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenylpolyglycol
  • formulation types here are emulsifiable concentrates (EC, EW), Sus-Pensions (SC), soluble concentrates (SL), dispersible concentrates (DC), pastes, pastilles, wettable powders, dusts (DP) or granules (GR, FG, GG, MG), which can either be soluble or dispersible in water.
  • EC emulsifiable concentrates
  • SC Sus-Pensions
  • SL soluble concentrates
  • DC dispersible concentrates
  • pastes pastes
  • pastilles wettable powders
  • dusts DP
  • granules granules
  • GR, FG, GG, MG granules
  • formulations are: 1. Products for dilution in water
  • a copper salt-polylysine mixture according to the invention 10 parts by weight of a copper salt-polylysine mixture according to the invention are dissolved in water or a water-soluble solvent. Alternatively, wetting agents or other aids are added. A dilution in water results in a solution.
  • a copper salt-polylysine mixture according to the invention 40 parts by weight of a copper salt-polylysine mixture according to the invention are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (5% each).
  • This mixture is introduced into water using an emulsifying machine (Ultraturax) and brought to a homogeneous emulsion. Dilution in water results in an emulsion.
  • E Suspensions 20 parts by weight of a copper salt-polylysine mixture according to the invention are comminuted in a stirred ball mill to form a fine active ingredient suspension with the addition of dispersing and wetting agents and water or an organic solvent. Dilution in water results in a stable suspension.
  • a copper salt-polylysine mixture according to the invention 50 parts by weight of a copper salt-polylysine mixture according to the invention are finely ground with the addition of dispersing and wetting agents and produced using technical equipment (e.g. extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution.
  • technical equipment e.g. extrusion, spray tower, fluidized bed
  • Water-dispersible and water-soluble powder 75 parts by weight of a copper salt-polylysine mixture according to the invention are ground in a rotor-strator mill with the addition of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution.
  • a copper salt-polylysine mixture according to the invention is finely ground and combined with 95.5% carriers.
  • Common processes are extrusion, spray drying or fluidized bed. This gives granules for direct application.
  • Mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g., are used to produce directly sprayable solutions, emulsions, pastes or oil dispersions.
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attack clay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.
  • Mineral earths such as silica gels, silicates, talc, kaolin, attack clay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics
  • compositions according to the invention All embodiments of the above-mentioned fungicidally active agrochemical compositions are referred to as "compositions according to the invention”.
  • Another object of the present invention is a method for producing a composition according to the invention, characterized in that at least one copper salt is added to the polylysine, the polylysine derivative or a mixture of polylysine and a polylysine derivative.
  • This can be in the solid phase, for example by mixing the components, or in the liquid phase, for example by mixing of the components in a solvent according to procedures known to those skilled in the art. Suitable solvents are those mentioned under (e).
  • the solvent can be removed after the production has taken place or can remain as a further component (e) in the composition according to the invention.
  • a solid composition according to the invention can be mixed with a solvent (e) in a known manner.
  • composition according to the invention containing, as a further component, a basic nitrogen compound f) and optionally a solvent (e) is preferably based on reacting or mixing the copper salt with a basic nitrogen compound f).
  • the reaction product thus obtained is reacted or mixed with polylysine and / or a polylysine derivative.
  • Another preferred variant consists in first reacting or mixing the copper salt with polylysine and / or a polylysine derivative and then adding the basic nitrogen compound.
  • auxiliaries (g) can also be added during the production.
  • the final product obtained can be dried before further processing.
