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WO2012163679A1 - Procédé pour lutter contre des micro-organismes phytopathogènes avec des sels de cuivre particulaires, modifiés par des copolymères amps - Google Patents

Procédé pour lutter contre des micro-organismes phytopathogènes avec des sels de cuivre particulaires, modifiés par des copolymères amps Download PDF

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Publication number
WO2012163679A1
WO2012163679A1 PCT/EP2012/059105 EP2012059105W WO2012163679A1 WO 2012163679 A1 WO2012163679 A1 WO 2012163679A1 EP 2012059105 W EP2012059105 W EP 2012059105W WO 2012163679 A1 WO2012163679 A1 WO 2012163679A1
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Prior art keywords
copper
suspension
monomer
copper salt
acid
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English (en)
Inventor
Karl-Heinrich Schneider
Michael Göbel
Jelan KUHN
Sarah Dunker
Daniel SILBERNAGEL
Stefan Orsten
Paul KEMPER
Bolette Urtel
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BASF SE
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BASF SE
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    • 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
    • A01N25/08—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 solids as carriers or diluents
    • A01N25/10—Macromolecular 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

Definitions

  • the present invention relates to a method for controlling phytopathogenic micro- 5 organisms by treating the crop to be protected, the soil or the plant reproduction
  • the invention also relates to an aqueous suspension of the abovementioned copper salt particles and the use of this suspension in crop protection. Combinations of preferred 0 features with other preferred features are encompassed by the present invention.
  • Crop protection agents based on copper compounds have long been known and valuable aids for controlling fungi in agriculture.
  • One of the oldest examples is
  • US 2002/01 12407 discloses the production of inorganic nanoparticulate particles having a mean size of from 2 to 500 nm, preferably ⁇ 100 nm (determined by dynamic light scattering, DLS), by partial or complete alkaline hydrolysis of at least one metal compound which is either dissolved in an aqueous medium or suspended in
  • WO 2010/003870 discloses a method for the preparation of surface-modified nanoparticulate copper compounds. There, an aqueous solution of copper ions and a solution of anions forming a precipitate with copper are mixed in the presence of a polymer and copper salts are thus precipitated. The use of nanoparticles and of the5 aqueous dispersion comprising the nanoparticles as an antimicrobial active substance is likewise disclosed.
  • WO 2005/1 10692 describes aqueous suspensions comprising microparticulate copper compounds (e.g. copper hydroxide, copper carbonate) for wood preservation.
  • The0 suspensions having mean particle sizes in the range of from about 200 nm to about 400 nm were prepared by wet milling in the presence of dispersants.
  • the wood preservative preparations disclosed in WO 2006/042128 comprise, inter alia, sparingly soluble copper compounds which are likewise brought into finely divided form by milling.
  • US 2005/0256026 discloses an aqueous slurry of copper salts, quaternary ammonium salts and dispersant.
  • a disadvantage of milling methods is that particles having a mean particle size of ⁇ 100 nm were obtainable only with great effort and by means of a very large energy input.
  • the copper-containing formulation for use in the method should be capable of being prepared as easily and economically as possible.
  • the plants or seeds to be protected should be brought into contact with as small an amount of copper compounds as possible and/or should be damaged as little as possible.
  • the method and the formulation should be suitable in particular for use in cultivation of grapevines, fruit and vegetables.
  • the object was achieved by a method for controlling phytopathogenic microorganisms by treating the crop to be protected, the soil or the plant propagation material with an effective amount of copper salt particles which comprise a water-soluble polymer and have a primary particle diameter of from 1 to 200 nm, the copper salt comprising an anion which is not hydroxide and forms a precipitate with copper ions, and wherein the water-soluble polymer is a polycarboxylate which comprises a) acrylic acid, methacrylic acid, and/or maleic acid (monomer A), and b) a monomer comprising sulfonic acid groups (monomer B), in polymerized form.
  • the water-soluble polymer is a polycarboxylate which comprises a) acrylic acid, methacrylic acid, and/or maleic acid (monomer A), and b) a monomer comprising sulfonic acid groups (monomer B), in polymerized form.
  • the object was achieved by a method for controlling phytopathogenic microorganisms by treating the inanimate industrial material with an effective amount of copper salt particles which comprise a water-soluble polymer and have a primary particle diameter of from 1 to 200 nm, the copper salt comprising an anion which is not hydroxide and forms a precipitate with copper ions, and wherein the water-soluble polymer is a polycarboxylate which comprises a) acrylic acid, methacrylic acid, and/or maleic acid (monomer A), and b) a monomer comprising sulfonic acid groups
  • Inanimate materials are for example adhesives, sizes, wood, paper and card, textiles, leather, paint dispersions, plastic material, cooling lubricants, fibers and fabrics. Such materials may be protected against infestation and destruction by unwanted
  • Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Por/ ' a spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as
  • the copper salt comprises an anion which is not hydroxide and forms a precipitate with copper ions (in particular in water at 20°C and a concentration of 0.1 mol/l of the copper salt, no later than 1 h after mixing of the ions).
  • Preferred anions are anions of phosphoric acid, carbonic acid, boric acid, sulfurous acid or anions of organic acids, such as oxalic acid, benzoic acid, maleic acid, etc., and polyborates, such as B4O7 2" .
  • the anions carbonate, phosphate, hydrogen phosphate, oxalate, borate and tetraborate ions are particularly preferred, in particular oxalate and carbonate anions.
  • the copper salt may comprise further anions.
  • Suitable further anions are also the abovementioned anions which are not hydroxide and form a precipitate with copper ions.
  • Preferred further anions are anions of mineral acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, boric acid, sulfurous acid, etc., or anions of organic acids, such as oxalic acid, benzoic acid, maleic acid, etc., and polyborates, such as B 4 07 2" or hydroxide (OH-).
  • the further anions are preferably hydroxide anions.
  • the further anions are hydroxide anions or the polycarboxylates described below (preferably polycarboxylates based on acrylic acid, methacrylic acid, maleic acid or mixtures thereof).
  • polycarboxylates some of the carboxylate groups may be present in the polymer in anionic form and, as anions, therefore form salts.
  • the copper salt comprises carbonate anions and hydroxide anions.
  • the copper salt may also comprise further metal ions, for example ions of alkaline earth metals or transition metals, preferably magnesium, calcium, chromium, cobalt, nickel, zinc or silver ions, particularly preferably zinc or silver ions.
  • the further metal ions are present in smaller numbers than the copper ions. Preferably, no further metal ions are present.
  • the copper salt may also comprise water of crystallization.
  • the secondary particle diameter can therefore often also be designated as aggregate size or agglomerate size.
  • the secondary particle diameter can be determined, for example, by dynamic light scattering, but the primary particle diameter cannot be determined.
  • a change in the secondary particle diameter may occur if, for example, the primary particles combine to form increasingly larger aggregates of primary particles.
  • the primary particle diameter of the copper salt particles is in general in the range from 0.1 to 200 nm, preferably from 1 to 100 nm, in particular from 1 to 50 nm.
  • the primary particle diameter is preferably determined via transmission electron microscopy (TEM).
  • the secondary particle diameter usually designates the mean particle diameter which is determined according to the volume fraction from the particle size distributions.
  • the particle size distributions can be measured by light scattering (for example on a Zetasizer Nano S apparatus from Malvern Instruments).
  • the secondary particle diameter of the copper salt particles is in general in the range from 0.1 to 300 nm, preferably from 1 to 200 nm.
  • the copper salt particles are preferably amorphous.
  • Amorphous means that the molecular building blocks of a homogeneous solid are not arranged in crystal latices.
  • An amorphous form of the copper salt particles means that it is substantially free of crystalline copper salt, preferably from 80 to 100% by weight, in particular from 90 to 100% by weight, of the copper salt being present in amorphous form.
  • Amorphous forms can be distinguished from crystalline forms by various methods, for example by microscopic examination in polarized light, differential scanning calorimetry, X-ray diffraction or solubility comparisons. X-ray diffraction is preferred. The choice of the method depends, for example, on the fineness of the particles.
