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EP0730517A1 - Timber preservative containing a copper compound - Google Patents

Timber preservative containing a copper compound

Info

Publication number
EP0730517A1
EP0730517A1 EP95900121A EP95900121A EP0730517A1 EP 0730517 A1 EP0730517 A1 EP 0730517A1 EP 95900121 A EP95900121 A EP 95900121A EP 95900121 A EP95900121 A EP 95900121A EP 0730517 A1 EP0730517 A1 EP 0730517A1
Authority
EP
European Patent Office
Prior art keywords
methyl
phenyl
wood
copper
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP95900121A
Other languages
German (de)
French (fr)
Inventor
Hans-Ulrich Buschhaus
Klaus Stroech
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0730517A1 publication Critical patent/EP0730517A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • 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
    • A01N59/14—Boron; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/16—Inorganic impregnating agents
    • B27K3/22—Compounds of zinc or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B27K3/343—Heterocyclic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds

Definitions

  • the application relates to a wood preservative containing at least one Kup 'ferverbin- dung, a TnazolENS and at least one alkanolamine.
  • Wood preservatives based on inorganic copper compounds with alkanolamines as complexing agents are known (EP 89 958).
  • the efficacy of these agents against wood-destroying Basidiomycetes is not sufficient in spite of the high copper content compared to known copper and chromate salts with a comparable copper content.
  • wood preservatives based on copper compounds and alkanolamines which contain a tnazole compound and an emulsifier or a phosphonium compound and are effective against wood-destroying Basidiomy ⁇ ceten (DE 4 112 652 / WO 93/02557 / WO 91/11306).
  • the aim and object of the present invention was to find a wood preservative which is highly effective and good against wood-staining and wood-destroying fungi and preferably also against wood-damaging insects, in particular against wood-destroying longhorn beetles (Cerambycidae, Lyctidae, Bostrychidae and Anobiidae) Has long-term action, the effectiveness of the fungicide not being impaired by the insecticide or vice versa.
  • the wood preservative should have a good penetration into wood and wood-based materials.
  • a clear, easy-to-use and storage-stable formulation should be provided, which contains no additional emulsifier.
  • wood preservatives can be produced using suitable alkanolamines or alkanolamine mixtures without using additional emulsifiers.
  • the invention therefore relates to a wood preservative comprising, in addition to at least one copper compound, at least one triazole compound and special alkanolamines or alkanolamine mixtures and, if appropriate, a further fungicide and / or insecticide, and, if appropriate, an emulsifier.
  • the advantage of the agents according to the invention is that e.g. Triazole compounds which are not soluble in water are present in the form of aqueous emulsions or clear aqueous concentrates in spite of the copper compound content in the new compositions. When diluted with water, clear aqueous liquids are formed.
  • organic solvents e.g. alcohols (ethanol, isopropanol), glycols (ethylene glycol, propylene glycol), glycol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether), glycol ether esters (butyl glycol acetate), dimethylformamide, N-methylpyrrolidone homogeneous concentrates are obtained.
  • the solvents also act as solubilizers for the fungicides.
  • arylcarboxylic acids, cycloalkylcarboxylic acids or aliphatic C5-C20-- ⁇ ionic or dicarboxylic acids or corresponding amine, alkali or copper salts are used, the use of solvents can be reduced to a minimum in order to obtain homogeneous concentrates. In any case, the mixture or concentrate contains water as an ingredient.
  • the copper compounds can be used as water-soluble or water-insoluble compounds, for example copper sulfate, copper acetate, copper hydroxide, copper oxide, copper borate, copper fluoride, copper hydroxide carbonate, copper chloride, copper phosphate.
  • copper sulfate copper acetate
  • copper hydroxide copper oxide
  • copper borate copper fluoride
  • copper hydroxide carbonate copper chloride
  • copper phosphate copper phosphate
  • Alkanolamines are compounds of the general formula (I)
  • R * denotes optionally substituted alkyl, substituted aryl, substituted alkenyl, alkylcarbonyl, arylcarbonyl, substituted alkenylcarbonyl or alkynylcarbonyl,
  • R ⁇ has the meaning of R *, H or R- *,
  • R 3 denotes (CH 2 -CH 2 -O) n H, (CH 2 -CHCH 3 -O) m H,
  • n 1 to 40
  • n 1 to 40.
  • alkanolamines are ethoxylated or propoxylated alkanolamines such as tallow fatty amine x 10 ethylene oxide (E0), coconut fatty amine x 5E0, tallow fatty alkyl propylene diamine x 5E0, stearic acid ethanolamine, methylstearylamine x 4E0, alkylaminomethylphenol x 10E0 and their salts or their propoxide.
  • E0 tallow fatty amine x 10 ethylene oxide
  • coconut fatty amine x 5E0 coconut fatty amine x 5E0
  • tallow fatty alkyl propylene diamine x 5E0 stearic acid ethanolamine
  • methylstearylamine x 4E0 alkylaminomethylphenol x 10E0 and their salts or their propoxide.
  • alkanolamines such as e.g. Isopropanolamine, aminoethylethanolamine, diethanolamine,
  • Preferred alkanolamine mixtures contain 50 to 90% monoethanolamine and 5 to 50% of another alkanolamine, which is an ethoxylated or propoxy-modified fatty amide or fatty amine.
  • the amount of alkanolamines added is advantageously such that a pH of 7 or more, preferably 8.5 to 10.5, is established in the dilute aqueous impregnation solution.
  • the amount of alkanolamines is said to be well Complex formation of the copper is sufficient, as well as being solution-mediating for the triazole compounds.
  • the following compounds are preferably used as triazole compounds: amitroles, azocyclotin, BAS 840F, bitertanol, difenoconazole, fenbuconazole, fenchlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol, imibenconazole, isozofos, myclobutanil, epoxyconazole, paclazazazole, paconazole, paconazole, pentaconazole, pentaconazole, pentaconazole, pentaconazole, pentaconazole, pentaconazole, pentaconazole, pentaconazole, pentaconazole, pentaconazole, pentone - 1 - (4-chlorophenyl) -2- (1 H- 1, 2,4-triazol-1-yl) -cycloheptanol, tetraconazole,
  • triazole compounds are very particularly preferred: azaconazole, bromuconazole, cyproconazole, dichlobutrazole, diniconazole, hexaconazole, metaconazole, penconazole, propiconazole and tebuconazole.
  • triazole compounds such as e.g. Tebuconazole, in
  • fungicides or insecticides are also preferably used as synergistic fungicidal or insecticidal mixing partners.
  • Naphthalene derivatives such as:
  • Sulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet; Captan, Captofol;
  • Benzimidazoles such as Carbendazim, Benomyl, Furathiocarb, Fuberidazole, Thiophonat-methyl, Thiabendazole or their salts;
  • Morpholine derivatives such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph; Aldimorph, fenpropidine and their arylsulfonic acid salts, e.g. p-toluenesulfonic acid and p-dodecylphenyl sulfonic acid;
  • Dithiocarbamate Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam, Metiram, Thiram Zeneb, Ziram: benzothiazoles such as 2-mercaptobenzothiazole; Benzamides such as 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; Boron compounds such as boric acid, boric acid ester, borax;
  • Formaldehyde and formaldehyde-releasing compounds such as benzyl alcohol mono- (poly) -hemiformal, oxazolidines, hexa-hydro-S-triazines, N-methylolchloroacetamide, paraformadehyde, nitropyrin, oxolinic acid, tecloftalam;
  • Aldehydes such as cinnamaldehyde, formaldehyde, glutardialdehyde, ⁇ -bromocinnamaldehyde; Thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate, etc; quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethaylammonium chloride;
  • Iodine derivatives such as diiodomethyl-p-tolyl sulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenylethyl carbamate, 2,3,3-triiodallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-hexyl carbamate, 3-iodo-2-propynyl cyclohexyl carbamate, 3-iodo-2-propynyl phenyl carbamate;
  • Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol and their alkali and alkaline earth metal salts.
  • Microbicides with activated halogen group such as chloroacetamide, bronopol, bronidox, tectamers such as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane, ⁇ -bromo- ⁇ -nitrostyrene;
  • Pyridines such as l-hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrithione;
  • Metal soaps such as tin, copper, zinc naphtenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;
  • Metal salts such as sodium dichromate, potassium dichromate, potassium chromate, copper borate, zinc fluorosilicate, copper fluorosilicate.
  • Oxides such as tributyltin oxide, Cu 2 O, CuO, ZnO;
  • Dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetramethylthiuram disulfide, potassium N-methyldithiocarbamate;
  • Nitriles such as 2,4,5, 6-tetrachloroisophthalonitrile, disodium cyano-dithioimidocarbamate;
  • Quinolines such as 8-hydroxyquinoline and their Cu salts; Mucochloric acid, 5-hydroxy-2 (5H) furanone;
  • Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, ⁇ -l (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxy-pyrazole, chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, diazinon, dichlorvos, Dimethoate, Ethoate, Ethoprophos, Etrimfos, Fenitrothion, Fenthion, Heptenophas, Parathion, Parathion-methyl, Phosalone, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulfprofos, Triazophos and Trichlorphon;
  • Carbamates such as aldicarb, bendiocarb, ⁇ -2- (l-methylpropyl) phenylmethyl carbamate, butocarboxime, butoxycarboxime, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarb;
  • Organosilicon compounds preferably dimethyl (phenyl) silylmethyl-3-phenoxybenzyl ether such as dimethyl (4-ethoxyphenyl) silylmethyl-3-phenoxybenzyl ether or
  • (Dimethylphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether such as e.g. Dimethyl- (9-ethoxy-phenyl) -silylmethyl-2-phenoxy-6-pyridylmethylether or [(phenyl) -3 - (3-phenoxyphenyl) -propyl] (dimethyl) -silanes such as e.g. (4-ethoxyphenyl) - [3- (4-fluoro-3-phenoxyphenyl-propyl] dimethyl silane, silafluofen;
  • Pyrethroids such as Allethrin, Alphamethrin, Bioresmethrin, Byfenthrin, Cycloprothrin, Cyfluthrin, Decamethrin, Cyhalothrin, Cypermethrin, Deltamethrin, Alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- (2-chloro-2-trif -methylvinyl) cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin, resmethrin and tralomethrin;
  • Nitroimines and nitromethylenes such as l - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-1 H -imidazol-2-amine (imidacloprid), N - [(6-chloro 3-pyridyl) methyl-] N2-cyano-N 1 -methyl acetamide (NI-25);
  • Particularly preferred wood preservatives contain as insecticides:
  • the synergistic effect of the mixtures is observed in mixing ratios from 99: 1 to 1:99, preferably from 3: 1 to 1: 3, very particularly preferably in a ratio of 1: 1.
  • the ratio of copper ions to the fungicide or to the sum of the fungicide mixture should be at least 1: 2.5 to 1000: 1; mixtures with 5: 1 to 500: 1 are preferred, very particularly preferably 10: 1 to 100: 1.
  • Additive boron salts or boric acid and nitrite are preferably added in a ratio of 1:50 to 50: 1 in relation to the copper ions.
  • the exact amount is to be based on the specific fungicide or fungicide mixture and Just like the amount of emulsifier to be added if appropriate, depends on the water solubility of the finished mixture obtained.
  • Aliphatic carboxylic acids can be added to improve the homogeneity of the concentrates.
  • Such acids are e.g. Propionic acid, hexanoic acid, heptanoic acid, branched carboxylic acids such as e.g. 2-ethylene hexanoic acid, isooctanoic acid, neocarboxylic acids, aliphatic dicarboxylic acids such as e.g. Sebacic acid, cycloalkylcarboxylic acids such as e.g. Cyclohexanoic acid, aryl carboxylic acids such as e.g. Benzoic acid, 3- or 4-hydroxybenzoic acid.
  • Polyethyleneimines (PEI, polymine) are known and are formed by polymerizing 1,2-ethyleneimine. In them the nitrogen is primary (end group), secondary and tertiary (branching). Polyethyleneimines with n greater than 10 are suitable; very good results are achieved when using PEI with a degree of polymerization n between 50 and 1,000.
  • the wood preservatives may optionally contain other compounds, e.g. Compounds with a fungicidal anion such as a boron compound (e.g. alkali borate, amine borate, boric acid, boric acid ester), fluorides (e.g. potassium fluoride and / or salts of fluoroboric acid and / or fluorophosphoric acid and / or difluorophosphoric acid).
  • a boron compound e.g. alkali borate, amine borate, boric acid, boric acid ester
  • fluorides e.g. potassium fluoride and / or salts of fluoroboric acid and / or fluorophosphoric acid and / or difluorophosphoric acid.
  • these combinations of active substances have a particularly high, microbicidal, in particular fungicidal activity, combined with a broad spectrum of activity against microorganisms and insects relevant in wood protection; they are particularly effective against mold, wood-staining and wood-destroying fungi and insects.
  • microorganisms are mentioned by way of example, but without limitation: A: Wood-staining fungi:
  • A2 Deuteromycetes: Aspergillus like Aspergillus niger
  • Aureobasidium such as Aureobasidium pullulans
  • Dactylium such as Dactylium fusarioides
  • Penicillium such as Penicillium brevicaule or Penicillium variable
  • S clerophoma such as S clerophoma pithyophila
  • Acopularia such as Scopularia phycomyces Trichoderma such as Trichoderma viride or Trichoderma lignorum
  • A3 Zygomycetes: Mucor like Mucor spinorus
  • Chaetomium such as Chaetomium globosum or Chaetomium alba-arenulum Humicola such as Humicola grisea
  • Coniophora such as Coniophora cerena Coriolus such as Coriolus versicolor
  • Donkioporia such as Donkioporia expansa Glenospora such as Glenospora graphii Gloeophyllum like Gloeophyllum abietinum or Gloeophyllum adoratum or Gloeophyllum protactum or Gloeophyllum sepiarium or Gloeophyllum trabeum
  • Lentinus such as Lentinus cyathiformes or Lentinus edodes like Lentinus lepideus or Lentinus grinus or Lentinus squarrolosus Paxillus like Paxillus panuoides
  • Pleurotus such as Pleurotus ostreatus Poria such as Poria monticola or Poria placenta or Poria vaillantii or Poria vaporaria
  • Serpula such as Serpula himantoides or Serpula lacrymans
  • Chlorophorus pilosis Anobium puncratum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus Planicollis, Lyctus linearis, Lycus pubescens, speculum, Trogoxy Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus
  • Kalotermes flavicollis Cryptotermers brevis, Heterotermes ündicola; Reticulitermes flavipes, Reticulitermes santonensis, Reticuliter ⁇ ies lucilugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
  • the amount of the agents or concentrates used depends on the type and occurrence of the insects, microorganisms, the number of bacteria and on the medium. The optimal amount can be determined in each case by test series. In general, however, it is sufficient to use 0.001 to 20% by weight, preferably 0.05 to 10% by weight, of the active compound mixture, based on the material to be protected.
  • the insecticides are generally present in an application concentration of 0.00001% to 10%, preferably 0.00001% to 5%, particularly preferably 0.001% to 1%.
  • the formulations mentioned can be prepared in a manner known per se, e.g. by mixing the constituents, if appropriate with the addition of a solvent or diluent, dispersant and / or binder or fixative, water repellent, if appropriate siccatives and UV stabilizers and if appropriate dyes and pigments and further processing aids.
  • the solvent and / or diluent used is, where appropriate, an organic chemical solvent or solvent mixture and / or an oily or oil-like low-volatile organic chemical solvent or solvent mixture and / or a polar organic chemical solvent or solvent mixture.
  • aliphatic organic chemical solvents containing hydroxyl and / or ester and / or ether groups such as, for example, glycol ethers, esters or the like, are used.
  • the known organic water-borne synthetic resins and / or synthetic oils which are soluble or dispersible or emulsifiable and / or bindable drying oils, in particular binders consisting of or containing an acrylate resin can be used as organic-chemical binders.
  • a vinyl resin for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or synthetic resin.
  • the synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances up to 10% by weight can also be used as binders. In addition, known dyes, pigments, water-repellants, odor correctors and inhibitors or anticorrosive agents and the like can be used.
  • binder mentioned can be replaced by a fixing agent (mixture) or a plasticizer (mixture). These additives are intended to prevent volatilization of the active ingredients and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).
  • the plasticizers come from the chemical classes of phthalic acid esters such as di-butyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, higher glycerol glycol or glycerol ether , Glycerol ester and p-toluenesulfonic acid ester.
  • phthalic acid esters such as di-butyl, dioctyl or benzyl butyl phthalate
  • phosphoric acid esters such as tributyl phosphate
  • adipic acid esters such as di- (2-ethylhexyl) adipate
  • stearates such as buty
  • Fixing agents are chemically based on polyalkyl alkyl ethers such as Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.
  • wood which can be protected by the agent according to the invention or mixtures containing it, is to be understood as an example: timber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wooden cladding. Wooden windows and doors, plywood, chipboard, carpentry or wood products that are used in general in house construction or joinery.
  • a particularly effective wood protection is achieved by industrial impregnation processes, e.g. vacuum, double vacuum or pressure processes.
  • the water-thinnable wood preservatives generally contain - in concentrated form - the triazole / fungicide or insecticide mixture in amounts of 0.01 to 95% by weight, in particular 0.01 to 60% by weight.
  • the water-thinnable wood preservatives contain - in concentrated form - the copper, calculated as metal, preferably in an amount of 1.0 to 15.0% (weight percent).
  • Suitable concentrates are e.g. out
  • the invention also extends equally to the impregnation solutions which can be prepared by diluting the concentrates with water and correspondingly lower individual concentrations.
  • the application concentration is, for example, 0.01 to 1.50% by weight of metal, for example copper, in the aqueous impregnation solution, depending on the type of impregnation and the degree of hazard of the wood to be impregnated.
  • Impregnation solution for protecting wood can be applied by handicraft processes such as spraying, brushing, dipping, troughs or by industrial processes such as boiler pressure processes, alternating pressure processes, double vacuum processes.
  • “Wood” means both solid wood and wood-based materials such as chipboard and plywood; if necessary, the wood preservative can also be introduced using the glue mixing process.
  • the copper fixation of the wood preservatives according to the invention is high; when used for industrial processes, it is more than 90%.
  • the concentrates or solutions can be colored using water-soluble or water-emulsifiable dyes and / or pigment preparations.
  • wax, paraffin and / or acrylate dispersions it is possible to add wax, paraffin and / or acrylate dispersions to achieve a water-repellent effect or to improve the fixation.
  • the concentrates can also be incorporated into binder-containing water-thinnable systems (primers, glazes).
  • the means according to the invention advantageously make it possible to replace the previously available means with more effective ones. They show good stability and advantageously have a broad spectrum of activity. Examples

