WO2006108835A2 - Utilisation de polylysine dans des formulations biocides contenant du cuivre - Google Patents

Utilisation de polylysine dans des formulations biocides contenant du cuivre Download PDF

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Publication number
WO2006108835A2
WO2006108835A2 PCT/EP2006/061508 EP2006061508W WO2006108835A2 WO 2006108835 A2 WO2006108835 A2 WO 2006108835A2 EP 2006061508 W EP2006061508 W EP 2006061508W WO 2006108835 A2 WO2006108835 A2 WO 2006108835A2
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WIPO (PCT)
Prior art keywords
polylysine
copper
derivatives
combination
plants
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PCT/EP2006/061508
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German (de)
English (en)
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WO2006108835A3 (fr
Inventor
Randall Evan Gold
Maximilian Angel
Thomas Pfeiffer
John-Bryan Speakman
Karl-Heinrich Schneider
Harald Köhle
Maria Scherer
Dieter Strobel
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Basf Aktiengesellschaft
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Publication of WO2006108835A2 publication Critical patent/WO2006108835A2/fr
Publication of WO2006108835A3 publication Critical patent/WO2006108835A3/fr

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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
    • 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 the use of polylysine, polylysine derivatives or a combination of polylysine and polylysine derivatives in copper-containing biocidal formulations and to methods of controlling microorganisms based on the above-mentioned formulations.
  • Polylysine is bactericidal (Antimicrobial Agents and Chemotherapy 1983, Vol.24, 1, 107-113, The J. of Antibiotics 1984, Vol.37, 11, 1449, Biochem., And Biophys. Res. Commun. 122, 401).
  • polylysine refers to crosslinked and un-crosslinked polymers or oligomers of lysine having a weight average molecular weight of from 300 to 2,000,000 g / mol. Preference is given to polylysine having average molecular weights of 500 to 100,000 g / mol. Particularly preferred is polylysine having average molecular weights of 1000 to 50,000 g / mol.
  • the amino groups of the lysine units can be linked via the ⁇ - and / or ⁇ -position.
  • the polymer chains can be crosslinked by lysine, in particular in the case of relatively high molecular weight polylysine, by reacting both amino groups of a lysine unit, the second amino group being condensed with a further polylysine chain.
  • Crosslinking of this kind can take place depending on the reaction conditions during the preparation of the polylysine.
  • the preparation of polylysine is known and can be carried out, for example, according to the procedure described in JP 97-33122 or EP-A 256 423.
  • the condensation can also be effected by thermal means, for example at temperatures above 100 G C via the ⁇ - and ⁇ -amino groups, wherein the ⁇ -amino groups preferentially react.
  • unreacted polylysine is used.
  • polylysine derivative denotes crosslinked and uncrosslinked copolymers or cooligomers of lysine with other 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 Pat
  • polylysine derivatives having an average molecular weight (weight average) of from 300 to 2,000,000 g / mol are used. Preference is given to polylysine derivatives having a molecular weight of 500 to 100,000 g / mol. Particular preference is given to using polylysine derivatives having a molar mass of from 1000 to 50 000 g / mol.
  • the lysine units present can be linked via the amino groups in the ⁇ - and / or ⁇ -position.
  • the polymer chains can be crosslinked by lysine and / or by the additionally contained monomers, in particular in the case of relatively high molecular weight polylysene derivatives, by reacting both amino groups of the lysine (analogously to polylysine a) during crosslinking via a lysine unit, and / or during crosslinking via an additionally contained monomer unit, the second functional group of the monomer reacts with a further chain of a polylysine derivative.
  • Crosslinking of this type may take place depending on the reaction conditions during the preparation of the polylysine derivative.
  • Polylysine and polylysine derivatives may also be alkoxylated (see WO 00/71601) and crosslinked (see WO 00/71600). In contrast to a possible crosslinking during the polymerization with, for example, lysine, this crosslinking takes place selectively and in the subsequent polymerization.
  • Suitable crosslinkers are the compounds mentioned in WO 00/71600, for example bisglycidyl ethers of polyethylene glycol.
  • crosslinker can also shade (eg, elongation, tear strength, Young's modulus, tackiness, solubility) of compositions containing copper salts according to the invention. This is particularly advantageous because thus the release of the copper ions and the adhesion of the mixtures or complexes or their films can be controlled on surfaces.
  • 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, especially from the L-enantiomer, or from the D, L-racemate or a mixture thereof.