  • the water-soluble polymer may be present in the copper salt particles in various ways. In one embodiment, it is possible for the surface of the particles to be modified with the polymer. There, the polymer is present at least partly on the surface of the particles. In a further embodiment, the polymer is present partly internally in the copper salt particles. Particularly with the use of anionic, water-soluble polymers (such as the polycarboxalates), the polymers can partly form salts with the copper ions. Usually, the water-soluble polymer does not form a chemically crosslinked capsule shell around the copper salt.
  • the water-soluble polymers may be polycarboxylates which comprise a) acrylic acid, methacrylic acid, and/or maleic acid (monomer A), and b) a monomer comprising sulfonic acid groups (monomer B), in polymerized form.
  • the molecular weight is in general in the range of from about 800 to about
  • the molecular weight is in the range from 5000 to about
  • the molecular structure may be either linear or branched, a linear structure being preferred.
  • polycarboxylates to be used according to the invention can be used both in the form of the free acid and partly or completely neutralized in the form of their alkali metal, alkaline earth metal or ammonium salts. However, they can also be used as salts of the respective polycarboxylic acid and triethylamine, ethanolamine,
  • Suitable monomers A are acrylic acid, methacrylic acid, and maleic acid, and also mixtures thereof.
  • the monomers A can also be used in the form of their salts, such as sodium salt or potassium salt.
  • a water-soluble polymer which comprises maleic acid in polymerized form is also obtainable by first incorporating maleic anhydride in polymerized form and then hydrolyzing it to the maleic acid.
  • Preferred monomers A are acrylic acid and methacrylic acid. Acrylic acid is particularly preferred monomer A.
  • Preferred monomers B are ethylenically unsaturated monomers comprising at least one (preferably exactly one) sulfonic acid group.
  • the monomers B may also comprise the sulfonic acid group in the form of salts, such as sodium, potassium, or ammonium salts. Suitable examples are: vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate or 2- acrylamido-2-methylpropanesulfonic acid (AMPS), and mixtures of the aforementioned monomers.
  • Particularly preferred monomers B are allylsulfonic acid and AMPS. AMPS is specifically preferred.
  • the polycarboxylate comprises
  • macromonomers are understood as meaning substances which, at a molecular weight of preferably less than 500 000 D, in particular in the range from 300 to 100 000 D, particularly preferably in the range from 500 to 20 000 D, very particularly preferably in the range from 800 to 15 000 D, have a substantially linear molecular structure and carry a polymerizable terminal group at one end.
  • Suitable macromonomers are monomers based on polyalkylene glycols which are provided with a polymerizable terminal group at one end.
  • Said polymerizable terminal group may be, for example, a vinyl, allyl, (meth)acrylic acid or (meth)acrylamide group, the corresponding macromonomers being described by the following formulae
  • R 2 is H or methyl
  • R 3 is as defined below and
  • R 3 to R 8 are -(CH 2 ) 2 - -(CH 2 ) 3 - -(CH 2 ) 4 - -CH 2 -CH(CH 3 )-, -CH 2 -CH(CH 2 -CH 3 )-, -CH 2 -CHOR 11 -CH 2 -;
  • R 10 is Ci-Cie-alkyl
  • B is -(CH 2 )r, arylene, optionally substituted
  • n is from 1 to 8;
  • s is from 0 to 500, preferably from 0 to 20;
  • t is from 1 to 8;
  • u is from 1 to 5000, preferably from 1 to 1000, particularly preferably from 1 to 100;
  • v is from 0 to 5000, preferably from 0 to 1000;
  • w is from 0 to 5000, preferably from 0 to 1000;
  • x is from 1 to 5000, preferably from 1 to 1000;
  • y is from 0 to 5000, preferably from 0 to 1000;
  • z is from 0 to 5000, preferably from 0 to 1000.
  • Preferred compounds are those in which the polyalkylene glycol radical P is derived from a polyalkylene glycol which has been prepared using ethylene oxide, propylene oxide and butylene oxide and polytetrahydrofuran.
  • the result is a polyalkylene glycol radical P having the following structural units: -(CH 2 ) 2 -0-, -(CH 2 ) 3 -0-, -(CH 2 ) 4 -0-, -CH 2 -CH(CH 3 )-0- -CH 2 -CH(CH 2 -CH 3 )-0-, -CH 2 -CHOR 11 -CH 2 -0-.
  • C-i-Cs-alkyl chains preferably methyl, ethyl, n-propyl, 1 -methyl- ethyl, n-butyl, 1 -methylpropyl, 2-methylpropyl, 1 ,1 -dimethylethyl, n-pentyl, 1 -methyl- butyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, n-hexyl,
  • Ci-C6-alkyl chains particularly preferably Ci-C 4 -alkyl chains, may be mentioned as preferred members of the abovementioned alkyl radicals.
  • monomer C is a macromonomer of formula (IX)
  • R 21 represents hydrogen or methyl
  • R 22 represents identical or different, linear or branched C 2 -C6-alkylene radicals, which may be arranged blockwise or randomly
  • R 23 represents hydrogen or a straight-chain or branched Ci-C 4 -alkyl radical, and o represents a natural number from 3 to 50.
  • R 23 is methyl.
  • the alkylene radicals may also be arranged blockwise and randomly, i.e., be arranged blockwise in one or more blocks composed of identical alkylene oxide radicals and in addition randomly in one or more blocks composed of two or more different alkylene oxide radicals. This is co-comprised by the formulation "arranged blockwise or randomly".
  • the macromonomer of formula (IX) comprises an average from 3 to 50, preferably from 8 to 45, more preferably from 10 to 45 and specifically from 20 to 45 alkylene oxide units.
  • the number of alkylene oxide units present can be on average 22 or 44 for example.
  • the index o relates to the average number of alkylene oxide units.
  • Preferred alkylene oxide units R 22 -0 are ethylene oxide, 1 ,2-propylene oxide and 1 ,2-butylene oxide, particular preference being given to ethylene oxide and
  • the macromonomer of formula (IX) comprises ethylene oxide units only.
  • monomer C is a macromonomer of formula (X)
  • R 31 represents hydrogen or methyl
  • R 32 represents identical or different C2-C6- alkylene radicals, which may be linear or branched and arranged blockwise or randomly
  • R 33 represents hydrogen or a straight-chain or branched Ci-C4-alkyl radical
  • r represents 0, 1 , 2 and o represents any number from 3 to 50.
  • R 33 is hydrogen or methyl.
  • the alkylene radicals may also be arranged blockwise and randomly, i.e., be arranged blockwise in one or more blocks composed of identical alkylene oxide radicals and in addition randomly in one or more blocks composed of two or more different alkylene oxide radicals. This is co-comprised by the formulation "arranged blockwise or randomly”.
  • the macromonomer of formula (X) preferably comprises an average from 8 to 40, more preferably from 10 to 30 and specifically from 10 to 25 alkylene oxide units.
  • the index o in formula (I) relates to the average number of alkylene oxide units.
  • Preferred alkylene oxide units R 32 -0 are ethylene oxide, 1 ,2- propylene oxide and 1 ,2-butylene oxide, particular preference being given to ethylene oxide and 1 ,2-propylene oxide.
  • the macromonomers of formula (X) comprise ethylene oxide units only.
  • the macromonomers of formula (X) comprise ethylene oxide and 1 ,2-propylene oxide units, which can be arranged blockwise or randomly.
  • the polycarboxylates may comprise further monomers D which are incorporated in the form of polymerized units in the polymer chain, for example the esters, amides and nitriles of the abovementioned carboxylic acids, such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyisobutyl acrylate, hydroxyisobutyl methacrylate, methyl maleate, dimethyl maleate, monoethyl maleate, diethyl maleate, 2-ethylhexyl acrylate
  • methacrylate and the salts of the last-mentioned basic monomers with carboxylic acids or mineral acids and the quaternized products of the basic (meth)acrylates are also suitable as further monomers D which can be incorporated in the form of polymerized units.
  • the monomers comprising acid groups can be used in the polymerization in the form of the free acid groups and in a form partly or completely neutralized with bases.