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

Abstract

The present application concerns an agent or concentrate for preserving timber or timber materials containing at least one copper compound, at least one triazole compound and special alkanol amines. The timber preservative may also contain further active agents and auxiliaries.

Description

Holzschutzmittel enthaltend eine KupferverbindungWood preservative containing a copper compound
Die Anmeldung betrifft Holzschutzmittel, enthaltend mindestens eine Kup'ferverbin- dung, eine Tnazolverbindung und mindestens ein Alkanolamin.The application relates to a wood preservative containing at least one Kup 'ferverbin- dung, a Tnazolverbindung and at least one alkanolamine.
Holzschutzmittel auf der Basis anorganischer Kupferverbindungen mit Alkanolaminen als Komplexbildner sind bekannt (EP 89 958). Die Wirksamkeit dieser Mittel gegen¬ über holzzerstörenden Basidiomyceten reicht trotz hoher Kupfergehalte im Vergleich zu bekannten kupfer- und chromathaltigen Salzen mit vergleichbarem Kupfergehalt nicht aus.Wood preservatives based on inorganic copper compounds with alkanolamines as complexing agents are known (EP 89 958). The efficacy of these agents against wood-destroying Basidiomycetes is not sufficient in spite of the high copper content compared to known copper and chromate salts with a comparable copper content.
Ebenfalls bekannt sind Holzschutzmittel auf der Basis von Kupferverbindungen und Alkanolaminen, die eine Tnazolverbindung und einen Emulgator oder eine Phospho- niumverbindung enthalten und Wirksamkeit gegenüber holzzerstörenden Basidiomy¬ ceten besitzen (DE 4 112 652 / WO 93/02557 / WO 91/11306).Also known are wood preservatives based on copper compounds and alkanolamines, which contain a tnazole compound and an emulsifier or a phosphonium compound and are effective against wood-destroying Basidiomy¬ ceten (DE 4 112 652 / WO 93/02557 / WO 91/11306).
Ziel und Aufgabe der vorliegenden Erfindung war es nun, ein Holzkonservie- rungsmittel zu finden, daß gegenüber holzverfärbenden und holzzerstörenden Pilzen sowie vorzugsweise auch gegenüber holzschädigenden Insekten, insbesondere gegenüber holzzerstörenden Bockkäfern (Cerambycidae, Lyctidae, Bostrychidae und Anobiidae) einschließlich Termiten hochwirksam ist und eine gute Langzeitwirkung aufweist, wobei die Wirksamkeit des Fungizides durch das Insektizid nicht beein¬ trächtigt wird bzw. umgekehrt. Darüber hinaus sollte das Holzkonservierungsmittel ein gutes Eindringvermögen in Holz und in Holzwerkstoffen aufweisen. Weiterhin sollte eine klare, gut handhabbare und lagerstabile Formulierung bereitgestellt werden, die keinen zusätzlichen Emulgator enthält.The aim and object of the present invention was to find a wood preservative which is highly effective and good against wood-staining and wood-destroying fungi and preferably also against wood-damaging insects, in particular against wood-destroying longhorn beetles (Cerambycidae, Lyctidae, Bostrychidae and Anobiidae) Has long-term action, the effectiveness of the fungicide not being impaired by the insecticide or vice versa. In addition, the wood preservative should have a good penetration into wood and wood-based materials. Furthermore, a clear, easy-to-use and storage-stable formulation should be provided, which contains no additional emulsifier.
Überraschenderweise wurde nun gefunden, daß ebensolche Holzschutzmittel unter Verwendung von geeigneten Alkanolaminen bzw. Alkanolamingemischen hergestellt werden können, ohne daß zusätzliche Emulgatoren Verwendung finden.Surprisingly, it has now been found that such wood preservatives can be produced using suitable alkanolamines or alkanolamine mixtures without using additional emulsifiers.
Gegenstand der Erfindung ist daher ein Holzschutzmittel, enthaltend neben mindestens einer Kupferverbindung mindestens eine Triazolverbindung und spezielle Alkanolamine oder Alkanolamingemische und gegebenenfalls ein weiteres Fungizid und/oder Insektizid, sowie gegebenenfalls einen Emulgator.The invention therefore relates to a wood preservative comprising, in addition to at least one copper compound, at least one triazole compound and special alkanolamines or alkanolamine mixtures and, if appropriate, a further fungicide and / or insecticide, and, if appropriate, an emulsifier.
Der Vorteil der erfindungsgemäßen Mittel liegt darin, daß z.B. Triazolverbindungen, die im Wasser nicht löslich sind, trotz des Gehalts an Kupferverbindungen in den neuen Mitteln in Form wäßriger Emulsionen oder klarer wäßriger Konzentrate vorliegen. Beim Verdünnen mit Wasser entstehen klare wäßrige Flüssigkeiten.The advantage of the agents according to the invention is that e.g. Triazole compounds which are not soluble in water are present in the form of aqueous emulsions or clear aqueous concentrates in spite of the copper compound content in the new compositions. When diluted with water, clear aqueous liquids are formed.
Durch Zugabe von geringen Mengen an organischen Lösungsmitteln zum Holzschutz- mittel, z.B. Alkoholen (Ethanol, Isopropanol), Glykolen (Ethylenglykol, Propylengly- kol), Glykolethern (Ethylenglykolmonomethylether, Ethylenglykolmonoethylether), Glykoletherestern (Butylglykolacetat), Dimethylformamid, N-Methylpyrrolidon kön¬ nen homogene Konzentrate erhalten werden. Die Lösungsmittel wirken dabei zusätz¬ lich als Lösungsvermittler für die Fungizide. Bei der zusätzlichen Verwendung von Arylcarbonsäuren, Cycloalkylcarbonsäuren oder aliphatischen C5-C20--γIono- oder Dicarbonsäuren oder entsprechenden Amin-, Alkali- oder Kupfersalzen kann der Einsatz an Lösungsmitteln jedoch auf ein Minimum reduziert werden, um homogene Konzentrate zu erhalten. In jedem Fall enthält die Mischung oder das Konzentrat Wasser als ein Bestandteil.By adding small amounts of organic solvents to the wood preservative, e.g. alcohols (ethanol, isopropanol), glycols (ethylene glycol, propylene glycol), glycol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether), glycol ether esters (butyl glycol acetate), dimethylformamide, N-methylpyrrolidone homogeneous concentrates are obtained. The solvents also act as solubilizers for the fungicides. If arylcarboxylic acids, cycloalkylcarboxylic acids or aliphatic C5-C20-- γ ionic or dicarboxylic acids or corresponding amine, alkali or copper salts are used, the use of solvents can be reduced to a minimum in order to obtain homogeneous concentrates. In any case, the mixture or concentrate contains water as an ingredient.
Die Kupferverbindungen können als wasserlösliche oder wasserunlösliche Verbin¬ dungen eingesetzt werden, z.B. Kupfersulfat, Kupferacetat, Kupferhydroxid, Kupfer¬ oxid, Kupferborat, Kupferfluorid, Kupferhydroxidcarbonat, Kupferchlorid, Kupferphosphat. - JThe copper compounds can be used as water-soluble or water-insoluble compounds, for example copper sulfate, copper acetate, copper hydroxide, copper oxide, copper borate, copper fluoride, copper hydroxide carbonate, copper chloride, copper phosphate. - J
Alkanolamine sind Verbindungen der allgemeinen Formel (I)Alkanolamines are compounds of the general formula (I)
in welcherin which
R* gegebenenfalls substituiertes Alkyl, substituiertes Aryl, substituiertes Alkenyl, Alkylcarbonyl, Arylcarbonyl, substituiertes Alkenylcarbonyl oder Alkinyl- carbonyl bedeutet,R * denotes optionally substituted alkyl, substituted aryl, substituted alkenyl, alkylcarbonyl, arylcarbonyl, substituted alkenylcarbonyl or alkynylcarbonyl,
R^ die Bedeutung von R*, H oder R-* hat,R ^ has the meaning of R *, H or R- *,
R3 (CH2-CH2-O)nH, (CH2-CHCH3-O)mH bedeutet,R 3 denotes (CH 2 -CH 2 -O) n H, (CH 2 -CHCH 3 -O) m H,
n 1 bis 40 bedeutet undn is 1 to 40 and
m 1 bis 40 bedeutet.m means 1 to 40.
Als Alkanolamin kommen insbesondere ethoxilierte oder propoxilierte Alkanolamine wie Talgfettamin x 10 Ethylenoxid (E0), Kokosfettamin x 5E0, Talgfettalkylpropylen- diamin x 5E0, Stearinsäureethanolamid, Methylstearylamin x 4E0, Alkylaminomethyl- phenol x 10E0 sowie deren Salze oder deren Propylenoxid Analoga in Frage. Von be- sonderem Interesse sind auch Mischungen dieser Alkanolamine mit weiteren Alkanol¬ aminen wie z.B. Isopropanolamin, Aminoethylethanolamin, Diethanolamin, Tri- ethanolamin, Methylethanolamin insbesondere Monoethanolamin.Particularly suitable alkanolamines are ethoxylated or propoxylated alkanolamines such as tallow fatty amine x 10 ethylene oxide (E0), coconut fatty amine x 5E0, tallow fatty alkyl propylene diamine x 5E0, stearic acid ethanolamine, methylstearylamine x 4E0, alkylaminomethylphenol x 10E0 and their salts or their propoxide. Mixtures of these alkanolamines with further alkanolamines, such as e.g. Isopropanolamine, aminoethylethanolamine, diethanolamine, triethanolamine, methylethanolamine, especially monoethanolamine.
Bevorzugte Alkanolamin-Gemische enthalten 50 bis 90 % Monoethanolamin und 5 bis 50 % eines weiteren Alkanolamins, welches ein ethoxyliertes oder propoxyüertes Fettamid oder Fettamin ist.Preferred alkanolamine mixtures contain 50 to 90% monoethanolamine and 5 to 50% of another alkanolamine, which is an ethoxylated or propoxy-modified fatty amide or fatty amine.
Hierbei wird die Menge der zugesetzten Alkanolamine vorteilhaft so bemessen, daß sich in der verdünnten wäßrigen Imprägnierlösung ein pH- Wert von 7 oder mehr, vor¬ zugsweise 8,5 bis 10,5, einstellt. Die Menge der Alkanolamine soll swohl zur Komplexbildung des Kupfers ausreichen, als auch lösungsvermittelnd für die Triazolverbindungen sein.The amount of alkanolamines added is advantageously such that a pH of 7 or more, preferably 8.5 to 10.5, is established in the dilute aqueous impregnation solution. The amount of alkanolamines is said to be well Complex formation of the copper is sufficient, as well as being solution-mediating for the triazole compounds.