  • the thermal condensation can be carried out according to WO 00/71600.
  • polylysine or polylysine derivatives or a combination of polylysine and polylysine derivatives As an abbreviation for the term "polylysine or polylysine derivatives or a combination of polylysine and polylysine derivatives" the term “polylysine” is used below.
  • the present invention relates to methods for controlling microorganisms in materials and / or aqueous systems and in plants and / or seeds, characterized in that a formulation comprising a synergistic mixture of polylysine and at least one copper salt on the respective pest or on or in the before applied to the respective pest to be protected materials or aqueous systems or plants, soils and / or seeds and the use of a synergistic mixture of polylysine and copper in biocidal formulations.
  • microorganism are here both bacteria, which can cause bacterioses in plants as well as fungi, yeasts bacteria and algae, which cause damage in materials or technical aqueous systems, furthermore Rickettsia and Mycoplasma-like organisms.
  • biocidal formulation here describes substances / formulations which can be used against microorganisms in industrial materials or aqueous systems as well as in crop protection, preferably in crop protection for controlling bacterioses in plants, wherein in a very preferred embodiment of the invention the term “biocide” is to be equated with the term "bactericidal”.
  • Bacteria causing bacterioses in plants are eg: Erwinia species (E. amylovora: "fire blight” in pear and apple, E. carotovora: “wet rot” in vegetables and potatoes)
  • Agrobacterium species such as, for example, A. tumefaciens, a phytopathogenic Gram-negative soil bacterium which, in infected plants, causes the formation of cancerous structures, called gallbladders, and can infest numerous dicotyledonous plants. Over 640 species from 331 plant genera have been described (CMI 1 1964-1986).
  • a tumefaciens can attack stone and pome fruit, vine, roses, various berry bushes, chrysanthemums and various nursery trees.
  • Xanthomonas species such as X. axonopodis, X. campestris, X. oryzae, X. translucens) on various vegetables, rice, wheat and citrus fruits.
  • X. campestris a typical seed-borne pathogen, infests the following host plants: green bean, lettuce, cotton, alfalfa, Brassica spp., Crucifers. Tomatoes, peppers, soya, sorghum, ornamental plants and flower bulbs (such as begonias, geraniums, zinnias) Shrubs and trees such as hazel, poplar, walnut, grasses (such as Lolium, Festuca, Phleum, Poa, Arrhenatherum, Agrostis, Bromus, Alopecurus, Dacty-Hs), strawberry, citrus and peach.
  • Pseudomonas men e.g. P. savastanoi, P. syringae, P. solanacearum on fruit trees, vegetables, shades, such as tobacco, tomatoes, potatoes and legumes.
  • Gram-positive pathogens such as Clavibacter michiganensis, Rhodococcus fascians and Streptomyces scabies on vegetables and potatoes. Tomatoes, peppers, tobacco natural host plants.
  • Alternaria spp. e.g., A alternata, A. tenuis
  • Aspergillus spp. eg A. nige ⁇
  • Aureobasidium spp. eg A pullulans
  • Chaetomium spp. eg C. globosum
  • Cladosporium spp. eg C. resinae
  • Coniophora spp. eg C. tenuis
  • Lentinus spp. eg L. tigrinus
  • Penicillium spp eg P. expansum, P. funiculosum, P. glaucum
  • Polysporus spp eg P. versicolo ⁇ , Sclerophoma spp. (eg S. pityophiliä), Trichoderma spp. viride)
  • the materials are cellulosic materials, such as wood, fungus
  • Ascomycetes such as Ophiostoma spp. (eg O. piceae, O. piliferum), Ceratocystis spp. (eg C. coerulescens), Aureobasidium pullulans, Sclerophoma spp. (eg S. pityophila); Deuteromycetes such as Aspergillus spp. (eg A. n / g 'e ⁇ , Cladosporium spp. spp (eg C. sphaerospermum), Penicillium. spp (eg P. funiculosum), Trichoderma. (eg 7! spp viride), alternaria. (eg A. alternata), Paecilomyces spp. (eg P. variotii); and Zygomycetes such as Mucorspp. (eg M. hiemalis);
  • Ophiostoma spp. eg O. pic
  • Ascomycetes such as Chaetomium spp. (eg C. globosum), Humicola spp. (eg, # grisea), Petriella spp. (eg / 3 I setifera), Trichurus spp. (eg 7! spiralis); Basidiomycetes such as Coniophora spp. (eg C direna), Coriolus spp. (eg C. versicolor), Gloeophyllum spp. (eg G. trabeum), Lentinus spp. (eg Lepidus), Pleurotus spp. (eg P ostreatus), Poria spp. (eg, P. placenta, P. vaillantii), Serpula spp. (eg S. lacrymans) and Tyromyces spp. (eg 71 palustris);
  • Candida spp. e.g., C. albicans
  • Bacteria that cause damage in materials or technical aqueous systems are:
  • Citrobacter spp. e.g., C. freundil
  • Desulfovibrio spp. e.g., Z. desulfricans
  • Escherichia spp. e.g., E c ⁇ //
  • Klebsiella spp. e.g., / C pneumoniae
  • Proteus spp. e.g., P. mirabilis, P. vulgaris
  • Pseudomonas spp. e.g., P. aeruginosa
  • Staphylococcus spp. e.g., S. aureus
  • Streptoverticillium spp. e.g., S. rubrireticu / i
  • material non-living materials, such as those obtained in technical and industrial processes or intended for use in the art.