  • copolymerizable monomers D are N-vinylcaprolactam
  • N-vinylimidazole N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, vinyl acetate, vinyl propionate, isobutene, styrene, ethylene oxide, propylene oxide or ethyleneimine and compounds having more than one polymerizable double bond, such as, for example, diallylammonium chloride, ethylene glycol dimethacrylate, diethylene glycol diacrylate, allyl methacrylate, trimethylolpropane triacrylate, triallylamine,
  • the polycarboxylate consists of the polymerized monomers A and B and also optionally monomer C and optionally monomer D.
  • the monomer A is usually present in the polycarboxylate at not less than 20% by weight, preferably not less than 30% by weight and more preferably not less than 40% by weight, based on the sum total of the monomers used.
  • the polycarboxylate typically not be present in the polycarboxylate at not less than 20% by weight, preferably not less than 30% by weight and more preferably not less than 40% by weight, based on the sum total of the monomers used.
  • polycarboxylate comprises not more than 90% by weight of monomer A, preferably not more than 80% by weight and more preferably not more than 75% by weight.
  • the monomer B is usually present in the polycarboxylate at not less than 1 % by weight, preferably not less than 3% by weight and more preferably not less than 5% by weight, based on the sum total of the monomers used.
  • the polycarboxylate comprises not more than 70% by weight of monomer B, preferably not more than 50% by weight and more preferably not more than 40% by weight.
  • the monomer C is usually present in the polycarboxylate at not less than 1 % by weight, preferably not less than 3% by weight and more preferably not less than 5% by weight, based on the sum total of the monomers used.
  • the polycarboxylate comprises not more than 70% by weight of monomer B, preferably not more than 50% by weight and more preferably not more than 40% by weight.
  • the monomers D are usually present at not more than 30% by weight, preferably at not more than 20% by weight and particularly at not more than 10% by weight, all based on the sum total of the monomers used.
  • Monomer A and monomer B are usually present in the polycarboxylate at not less than 30% by weight, preferably at not less than 50% by weight and more preferably at not less than 70% by weight in sum total, based on the sum total of the monomers used.
  • the weight ratio of monomer A to monomer B is usually in the range from 50:1 to 1 :5, preferably in the range from 40:1 to 1 :1 and specifically in the range from 30:1 to 1 .5:1.
  • the polycarboxylates are obtainable by free-radical polymerization of the monomers. Any known free-radical method of polymerization can be used. In addition to polymerization in bulk, it is particularly the methods of solution polymerization and emulsion polymerization which are suitable, of which solution polymerization is preferred.
  • the polymerization is preferably carried out in water as solvent. However, it can also be performed in alcoholic solvents, more particularly C1-C4 alcohols, such as methanol, ethanol and isopropanol, or mixtures thereof with water.
  • alcoholic solvents more particularly C1-C4 alcohols, such as methanol, ethanol and isopropanol, or mixtures thereof with water.
  • polymerization initiators include not only thermally, redox-chemically but also photochemically (photoinitiators) decomposing compounds that form free radicals in the course of their decomposition. These initiators can be used in combination with reducing compounds as initiator-regulator systems. Examples of such reducing compounds are phosphorus-containing compounds, such as phosphorous acid, hypophosphites and phosphinates, sulfur-containing compounds, such as mercaptans, 2-mercaptoethanol, sodium hydrogen sulfite, sodium sulfite and sodium formaldehyde- sulfoxilate, and also hydrazine.
  • reducing compounds are phosphorus-containing compounds, such as phosphorous acid, hypophosphites and phosphinates, sulfur-containing compounds, such as mercaptans, 2-mercaptoethanol, sodium hydrogen sulfite, sodium sulfite and sodium formaldehyde- sulfoxilate, and also hydrazine.
  • the polymerization temperature is generally in the range from 20 to 200°C, preferably in the range from 20 to 150°C and more preferably in the range from 20 to 120°C.
  • the polymerization can be carried out under atmospheric pressure, but is preferably performed in a closed system under the autogenous pressure which develops.
  • the copolymers can be obtained in the acidic state, but they can also be fully or partially neutralized, if desired for their planned use, during the polymerization or after completion of the polymerization, by adding bases, more particularly aqueous sodium hydroxide solution.
  • the preferred pH for the aqueous copolymer solutions is in the range from 2 to 89 and preferably in the range from 3 to 8.5.
  • the polycarboxylates can be used directly in the form of the aqueous solutions obtained in water in the case of preparation via solvent polymerization, or in dried form (obtained by, for example, spray drying, spray granulation, fluidized spray drying, roll drying or freeze drying).
  • the copper salt particles are preferably obtainable, and are obtainable in particular, by a method comprising the steps:
  • solution 1 preparation of an aqueous solution comprising copper ions (solution 1 ) and of an aqueous solution comprising at least one anion which is not hydroxide and forms a precipitate with copper ions (solution 2), at least one of the two solutions 1 and 2 comprising at least one water-soluble polymer,
  • step b) mixing of the solutions 1 and 2 prepared in step a) at a temperature in the range of from 0 to 100°C, the copper salt particles forming with formation of an aqueous dispersion, and
  • the preparation method may comprise in step d):
  • step c
  • the preparation of the solution 1 described in step a) can be effected, for example, by dissolving the water-soluble copper salt in water or an aqueous solvent mixture.
  • An aqueous solvent mixture may also comprise, for example, water-miscible alcohols, ketones or esters, such as methanol, ethanol, acetone or ethyl acetate, in addition to water.
  • the water content of such a solvent mixture is usually at least 50% by weight, preferably at least 80% by weight.
  • the water-soluble copper salts may be, for example, copper(ll) halides, acetates, sulfates or nitrates.
  • Preferred copper salts are copper chloride, copper acetate, copper sulfate and copper nitrate.
  • solution 1 may also comprise further metal ions (M k+ ), from which, together with the copper ions, the copper salt particles optionally form in step b).
  • M k+ may be ions of alkaline earth metals or transition metals, preferably magnesium, calcium, chromium, cobalt, nickel, zinc or silver ions, particularly preferably zinc or silver ions.
  • the further metal ions are present in smaller numbers than the copper ions.
  • Solution 2 may comprise at least one anion which is not hydroxide and forms a precipitate with copper ions.
  • Said anions may be, for example, anions of mineral acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, boric acid, sulfurous acid, etc., or anions of organic acids, such as oxalic acid, benzoic acid, maleic acid, etc., and polyborates, such as B4O7 2" .
  • solution 2 can of course additionally comprise hydroxide ions.
  • the anion which forms the precipitate with copper ions may be formed from a precursor compound only in the course of the reaction taking place in step b).
  • the anion is present here in the precursor compound in masked form and is liberated therefrom on mixing of the solutions 1 and 2 and/or by a change in
  • the precursor compound may be present either in solution 1 or in solution 2 or in both solutions.
  • Dimethyl carbonate may be mentioned as such a precursor compound, from which carbonate ions can be liberated in an alkali medium.
  • Oxalic acid may be mentioned as a further example of such a precursor compound, from which oxalate anions can be liberated in an alkaline medium.
  • solution 1 comprises the precursor compound and solution 2 comprises a reagent (preferably an inorganic base, such as an alkali or alkaline earth metal hydroxide) to liberate the anion which combines with copper ions to form a precipitate.
  • solution 2 may be free of the anion which combines with copper ions to form a precipitate.
  • a suitable, alternative embodiment of process step a) is as follows: a) preparing an aqueous solution comprising copper ions and a precursor compound of an anion which is not a hydroxide and combines with copper ions to form a precipitate (solution 1 ), and an aqueous solution comprising a reagent for liberating the anion which combines with copper ions to form a precipitate (solution 2), wherein at least one of the two solutions 1 and 2 comprises at least one water-soluble polymer.
  • the concentration of the water-soluble polymers in the solutions 1 and/or 2 prepared in step a) of the method is as a rule in the range of from 0.1 to 30 g/l, preferably from 1 to 25 g/l, particularly preferably from 5 to 20 g/l.
  • the concentration of the water-soluble polymers in the solutions 1 and/or 2 prepared in step a) of the method is generally in the range of from 1 to 200 g/l, preferably of from 5 to 130 g/l, more preferably of from 10 to 80 g/l.