Als Triazolverbindungen werden vorzugsweise folgende Verbindungen eingesetzt: Amitrole, Azocyclotin, BAS 840F, Bitertanol, Difenoconazole, Fenbuconazole, Fenchlorazole, Fenethanil, Fluquinconazole, Flusilazole, Flutriafol, Imibenconazole, Isozofos, Myclobutanil, Epoxyconazole, Paclobutrazol, Penconazole, Propiconazole, (±)-cis- 1 -(4-chlorphenyl)-2-( 1 H- 1 ,2,4-triazol- 1 -yl)-cycloheptanol, Tetraconazole, Tri- adimefon, Triadimenol, Triapenthenol, Triflumizole, Uniconazole.The following compounds are preferably used as triazole compounds: amitroles, azocyclotin, BAS 840F, bitertanol, difenoconazole, fenbuconazole, fenchlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol, imibenconazole, isozofos, myclobutanil, epoxyconazole, paclazazazole, paconazole, paconazole, pentaconazole, pentaconazole, pentaconazole, pentaconazole, pentaconazole, pentaconazole, pentone - 1 - (4-chlorophenyl) -2- (1 H- 1, 2,4-triazol-1-yl) -cycloheptanol, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, uniconazole.
Ganz besonders bevorzugt sind folgende Triazolverbindungen: Azaconazole, Bromuconazole, Cyproconazole, Dichlobutrazol, Diniconazole, Hexa- conazole, Metaconazole, Penconazole, Propiconazole und Tebuconazole.The following triazole compounds are very particularly preferred: azaconazole, bromuconazole, cyproconazole, dichlobutrazole, diniconazole, hexaconazole, metaconazole, penconazole, propiconazole and tebuconazole.
Vorzugsweise werden die Triazolverbindungen wie z.B. Tebuconazole, inPreferably the triazole compounds such as e.g. Tebuconazole, in
Kombination mit sich synergistisch ergänzenden weiteren Fungiziden und/oderCombination with other synergistically complementary fungicides and / or
Insektiziden eingesetzt. Als Fungizide genannt seien neben den schon erwähnten Triazolen:Insecticides used. In addition to the triazoles already mentioned, fungicides include:
Methyl-(E)-methoximino[α-(o-tolyloxy)-o-tolyl)]acetate, Methyl-(E)-2-{2-[6-(2- cyanphenoxy)-pyrimidin-4-yl-oxy]phenyl}-3-methoxyacrylat, Methfuroxam, Carb- oxin, Fenpiclonil, 4(2,2-Difluoro- 1 ,3-benzodioxol-4-yl)- lH-pyrrol-3-carbonitriL, Butenafine und/oder 3-Iodo-2-propinyl-n-butylcarbamate.Methyl- (E) methoximino [α- (o-tolyloxy) -o-tolyl)] acetate, methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yl-oxy ] phenyl} -3-methoxyacrylate, methfuroxam, carboxin, fenpiclonil, 4 (2,2-difluoro-1,3-benzodioxol-4-yl) - 1H-pyrrole-3-carbonitrile, butenafine and / or 3-iodo -2-propynyl-n-butyl carbamate.
Als synergistische fungizide bzw. insektizide Mischpartner werden bevorzugt auch die folgenden Fungizide bzw. Insektizide eingesetzt.The following fungicides or insecticides are also preferably used as synergistic fungicidal or insecticidal mixing partners.
Imazalil, Pefurazoate, Prochloraz, Triflumizole, 2-(l-tert-Butyl)-l-(2-chlorphenyl)-3- (l,2,4-triazol-l-yl)-propan-2-ol, Thiazolcarboxanilide wie 2',6'-Dibromo-2-methyl-4- trifluoromethoxy-4'-trifluoromethyl-l,3-thiazole-5-carboxanilide sowie deren Metall- salze und Säureaddukte.Imazalil, pefurazoate, prochloraz, triflumizole, 2- (l-tert-butyl) -l- (2-chlorophenyl) -3- (l, 2,4-triazol-l-yl) -propan-2-ol, thiazole carboxanilides such as 2 ', 6'-dibromo-2-methyl-4-trifluoromethoxy-4'-trifluoromethyl-l, 3-thiazole-5-carboxanilides and their metal salts and acid adducts.
Methyl(E)-2-[2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl]3-methoxyacrylate, methyl(E)-2-[2-[6-(2-thioamidophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacry- late, methyl(E)-2-[2-[6-(2-fluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacry- late, methyl(E)-2-[2-[6-(2,6-difluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxy- acrylate, methyl(E)-2-[2-[3-(pyrimidin-2-yloxy)phenoxy]phenyl]-3-methoxyacrylate, methyl(E)-2-[2-[3-(5-methylpyrimidin-2-yloxy)-phenoxy]phenyl]-3-methoxyacrylate, methyl(E)-2-[2-[3-(phenyl-sulfonyloxy)phenoxy]phenyl]-3-methoxyacrylate, methyl- (E)-2-[2-[3-(4-nitrophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl(E)-2-[2- phenoxyphenyl]-3-methoxyacrylate, methyl(E)-2-[2-(3,5-dimethylbenzoyl)pyrrol- 1 - yl]-3-πιethoxyacrylate, methyl(E)-2-[2-(3-methoxyphenoxy)phenyl]-.3-methoxyacry- late, methyl(E)-2-[2-(2-phenylethen-l-yl)-phenyl]-3-methoxyacrylate, methyl(E)-2-[2- (3,5-dichlorophenoxy)pyridin-3-yl]-3-methoxyacrylate, methyl(E)-2-(2-(3-( 1,1,2,2- tetrafluoroethoxy)phenoxy)phenyl)-3-methoxyacrylate, methyl(E)-2-(2-[3-(alpha-hy- droxybenzyl)phenoxy]phenyl)-3-methoxyacrylate, methyl(E)-2-(2-(4-phenoxypyridin- 2-yloxy)phenyl)-3 -methoxyacrylate, methyl(E)-2-[2-(3 -n-propyloxyphenoxy)- phenyl] 3 -methoxyacrylate, methyl(E)-2- [2-(3 -isopropyloxyphenoxy)phenyl]-3 -meth¬ oxyacrylate, methyl(E)-2-[2-[3-(2-fluorophenoxy)pehnoxy]phenyl]-3-methoxyacry- late, methyl(E)-2-[2-(3-ethoxyphenoxy)phenyl]-3 -methoxyacrylate, methyl(E)-2-[2- (4-tert. -butylpyridin-2-yloxy)phenyl]-3 -methoxyacrylate, methyl(E)-2-[2-[3 -(3 -cyano- phenoxy)phenoxy]phenyl]-3-methoxyacιylate, methyl(E)-2-[2-(3-methylpyridin-2- yloxymethyl)phenyl] -3 -methoxyacrylate, methyl(E)-2-[2-[6-(2-methylphenoxy)pyrimi- din-4-yloxy]phenyl]-3-methoxyacrylate, methyl(E)-2-[2-(5-bromopyridin-2-yloxyme- thyl)phenyl]-3 -methoxyacrylate, methyl(E)-2-[2-(3 -(3 -iodopyridin-2-yloxy)phenoxy)- phenyl]-3-methoxyacrylate, methyl(Ε)-2-[2-[6-(2-chloropyridin-3-yloxy)pyrimidin-4- yloxy]phenyl]-3-methoxyacrylate, (E),(E)methyl-2-[2-(5,6-dimethylpyrazin-2-ylme- thyloximinomethyl)phenyl]-3-methoxyacrylate, (E)-methyl-2-{2-[6-(6-methylpyridin- 2-yloxy)pyrimidin-4-yloxy]phenyl } -3 -methoxyacrylate, (E), (E)methyl-2- { 2-(3 -meth- oxyphenyl)methyloximinomethyl]phenyl } -3 -methoxyacrylate, (E)methyl-2- { 2-(6-(2- azidophenoxy)-pyrimidin-4-yloxy]phenyl}3-methoxyacrylate, (E),(E)methyl-2-{2-[6- phenylpyrimidin-4-yl)-methyloximinomethyl]phenyl}-3-methoxyacrylate, (E),(E)methyl-2-{2-[(4-chlorophenyl)-methyloximinomethyl]phenyl}-3-methoxyacry- late, (E)methyl-2- { 2-[6-(2-n-propylphenoxy)- 1,3,5 -triazin-4-yloxy]phenyl } -3 -meth- oxyacrylate, (E),(E)methyl-2- { 2-[(3-nitrophenyl)methyloximinomethyl]phenyl} -3 - methoxyacrylate; Succinat-Dehydrogenase Inhibitoren wie:Methyl (E) -2- [2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl] 3-methoxyacrylates, methyl (E) -2- [2- [6- (2-thioamidophenoxy) pyrimidine- 4-yloxy] phenyl] -3-methoxyacry- late, methyl (E) -2- [2- [6- (2-fluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacry- latex, methyl (E) -2- [2- [6- (2,6-difluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylates, methyl (E) -2- [2- [3- (pyrimidin-2-yloxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (5-methylpyrimidin-2-yloxy) phenoxy] phenyl] -3-methoxyacrylate, methyl ( E) -2- [2- [3- (phenylsulfonyloxy) phenoxy] phenyl] -3-methoxyacrylates, methyl- (E) -2- [2- [3- (4-nitrophenoxy) phenoxy] phenyl] -3 -methoxyacrylate, methyl (E) -2- [2-phenoxyphenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3,5-dimethylbenzoyl) pyrrole-1 - yl] -3-πιethoxyacrylate, methyl ( E) -2- [2- (3-methoxyphenoxy) phenyl] -. 3-methoxyacrylate, methyl (E) -2- [2- (2-phenylethen-l-yl) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3,5-dichlorophenoxy) pyridin-3-yl] -3-methoxyacrylate, methyl (E) -2- (2- (3- (1,1,2,2- tetrafluoroethoxy) phenoxy) phenyl) -3-methoxyacrylate, methyl (E) -2- (2- [3- (alpha-hydroxybenzyl) phenoxy] phenyl) -3-methoxyacrylate, methyl (E) -2- (2- (4-phenoxypyridin-2-yloxy) phenyl) -3-methoxyacrylate, methyl (E) -2- [2- (3-n-propyloxyphenoxy) phenyl] 3-methoxyacryl ate, methyl (E) -2- [2- (3-isopropyloxyphenoxy) phenyl] -3-methoxyacrylates, methyl (E) -2- [2- [3- (2-fluorophenoxy) phenoxy] phenyl] -3 -methoxyacrylate, methyl (E) -2- [2- (3-ethoxyphenoxy) phenyl] -3 -methoxyacrylate, methyl (E) -2- [2- (4-tert. -butylpyridin-2-yloxy) phenyl] -3 -methoxyacrylate, methyl (E) -2- [2- [3 - (3 -cyano-phenoxy) phenoxy] phenyl] -3-methoxyaclylate, methyl (E) -2- [2- (3-methylpyridin-2-yloxymethyl) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [6- (2-methylphenoxy) pyrimid-4-yloxy] phenyl] -3- methoxyacrylates, methyl (E) -2- [2- (5-bromopyridin-2-yloxymethyl) phenyl] -3-methoxyacrylates, methyl (E) -2- [2- (3 - (3 -iodopyridin-2- yloxy) phenoxy) - phenyl] -3-methoxyacrylate, methyl (Ε) -2- [2- [6- (2-chloropyridin-3-yloxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, (E) , (E) methyl-2- [2- (5,6-dimethylpyrazin-2-ylmethyloximinomethyl) phenyl] -3-methoxyacrylate, (E) -methyl-2- {2- [6- (6-methylpyridine- 2-yloxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylates, (E), (E) methyl-2- {2- (3-meth-oxyphenyl) methyloximinomethyl] phenyl} -3-methoxyacrylates, (E) methyl-2- {2- (6- (2-azidophenoxy) pyrimidin-4-yloxy] phenyl} 3-methoxyacrylates, (E), (E) methyl-2- {2- [6- phenylpyrimidin-4-yl ) -methyloximinomethyl] phenyl} -3-methoxyacrylate, (E), (E) methyl-2- {2 - [( 4-chlorophenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate, (E) methyl-2- {2- [6- (2-n-propylphenoxy) -1,3,5-triazin-4-yloxy] phenyl } -3-meth-oxyacrylates, (E), (E) methyl-2- {2 - [(3-nitrophenyl) methyloximinomethyl] phenyl} -3 - methoxyacrylates; Succinate dehydrogenase inhibitors such as:
Fenfuram, Furcarbanil, Cyclafluramid, Furmecyclox, Seedvax, Metsulfovax, Pyro- carbolid, Oxycarboxin, Shirlan, Mebenil (Mepronil), Benodanil, Flutolanil (Moncut);Fenfuram, furcarbanil, cyclafluramide, furmecyclox, seedvax, metsulfovax, pyrocarbolide, oxycarboxin, shirlan, mebenil (mepronil), benodanil, flutolanil (moncut);
Naphthalin-Derivate wie:Naphthalene derivatives such as:
Terbinafine, Naftifine, Butenafine, 3-Chloro-7-(2-aza-2,7,7-trimethyl-oct-3-en-5-in);Terbinafine, naftifine, butenafine, 3-chloro-7- (2-aza-2,7,7-trimethyl-oct-3-en-5-in);
Sulfenamide wie Dichlofluanid, Tolylfluanid, Folpet, Fluorfolpet; Captan, Captofol;Sulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet; Captan, Captofol;
Benzimidazole wie Carbendazim, Benomyl, Furathiocarb, Fuberidazole, Thiophonat- methyl, Thiabendazole oder deren Salze;Benzimidazoles such as Carbendazim, Benomyl, Furathiocarb, Fuberidazole, Thiophonat-methyl, Thiabendazole or their salts;
Morpholinderivate wie Tridemorph, Fenpropimorph, Falimorph, Dimethomorph, Dodemorph; Aldimorph, Fenpropidin und ihre arylsulfonsauren Salze, wie z.B. p- Toluolsulfonsäure und p-Dodecylphenyl-sulfonsäure;Morpholine derivatives such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph; Aldimorph, fenpropidine and their arylsulfonic acid salts, e.g. p-toluenesulfonic acid and p-dodecylphenyl sulfonic acid;