  • reaction can be carried out in a solvent by procedures known to those skilled in the art. Suitable solvents are the solvents (e).
  • compositions according to the invention which additionally contain at least one further fungicidal active ingredient (d) are hereinafter referred to as "formulations according to the invention".
  • Formulations according to the invention can be prepared by adding copper, polylysine and / or at least one polylysine derivative together with at least one further fungicidal active ingredient and with auxiliaries suitable for the formulation and formulating it in a known manner.
  • the formulation according to the invention can be prepared by adding at least one further fungicidal active ingredient and auxiliaries suitable for the formulation to the composition according to the invention and formulating it in a known manner.
  • the formulation with the further fungicidal active ingredient and with the auxiliaries suitable for the formulation can be prepared in the solid or liquid phase.
  • the formulation according to the invention can be obtained by adding an agrochemical formulation of a further fungicidal active ingredient to the compositions according to the invention.
  • An agrochemical formulation denotes all formulations of fungicidal active substances which do not contain copper, preferably formulations of the fungicidal active substances mentioned as preferred.
  • Formulations according to the invention can also be obtained by adding polylysine and / or at least one polylysine derivative to a formulation which, in addition to copper as the fungicidal active ingredient, may optionally contain at least one further fungicidal active ingredient.
  • Cuprimicin * -500 (copper salt (s) and streptomycin and oxytetracycline)
  • the resulting formulations according to the invention can be liquid or solid (for example EC, EW, SC, SL, DC, or wettable powders or water-dispersible granules) which can be either soluble or dispersible in water).
  • compositions and formulations according to the invention are suitable for combating phytopathogenic fungi.
  • the present invention thus relates to a process for combating phytopathogenic fungi, characterized in that a composition according to the invention is applied to the respective harmful organism or to the materials, plants, soil and seeds to be protected from the respective harmful organism.
  • compositions and formulations according to the invention are also suitable for combating harmful fungi such as Paecilomyces variotü in the protection of materials (e.g. wood, paper, dispersions for painting, fibers or fabrics) and in the protection of stored products.
  • harmful fungi such as Paecilomyces variotü
  • materials e.g. wood, paper, dispersions for painting, fibers or fabrics
  • the application rates of the active ingredients are from 0.01 to 10 kg / ha, preferably 0.05 to 5 kg / ha, in particular 0.05 to 2 kg / ha.
  • application rates of mixture of 0.1 to 2.5 kg / 100 kg of seed preferably 0.1 to 1.0 kg / 100 kg, in particular 1 to 0.5 kg / 100 kg, are generally used.
  • the amount of composition applied depends on the type of application and the desired effect. Usual application rates in material protection are, for example, 0.0001 g to 2 kg, preferably 0.005 g to 1 kg, of copper-lysine mixture according to the invention per cubic meter of material treated. The use in wood protection is preferred.
  • the method for controlling harmful fungi is carried out by applying the formulation according to the invention by spraying or dusting the seeds, the plants or the soil before or after the plants have been sown or before or after the plants have emerged.
  • a composition according to the invention or a formulation according to the invention can be used directly or after dilution with water, or a composition according to the invention can be used before application to the respective harmful organism or the materials, plants, soil and seeds to be protected from the respective harmful organism with a commercially available one Mix fungicidal formulation.
  • a copper-containing formulation which may contain at least one further fungicidal active ingredient in addition to copper as the fungicidal active ingredient, can be admixed with polylysine and / or a polylysine derivative before application to the harmful organism.
  • Examples of copper-containing formulations, which may contain a further fungicidal active ingredient in addition to copper as the fungicidal active ingredient are the commercially available copper-containing formulations listed above.