  • Materials preferred in the context of the present invention are cellulose-containing materials, very particularly preferably wood.
  • aqueous systems is to be understood here as meaning “aqueous technical systems” as well as “products for technical applications based on water”.
  • aqueous systems in the context of this invention describes plants, in particular chemical plants, production plants or machines, in which water or predominantly aqueous mixtures are used as auxiliaries or reaction media.
  • Examples include reaction vessels, storage boilers, boilers, water cooling circuits, heat exchanger circuits, service water circuits, ballast water tanks, fish farms or air conditioning systems.
  • water-based products that are used in the technical, industrial, commercial, craft or in the field of household. The term also covers the area of the food industry.
  • water-based means in a manner known in principle that the solvent or diluent used in the products predominantly consists of water and only small amounts of water-miscible or dispersible organic solvents are additionally present
  • water-based products include, in particular, coating materials, paints, impregnating substances, aqueous basecoats or paints, printing inks, such as, for example, flexographic printing inks or inkjet inks, dispersions, for example acrylate, styrene-acrylate dispersions, and the formulations of such dispersions for example, as a wall paint, coating, textile auxiliaries
  • Other examples include polyurethane dispersions and their use, for example for the production of clearcoats for wood, paper or plastic coatings.
  • the present invention therefore relates to methods for controlling microorganisms in materials and / or aqueous systems and in plants and / or seeds, characterized in that a formulation comprising a synergistic mixture of polylysine and at least one copper salt on the respective pest or on or in the before the respective pest to be protected materials or aqueous systems or plants, soils and / or seeds is applied and the use of a synergistic mixture of polylysine and at least one copper salt, in biocidal formulations to improve the biocidal effect of copper.
  • the improvement of the biocidal effect consists in a reduction of the amount of copper consumed. This also improves the environmental compatibility, as copper, unlike organic compounds can not be degraded and thus accumulates in ecosystems.
  • formulations comprising a synergistic mixture of polylysine and at least one copper klare for controlling yeasts, bacteria and algae, which cause damage in materials or technical aqueous systems, and used in bacteria bacteriosis causing bacteria, particularly preferably for controlling yeasts, bacteria and Algae, which cause damage in materials or technical aqueous systems, as well as bacteria causing bacteriosis in plants and most preferably for controlling bacterial bacteria in plants.
  • the present invention relates to methods of controlling yeasts, bacteria and algae which cause damage in materials, preferably cellulosic materials, most preferably wood.
  • the present invention relates to methods for controlling bacterioses in plants, characterized in that a formulation comprising a synergistic mixture of polylysine and at least one copper salt on the respective pest or on the plants, soils to be protected from the respective pest or the use of a synergistic mixture of polylysine and at least one copper salt in biocidal formulations for crop protection to improve the biocidal effect of copper.
  • a synergistic mixture of polylysine and at least one copper salt in biocidal formulations, preferably in bactericidal formulations for crop protection, it is possible, for example, to add at least one copper salt with polylysine so as to obtain a biocidal copper-containing formulation according to the invention.
  • copper salt is to be understood as meaning monovalent or, preferably, divalent copper salts of inorganic and organic acids, eg 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 paramate, copper stearate, copper caprylate, copper decanoate, copper undecylenate, copper decanoate, Copper linoleate, copper oleate, copper borate, copper me
  • copper compounds Mixed salts with ammonium, alkali and alkaline earth metals in question.