Dithiocarbamate, Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam, Metiram, Thiram Zeneb, Ziram: Benzthiazole wie 2-Mercaptobenzothiazol; Benzamide wie 2,6-Dichloro-N-(4-trifluoromethylbenzyl)-benzamide; Borverbindungen wie Borsäure, Borsäureester, Borax;Dithiocarbamate, Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam, Metiram, Thiram Zeneb, Ziram: benzothiazoles such as 2-mercaptobenzothiazole; Benzamides such as 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; Boron compounds such as boric acid, boric acid ester, borax;
Formaldehyd und Formaldehydabspaltende Verbindungen wie Benzylalkoholmono- (poly)-hemiformal, Oxazolidine, Hexa-hydro-S-triazine, N-Methylolchloracetamid, Paraformadehyd, Nitropyrin, Oxolinsäure, Tecloftalam;Formaldehyde and formaldehyde-releasing compounds such as benzyl alcohol mono- (poly) -hemiformal, oxazolidines, hexa-hydro-S-triazines, N-methylolchloroacetamide, paraformadehyde, nitropyrin, oxolinic acid, tecloftalam;
Tris-N-(cyclohexyldiazeniumdioxy)-aluminium, N-(Cyclo-hexyldiazeniumdioxy)-tri- butylzinn bzw. K-Salze, Bis-N-(cyclohexyldiazeniumdioxy)-kupfer.Tris-N- (cyclohexyldiazeniumdioxy) aluminum, N- (cyclohexyldiazeniumdioxy) tri-butyltin or K salts, bis-N- (cyclohexyldiazeniumdioxy) copper.
N-Methylisothiazolin-3-on, 5-Chlor-N-methylisothiazolin-3-on, 4,5-Dichloro-N-octyl- isothiazolin-3-on, N-Octyl-isothiazolin-3-on, 4,5-Trimethylen-isothiazohnone, 4,5- Benzisothiazolinone, N-Methylolchloracetamid;N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octyl-isothiazolin-3-one, N-octyl-isothiazolin-3-one, 4,5- Trimethylene-isothiazohnone, 4,5-benzisothiazolinone, N-methylolchloroacetamide;
Aldehyde wie Zimtaldehyd, Formaldehyd, Glutardialdehyd, ß-Bromzimtaldehyd; Thiocyanate wie Thiocyanatomethylthiobenzothiazol, Methylenbisthiocyanat, usw; quartäre Ammoniumverbindungen wie Benzyldimethyltetradecylammoniumchlorid, Benzyldimethyldodecylammoniumchlorid, Didecyldimethaylammoniumchlorid;Aldehydes such as cinnamaldehyde, formaldehyde, glutardialdehyde, β-bromocinnamaldehyde; Thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate, etc; quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethaylammonium chloride;
Iodderivate wie Diiodmethyl-p-tolylsulfon, 3-Iod-2-propinyl-alkohol, 4-Chlorphenyl- 3-iodpropargylformal, 3-Brom-2,3-diiod-2-propenylethylcarbamat, 2,3,3-Triiodallyl- alkohol, 3-Brom-2,3-diiod-2-propenylalkohol, 3-Iod-2-propinyl-n-hexylcarbamat, 3- Iod-2-propinyl-cyclohexylcarbamat, 3-Iod-2-propinyl-phenylcarbamat;Iodine derivatives such as diiodomethyl-p-tolyl sulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenylethyl carbamate, 2,3,3-triiodallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-hexyl carbamate, 3-iodo-2-propynyl cyclohexyl carbamate, 3-iodo-2-propynyl phenyl carbamate;
Phenolderivate wie Tribromphenol, Tetrachlorphenol, 3-Methyl-4-chlorphenol, 3,5- Dimethyl-4-chlorphenol, Phenoxyethanol, Dichlorphen, o-Phenylphenol, m-Phenyl- phenol, p-Phenylphenol, 2-Benzyl-4-chlorphenol und deren Alkali- und Erdalkali- metallsalze.Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol and their alkali and alkaline earth metal salts.
Mikrobizide mit aktivierter Halogengruppe wie Chloracetamid, Bronopol, Bronidox, Tectamer wie 2-Brom-2-nitro-l,3-propandiol, 2-Brom-4'-hydroxy-acetophenon, 2,2- Dibrom-3-nitril-propionamid, 1 ,2-Dibrom-2,4-dicyanobutan, ß-Brom-ß-nitrostyrol;Microbicides with activated halogen group such as chloroacetamide, bronopol, bronidox, tectamers such as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane, β-bromo-β-nitrostyrene;
Pyridine wie l-Hydroxy-2-pyridinthion (und ihre Na-, Fe-, Mn-, Zn-Salze), Tetrachlor-4-methylsulfonylpyridin, Pyrimethanol, Mepanipyrim, Dipyrithion;Pyridines such as l-hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrithione;
Metallseifen wie Zinn-, Kupfer-, Zinknaphtenat, -octoat, 2-ethylhexanoat, -oleat, -phosphat, -benzoat;Metal soaps such as tin, copper, zinc naphtenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;
Metallsalze wie Natriumdichromat, Kaliumdichromat, Kaliumchromat, Kupferborat, Zinkfluorosilikat, Kupferfluorosilikat.Metal salts such as sodium dichromate, potassium dichromate, potassium chromate, copper borate, zinc fluorosilicate, copper fluorosilicate.
Oxide wie Tributylzinnoxid, Cu2O, CuO, ZnO;Oxides such as tributyltin oxide, Cu 2 O, CuO, ZnO;
Dialkyldithiocarbamate wie Na- und Zn-Salze von Dialkyldithiocarbamaten, Tetramethylthiuramdisulfid, Kalium-N-methyl-dithiocarbamat;Dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetramethylthiuram disulfide, potassium N-methyldithiocarbamate;
Nitrile wie 2,4,5, 6-Tetrachlorisophthalodinitril, Dinatrium-cyano-dithioimidocarba- mat;Nitriles such as 2,4,5, 6-tetrachloroisophthalonitrile, disodium cyano-dithioimidocarbamate;
Chinoline wie 8-Hydroxychinolin und deren Cu-Salze; Mucochlorsäure, 5-Hydroxy-2(5H)-furanon;Quinolines such as 8-hydroxyquinoline and their Cu salts; Mucochloric acid, 5-hydroxy-2 (5H) furanone;
4,5-Dichlorodithiazolinon, 4,5-Benzdithiazolinon, 4,5-Trimethylendithiazolinon, 4,5- Dichlor-(3 H)- 1 ,2-dithiol-3 -on, 3 , 5 -Dimethyl-tetrahydro- 1,3,5 -thiadiazin-2-thion, N-(2-p-Chlorbenzoylethyl)-hexaπιiniumchlorid, Kalium-N-hydroxymethyl-N'-methyl- dithiocarbamat,4,5-dichlorodithiazolinone, 4,5-benzdithiazolinone, 4,5-trimethylene dithiazolinone, 4,5-dichloro- (3 H) - 1, 2-dithiol-3-one, 3, 5 -dimethyl-tetrahydro-1,3 , 5 -thiadiazin-2-thione, N- (2-p-chlorobenzoylethyl) hexaπιinium chloride, potassium N-hydroxymethyl-N'-methyldithiocarbamate,
2-Oxo-2-(4-hydroxy-phenyl)acethydroximsäure-chlorid,2-oxo-2- (4-hydroxy-phenyl) acethydroximic acid chloride,
Phenyl-(2-chlor-cyan-vinyl)sulfon,Phenyl- (2-chloro-cyano-vinyl) sulfone,
Phenyl-( 1 ,2-dichlor-2-cyan-vinyl)sulfon;Phenyl- (1,2-dichloro-2-cyano-vinyl) sulfone;
Ag, Zn oder Cu-haltige Zeolithe allein oder eingeschlossen in polymere Wirkstoffe;Zeolites containing Ag, Zn or Cu alone or included in polymeric active substances;
Phosphorsäureester wie Azinphos-ethyl, Azinphos-methyl, α-l(4-Chlorphenyl)-4-(O- ethyl, S-propyl)phosphoryloxy-pyrazol, Chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, Diazinon, Dichlorvos, Dimethoate, Ethoate, Ethoprophos, Etrimfos, Fenitrothion, Fenthion, Heptenophas, Parathion, Parathion-methyl, Phosalone, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulfprofos, Triazophos und Trichlorphon;Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, α-l (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxy-pyrazole, chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, diazinon, dichlorvos, Dimethoate, Ethoate, Ethoprophos, Etrimfos, Fenitrothion, Fenthion, Heptenophas, Parathion, Parathion-methyl, Phosalone, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulfprofos, Triazophos and Trichlorphon;
Carbamate wie Aldicarb, Bendiocarb, α-2-(l-Methylpropyl)-phenylmethylcarbamat, Butocarboxim, Butoxycarboxim, Carbaryl, Carbofuran, Carbosulfan, Cloethocarb, Isoprocarb, Methomyl, Oxamyl, Pirimicarb, Promecarb, Propoxur und Thiodicarb;Carbamates such as aldicarb, bendiocarb, α-2- (l-methylpropyl) phenylmethyl carbamate, butocarboxime, butoxycarboxime, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarb;
Organosiliciumverbindungen, vorzugsweise Dimethyl(phenyl)silyl-methyl-3 -phenoxy- benzylether wie Dimethyl-(4-ethoxyphenyl)-silylmethyl-3-phenoxybenzylether oderOrganosilicon compounds, preferably dimethyl (phenyl) silylmethyl-3-phenoxybenzyl ether such as dimethyl (4-ethoxyphenyl) silylmethyl-3-phenoxybenzyl ether or
(Dimethylphenyl)-silyl-methyl-2-phenoxy-6-pyridylmethylether wie z.B. Dimethyl-(9- ethoxy-phenyl)-silylmethyl-2-phenoxy-6-pyridylmethylether oder [(Phenyl)-3 -(3 - phenoxyphenyl)-propyl](dimethyl)-silane wie z.B. (4-Ethoxyphenyl)-[3-(4-fluoro-3- phenoxyphenyl-propyl] dimethyl-silan, Silafluofen;(Dimethylphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether such as e.g. Dimethyl- (9-ethoxy-phenyl) -silylmethyl-2-phenoxy-6-pyridylmethylether or [(phenyl) -3 - (3-phenoxyphenyl) -propyl] (dimethyl) -silanes such as e.g. (4-ethoxyphenyl) - [3- (4-fluoro-3-phenoxyphenyl-propyl] dimethyl silane, silafluofen;
Pyrethroide wie Allethrin, Alphamethrin, Bioresmethrin, Byfenthrin, Cycloprothrin, Cyfluthrin, Decamethrin, Cyhalothrin, Cypermethrin, Deltamethrin, Alpha-cyano-3- phenyl-2-methylbenzyl-2,2-dimethyl-3-(2-chlor-2-trifluor-methylvinyl)cyclopropan- carboxylat, Fenpropathrin, Fenfluthrin, Fenvalerate, Flucythrinate, Flumethrin, Fluvalinate, Permethrin, Resmethrin und Tralomethrin;Pyrethroids such as Allethrin, Alphamethrin, Bioresmethrin, Byfenthrin, Cycloprothrin, Cyfluthrin, Decamethrin, Cyhalothrin, Cypermethrin, Deltamethrin, Alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- (2-chloro-2-trif -methylvinyl) cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin, resmethrin and tralomethrin;
Nitroimine und Nitromethylene wie l-[(6-Chlor-3-pyridinyl)-methyl]-4,5-dihydro-N- nitro- 1 H-imidazol-2-amin (Imidacloprid), N-[(6-Chlor-3-pyridyl)methyl-]N2-cyano- N1-methylacetamide (NI-25);Nitroimines and nitromethylenes such as l - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-1 H -imidazol-2-amine (imidacloprid), N - [(6-chloro 3-pyridyl) methyl-] N2-cyano-N 1 -methyl acetamide (NI-25);