  • step a) of the method in general at least 10 g of water-soluble polymer per mole of copper ions, preferably at least 50 g/mol, in particular at least 80 g/mol, are used in step a) of the method. In general, up to 5000 g of water-soluble polymer per mol of copper ions are used, preferably up to 1000 g/mol, in particular at least 700 g/mol.
  • the mixing of the two solutions 1 and 2 in step b) of the method is effected at a temperature in the range of from 0°C to 100°C, preferably in the range of from 10°C to 95°C, particularly preferably in the range of from 15°C to 80°C.
  • the time for mixing the two solutions in step b) of the method is, for example, in the range of from 1 second to 6 hours, preferably in the range of from 1 minute to 2 hours. In general, mixing time in the batchwise procedure is longer than in the continuous procedure.
  • the mixing in step b) of the method can be effected, for example, by combining an aqueous solution of a copper salt, for example a copper acetate or copper nitrate, with an aqueous solution of a mixture of a polyacrylate and oxalic acid.
  • a aqueous solution of a mixture of a polyacrylate and a copper salt for example of copper acetate or copper nitrate, can also be combined with an aqueous oxalic acid solution.
  • an aqueous solution of a mixture of a polyacrylate and a copper salt for example of copper acetate or copper nitrate, can also be combined with an aqueous solution of a mixture of a polyacrylate and oxalic acid.
  • the mixing in step b) of the method is effected by metering an aqueous solution of a mixture of a polyacrylate and oxalic acid into an aqueous solution of a mixture of polyacrylate and a copper salt, for example a copper acetate or a copper nitrate, or by metering an aqueous oxalic acid solution into an aqueous solution of a mixture of a polyacrylate and a copper salt, for example of copper acetate or copper nitrate.
  • the surface-modified nanoparticulate copper compounds which form an aqueous suspension result.
  • the mixing is effected with simultaneous stirring of the mixture. After the two solutions 1 and 2 have been completely combined, the stirring is preferably continued for a time in the range from 30 minutes to 5 hours at a temperature in the range from 0°C to 100°C.
  • step b) of the method is preferably carried out in a tubular reactor.
  • the aqueous dispersion formed in step b) can be concentrated in step c) of the method, for example if a higher solids content is desired.
  • the concentration can be carried out in a manner known per se, for example by distilling off the water (at atmospheric pressure or at reduced pressure), filtering or centrifuging.
  • Suitable byproducts are primarily salts which are dissolved in water and form in the reaction according to the invention between the solutions 1 and 2, in addition to the desired surface-modified nanoparticulate copper compound, for example sodium chloride, sodium nitrate or ammonium chloride.
  • Such byproducts can be substantially removed from the aqueous dispersion, for example, by means of a membrane method, such as nanofiltration, ultrafiltration, microfiltration or crossflow filtration.
  • the filter cake obtained can be dried in a manner known per se, for example by spray drying or in a drying oven at temperatures of from 40 to 100°C (preferably from 50 to 80°C under atmospheric pressure to constant weight).
  • copper salt particles are used in an effective amount.
  • the expression "effective amount” means an amount of the copper particles which is sufficient for controlling phytophatogenic microorganisms, in particular fungi and bacteria (especially fungi), on the crops to be protected or on the seeds and does not lead to considerable damage to the treated crops or seeds. Such an amount may vary within a wide range as influenced by numerous factors, such as, for example, the pathogen to be controlled, the plant treated in each case, the climatic conditions.
  • the effective amount of the copper salt particles is usually based on the amount of Cu 2+ ions.
  • the effective amount is in the range of from 1 to 1000 g/ha, particularly preferably from 10 to 500 g/ha, in particular from 20 to 300 g/ha and especially from 50 to 200 g/ha.
  • plant propagation materials e.g. seed
  • in general amounts of from 0.1 to 1000 g/100 kg of propagation material or seed, preferably from 1 to 1000 g/100 kg, particularly preferably from 1 to 100 g/100 kg, in particular from 5 to 100 g/100 kg are used.
  • the method according to the invention for controlling phytopathogenic microorganisms is preferably effected by treating the crops to be protected from pathogens, the plant propagation material and/or the pathogens on the crop to be protected or on the plant propagation material with an effective amount of the copper salt particles.
  • the crop to be protected from pathogen infestation and/or the pathogens on the crop to be protected is or are treated with an effective amount of the copper salt particles.
  • the treatment is preferably effected by spray application.
  • the method according to the invention and the copper salt particles according to the invention are particularly suitable as fungicides for controlling harmful fungi. They are distinguished by outstanding efficiency against a broad spectrum of phytopathogenic fungi, including soil-borne pathogens, which originate in particular from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes),
  • Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some of them are systemically active and can be used in crop protection as foliar fungicides, as fungicides for seed dressing and as soil fungicides. In addition, they are suitable for controlling fungi which, inter alia, attack wood or the roots of plants. They can be applied both before and after the infection of the plants, plant propagation materials, e.g. seeds, by the fungi. Preferably, they are applied before the infection of plants (i.e. protectively). Plant propagation materials can be treated prophylactically together with or before sowing or together with or before
  • the method according to the invention and the copper salt particles according to the invention are suitable for controlling bacteria (such as Pseudomona spec, Erwinia spec, Xanthomonas spec, Rhizobium spec, Agrobacterium spec, Rhizomonas spec, Clavibacter spec, Streptomyces spec.) in a very wide range of crops.
  • bacteria such as Pseudomona spec, Erwinia spec, Xanthomonas spec, Rhizobium spec, Agrobacterium spec, Rhizomonas spec, Clavibacter spec, Streptomyces spec.
  • the control of bacteria is preferably effected in the cultivation of fruit and vegetables. Examples are Pseudomona spec, on tobacco, potatoes, tomatoes and leguminous plants, and Erwinia spec, on fruit, vegetables and potatoes.
  • crops or cereals for example wheat, rye, barley, triticale, oats or rice; beets, for example sugar beets or fodder beets; pomaceous fruits, stone fruits and soft fruits, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, currants or gooseberries; leguminous plants, for example beans, lentils, peas, lucerne or soybeans; oil plants, for example oilseed rape, mustard, olives, sunflowers, coconut, cocoa, castor beans, oil palms, peanuts or soybeans; cucurbits, for example pumpkins, cucumbers or melons; fiber plants, for example cotton, flax, hemp or jute; citrus fruits, for example oranges, lemons, grapefruits or mandarins; vegetable plants, for example spinach, lettuce, asparagus, cabbage plants, carrots, onions, tomatoes, potatoes, pumpkins or bell peppers; laurel plants, for example avocados, cinnamon or camphor; energy and raw
  • Further crops are agricultural crops, e.g. potatoes, sugar beet, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, oilseed rape, leguminous plants, sunflowers, coffee or sugar cane; fruit, grape vines and ornamental plants and vegetable plants, e.g. cucumbers, tomatoes, beans and pumpkins, and on the propagation material, e.g. seeds, and the harvested material of these plants.
  • agricultural crops e.g. potatoes, sugar beet, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, oilseed rape, leguminous plants, sunflowers, coffee or sugar cane
  • fruit, grape vines and ornamental plants and vegetable plants e.g. cucumbers, tomatoes, beans and pumpkins
  • propagation material e.g. seeds
  • plant propagation materials includes all generative parts of the plant, for example seeds and vegetative plant parts, such as seedlings and tubers (for example potatoes), which can be utilized for propagating a plant. These include seeds, roots, fruits, tubers, bulbs, rhizomes, shoots and other plant parts including seedlings and young plants which are transplanted after germination or after emergence.
  • the young plants can be protected by partial or complete treatment, for example by immersion or watering, from harmful fungi.
  • the treatment of plant propagation materials is used for controlling a multiplicity of pathogens in cereal crops, e.g. wheat, rye, barley or oats; rice, corn, cotton and soybeans.
  • crops also includes those plants which were modified by breeding, mutagenesis or genetic engineering, including the agricultural products on the market or undergoing development. Genetically modified plants and plants whose genetic material have been modified in a manner which does not occur under natural conditions by crossing, mutations or natural recombination (i.e. reassembly of the genetic information). As a rule, one or more genes are integrated into the genetic material of the plant to improve the properties of the plant.