  • ammonium copper (II) sulfate copper (II) magnesium sulfate, copper naphthenate, copper 8-quinolates and copper (II) potassium sulfate.
  • the weight ratio of polylysine to copper can be varied within wide limits, it is usually 100: 1 to 1:20, in particular 20: 1 to 1:20 parts by weight, preferably 7: 1 to 1:10, particularly preferably 5: 1 to 1: 3 parts by weight, more preferably 3: 1 to 1: 1 parts by weight.
  • the formulations preferably contain 0.01 to 95 wt .-% polylysine and 0.01 to 80 wt .-%, in particular 0.01 to 50 wt .-% of at least one copper salt, based on copper, and optionally further ingredients.
  • formulations according to the invention may be composed as follows, the ingredients being 100% complementary:
  • a solvent or solvent mixture preferably 0.1 to 95 wt .-%, or
  • auxiliaries suitable for the formulation preferably from 0.1 to 98% by weight, or
  • At least one further active substance means that, in addition to copper, one or more further active compounds of the abovementioned composition can be added as further components.
  • active ingredient 1 microbiocidal active ingredients - ie bactericides, algicides, molluscicides and active ingredients against” sea animals as found on Schiffêt coatings - and plant protection agents (pesticides), which includes herbicides, fungicides, insecticides, growth regulators and bactericides for include plant protection.
  • microbicides indicates, but is not limited to, possible drugs:
  • Acylalanines e.g. benalaxyl, furalaxyl, metalaxyl, ofurace, oxadixyl,
  • Amine derivatives e.g. aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine, tridemorph anilinopyrimidines e.g. pyrimethanil, mepanipyrim or cyrodinyl,
  • Antibiotics e.g. cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin, validamycin A
  • Azoles e.g. bitertanol, bromuconazole, cyazofamide, cyproconazole, difenoconazole, dinitroconazole, epoxiconazole, etridazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, fuberidazole, hexaconazole, hymexazole, imazalil, imibenconazole, metconazole, myclobutanil, penconazole, perfurazoate, propiconazole, prochloraz, prothiocona- zole, simeconazole, tebuconazole, tetraconazole, thiabendazole triadimefon, triadimnol, triflumizol, triticonazole, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluoroph
  • Dicarboximides eg iprodion, myclozolin, procymidone, vinclozolin, dithiocarbamates eg ferbam, nabam, maneb, mancozeb, metam, metiram, propineb, polycarbamate, thiram, ziram, zineb, heterocyclic compounds eg anilazine, benomyl, boscalid, carbendazim, carboxy, o-xycarboxin , cyazofamide, dazomet, dithianon, ethirimol, dimethirimol, famoxadone, fenamidom, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarilm, octhilinone, probenazole, proquinazid, pyrifenox, pyroquilon, quinoxyfen, sil
  • Strobilurins e.g. azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxymethyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin, sulfenic acid derivatives e.g. captafol, captan, dichlofluanid, folpet, tolylfluanid, cinnemamides and analogs e.g. dimethomorph, flumetover or flumorph, amide fungicides e.g.
  • R 1 , R 2 are independently halogen, methyl or halomethyl; stand.
  • Another active ingredient used is preferably a pesticide, particularly preferably a fungicide or bactericide for crop protection.
  • strobilurins which, in addition to their fungicidal activity, are also able to For example, azoxystrobin, dimoxystrobin, e-nestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin, preferably pyraclostrobin, are used to immunize plants against bacterial infections.
  • further substances which can be used are plant resistance-inducing substances, e.g. Acibenzolar-S-methyl, 2,6-dichloroisonicotinic acid, D, L-.beta.-aminobutyric acid, culture filtrates of Bacillus subtilis strains, menadione or prohexadione-calcium, a growth regulator with plant resistance-promoting properties.
  • plant resistance-inducing substances e.g. Acibenzolar-S-methyl, 2,6-dichloroisonicotinic acid, D, L-.beta.-aminobutyric acid, culture filtrates of Bacillus subtilis strains, menadione or prohexadione-calcium, a growth regulator with plant resistance-promoting properties.
  • the ratio of the further active ingredient to copper is preferably 50: 1 to 1: 1000, preferably 1: 1 to 1: 100, in particular 1: 1 to 1:10 (parts by weight of active ingredient: copper).