Abamectin, AC 303, 630, Acephate, Acrinathrin, Alanycarb, Aldoxycarb, Aldrin, Amitraz, Azamethiphos, Bacillus thuringiensis, Phosmet, Phosphamidon, Phosphine, Prallethrin, Propaphos, Propetamphos, Prothoate, Pyraclofos, Pyrethrins, Pyridaben, Pyridafenthion, Pyriproxyfen, Quinalphos, RH-7988, Rotenone, Sodium fluoride, Sodium hexafluorosilicate, Sulfotep, Sulfuryl fluoride, Tar Oils, Teflubenzuron, Tefluthrin, Temephos, Terbufos, Tetrachlorvinphos, Tetramethrin, O-2-tert.-Butyl- pyrimidin-5-yl-o-isopropyl-phosphorothiate, Thiocyclam, Thiofanox, Thiometon, Tralomethrin, Triflumuron, Trimethacarb, Vamidothion, Verticillium Lacanii, XMC, Xylylcarb, Benfuracarb, Bensultap, Bifenthrin, Bioallethrin, MERbioallethrin (S)- cyclopentenyl isomer, Bromophos, Bromophos-ethyl, Buprofezin, Cadusafos, Calcium Polysulfide, Carbophenothion, Cartap, Chinomethionat, Chlordane, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chloropicrin, Chlorpyrifos, Cyanophos, Beta-Cyfluthrin, Alpha-cypermethrin, Cyophenothrin, Cyromazine, Dazomet, DDT, Demeton-S-methylsulphon, Diafenthiuron, Dialifos, Dicrotophos, Diflubenzuron, Dinoseb, Deoxabenzofos, Diaxacarb, Disulfoton, DNOC, Empenthrin, Endosulfan, EPN, Esfenvalerate, Ethiofencarb, Ethion, Etofenprox, Fenobucarb, Fenoxycarb, Fensulfothion, Fipronil, Flucycloxuron, Flufenprox, Flufenoxuron, Fonofos, Formetanate, Formothion, Fosmethilan, Furathiocarb, Heptachlor, Hexaflumuron, Hydramethylnon, Hydrogen Cyanide, Hydroprene, BPSP, Isazofos, Isofenphos, Isoprothiolane, Isoxathion, lodfenphos, Kadethrin, Lindane, Malathion, Mecarbam, Mephosfolan, Mercurous, chloride, Metam, Metarthizium, anisopliae, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methoprene, Methoxy- chlor, Methyl isothiocyanate, Metholcarb, Mevinphos, Monocrotophos, Naled, Neo- diprion sertifer NPV, Nicotine, Omethoate, Oxydemeton-methyl, Pentachlorophenol, Petroleum oils, Phenothrin, Phenthoate, Phorate; Acypetacs, 2-Aminobutane, Ampropylfos, Anilazine, Benalaxyl, Bupirimate, Chinomethionat, Chloroneb, Chlozolinate, Cymoxanil, Dazomet, Diclomezine, Dichloram, Diethofencarb, Dimethirimol, Diocab, Dithianon, Dodine, Drazoxolon, Edifenphos, Ethirimol, Etridiazole, Fenarimol, Fenitropan, Fentin acetate, Fentin Hydroxide, Ferimzone, Fluazinam, Fluromide, Flusulfamide, Flutriafol, Fosetyl, Fthalide, Furalaxyl, Guazatine, Hymexazol, Iprobenfos, Iprodione, Isoprothiolane, Metalaxyl, Methasulfocarb, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadiyl, Perflurazoate, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Procymidone, Propamocarb, Propineb, Pyrazophos, Pyrifenox, Pyroquilon, Quintozene, Tar Oils, Tecnazene, Thicyofen, Thiophanate-methyl, Tolclofos-methyl, Triazoxide, Trichlamide, Tricyclazole, Triforine, Vinclozolin.Abamectin, AC 303, 630, Acephate, Acrinathrin, Alanycarb, Aldoxycarb, Aldrin, Amitraz, Azamethiphos, Bacillus thuringiensis, Phosmet, Phosphamidon, Phosphine, Prallethrin, Propaphos, Propetamphos, Prothoate, Pyraclofos, Pyrethriproxyphid, Pyrethridafid, Pyrethridafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafide, RH-7988, Rotenone, Sodium fluoride, Sodium hexafluorosilicate, Sulfotep, Sulfuryl fluoride, Tar Oils, Teflubenzuron, Tefluthrin, Temephos, Terbufos, Tetrachlorvinphos, Tetramethrin, O-2-tert.-Butyl-pyrimidin-5-yl-o-isopropyl -phosphorothiate, thiocyclam, thiofanox, thiometone, tralomethrin, triflumuron, trimethacarb, vamidothion, verticillium lacanii, XMC, xylylcarb, benfuracarb, bensultap, bifenthrin, bioallethrin, MERbioomerophenoz, bromine, cyclophone, bromophosphate, bromophosphate Calcium polysulfide, carbophenothione, cartap, quinomethionate, chlordane, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorpyrifos, cyanophos, beta-cyfluthrin, alpha-cypermethrin, cyophene othrin, Cyromazine, Dazomet, DDT, Demeton-S-methylsulphone, Diafenthiuron, Dialifos, Dicrotophos, Diflubenzuron, Dinoseb, Deoxabenzofos, Diaxacarb, Disulfoton, DNOC, Empenthrin, Endosulfan, EPN, Etobucarboxate, Ethenucarboxate, Ethfenucarboxate, Ethfenucarboxate, Ethfenucarboxate, Ethenucarboxate, Fensulfothion, Fipronil, Flucycloxuron, Flufenprox, Flufenoxuron, Fonofos, Formetanate, Formothion, Fosmethilan, Furathiocarb, Heptachlor, Hexaflumuron, Hydramethylnon, Hydrogen Cyanide, Hydroprene, BPSP, Isazofos, Kiflorathathophone, Isoxphanophamophene, Isoxinophone, Isoxinophone, Isoxinophone, Isoxinophone, Isoxinophone, Isoxinophone, Isoxinophone, Isoxinophone, Isoxinophone, Isoxinophone, Isoxinophone, Isoxinophone , Mephosfolan, Mercurous, chloride, Metam, Metarthizin, anisopliae, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methoprene, Methoxychloro, Methyl isothiocyanate, Metholcarb, Mevinphos, Monocrotophos, Naled, Neodiprion sertydemetono NPV, Nicotine methyl, pentachlorophenol, petroleum oils, phenothrin, phenthoates, phorates; Acypetacs, 2-aminobutane, Ampropylfos, anilazine, benalaxyl, Bupirimate, chinomethionat, chloroneb, chlozolinate, cymoxanil, dazomet, Diclomezine, Dichloram, diethofencarb, dimethirimol, Diocab, dithianon, dodine, Drazoxolon, edifenphos, ethirimol, etridiazole, fenarimol, Fenitropan, fentin acetate, fentin hydroxide, Ferimzone, fluazinam, Fluromide, flusulfamide, flutriafol, fosetyl, Fthalide, furalaxyl, guazatine, hymexazol, iprobenfos, iprodione, isoprothiolane, metalaxyl, methasulfocarb, nitro Thal-isopropyl, nuarimol, ofurace, Oxadiyl, Perflurazoate, pencycuron, Phosdiphen, Pimaricin, Piperalin, Procymidone, Propamocarb, Propineb, Pyrazophos, Pyrifenox, Pyroquilon, Quintozene, Tar Oils, Tecnazene, Thicyofen, Thiophanate-methyl, Tolclofos-methyl, Triazoxide, Trichlamide, Tricyclazole, Triforoline.
Besonders bevorzugte Holzschutzmittel enthalten als Insektizide:Particularly preferred wood preservatives contain as insecticides:
Chlorpyrifos, Phoxim, Silafluofen, Cyfluthrin, Cypermethrin, Deltamethrin, Per- methrin, Imidacloprid, Hexaflumuron, Lindan.Chlorpyrifos, phoxim, silafluofen, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, hexaflumuron, lindane.
Besonders bevorzugt ist der Einsatz von synergistischen Mischungen aus Tebuconazole und Propiconazole und/oder Bromoconazole und/oder Hexaconazole, Cyproconazole und Bromoconazole und/oder Metaconazole und/oder Hexaconazole, Hexaconazole und Bromoconazole und/oder Metaconazole und/oder Penconazole, Penconazole und Cyproconazole und/oder Metaconazole und/oder Bromoconazole, Propiconazole und Cyproconazole und/oder Hexaconazole und/oder Penconazole.The use of synergistic mixtures of tebuconazole and propiconazole and / or bromoconazole and / or hexaconazole, cyproconazole and bromoconazole and / or metaconazole and / or hexaconazole, hexaconazole and bromoconazole and / or metaconazole and / or penconazole and penconazole, penconazole is particularly preferred. or metaconazole and / or bromoconazole, propiconazole and cyproconazole and / or hexaconazole and / or penconazole.
Die synergistische Wirkung der Mischungen wird in Mischungsverhältnissen von 99:1 bis 1:99, bevorzugt von 3:1 bis 1:3, ganz besonders bevorzugt im Verhältnis 1:1 beobachtet.The synergistic effect of the mixtures is observed in mixing ratios from 99: 1 to 1:99, preferably from 3: 1 to 1: 3, very particularly preferably in a ratio of 1: 1.
Das Verhältnis von Kupferionen zum Fungizid bzw. zur Summe Fungizidmischung sollte mindestens 1:2,5 bis 1 000:1 betragen; bevorzugt sind Mischungen mit 5:1 bis 500:1, ganz besonders bevorzugt 10:1 bis 100:1.The ratio of copper ions to the fungicide or to the sum of the fungicide mixture should be at least 1: 2.5 to 1000: 1; mixtures with 5: 1 to 500: 1 are preferred, very particularly preferably 10: 1 to 100: 1.
Additive Borsalze oder Borsäure sowie Nitrit (als z.B. Natriumnitrit) sind in Bezug auf die Kupferionen im Verhältnis 1:50 bis 50:1 bevorzugt zuzugeben. Die genaue Menge ist jeweils am speziellen Fungzid bzw. Fungizidgemisch zu orientieren und richtet sich ebenso wie die Menge an gegebenenfalls zuzugegebenden Emulgator nach der Wasserlöslichkeit der erhaltenden fertigen Mischung.Additive boron salts or boric acid and nitrite (for example sodium nitrite) are preferably added in a ratio of 1:50 to 50: 1 in relation to the copper ions. The exact amount is to be based on the specific fungicide or fungicide mixture and Just like the amount of emulsifier to be added if appropriate, depends on the water solubility of the finished mixture obtained.
Aliphatische Carbonsäuren können zur Verbesserung der Homogenität der Konzen¬ trate zugesetzt werden. Solche Säuren sind z.B. Propionsäure, Hexansäure, Heptan- säure, verzweigte Carbonsäuren wie z.B. 2-Ethylenhexansäure, Isooctansäure, Neo- carbonsäuren, aliphatische Dicarbonsäuren wie z.B. Sebacinsäure, Cycloalkylcarbon¬ säuren wie z.B. Cyclohexansäure, Arylcarbonsäuren wie z.B. Benzoesäure, 3- oder 4- Hydroxybenzoesäure.Aliphatic carboxylic acids can be added to improve the homogeneity of the concentrates. Such acids are e.g. Propionic acid, hexanoic acid, heptanoic acid, branched carboxylic acids such as e.g. 2-ethylene hexanoic acid, isooctanoic acid, neocarboxylic acids, aliphatic dicarboxylic acids such as e.g. Sebacic acid, cycloalkylcarboxylic acids such as e.g. Cyclohexanoic acid, aryl carboxylic acids such as e.g. Benzoic acid, 3- or 4-hydroxybenzoic acid.
Bei Verwendung der obengenannten Säuren ist es teilweise von Vorteil, durch Zusatz von komplexbildenden, polymeren Stickstofϊverbindungen wie z.B. Polyethyleniminen die Holzschutzmitteleindringung bei großtechnischen Verfahren zu verbessern.When using the abovementioned acids, it is sometimes advantageous to add complex-forming, polymeric nitrogen compounds such as e.g. Polyethyleneimines to improve the penetration of wood preservatives in industrial processes.
Polyethylenimine (PEI, Polymin) sind bekannt und entstehen durch Polymerisation von 1,2-Ethylenimin. In ihnen liegt der Stickstoff primär (Endgruppe), sekundär und tertiär (Verzweigung) vor. Geeignet sind Polyethylenimine mit n größer als 10; sehr gute Ergebnisse werden erzielt bei Verwendung von PEI mit einem Polymeri¬ sationsgrad n zwischen 50 und 1 000.Polyethyleneimines (PEI, polymine) are known and are formed by polymerizing 1,2-ethyleneimine. In them the nitrogen is primary (end group), secondary and tertiary (branching). Polyethyleneimines with n greater than 10 are suitable; very good results are achieved when using PEI with a degree of polymerization n between 50 and 1,000.
Die Holzschutzmittel können gegebenenfalls weitere Verbindungen, z.B. Verbindun¬ gen mit einem fungiziden Anion wie beispielsweise eine Borverbindung (z.B. Alkali- borat, Aminborat, Borsäure, Borsäureester), Fluoride (z.B. Kaliumfluorid und/oder Salze der Fluoroborsäure und/oder Fiuorophosphorsäure und/oder Difluorophosphor- säure), enthalten.The wood preservatives may optionally contain other compounds, e.g. Compounds with a fungicidal anion such as a boron compound (e.g. alkali borate, amine borate, boric acid, boric acid ester), fluorides (e.g. potassium fluoride and / or salts of fluoroboric acid and / or fluorophosphoric acid and / or difluorophosphoric acid).