  • Such genetic modifications also comprise posttranslational modifications of proteins, oligopeptides or polypeptides, for example by means of glycolylation or binding of polymers, such as, for example, prenylated, acetylated or farnelysated radicals or PEG radicals.
  • the method according to the invention and the copper salt particles according to the invention are especially suitable for controlling the following plant diseases:
  • A. Candida and sunflowers (for example A. tragopogonis); Alternaria spp. (black spot) on vegetables, oilseed rape (for example A. brassicola or A. brassicae), sugar beet (for example A. tenuis), fruit, rice, soybeans and also on potatoes (for example A. solani or A. alternata) and tomatoes (for example A. solani or A. alternata) and Alternaria spp. (black spot) on wheat; Aphanomyces spp. on sugar beet and vegetables; Ascochyta spp. on cereals and vegetables, for example A. tritici (leaf spot) on wheat and A.
  • Botrytis cinerea (teleomorph: Botryotinia fuckeliana: gray mold) on soft fruit and pomaceous fruit (inter alia strawberries), vegetables (inter alia lettuce, carrots, celery and cabbage), oilseed rape, flowers, grapevines, forest crops and wheat (ear mold); Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (blue stain) on deciduous trees and coniferous trees, for example C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spot) on corn (for example C.
  • zeae-maydis rice, sugar beet (for example C. beticola), sugar cane, vegetables, coffee, soybeans (for example C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (for example C. fulvum: tomato leaf mold, velvet leaf spot) and cereals, for example C. herbarum (black head mold, sooty mold) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helminthosporium or Bipolaris) spp. (leaf blotch, spot blotch) on corn (for example C. carbonum), cereals (for example
  • Glomerella Glomerella
  • spp. (leaf blight, anthracnose) on cotton (for example C. gossypii), corn (for example C. graminicola: stalk rot and leaf blight), soft fruit, potatoes (for example C. coccodes: wilt), beans (for example C. lindemuthianum) and soybeans (for example C. truncatum); Corticium spp., for example C. sasakii (sheath blight) on rice;
  • Corynespora cassiicola (leaf spot) on soybeans and ornamental plants; Cycloconium spp., for example C. oleaginum on olives; Cylindrocarpon spp. (for example fruit tree canker or grapevine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, grapevines (for example C. liriodendri, teleomorph: Neonectria liriodendri, black foot disease) and many ornamental trees; Dematophora (teleomorph: Rosellinia) necatrix (white root rot/ stem rot) on soybeans; Diaporthe spp. for example D. phaseolorum (stem canker) on soybeans; Drechslera (syn. Helminthosporium, teleomorph:
  • Pyrenophora Pyrenophora
  • corn, cereals such as barley (for example D. teres, net blotch) and on wheat (for example D. tritici-repentis: tan spot), rice and lawn; Esca disease (grapevine decline, apoplexy) on grapevines caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (before Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa;
  • Drechslera teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., for example Hemileia vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn.
  • Septoria tritici, septoria leaf blotch on wheat or M. fijiensis (black sigatoka disease, black leaf streak) on bananas; Peronospora spp. (downy mildew) on cabbage (for example P. brassicae), oilseed rape (for example P. parasitica), bulbous plants (for example P. destructor), tobacco (P. tabacina) and soybeans (for example
  • Ph. manshurica Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans
  • Phialophora spp. for example on grapevines (for example P. tracheiphila and P. tetra- spora) and soybeans (for example P. gregata: stem disease); Phoma lingam (root and stem rot) on oilseed rape and cabbage and P. betae (leaf spot) on sugar beet;
  • Plasmodiophora brassicae club root disease
  • Plasmopara spp. for example P. viticola (peronospora of grapevines, downy mildew) on grapevines and P. halstedii on sunflowers; Podosphaera spp.
  • Pseudoperonospora downy mildew on various plants, for example P. cubensis on cucumber plants or P. humili on hops; Pseudopezicula tracheiphila (red fire disease, anamorph: Phialophora) on grapevines; Puccinia spp. (rust) on various plants, for example P. triticina (brown rust of wheat), P. striiformis (stripe rust), P. hordei (dwarf leaf rust), P. graminis (stem rust, black rust) or P.
  • recondita brown rust of rye
  • cereals such as, for example, wheat, barley or rye, and on asparagus (for example P. asparagi); Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., for example P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on lawn and cereals; Pythium spp. (damping-off) on lawn, rice, corn, wheat, cotton, oilseed rape, sunflowers, sugar beet, vegetables and other plants (for example P.
  • Pyrenophora anamorph: Drechslera
  • tritici-repentis tan spot
  • P. teres net blotch
  • Pyricularia spp. for example P. oryzae (teleomorph: Magnaport
  • Ramularia spp. for example R. collo-cygni (leaf spot disease/physiological leaf spots) on barley and R. beticola on sugar beet; Rhizoctonia spp. on cotton, rice, potatoes, lawn, corn, oilseed rape, potatoes, sugar beet, vegetables and on various other plants, for example R. solani (root/stem rot) on soybeans, R. solani (sheath blight) on rice or R.
  • cerealis (sharp eye spot) on wheat or barley; Rhizopus stolonifer (soft rot) on strawberries, carrots, cabbage, grapevines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetable and agricultural crops, such as oilseed rape, sunflowers (for example Sclerotinia sclerotiorum) and soybeans (for example S. rolfsii); Septoria spp. on various plants, for example S.
  • Spongospora subterranea (powdery scab) on potatoes and viral diseases transmitted thereby; Stagonospora spp. on cereals, for example S. nodorum (leaf and glume blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat;
  • Synchytrium endobioticum on potatoes potato wart disease
  • Taphrina spp. for example T. deformans (leaf curl) on peach and T. pruni (pocket plum) on plums;
  • Thielaviopsis spp. black root rot
  • tobacco, pomaceous fruit, vegetable crops, soybeans and cotton for example T. basicola (syn. Chalara elegans); Tilletia spp. (common or stinking bunt) on cereals, such as, for example, T. tritici (syn. T. caries, common bunt of wheat) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (gray snow mold) on barley or wheat; Urocystis spp., for example U. occulta (stripe smut) on rye; Uromyces spp. (rust) on vegetable plants, such as beans (for example U.
  • U. phaseoli and sugar beet (for example U. betae); Ustilago spp. (smut) on cereals (for example U. nuda and U. avaenae), corn (for example U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (for example V. inaequalis) and pears; and; Verticillium spp. (wilt of leaves and shoots) on various plants, such as fruit trees and ornamental trees, grapevines, soft fruit, vegetable and agricultural crops, such as, for example, V. dahliae on strawberries, oilseed rape, potatoes and tomatoes.
  • the method according to the invention and the copper salt particles according to the invention are especially preferred for controlling plant diseases such as Peronosporaceae, especially the Oomycentes (downy mildew, such as, for example, Plasmopara viticola, Pseudoperonospora cubensis) and Phytophthora.
  • plant diseases such as Peronosporaceae, especially the Oomycentes (downy mildew, such as, for example, Plasmopara viticola, Pseudoperonospora cubensis) and Phytophthora.
  • the method according to the invention and the copper salt particles according to the invention are suitable for controlling bacterial diseases, especially on vegetables, fruit (in particular fruit trees), tobacco, and on the seeds of these plants. They are especially suitable for controlling the following plant diseases: Pseudomona species on tobacco, potatoes, tomatoes and legumes and in particular Erwinia species on fruit, vegetables and potatoes.
  • the copper salt particles can be used in the types customary for agrochemical compositions, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the copper salt particles are used in the form of a suspension in the method.
  • the copper salt particles are used in the form of granules in the method.
  • they are used in the form of the suspension according to the invention.
  • the type of composition depends on the respective intended use; it should in any case ensure a fine and uniform distribution of the compound according to the invention.
  • compositions here are suspensions (SC, OD, FS), emulsifiable concentrates (EC), emulsions (EW, EO, ES), pastes, lozenges, wettable powders or dusts (WP, SP, SS, WS, DP, DS) or granules (GR, FG, GG, MG) which may either be soluble or dispersible (wettable) in water, and gels for the treatment of plant
  • compositions for example EC, SC, OD, FS, WG, SG, WP, SP, SS, WS, GF
  • types of composition such as DP, DS, GR, FG, GG and MG are as a rule used undiluted.