  • solvents such as water, aromatic solvents (for example Solvesso products, xylene) 1 paraffins (for example petroleum fractions), alcoholates Ie (eg Methanoi, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-Butryolacton ), Pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters.
  • solvent mixtures can also be used.
  • solvents are water, N-methylpyrrolidone (NMP), cyclohexanone and gamma-butyrolactone.
  • Solvents are usually contained in liquid formulations in 0.1 to 98% by weight.
  • basic nitrogen compound are, for example, ammonia (formation of copper-amine complexes), primary and secondary amines such as e.g. Ethylene diamine and propylene diamine, preferably to understand ammonia.
  • Basic nitrogen compounds are optionally present in the formulations according to the invention in 0.1 to 80% by weight, preferably in 1 to 10, in particular 2 to 6, molar equivalents, based on copper.
  • the nitrogen compounds may also be present in one equivalent, less than one equivalent, or even less. Even higher amounts, such as up to 50 equivalents are possible.
  • formulation suitable for use is usually to be understood as meaning the following substance classes: Surface-active substances such as wetting agents, adhesives or dispersants, antifoams, thickeners, carriers, antifreeze.
  • Carriers are usually contained in solid formulations in 0.1 to 99% by weight. Other auxiliaries usually constitute from 0.1 to 30% by weight.
  • thickeners ie compounds which give the formulation a pseudoplastic flow behavior, ie high viscosity at rest and low viscosity in the agitated state
  • thickeners are, for example, polysaccharides or inorganic layer minerals such as xanthan gum (Kelzan® from Kelco), Rhodopol® 23 ( Rhone Poulenc) or Veegum® (RT Vanderbilt) or Attaclay® (Engelhardt).
  • Suitable antifoams are, for example, silicone emulsions (such as, for example, Silikon® SRE, Wacker or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.
  • bactericides may be added to stabilize the aqueous formulation.
  • suitable bactericides are Proxel® from the company ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas.
  • Suitable antifreeze agents are ethylene glycol, propylene glycol or glycerol.
  • Examples of carriers are ground natural minerals (eg kaolins, clays, talc, chalk) and ground synthetic minerals (eg finely divided silica, silicates).
  • Examples of emulsifiers are nonionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and Dispersant as mentioned below.
  • surfactants are alkali, alkaline earth, ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenoiether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers,
  • formulation types are emulsifiable concentrates, suspensions, soluble concentrates, dispersible concentrates, pastes, pastilles, wettable powders, dusts (DP) or granules (GR, FG 1 GG 1 MW), which may be either water soluble or dispersible.
  • Common formulation types for seed treatment are FS (flowable concentrates), LS (solutions), DS (powders for dry treatment), WS (water dispersible powders for slurry treatment), SS (water-soluble powders SS) and ES (emulsion).
  • 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 adjuvants are added. Dilution in water gives a solution.
  • a copper salt-polylysine mixture according to the invention 20 parts by weight of a copper salt-polylysine mixture according to the invention are dissolved in cyclohexanone with addition of a dispersant, e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion.
  • a dispersant e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion.
  • 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 addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5%).
  • This mixture is introduced by means of an emulsifier (Ultraturax) in water and brought to a homogeneous emulsion. Dilution in water results in an emulsion.
  • a copper salt-polylysine mixture according to the invention 20 parts by weight of a copper salt-polylysine mixture according to the invention are mixed with the addition of dispersants and wetting agents and water or an organic solvent. comminuted in a stirred ball mill to a fine suspension of active ingredient. Dilution in water gives a stable suspension.
  • Water-dispersible and Water-soluble Granules 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 prepared by means of technical equipment (eg extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules , Dilution in water results in a stable dispersion or solution.
  • technical equipment eg extrusion, spray tower, fluidized bed
  • WP, SP Water-dispersible and Water-Soluble Powders (WP, SP) 75 parts by weight of a copper salt-polylysine mixture according to the invention are ground in a rotor-stator mill with the addition of dispersants and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution.
  • H dusts (DP) 5 parts by weight of a copper salt-polylysine mixture according to the invention are finely ground and intimately mixed with 95% finely divided kaolin. This gives you a dust.
  • I granules 0.5 parts by weight of a copper salt-polylysine mixture according to the invention are finely ground and combined with 95.5% excipients. Common processes are extrusion, spray drying or fluidized bed. This gives granules for direct application.
  • the active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, scattering or Pouring be applied.