  • the fungicidal compositions can be applied curatively, eradicatively or protectively.
  • compositions are of particular importance for combating a large number of phytopathogenic fungi on various crop plants, such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soybeans, coffee, sugar cane, wine and fruit and ornamental plants and vegetable plants such as cucumbers, beans, tomatoes, potatoes and squashes, and on the seeds of these plants.
  • Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and vines, Fusarium and on different plants, Hemileia vastatrix on coffee Mycosphaerella species on cereals, bananas and peanuts, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on vines, Pseudoperonospora species on hops and cucumbers, Septoria tritici and Stagonospora nodorum on wheat, Ustilago species on cereals and sugar cane, and Venturia-A -en (scab) on apples and pears.
  • L-lysine monohydrate (821 g) and sodium hypophosphite (0.1 g) were heated in a 2.4 liter pressure apparatus under a nitrogen atmosphere for approximately 50 hours at 140 ° to 155 ° C., the internal pressure rising to 5 bar.
  • the reaction phase was interrupted after about 16 hours and a second time after about 8 hours and a sample was taken in each case.
  • the pressure apparatus was relaxed in each case and cooled to room temperature.
  • the reaction mixture was let down, cooled to room temperature, mixed with 641 g of water and filtered.
  • a viscous, orange product with a solids content of 49.6% by weight and a K value (1% in water) of 18.1 was obtained.
  • L-lysine monohydrate (821 g, 5.0 mol) and sodium hypophosphite (0.1 g) were introduced into a 2.5 liter pressure apparatus and blanketed with nitrogen.
  • the apparatus was then closed in a pressure-tight manner and heated to 200 ° C. for 6 hours, the internal pressure rising to 11.2 bar.
  • the pressure was then slowly released to normal pressure to remove water from the reaction mixture.
  • the reaction temperature was held at 200 ° C for 0.5 hours to remove remaining solvent and volatile products.
  • the reaction mixture was then stirred at 200 ° C. under a pressure of 20 mbar for 25 min.
  • the viscous melt was cooled to 115 ° C from the apparatus discharged and cooled to 20 to 25 ° C.
  • the molecular weight Mw of the polymer was 4300 g / mol.
  • L-lysine monohydrate (656.8 g, 4.0 mol), aminocaproic acid (524.7 g, 4.0 mol) and sodium hypophosphite (0.1 g) were introduced into a 2.5 liter pressure apparatus and blanketed with nitrogen.
  • the apparatus was then sealed pressure-tight and heated to 196 ° C. for 7 hours, the internal pressure rising to 8.2 bar.
  • the pressure was then slowly released to atmospheric pressure to remove volatile substances from the reaction mixture.
  • the viscous melt obtained was discharged from the apparatus and then cooled to 20 to 25 ° C.
  • the molecular weight Mw of the polymer was 7400 g / mol.
  • Leaves of potted vines of the "Müller-Thurgau" variety were sprayed to runoff point with an aqueous suspension in the active ingredient concentration given below.
  • the suspension or emulsion was prepared from a stock solution with 1% product in water.
  • the plants were placed in the greenhouse for 7 days after the spray coating had dried on. Only then were the leaves inoculated with an aqueous suspension of zoospores from Plasmopara viticola.
  • the vines were then placed for 48 hours in a steam-saturated chamber at 24 ° C and then for 5 days in a greenhouse at temperatures between 20 ° C and 30 ° C. After this time, the plants were again placed in a moist chamber for 16 hours in order to accelerate the sporangium carrier outbreak. The extent of the development of the infestation on the undersides of the leaves was then determined visually.
  • ⁇ corresponds to the fungal attack of the treated plants in% and ß corresponds to the fungal attack of the untreated (control) plants in%
  • ß corresponds to the fungal attack of the untreated (control) plants in%
  • a growth assay was carried out with Septoria tritici as an indicator fungus. Fungus growth was measured photometrically via the increase in absorbance or light scatter as a function of mycelial density. The measured values were converted into percentage growth inhibition, the extinction of the untreated controls being 0% inhibition and that of a killed spore suspension being defined as 100% inhibition as a reference.