  • the agrochemical compositions may furthermore also comprise assistants customary for crop protection agents, the choice of the assistants depending on the specific application form or the active substance.
  • assistants are solvents, solid carriers, surface-active substances (such as further solubilizers, protective colloids, wetting agents and adherents), organic and inorganic thickeners, bactericides, antifreezes, antifoams, optionally dyes and adhesives (e.g. for seed treatment).
  • Suitable solvents are water, organic solvents such as mineral oil fractions having a medium to high boiling point, such as kerosene and diesel oil, and furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g.
  • paraffins such as methanol, ethanol, propanol, butanol and cyclohexanol
  • 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 strongly polar solvents, for example amines, such as N-methylpyrrolidone.
  • solvent mixtures and mixtures of the abovementioned solvents and water can also be used.
  • Solid carriers are mineral earths, such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, 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 meal, bark, wood and nutshell meal, cellulose powder or other solid carriers.
  • mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, 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 meal, bark, wood and
  • Suitable surface-active substances are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, for example of ligninsulfonic acid (Borresperse ® types,
  • methylcellulose methylcellulose
  • hydrophobically modified starches polyvinyl alcohol (Mowiol ® types, Clariant, Switzerland), polycarboxylates (Sokalan ® types, BASF, Germany), polyalkoxylates, polyvinylamine (Lupamin ® types, BASF, Germany), polyethyleneimine (Lupasol ® types, BASF, Germany), polyvinylpyrrolidone and copolymers thereof.
  • thickeners i.e. compounds which impart modified flow behavior to the composition, i.e. high viscosity in the rest state and low viscosity in the agitated state
  • thickeners are polysaccharides and organic and inorganic layer minerals, such as xanthan gum (Kelzan ® , CP Kelco, USA), Rhodopol ® 23 (Rhodia, France) or Veegum ® (R.T.
  • Bactericides can be added for stabilizing the composition.
  • Bactericides are those based on dichlorophen and benzyl alcohol hemiformal (Proxel ® from ICI or Acticide ® RS from Thor Chemie and Kathon ® MK from Rohm & Haas) and isothiazolinone derivatives, such as alkylisothiazolinones and benzisothiazolinones (Acticide ® MBS from Thor Chemie).
  • suitable antifreezes are ethylene glycol, propylene glycol, urea and glycerol.
  • antifoams are silicone emulsions (such as, for example,
  • adhesives examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and cellulose ethers (Tylose ® , Shin-Etsu, Japan).
  • the agrochemical compositions comprise in general from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the copper salt particles.
  • the compounds are preferably used in a purity of from 90% to 100%, preferably from 95% to 100%.
  • water-soluble concentrates LS
  • suspensions FS
  • dusts DS
  • water-dispersible and water-soluble powders WS, SS
  • ES emulsions
  • EC emulsifiable concentrates
  • gels GF
  • the corresponding composition may be diluted from 2 to 10 times, so that from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, of active substance are present in the compositions to be used for the dressing.
  • the application may take place before or during sowing.
  • the treatment of plant propagation material in particular the treatment of seed, is known to the person skilled in the art and is effected by dusting, coating, pelletizing, immersion or impregnation of the plant propagation material, the treatment preferably being effected by pelletizing, coating and dusting or by furrow treatment, so that, for example, premature germination of the seed is prevented.
  • the concentrations and copper salt particles in the ready-to-use preparations can be varied within relatively large ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 %.
  • the active substances may also be used successfully in the ultra low volume method (ULV), it being possible to apply compositions having more than 95% by weight of active substance or even the active substance without additions.
  • UUV ultra low volume method
  • Oils of various types, wetting agents, adjuvants, herbicides, bactericides, other fungicides and/or pesticides can be added to the active substances or to the compositions comprising them, optionally also immediately before use (tank mix). These agents can be mixed with the compositions according to the invention in a weight ratio of from 1 :100 to 100:1 , preferably from 1 :10 to 10:1 .
  • Particularly suitable adjuvants in this context are: organically modified polysiloxanes, e.g. Break Thru S 240 ® ; alcohol alkoxylates, e.g.
  • Leophen ® RA Leophen ® RA.
  • further agrochemical active substances can be used in addition to the copper salt particles.
  • active substances is intended to illustrate the possible combinations but not to limit them:
  • azoxystrobin dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, trifloxystrobin, methyl 2-(ortho-((2,5-dimethylphenyloxy- methylene)phenyl)-3-methoxyacrylate, 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl- allylideneaminooxymethyl)phenyl)-2-methoxyimino-N-methylacetamide;
  • - carboxanilides benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboxin, fenfuram, fenhexamid, flutolanil, furametpyr, isopyrazam, isotianil, kiralaxyl, mepronil, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, penflufen (N-(2-(1 ,3-dimethylbutyl)phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4- carboxamide), penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, 2-amino- 4-methylthiazole-5-carboxanilide, N-(3',4',5'-trifluorobipheny
  • carpropamid carpropamid, diclocymet, mandipropamid, oxytetracycline, silthiofam, N-(6-methoxypyridin-3-yl)cyclopropanecarboxamide;
  • - triazoles azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole;
  • - pyridines fluazinam, pyrifenox, 3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]- pyridine, 3-[5-(4-methylphenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine;
  • - pyrimidines bupirimate, cyprodinil, diflumetorim, fenarimol, ferimzone, mepanipyrim, nitrapyrin, nuarimol, pyrimethanil;
  • nonaromatic 5-ring heterocycles famoxadone, fenamidon, flutianil, octhilinone, probenazole, allyl 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihydropyrazole-1 - thiocarboxalate;
  • acibenzolar-S-methyl acibenzolar-S-methyl, amisulbrom, anilazine, blasticidin-S, captafol, captan, quinomethionate, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat- methylsulfate, fenoxanil, folpet, oxolinic acid, piperalin, proquinazid, pyroquilon, quin- oxyfen, triazoxid, tricyclazole, 2-butoxy-6-iodo-3-propylchromen-4-one, 5-chloro-1 - (4,6-dimethoxypyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, 5-chloro-7-(4-methyl- piperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-
  • guanidines dodine, dodine free base, guazatine, guazatine acetate, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesilate);
  • nitrophenyl derivatives binapacryl, dicloran, dinobuton, dinocap, nitrothal-isopropyl, tecnazen;
  • fentin salts such as, for example, fentin acetate, fentin chloride, fentin hydroxide;
  • organophosphorus compounds edifenphos, fosetyl, fosetyl-aluminum, iprobenfos, phosphorous acid and its salts, pyrazophos, triclofos-methyl;
  • organochlorine compounds chlorthalonil, dichlofluanid, dichlorphen, flusulfamide, hexachlorobenzene, pencycuron, pentachlorophenol and salts thereof, phthalide, quintozene, thiophanate-methyl, tolylfluanide, N-(4-chloro-2-nitrophenyl)-N-ethyl- 4-methylbenzenesulfonamide;
  • - inorganic active substances phosphorous acid and its salts, Bordeaux mixture, copper salts, such as, for example, copper acetate, copper hydroxide, copper oxy- chloride, basic copper sulfate, sulfur;
  • abscisic acid amidochlor, ancymidol, 6-benzylaminopurine, brassinolid, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfid, indol-3-acetic acid, maleic hydrazide, mefluidid, mepiquat (mepiquat chloride), metconazole, naphthaleneacetic acid, N-6-benzyladenine, paclobutrazole, prohexadione (prohexadione-calcium), prohydrojasmone, thidiazuron, triapenthenol, tributyl phosphorotrithioate,
  • acetochlor alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamide, pretilachlor, propachlor, thenylchlor;
  • acifluorfen acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen;
  • - phenoxyacetic acids clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, mecoprop;
  • - pyridines aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr;
  • - triazines ametryn, atrazin, cyanazin, dimethametryn, ethiozin, hexazinone, meta- mitron, metribuzin, prometryn, simazin, terbuthylazin, terbutryn, triaziflam;
  • acetolactate synthase bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, orthosulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxime, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfon, pyroxsulam;
  • amicarbazone amicarbazone, aminotriazole, anilofos, beflubutamide, benazolin,
  • organo(thio)phosphates acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;
  • - pyrethroids allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalo- thrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau- fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin,
  • ecdyson antagonists halofen- ozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramate;
  • GABA antagonists endosulfan, ethiprol, fipronil, vaniliprol, pyrafluprol, pyriprol, 5-amino-1 -(2,6-dichloro-4-methylphenyl)-4-sulfinamoyl-1 H-pyrazole-3-thiocarbox- amide;
  • acaricides fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;
  • cryomazine - inhibitors of sloughing of insects
  • Biopesticides are preferred as further agrochemical active substances.