  • the forms of application depend entirely on the purposes of use; In any case, they should ensure the finest possible distribution of copper / polylysine.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water.
  • the substances can be homogenized in water by means of wetting agents, tackifiers, dispersants or emulsifiers. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water.
  • the active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
  • the active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.
  • UUV ultra-low-volume
  • the active substances may be added to oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, the specific bactericides mentioned as formulation auxiliaries, if appropriate also immediately before use (tank mix). These agents are usually added to the inventive compositions in a weight ratio of 1:10 to 10: 1.
  • mineral oil fractions of medium to high boiling point such as kerrosin or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg toluene, xy- lol, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethylsulfoxide; N-methylpyrrolidone or water into consideration.
  • mineral oil fractions of medium to high boiling point such as kerrosin or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg toluene, xy- lol, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol
  • Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.
  • Granules e.g. Coated, impregnated and homogeneous granules can be prepared by binding the active compounds to solid carriers.
  • Solid carriers are e.g. Mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, bark, wood and nutshell flour, cellulose powder and other solid carriers.
  • Mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground plastics,
  • soluble copper salts such as Kupferoxychiorid or copper hydroxide.
  • soluble copper salts e.g. Copper sulfate used.
  • the preparation of formulations according to the invention can be carried out by methods known to the person skilled in the art.
  • the preparation of a formulation according to the invention which contains copper alone as a biocidal active ingredient can be carried out, for example, by adding polylysine with at least one copper salt.
  • This may be in solid phase, e.g. by mixing the components or in the liquid phase, e.g. by mixing the components in a solvent according to procedures known in the art. Suitable solvents are those mentioned under (b).
  • polylysine is preferably used as the hydrochloride for practical reasons.
  • the solvent can be removed after the preparation or remain as further component (b) in the formulation according to the invention.
  • a solid composition according to the invention with a solvent (b) can be added in a known manner.
  • the preparation of a formulation according to the invention containing as further component a basic nitrogen compound c) and optionally a solvent (b) is preferably based on the fact that the copper salt is reacted or mixed with a basic nitrogen compound c).
  • the reaction product thus obtained is reacted or mixed with the basic polylysine.
  • Another preferred variant exists This involves first reacting or mixing the copper salt with polylysine and then adding the basic nitrogen compound. The reaction can be carried out in a solvent according to procedures known in the art. Suitable solvents are the solvents (b).
  • aids (e) can also be added during production.
  • the final product obtained can be dried before further processing.
  • Formulations according to the invention which additionally contain at least one further active ingredient (d) can be prepared by adding copper and polylysine together with at least one further active ingredient and with auxiliaries suitable for the formulation and formulated in a known manner.
  • the preparation of the formulation with the further active ingredient as well as with the formulation suitable auxiliaries can be carried out in solid or liquid phase.
  • a formulation which contains copper alone as a biocidal active substance can be mixed with polylysine and at least one further active ingredient and with auxiliaries suitable for the formulation and formulated in a known manner.
  • Oxicop * . Oxycop *, Oxiflow, Cuprar ⁇ kh-35 *, Cuprarikh-50 *, Parkens *, Cuprozin *, Nicuran *, combat *, BluDiamdond *, TopGun *, Recop *, Kupoxil *, Acicio *, Agro-Bakir *, Agroram *, Blitox *, BlueCap * , Bluevit *, Cobox *, Cobre Lainco *, Coprantol *, Cupramar *, Cupravit *, Copter *, Coupradin *, Crispobre *, Crystal *, Cuprenox * , Cuprex * , Cuprossina *, Cuproflow *, Cuproxima *, Devicop - per *, Dhanucop *, Dongoxyclorua * , Hektas bakir * , Hilcopper *, Kapper *, Koruma Bakir *, Micorsperse *, Midiltipi Virfix bakir * , Perecopper *, Pol
  • an agrochemical formulation comprising copper as the sole biocidal active substance with polylysine and with an agrochemical formulation of a further active substance which contains no copper or polylysine.
  • a formulation preferably denotes all formulations of fungicidal or bactericidal active ingredients or of active substances which induce a resistance induction in plants.
  • this agrochemical formulation of another active substance, which does not contain copper or polylysine may also be a commercially available formulation.