Überraschenderweise zeigen diese Wirkstofϊkombinationen eine besonders hohe, mikrobizide, insbesondere fungizide Wirkung, verbunden mit einem breiten Wirkspek¬ trum gegen im Holzschutz relevante Mikroorganismen und Insekten; sie sind vor allem wirksam gegen Schimmelpilze, holzverfärbende und holzzerstörende Pilze und Insekten. Beispielhaft - ohne jedoch zu limitieren - seinen die folgenden Gruppen von Mikroorganismen genannt: A: Holzverfärbende Pilze:Surprisingly, these combinations of active substances have a particularly high, microbicidal, in particular fungicidal activity, combined with a broad spectrum of activity against microorganisms and insects relevant in wood protection; they are particularly effective against mold, wood-staining and wood-destroying fungi and insects. The following groups of microorganisms are mentioned by way of example, but without limitation: A: Wood-staining fungi:
AI: AscomycetenAI: Ascomycetes
Ceratocystis wie Ceratocystis minorCeratocystis such as Ceratocystis minor
A2: Deuteromyceten: Aspergillus wie Aspergillus nigerA2: Deuteromycetes: Aspergillus like Aspergillus niger
Aureobasidium wie Aureobasidium pullulans Dactylium wie Dactylium fusarioides Penicillium wie Penicillium brevicaule oder Penicillium variabile S clerophoma wie S clerophoma pithyophilaAureobasidium such as Aureobasidium pullulans Dactylium such as Dactylium fusarioides Penicillium such as Penicillium brevicaule or Penicillium variable S clerophoma such as S clerophoma pithyophila
Acopularia wie Scopularia phycomyces Trichoderma wie Trichoderma viride oder Trichoderma lignorumAcopularia such as Scopularia phycomyces Trichoderma such as Trichoderma viride or Trichoderma lignorum
A3 : Zygomyceten: Mucor wie Mucor spinorusA3: Zygomycetes: Mucor like Mucor spinorus
B: Holzzerstörende Pilze:B: Wood-destroying mushrooms:
B 1 : Ascomyceten:B 1: Ascomycetes:
Chaetomium wie Chaetomium globosum oder Chaetomium alba-arenulum Humicola wie Humicola griseaChaetomium such as Chaetomium globosum or Chaetomium alba-arenulum Humicola such as Humicola grisea
Petriella wie Petriella setifera Trichurus wie Trichurus spiralisPetriella like Petriella setifera Trichurus like Trichurus spiralis
B2: Basidiomyceten:B2: Basidiomycetes:
Coniophora wie Coniophora puteana Coriolus wie Coriolus versicolorConiophora such as Coniophora puteana Coriolus such as Coriolus versicolor
Donkioporia wie Donkioporia expansa Glenospora wie Glenospora graphii Gloeophyllum wie Gloeophyllum abietinum oder Gloeophyllum adoratum oder Gloeophyllum protactum oder Gloeophyllum sepiarium oder Gloeophyllum trabeum Lentinus wie Lentinus cyathiformes oder Lentinus edodes wie Lentinus lepideus oder Lentinus grinus oder Lentinus squarrolosus Paxillus wie Paxillus panuoidesDonkioporia such as Donkioporia expansa Glenospora such as Glenospora graphii Gloeophyllum like Gloeophyllum abietinum or Gloeophyllum adoratum or Gloeophyllum protactum or Gloeophyllum sepiarium or Gloeophyllum trabeum Lentinus such as Lentinus cyathiformes or Lentinus edodes like Lentinus lepideus or Lentinus grinus or Lentinus squarrolosus Paxillus like Paxillus panuoides
Pleurotus wie Pleurotus ostreatus Poria wie Poria monticola oder Poria placenta oder Poria vaillantii oder Poria vaporaria Serpula wie Serpula himantoides oder Serpula lacrymansPleurotus such as Pleurotus ostreatus Poria such as Poria monticola or Poria placenta or Poria vaillantii or Poria vaporaria Serpula such as Serpula himantoides or Serpula lacrymans
Stereum wie Stereum hirsutum Tyromyces wie Tyromyces palustrisStereum like Stereum hirsutum Tyromyces like Tyromyces palustris
B3: DeuteromycetenB3: Deuteromycetes
Alternaria wie Alternaria tenius Cladosporium wie Cladosporium herbarumAlternaria like Alternaria tenius Cladosporium like Cladosporium herbarum
Alternaria tenuisAlternaria tenuis
Holzzerstörende Insekten wieWood-destroying insects like
Cl : KäferCl: Beetle
Hylotrupes bajulus. Chlorophorus pilosis, Anobium puncratum, Xesto- bium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus Planicollis, Lyctus linearis, Lyctus pubescens, Trogoxyton aequale, Minthes rugicollis, Xyleborus spec, Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutusHylotrupes bajulus. Chlorophorus pilosis, Anobium puncratum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus Planicollis, Lyctus linearis, Lycus pubescens, speculum, Trogoxy Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus
C2: HautflüglerC2: Skin wing
Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Uro- erus augurSirex juvencus, Urocerus gigas, Urocerus gigas taignus, Uro- erus augur
C3 : TermitenC3: termites
Kalotermes flavicollis, Cryptotermers brevis, Heterotermes ündicola; Reti- culitermes flavipes, Reticulitermes santonensis, Reticuliterπies lucilugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formo- sanus.Kalotermes flavicollis, Cryptotermers brevis, Heterotermes ündicola; Reticulitermes flavipes, Reticulitermes santonensis, Reticuliterπies lucilugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
Die Menge der eingesetzten Mittel bzw. Konzentrate ist von der Art und dem Vorkommen der Insekten, Mikroorganismen, der Keimzahl und von dem Medium abhängig. Die optimale Einsatzmenge kann bei der Anwendung jeweils durch Testreihen ermittelt werden. Im allgemeinen ist es jedoch ausreichend, 0,001 bis 20 Gew.-%, vorzugsweise 0,05 bis 10 Gew.-%, der Wirkstofftnischung, bezogen auf das zu schützende Material, einzusetzen.The amount of the agents or concentrates used depends on the type and occurrence of the insects, microorganisms, the number of bacteria and on the medium. The optimal amount can be determined in each case by test series. In general, however, it is sufficient to use 0.001 to 20% by weight, preferably 0.05 to 10% by weight, of the active compound mixture, based on the material to be protected.
Die Insektizide liegen im allgemeinen in einer Anwendungskonzentration von 0,00001 % bis 10 %, bevorzugt 0,00001 % bis 5 %, besonders bevorzugt 0,001% bis 1 % vor.The insecticides are generally present in an application concentration of 0.00001% to 10%, preferably 0.00001% to 5%, particularly preferably 0.001% to 1%.
Die genannten Formulierungen können in an sich bekannter Weise hergestellt werden, z.B. durch Vermischen der Bestandteile, gegebenenfalls unter Zusetzen von einem Lösungs- bzw. Verdünnungsmittel, Dispergier- und/oder Binde- oder Fixiermittel, Wasser-Repellent, gegebenenfalls Sikkative und UV- Stabilisatoren und gegebenenfalls Farbstoffen und Pigmenten sowie weiteren Verarbeitungshilfsmitteln.The formulations mentioned can be prepared in a manner known per se, e.g. by mixing the constituents, if appropriate with the addition of a solvent or diluent, dispersant and / or binder or fixative, water repellent, if appropriate siccatives and UV stabilizers and if appropriate dyes and pigments and further processing aids.
Als Lösungs- und/oder Verdünnungsmittel dient neben Wasser gegebenenfalls ein organisch-chemisches Lösungsmittel oder Lösungsmittelgemisch und/oder ein öliges oder ölartiges schwer flüchtiges organisch-chenisches Lösungsmitte oder Lösungs¬ mittelgemisch und/oder ein polares organisch-chemisches Lösungsmittel oder Lö- sungsmittelgemisch.In addition to water, the solvent and / or diluent used is, where appropriate, an organic chemical solvent or solvent mixture and / or an oily or oil-like low-volatile organic chemical solvent or solvent mixture and / or a polar organic chemical solvent or solvent mixture.
Nach einer bevorzugten Ausführungsform gelangen Hydroxyl- und oder Ester¬ und/oder Ethergruppen enthaltende aliphatische organisch-chemische Lösungsmittel wie beispielsweise Glycolether, Ester oder dergl. zur Anwendung.According to a preferred embodiment, aliphatic organic chemical solvents containing hydroxyl and / or ester and / or ether groups, such as, for example, glycol ethers, esters or the like, are used.
Als organisch-chemische Bindemittel können im Rahmen der vorliegenden Erfindung die an sich bekannten wasserverdünnbaren und/oder in den eingesetzten organisch- chemischen Lösungsmitteln löslichen oder dispergier- bzw. emulgierbaren Kunstharze und/oder bindende trocknende Öle, insbesondere Bindemittel bestehend aus oder enthaltend ein Acrylatharz, ein Vinylharz, z.B. Polyvinylacetat, Polyesterharz, Polykondensations- oder Polyadditionsharz, Polyurethanharz, Alkydharz bzw. modifiziertes Alkydharz, Phenolharz, Kohlenwasserstofrharz wie Inden-Cumaronharz, Siliconharz, trocknende pflanzliche und/oder trocknende Öle und/oder physikalisch trocknende Bindemittel auf der Basis eines Natur- und/oder Kunstharzes verwendet werden.In the context of the present invention, the known organic water-borne synthetic resins and / or synthetic oils which are soluble or dispersible or emulsifiable and / or bindable drying oils, in particular binders consisting of or containing an acrylate resin, can be used as organic-chemical binders. a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or synthetic resin.
Das als Bindemittel verwendete Kunstharz kann in Form einer Emulsion, Dispersion oder Lösung eingesetzt werden. Als Bindemittel können auch Bitumen oder bitumi¬ nöse Substanzen bis zu 10 Gew.-% verwendet werden. Zusätzlich können an sich bekannte Farbstoffe, Pigmente, wasserabweisende Mittel, Geruchskorrigentien und Inhibitoren bzw. Korrosionsschutzmittel und dergl. eingesetzt werden.The synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances up to 10% by weight can also be used as binders. In addition, known dyes, pigments, water-repellants, odor correctors and inhibitors or anticorrosive agents and the like can be used.
Das erwähnte Bindemittel kann ganz oder teilweise durch ein Fixierungs- mittel(gemisch) oder ein Weichmacher(gemisch) ersetzt werden. Diese Zusätze sollen einer Verflüchtigung der Wirkstoffe sowie einer -Kristallisation bzw. Ausfällen vorbeugen. Vorzugsweise ersetzen sie 0,01 bis 30 % des Bindemittels (bezogen auf 100 % des eingesetzten Bindemittels).All or part of the binder mentioned can be replaced by a fixing agent (mixture) or a plasticizer (mixture). These additives are intended to prevent volatilization of the active ingredients and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).