  • Biopesticides are generally known, for example from "The Manual of Biocontrol Agents (formerly The Biopesticide Manual", 4th edition 2009, Ed. Leonard Copping, British Crop Protection Council. Suitable biopesticides are naturally occurring substances (such as
  • microorganisms such as bacteria, fungi, protozoa, viruses, bacteriophages, yeasts
  • microbial pesticides bacteriophages, yeasts
  • Suitable microorganisms are bacteria such as Bacillus subtilis, Bacillus pumilus, Bacillus thuringiensis, Pseudomonas spp., and Streptomyces spp.
  • Such microorganisms are commercially available, for example from Agraquest under the brand name Braritone® (B. thuringiensis subspecies kurstaki BMP 123),
  • Suitable protozoa are, for example, Nosema locustae.
  • Suitable viruses are, for example, baculoviruses or granuloviruses of Cydia pomonella.
  • Suitable yeasts are, for example, Cryptococcus and Candida species.
  • Minerals which may be used are, for example, kaolins, sodium silicates or diatomaceous earth.
  • Suitable biochemical pesticides are, for example, extracts of Chenopodium ambrosioide (commercially available as Requiem® from Agraquest), extracts of the neem plant, or chitosan (e.g. ARMOUR-ZEN® from BotriZen Ltd., New Zealand).
  • Preferred biopesticides are microorganisms, in particular bacteria, especially Bacillus subtilis, Bacillus pumilus and Bacillus thuringiensis.
  • the invention furthermore relates to an aqueous suspension of copper salt particles which have a particle diameter of from 1 to 200 nm and comprise a water-soluble polymer, the copper salt comprising an anion which is not hydroxide and forms a precipitate with copper ions, and the suspension comprising not more than 1 .0% by weight of dissolved, inorganic salts.
  • aqueous suspension of copper salt particles which have a particle diameter of from 1 to 200 nm and comprise a water-soluble polymer, the copper salt comprising an anion which is not hydroxide and forms a precipitate with copper ions, and the suspension comprising not more than 1 .0% by weight of dissolved, inorganic salts.
  • Preferred anions and water-soluble polymers are described above.
  • the copper salt particles are preferably amorphous.
  • the suspension according to the invention comprises at least 0.1 g of copper ions per kg of suspension. Preferably, it comprises at least 0.5 g/kg, particularly preferably 2.5 g/kg and in particular at least 3.5 g/kg.
  • the content of copper ions can be determined by means of flame atomic absorption spectrometry.
  • the copper ions are preferably copper(l I) ions.
  • the suspension according to the invention advantageously has a particularly low content of dissolved, inorganic salts.
  • about 1 equivalent of soluble, inorganic salt per equivalent of copper salt is formed in the synthesis, one equivalent being defined as mole per charge.
  • Very low concentrations of dissolved, inorganic salt can be achieved in the suspension by the above-described method for the preparation of copper salt particles, in particular with the aid of step e) of the method.
  • the suspension according to the invention preferably comprises not more than
  • Dissolved, inorganic salts are in particular salts of chloride, nitrate or acetate.
  • the suspension according to the invention may comprise at least one further agrochemical active substance. Suitable further agrochemical active substances are described above.
  • the suspension according to the invention is obtainable, in particular is obtained, by a method comprising the steps
  • solution 1 preparation of an aqueous solution comprising copper ions (solution 1 ) and of an aqueous solution comprising at least one anion which is not hydroxide and forms a precipitate with copper ions (solution 2), at least one of the two solutions 1 and 2 comprising at least one water-soluble polymer,
  • step b) mixing of the solutions 1 and 2 prepared in step a) at a temperature in the range of from 0 to 100°C, the copper salt particles forming with formation of an aqueous suspension, and
  • Steps a) and b) correspond to the above-described steps a) and b) of the method for the preparation of copper salt particles.
  • dissolved, inorganic salts are separated off, preferably by filtration, in particular by filtration by means of membrane methods.
  • Suitable dissolved, inorganic salts are primarily salts which are dissolved in water and which, in the reaction between the solutions 1 and 2, form in addition to the desired surface-modified nanoparticulate copper compound, such as dissolved, inorganic salts (for example sodium chloride, sodium nitrate or ammonium chloride).
  • dissolved, inorganic salts for example sodium chloride, sodium nitrate or ammonium chloride.
  • Such byproducts can be substantially removed from the aqueous dispersion, for example, by means of a membrane method, such as nanofiltration, ultrafiltration, microfiltration or crossflow filtration.
  • the byproduct is separated off by means of ultrafiltration (UF).
  • concentration and removal of salt are effected by means of ultrafiltration in the concentration mode or optionally in the concentration and diafiltration mode, particularly preferably first in the concentration mode and then in the diafiltration mode.
  • the insoluble copper salt particles are virtually completely retained and excess, water-soluble polymer is partly or virtually completely retained by the membranes.
  • Dissolved, inorganic salt, solvent and other lower molecular weight compounds pass through the membrane into the permeate.
  • MK mf e ed/m r etentate or m°feed/m°retentate
  • MK concentration factor
  • R 1 -[c P ermeate/c r
  • diafiltration mode Permeate is separated off and the same amount of diafiltration medium (water) is run into the retentate, i.e. the amount of retentate is kept constant.
  • membranes with regard to membrane material, cut-off and geometry having a cut-off of from 2 to 500 kD or pore diameter from 3 to 200 nm can be used.
  • the upper limit is determined by the molecular weight or the size of the water-soluble polymer or the size of copper salt particles.
  • Polymer should be at least partly retained and copper salt particles should be virtually completely retained by the membrane.
  • Virtually none of the salts formed in the reaction and virtually none of any low molecular weight secondary compounds present in the polymeric protective colloid may be retained by the membrane.
  • the separation layers of the membranes may consist of organic polymers, ceramic, metal, carbon or combinations thereof and must be stable in the feed medium at the filtration temperature.
  • the separation layers are as a rule applied to a one-layer or multilayer porous substructure comprising the same materials as the separation layer or a plurality of different materials. Examples of possible material combinations are mentioned in the table below.
  • the ceramic used may be, for example, (X-AI2O3, Zr02, ⁇ 2, SiC or mixed ceramic materials.
  • Suitable polymers are, for example, polyethylene, polypropylene, PTFE, PVDF, polysulfone, polyethersulfone, polyether ether ketone, polyamide, polyacrylonitrile or polyester.
  • the membranes can be used in flat, tubular, multichannel element, hollow fiber, capillary or helical geometry, for which corresponding pressure housings which permit separation between retentate (Cu-containing) and permeate (Cu-free filtrate) are available.
  • polymeric membranes are used in helical, tubular or hollow fiber geometry.
  • the following membranes can be used:
  • tubular membrane tubular membrane
  • 2 multichannel element
  • 3 flat membrane for helical, pocket, plate stack or other modules with moving membrane or stirred units between the membranes
  • PVDF polyvinylidine fluoride
  • the optimum transmembrane pressures between retentate and permeate are from 0.2 to 10 bar, preferably from 0.5 to 5 bar, depending on the membrane type. Higher transmembrane pressures lead as a rule to higher permeate flows. Where a plurality of modules are connected in the series, the transmembrane pressure for each module can be reduced by increasing the permeate pressure and hence adapted.
  • relative velocity between membrane and suspension of 0.5 - 25 m/s is generally produced by circulation by pumping, mechanical movement of the membrane or stirring units between the membranes.
  • the operating temperature is dependent on the membrane stability and thermal stability of the synthesis suspension. Higher temperatures lead as a rule to higher permeate flows.