  • the present invention relates to processes for combating microorganisms in industrial materials and aqueous technical systems and of bacterioses in plants, characterized in that a formulation comprising a synergistic mixture of polylysine and at least one copper salt on the respective pest or applied to the materials to be protected from the respective pest or aqueous technical systems or plants, soils and / or seeds, preferably methods for controlling bacterioses in plants, characterized in that a formulation comprising a sy nergistic mixture of polylysine and at least one copper salt applied to the respective pest or on the before the respective pest to be protected plants, soils and / or seeds.
  • the copper / polylysine formulation according to the invention is added, for example, to the cooling or heat exchanger circuit, or else to the product, ie, for example, to the aqueous dispersion.
  • concentration used depends on the desired application and is chosen accordingly by the person skilled in the art. Thus, for long-term prevention, the skilled person will normally only use a relatively small amount of the biocidal additive. If a sudden infestation with microorganisms must be combated, he will select a higher concentration.
  • the copper When used in aqueous systems, the copper is used in amounts of 0.001 to 5 wt.%, Preferably 0.005 to 1 wt.% And particularly preferably 0.01 to 0.5 wt.%.
  • the application rates of copper are 10-2000 g Cu / ha, preferably 20-600 g Cu / ha and more preferably 50-300 g Cu / ha.
  • the formulation according to the invention can also be used in a method for protecting materials, preferably cellulose-containing materials, preferably wood, by applying a formulation according to the invention to the surface of the material.
  • the application rate of the formulation of the invention depends on the type of application and the desired effect. Usual application rates are, for example, 0.0001 g to 2 kg, preferably 0.005 g to 1 kg of copper per cubic meter of material treated in the material protection. The application in wood preservation is preferred.
  • the method for controlling bacterioses in plants is carried out by the application of the formulations according to the invention by spraying or dusting the seeds, the plants or the soil before or after the sowing of the plants or before or after the emergence of the plants.
  • the application of the biocidal compositions can be curative, eradicative or protective.
  • the application rates of the active ingredient copper are, depending on the type of copper salt and the desired effect at 10 - 2000 g copper / ha, preferably 20-600 g copper / ha and particularly preferably 50-300 g copper / ha ..
  • the present invention also includes seed which has been treated with the formulations according to the invention.
  • seed treatment copper application rates of 0.1 to 10 kg / 100 kg of seed, preferably 1 to 5 kg / 100 kg, in particular 1 to 2.5 kg / 100 kg of seed, are generally used.
  • formulations (or compositions) according to the invention for combating a large number of bacterioses on various crop plants such as wheat, rye, barley, oats, rice, maize, grass, bananas, cotton, soya, coffee, sugar cane, wine, fruit - and ornamental plants and vegetables such as cucumbers, beans, tomatoes, potatoes and cucurbits, as well as the seeds of these plants.

Abstract

La présente invention concerne l'utilisation de polylysine, de dérivés de polylysine ou d'une combinaison de polylysine et de dérivés de polylysine dans des formulations biocides contenant du cuivre, ainsi qu'un procédé pour lutter contre des micro-organismes, à l'aide des formulations susmentionnées.
PCT/EP2006/061508 2005-04-15 2006-04-11 Utilisation de polylysine dans des formulations biocides contenant du cuivre WO2006108835A2 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011077071A1 (de) * 2011-06-07 2012-12-13 Beiersdorf Ag Wirkstoffkombinationen aus Epsilon-Polylysin und Climbazol
US10470459B2 (en) 2014-05-28 2019-11-12 Ipabc Ltd Antimicrobial preparations, methods for preparing the same and uses thereof to combat microorganisms
WO2020094823A1 (fr) * 2018-11-09 2020-05-14 Basf Se Dérivés de poly-lysine pour augmenter l'efficacité de formulations agrochimiques
US20220110319A1 (en) * 2019-09-24 2022-04-14 Tda Research, Inc Photodynamic method of inhibiting growth of a microbial plant pathogen

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011077071A1 (de) * 2011-06-07 2012-12-13 Beiersdorf Ag Wirkstoffkombinationen aus Epsilon-Polylysin und Climbazol
US10470459B2 (en) 2014-05-28 2019-11-12 Ipabc Ltd Antimicrobial preparations, methods for preparing the same and uses thereof to combat microorganisms
WO2020094823A1 (fr) * 2018-11-09 2020-05-14 Basf Se Dérivés de poly-lysine pour augmenter l'efficacité de formulations agrochimiques
US20220110319A1 (en) * 2019-09-24 2022-04-14 Tda Research, Inc Photodynamic method of inhibiting growth of a microbial plant pathogen

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