Die Weichmacher stammen aus den chemischen Klassen der Phthalsäureester wie Di- butyl-, Dioctyl- oder Benzylbutylphthalat, Phosphorsäureester wie Tributylphosphat, Adipinsäureester wie Di-(2-ethylhexyl)-adipat, Stearate wie Butylstearat oder Amylstearat, Oleate wie Butyloleat, Glycerinether oder höhermolekulare Glykolether, Glycerinester sowie p-Toluolsulfonsäureester.The plasticizers come from the chemical classes of phthalic acid esters such as di-butyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, higher glycerol glycol or glycerol ether , Glycerol ester and p-toluenesulfonic acid ester.
Fixierungsmittel basieren chemisch auf Polyπnylalkylethern wie z.B. Polyvinylmethyl- ether oder Ketonen wie Benzophenon, Ethylenbenzophenon.Fixing agents are chemically based on polyalkyl alkyl ethers such as Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.
Unter Holz, welches durch das erfindungsgemäße Mittel bzw. dieses enthaltende Mi¬ schungen geschützt werden kann, ist beispielhaft zu verstehen: Bauholz, Holzbalken, Eisenbahnschwellen, Brückenteile, Bootsstege, Holzfahrzeuge, Kisten, Paletten, Con- tainer, Telefonmasten, Holzverkleidungen. Holzfenster und -türen, Sperrholz, Spanplatten, Tischlerarbeiten oder Holzprodukte, die ganz allgemein beim Hausbau oder in der Bautischlerei Verwendung finden.By wood, which can be protected by the agent according to the invention or mixtures containing it, is to be understood as an example: timber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wooden cladding. Wooden windows and doors, plywood, chipboard, carpentry or wood products that are used in general in house construction or joinery.
Ein besonders effektiver Holzschutz wird durch großtechnische Imprägnierverfahren, z.B. Vakuum, Doppelvakuum oder Druckverfahren, erzielt. Die wasserverdünnbaren Holzschutzmittel enthalten - in konzentrierter Form - die Triazol/Fungizid- bzw. Insektizidmischung im allgemeinen in Mengen von 0,01 bis 95 Gew.-%, insbesondere 0,01 bis 60 Gew.-%.A particularly effective wood protection is achieved by industrial impregnation processes, e.g. vacuum, double vacuum or pressure processes. The water-thinnable wood preservatives generally contain - in concentrated form - the triazole / fungicide or insecticide mixture in amounts of 0.01 to 95% by weight, in particular 0.01 to 60% by weight.
Die wasserverdünnbaren Holzschutzmittel enthalten - in konzentrierter Form - das Kupfer berechnet als Metall vorzugsweise in einer Menge von 1,0 bis 15,0 % (Gewichtsprozent) .The water-thinnable wood preservatives contain - in concentrated form - the copper, calculated as metal, preferably in an amount of 1.0 to 15.0% (weight percent).
Geeignete Konzentrate bestehen z.B. ausSuitable concentrates are e.g. out
0,50 bis 45 % Kupferverbindungen0.50 to 45% copper compounds
5,00 bis 50 % erfindungsgemäße Alkanolamine5.00 to 50% alkanolamines according to the invention
0,25 bis 4 % Triazol bzw. Triazol/Fungizid- bzw. Insektizid-Mischung0.25 to 4% triazole or triazole / fungicide or insecticide mixture
0,5 bis 30 % weitere Alkanolamine0.5 to 30% more alkanolamines
0 bis 40 % Verbindung mit einem fungiziden anorganischen oder organi¬ schen Anion0 to 40% compound with a fungicidal inorganic or organic anion
0 bis 40 % organische Lösungsmittel0 to 40% organic solvents
0 bis 40 % emer aliphatischen Mono- oder Dicarbonsäure und/oder Cycloal- kylcarbonsäure und/oder Cycloarylcarbonsäure und/oder Bor¬ säure oder eines Borates0 to 40% emer aliphatic mono- or dicarboxylic acid and / or cycloalkanes kylcarbonsäure and / or acid Cycloarylcarbonsäure and / or boric or a borate
0 bis 15 % einer komplexbildenden, polymeren Stickstoflverbindung0 to 15% of a complex-forming, polymeric nitrogen compound
wobei die Summe jeweils 100 Gew.-% ergibt, sowie gegebenenfalls untergeordnete Mengen an anderen Bestandteilen, wie z.B. Ammoniak, Korrosionsinhibitoren, kom¬ plexbildenden Säuren (z.B. Nitrilotriessigsäure, Ethylendiamintetraessigsäure bei Ver¬ wendung von Wasser mit höheren Härtegraden) und erforderlichenfalls Wasser, dessen Anteil jedoch im allgemeinen gering gehalten werden kann und das im wesent¬ lichen der Handhabung dient.the sum being 100% by weight, as well as minor amounts of other components, e.g. Ammonia, corrosion inhibitors, complex-forming acids (e.g. nitrilotriacetic acid, ethylenediaminetetraacetic acid when using water with higher degrees of hardness) and, if necessary, water, the proportion of which, however, can generally be kept low and which essentially serves for handling.
Die Erfindung erstreckt sich jedoch neben den Holzschutzmitteln (Konzentrate) glei¬ chermaßen auch auf die durch Verdünnung der Konzentrate mit Wasser herstellbaren Imprägnierlösungen entsprechend geringerer Einzelkonzentration. Die -Anwendungs¬ konzentration beträgt z.B. 0,01 bis 1,50 Gew.-% Metall, z.B. Kupfer, in der wäßrigen Imprägnierlösung, je nach Art der Imprägnierung und des Gefährdungsgrades des zu imprägnierenden Holzes. Durch Auflösen der Kupfersalze, gegebenenfalls unter Wärmezufuhr, in den Alkanol¬ aminen, gegebenenfalls unter Säure-, Wasser- oder Lösungsmittelzugabe, und gegebe¬ nenfalls anschließender Zugabe des Emulgators, der Triazolverbindungen und des synergistischen Mischpartners entstehen hochkonzentrierte Pasten, flüssige Konzen- träte oder auch Zwei-Phasen-Mischungen, die nach dem Verdünnen mit Wasser zum Imprägnieren von Holz verwendet werden können. Sie ergeben auch bei hoher Konzentration in Wasser ein klare Flüssigkeit.However, in addition to the wood preservatives (concentrates), the invention also extends equally to the impregnation solutions which can be prepared by diluting the concentrates with water and correspondingly lower individual concentrations. The application concentration is, for example, 0.01 to 1.50% by weight of metal, for example copper, in the aqueous impregnation solution, depending on the type of impregnation and the degree of hazard of the wood to be impregnated. By dissolving the copper salts, if necessary with the supply of heat, in the alkanolamines, if appropriate with the addition of acid, water or solvent, and if appropriate subsequently adding the emulsifier, the triazole compounds and the synergistic mixing partner, highly concentrated pastes, liquid concentrates or else are formed Two-phase mixtures that can be used to impregnate wood after dilution with water. They produce a clear liquid even at high concentrations in water.
Die Anwendung von Imprägnierlösung zum Schutz von Holz kann durch handwerk¬ liche Verfahren wie Sprühen, Streichen, Tauchen, Trogtränken oder durch großtechnische Verfahren wie Kesseldruckverfahren, Wechseldruckverfahren, Doppelvakuumverfahren erfolgen. Unter "Holz" sind sowohl massives Holz als auch Holzwerkstoffe wie Spanplatten, Sperrholz zu verstehen; hier kann gegebenenfalls das Holzschutzmittel auch im Leimuntermischverfahren eingebracht werden.Impregnation solution for protecting wood can be applied by handicraft processes such as spraying, brushing, dipping, troughs or by industrial processes such as boiler pressure processes, alternating pressure processes, double vacuum processes. "Wood" means both solid wood and wood-based materials such as chipboard and plywood; if necessary, the wood preservative can also be introduced using the glue mixing process.
Die Kupferfixierung der erfindungsgemäßen Holzschutzmittel ist hoch, bei Einsatz für großtechnische Verfahren liegt sie bei mehr als 90 %.The copper fixation of the wood preservatives according to the invention is high; when used for industrial processes, it is more than 90%.
Die Konzentrate oder Lösungen können durch wasserlösliche oder in Wasser emul- gierbare Farbstoffe und/oder Pigmentpräparationen eingefärbt werden.The concentrates or solutions can be colored using water-soluble or water-emulsifiable dyes and / or pigment preparations.
Eine Zugabe von Wachs-, Paraffin- und/oder Acrylatdispersionen zur Erzielung einer wasserabweisenden Wirkung oder Verbesserung der Fixierung ist möglich.It is possible to add wax, paraffin and / or acrylate dispersions to achieve a water-repellent effect or to improve the fixation.
Die Konzentrate können gegebenenfalls auch in bindemittelenthaltende wasserver- dünnbare Systeme (Grundierungen, Lasuren) eingearbeitet werden.If necessary, the concentrates can also be incorporated into binder-containing water-thinnable systems (primers, glazes).
Die erfindungsgemäßen Mittel ermöglichen in vorteilhafter Weise, die bisher verfüg¬ baren Mittel durch effektivere zu ersetzen. Sie zeigen eine gute Stabilität und haben in vorteilhafter Weise ein breites Wirkungsspektrum. BeispieleThe means according to the invention advantageously make it possible to replace the previously available means with more effective ones. They show good stability and advantageously have a broad spectrum of activity. Examples
Beispiel 1example 1
43,5 % Alkanolamin-Gemisch, bestehend aus43.5% alkanolamine mixture consisting of
25 % ethoxiliertes Talkfettamin25% ethoxylated talc fatty amine
75 % Monoethanolamin75% monoethanolamine
14,0 % Cu(OH)2CuCO3 14.0% Cu (OH) 2 CuCO 3
7,5 % Borsäure7.5% boric acid
6,0 % Propionsäure6.0% propionic acid
19,0 % Wasser19.0% water
4,0 % Propiconazol4.0% propiconazole
6,0 % Propylenglykol6.0% propylene glycol
Beispiel 2Example 2
43,5 % Alkanolamin-Gemisch, bestehend aus43.5% alkanolamine mixture consisting of
25 % ethoxiliertes Kokosfettamin25% ethoxylated coconut fatty amine
75 % Monoethanolamin75% monoethanolamine
14,0 % Cu(OH)2CuCO3 14.0% Cu (OH) 2 CuCO 3
22,0 % Benzoesäure22.0% benzoic acid
10,5 % Wasser10.5% water
1,0 % Tebuconazole1.0% tebuconazole
9,0 % Propylenglykol Beispiel 39.0% propylene glycol Example 3
43,5 % Alkanolamin-Gemisch, bestehend aus43.5% alkanolamine mixture consisting of
25 % ethoxiliertes Methylstearylamin 75 % Monoethanolamin25% ethoxylated methylstearylamine 75% monoethanolamine
14,0 % Cu(OH)2CuCO3 14.0% Cu (OH) 2 CuCO 3
22,0 % Benzoesäure22.0% benzoic acid
10,5 % Wasser10.5% water
2,5 % Propiconazol2.5% propiconazole
1,5 % Tebuconazole1.5% tebuconazole
,0 % Propylenglykol , 0% propylene glycol