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

Abstract

L'invention concerne des compositions agrochimiques fongicides contenant: a) au moins un sel de cuivre, b) de la polylysine et/ou c) au moins un dérivé de polylysine. L'invention concerne également l'utilisation de polylysine, de dérivés de polylysine ou une combinaison de polylysine et de dérivés de polylysine dans des formulations fongicides contenant du cuivre.
EP04790441A 2003-10-17 2004-10-15 Nouvelles formulations contenant du cuivre Withdrawn EP1677605A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10349096 2003-10-17
PCT/EP2004/011586 WO2005036968A1 (fr) 2003-10-17 2004-10-15 Nouvelles formulations contenant du cuivre

Publications (1)

Publication Number Publication Date
EP1677605A1 true EP1677605A1 (fr) 2006-07-12

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ID=34442190

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EP04790441A Withdrawn EP1677605A1 (fr) 2003-10-17 2004-10-15 Nouvelles formulations contenant du cuivre

Country Status (14)

Country Link
US (1) US20080004177A1 (fr)
EP (1) EP1677605A1 (fr)
KR (1) KR20070019955A (fr)
CN (1) CN1867257A (fr)
AR (1) AR046120A1 (fr)
AU (1) AU2004281534A1 (fr)
BR (1) BRPI0415392A (fr)
CO (1) CO5700679A2 (fr)
EC (1) ECSP066481A (fr)
MX (1) MXPA06003407A (fr)
NZ (1) NZ546517A (fr)
TW (1) TW200528030A (fr)
WO (1) WO2005036968A1 (fr)
ZA (1) ZA200603844B (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006108835A2 (fr) * 2005-04-15 2006-10-19 Basf Aktiengesellschaft Utilisation de polylysine dans des formulations biocides contenant du cuivre
US20090162410A1 (en) * 2007-12-21 2009-06-25 Jun Zhang Process for preparing fine particle dispersion for wood preservation
US9670432B2 (en) * 2013-02-24 2017-06-06 Saeed Mir Heidari Biological method for preventing rancidity, spoilage and instability of hydrocarbon and water emulsions and also increase the lubricity of the same
UA126803C2 (uk) * 2013-11-26 2023-02-08 Юпл Лімітед Фунгіцидна комбінація та спосіб лікування іржі сої із застосуванням такої комбінації
US9474282B2 (en) 2013-12-13 2016-10-25 Tony John Hall Acid-solubilized copper-ammonium complexes and copper-zinc-ammonium complexes, compositions, preparations, methods, and uses
NZ737866A (en) 2015-06-08 2022-07-01 Vm Agritech Ltd Antimicrobial and agrochemical compositions
CN106727670B (zh) * 2016-11-17 2019-06-14 温州医科大学 一种抗细菌兼抗真菌作用的胶束制剂及制备方法
WO2018140458A1 (fr) 2017-01-24 2018-08-02 Germains Seed Technology, Inc. Formulations de traitement de semences antifongiques, semences traitées, et procédés associés
CN110678498A (zh) * 2017-05-12 2020-01-10 巴斯夫欧洲公司 聚赖氨酸衍生物及其在固体基组合物中的用途
CN108513761A (zh) * 2018-04-28 2018-09-11 樟树市狮王生物科技有限公司 一种针对银杏果的抑菌催芽方法
WO2020094823A1 (fr) * 2018-11-09 2020-05-14 Basf Se Dérivés de poly-lysine pour augmenter l'efficacité de formulations agrochimiques
CN111391050B (zh) * 2020-03-26 2021-12-17 广州海有生物科技有限公司 一种环保防腐剂及其制备方法
TW202234998A (zh) * 2020-12-02 2022-09-16 以色列商亞達瑪馬克天辛有限公司 銅基殺菌劑組成物
CN114938809A (zh) * 2022-04-29 2022-08-26 中国农业科学院植物保护研究所 武夷菌素和ε-聚赖氨酸的复配组合物及杀菌方法和应用

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FR2823202B1 (fr) * 2001-04-10 2004-03-05 Penn Ar Bed Engrais a base d'hydroxyde de cuivre ayant des proprietes fongiciels contre de nombreuses maladies cryptogamiques et un procede d'obtention d'un tel engrais

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Also Published As

Publication number Publication date
ECSP066481A (es) 2006-11-24
CO5700679A2 (es) 2006-11-30
ZA200603844B (en) 2007-11-28
MXPA06003407A (es) 2006-06-27
AU2004281534A1 (en) 2005-04-28
NZ546517A (en) 2008-11-28
US20080004177A1 (en) 2008-01-03
BRPI0415392A (pt) 2006-12-12
AR046120A1 (es) 2005-11-23
TW200528030A (en) 2005-09-01
WO2005036968A1 (fr) 2005-04-28
KR20070019955A (ko) 2007-02-16
CN1867257A (zh) 2006-11-22

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