  • the achievable permeate flows are greatly dependent on the membrane type and membrane geometry used, on the process conditions, on the feed composition (substantially the concentrations of the copper salt particles and of the water-soluble polymer).
  • the flows are typically from 2 to 200 kg/m 2 /h.
  • the process can be effected batchwise by repeated passage of the suspension through the membrane modules or continuously by a single passage through one or more feed and bleed stages connected in succession.
  • the invention furthermore relates to the use of the suspension according to the invention for controlling phytopathogenic microorganisms and/or undesired plant growth and/or undesired insect or mite infestation and/or for regulating the growth of plants by allowing the suspension to act on the respective pests, their habitat and/or the plants to be protected from the respective pest, the soil and/or undesired plants and/or the useful plants and/or their habitat.
  • the use for controlling phytopathogenic fungi and/or bacteria, in particular fungi is preferred.
  • the invention furthermore relates to the use of the suspension according to the invention for controlling undesired insect or mite infestation on plants and/or for controlling phytopathogenic microorganisms and/or for controlling undesired plant growth by treating seeds of useful plants with the suspension.
  • the invention furthermore relates to a method for controlling microorganisms by treating crops to be protected, soil, plant reproduction material or inanimate industrial materials with an effective amount of the suspension suspension according to the invention.
  • Advantages of the present invention are high fungicidal efficiency of the method and of the suspension with respect to phytopathogenic fungi. Owing to the high efficiency, the application of copper salts in the environment can be further reduced.
  • the lower content of dissolved, inorganic salts leads to very good plant tolerability of the suspension. Moreover, little undesired or environmentally harmful inorganic salts remain on the crops or in the soil.
  • the agrochemical formulations of the copper salt particles were very stable and easy to use. The method and the suspension lead to high resistance of the copper salt particles to rain. In the preparation of the suspension the method leads to a very low copper content in the wastewater.
  • the following examples illustrate the invention without limiting it.
  • Polycarboxylate A random copolymer comprising acrylic acid and AMPS in a weight ratio of 70/30.
  • the mean particle size is determined according to the volume fraction.
  • the copper content was determined by means of flame atomic absorption spectrometry.
  • polycarboxylates A and B are common general knowledge and are obtainable as in EP 10192194.8 (similarly to example 5 for example).
  • Solution 1 was prepared at room temperature and comprised 0.5 mol/l of copper acetate monohydrate.
  • Solution 2 comprised 0.27 mol/l of sodium hydroxide, and 0.13 mol/l of sodium carbonate.
  • Solution 3 comprised 93.2 g/l of polycarboxylate A. 400 ml of solution 1 were initially charged at a temperature of 25°C. 350 ml of solution 3 were metered into solution 1 over 5 minutes with stirring. This was followed by the metered addition of 750 ml of solution 2 over 10-25 minutes with stirring. The resulting reacting mixture was subsequently stirred for a further 15 minutes. The blue suspension obtained was filtered (pore size 10-16 ⁇ ) and the filtered suspension had an average particle size of 5 nm.
  • Solution 1 was prepared at room temperature and comprised 0.19 mol/l of copper acetate monohydrate and 71 g/l of polycarboxylate B.
  • Solution 2 comprised 0.27 mol/l of sodium hydroxide, and 0.13 mol/l of sodium carbonate.
  • 750 ml of solution 1 were initially charged at a temperature of 25°C.
  • 750 ml of solution 2 were metered into solution 1 over 10-25 minutes with stirring.
  • the filtered suspension had an average particle size of 9 nm.
  • Solution 1 was prepared at room temperature and comprised 0.265 mol/l of copper acetate monohydrate and 93.7 g/l of polycarboxylate B.
  • Solution 2 comprised

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Abstract

La présente invention concerne un procédé pour lutter contre des micro-organismes phytopathogènes par traitement de la culture à protéger, du sol ou du matériau de propagation des plantes avec une quantité efficace de particules de sels de cuivre qui comprennent un polymère soluble dans l'eau et qui ont un diamètre de particule primaire de 1 à 200 nm. L'invention concerne aussi une suspension aqueuse des particules de sels de cuivre susmentionnées et l'utilisation de cette suspension dans la protection des cultures.
PCT/EP2012/059105 2011-05-27 2012-05-16 Procédé pour lutter contre des micro-organismes phytopathogènes avec des sels de cuivre particulaires, modifiés par des copolymères amps Ceased WO2012163679A1 (fr)

Applications Claiming Priority (4)

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US201161490614P 2011-05-27 2011-05-27
EP11167871 2011-05-27
EP11167871.0 2011-05-27
US61/490,614 2011-05-27

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
US9382377B2 (en) 2011-08-10 2016-07-05 Basf Se Polymer mixtures as deposit inhibitors in water-bearing systems
RU2679267C1 (ru) * 2017-12-19 2019-02-06 Общество с ограниченной ответственностью "СФК удобрение" Способ приготовления медно-аммиачно-карбонатного раствора
WO2021026121A1 (fr) * 2019-08-07 2021-02-11 Corning Incorporated Dispersions biocides pour compositions de revêtement

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Publication number Priority date Publication date Assignee Title
EP1019219A1 (fr) 1997-10-01 2000-07-19 Vollmer Werke Maschinenfabrik Gmbh Dispositif de mesure sur une machine destinee a l'usinage de pieces avec des dents coupantes, notamment des lames de scie
US20020112407A1 (en) 2001-02-12 2002-08-22 Olivier Anthony Preparation of particles by hydrolysis of a metal cation in the presence of a polymer
US20050256026A1 (en) 2004-05-17 2005-11-17 Hodge Robert L Compatibilizing surfactant useful with slurries of copper particles
WO2005110692A2 (fr) 2004-05-17 2005-11-24 Phibro-Tech, Inc. Composition, procede de fabrication et traitement du bois avec une pate de conservation du bois contenant des particules biocides
WO2006042128A2 (fr) 2004-10-08 2006-04-20 Phibro-Tech, Inc. Produit de preservation du bois particulaire et procede de production
WO2010003870A1 (fr) 2008-07-08 2010-01-14 Basf Se Composés de cuivre nanoparticulaires modifiés en surface
WO2011067186A1 (fr) * 2009-12-02 2011-06-09 Basf Se Procédé de lutte contre les micro-organismes pathogènes avec des sels de cuivre en nanoparticules modifiés en surface

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Publication number Priority date Publication date Assignee Title
EP1019219A1 (fr) 1997-10-01 2000-07-19 Vollmer Werke Maschinenfabrik Gmbh Dispositif de mesure sur une machine destinee a l'usinage de pieces avec des dents coupantes, notamment des lames de scie
US20020112407A1 (en) 2001-02-12 2002-08-22 Olivier Anthony Preparation of particles by hydrolysis of a metal cation in the presence of a polymer
US20050256026A1 (en) 2004-05-17 2005-11-17 Hodge Robert L Compatibilizing surfactant useful with slurries of copper particles
WO2005110692A2 (fr) 2004-05-17 2005-11-24 Phibro-Tech, Inc. Composition, procede de fabrication et traitement du bois avec une pate de conservation du bois contenant des particules biocides
WO2006042128A2 (fr) 2004-10-08 2006-04-20 Phibro-Tech, Inc. Produit de preservation du bois particulaire et procede de production
WO2010003870A1 (fr) 2008-07-08 2010-01-14 Basf Se Composés de cuivre nanoparticulaires modifiés en surface
WO2011067186A1 (fr) * 2009-12-02 2011-06-09 Basf Se Procédé de lutte contre les micro-organismes pathogènes avec des sels de cuivre en nanoparticules modifiés en surface

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9382377B2 (en) 2011-08-10 2016-07-05 Basf Se Polymer mixtures as deposit inhibitors in water-bearing systems
RU2679267C1 (ru) * 2017-12-19 2019-02-06 Общество с ограниченной ответственностью "СФК удобрение" Способ приготовления медно-аммиачно-карбонатного раствора
WO2021026121A1 (fr) * 2019-08-07 2021-02-11 Corning Incorporated Dispersions biocides pour compositions de revêtement

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