Claims

Patentansprüche claims
1. Holzschutzmittel enthaltend neben mindestens einer Kupferverbindung min¬ destens eine Triazolverbindung und spezielle Alkanolamine oder ein Alka¬ nolamin-Gemisch und gegebenenfalls weitere Fungizide und/oder Insektizide..1. Wood preservative comprising, in addition to at least one copper compound, at least one triazole compound and special alkanolamines or an alkanolamine mixture and, if appropriate, further fungicides and / or insecticides.
2. Verfahren zum Schutz von Holz, dadurch gekennzeichnet, daß man das Holz mit einer wirksamen Menge einer Kombination von mindestens einer Kupferverbindung mit mindestens einer Triazolverbindung und speziellen Alkanolaminen oder Alkanolamingemischen und gegebenenfalls . weiteren Fungiziden und/oder Insektiziden behandelt. 2. Process for protecting wood, characterized in that the wood with an effective amount of a combination of at least one copper compound with at least one triazole compound and special alkanolamines or alkanolamine mixtures and optionally. treated further fungicides and / or insecticides.
EP95900121A 1993-11-22 1994-11-09 Timber preservative containing a copper compound Withdrawn EP0730517A1 (en)

Applications Claiming Priority (3)

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DE4339701A DE4339701A1 (en) 1993-11-22 1993-11-22 Wood preservative containing a copper compound
DE4339701 1993-11-22
PCT/EP1994/003687 WO1995014558A1 (en) 1993-11-22 1994-11-09 Timber preservative containing a copper compound

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DE19802699A1 (en) * 1998-01-24 1999-07-29 Bayer Ag Wood preservative with synergistically enhanced activity against basidiomycetes
JP4599762B2 (en) * 2001-05-01 2010-12-15 株式会社エス・ディー・エス バイオテック Antifouling method for wood
DE102005043138A1 (en) * 2005-09-10 2007-03-15 Lanxess Deutschland Gmbh Fungicidal mixtures for wood protection
CA2860239A1 (en) * 2011-12-23 2013-06-27 David Humphrey A wood preservative
EP2984932A1 (en) * 2014-08-15 2016-02-17 RÜTGERS Organics GmbH A composition of a timber formulation comprising cu salts and organic cyclic ingredients for the preservation of timber for decks

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SE459164B (en) * 1981-05-08 1989-06-12 Kenogard Ab WOOD PROTECTIVE BASED ON CONSERVATIVE METALS AND ORGANIC NITROGEN CONTAINING COMPOUNDS AND USE OF THE MEDICINE
DE3937658A1 (en) * 1989-11-11 1991-05-16 Wolman Gmbh Dr WOOD PRESERVATIVES
DE4033419A1 (en) * 1990-10-20 1992-04-23 Wolman Gmbh Dr POLYMOUS NITROGEN COMPOUNDS AND METAL FIXING SAEURS CONTAINING WOOD PROTECTION AGENTS
DE4112652A1 (en) * 1991-04-18 1992-10-22 Wolman Gmbh Dr WOOD PRESERVATIVES
ES2142828T3 (en) * 1991-08-01 2000-05-01 Hickson Int Plc PRESERVATIVES FOR WOOD AND OTHER CELLULOSIC MATERIALS.

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AU692488B2 (en) 1998-06-11
JPH09505248A (en) 1997-05-27

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