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WO1995011786A1 - Timber protecting medium containing a copper compound - Google Patents

Timber protecting medium containing a copper compound Download PDF

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Publication number
WO1995011786A1
WO1995011786A1 PCT/EP1994/003370 EP9403370W WO9511786A1 WO 1995011786 A1 WO1995011786 A1 WO 1995011786A1 EP 9403370 W EP9403370 W EP 9403370W WO 9511786 A1 WO9511786 A1 WO 9511786A1
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WO
WIPO (PCT)
Prior art keywords
methyl
wood
acid
copper
phenyl
Prior art date
Application number
PCT/EP1994/003370
Other languages
German (de)
French (fr)
Inventor
Lutz Heuer
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE4340853A external-priority patent/DE4340853A1/en
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU78136/94A priority Critical patent/AU7813694A/en
Publication of WO1995011786A1 publication Critical patent/WO1995011786A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/08—Amines; Quaternary ammonium compounds containing oxygen or sulfur
    • 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • 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 wood preservatives containing at least one copper compound, a triazole compound which is synergistically supplemented with at least one further fungicide and / or insecticide, at least one alkanolamine and, if appropriate, an emulsifier.
  • 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 in comparison to known copper- and chromate-containing salts with a comparable copper content.
  • wood preservatives based on copper compounds and alkanolamines which contain a triazole compound and an emulsifier or which contain a phosphonium compound and are effective against wood-destroying basidio mycetes (DE 4 112 652 / WO 93/02557 / WO 91/11306).
  • synergistic mixtures for protecting wood based on, for example: propiconazole and tebuconazole (EP 393.746, EP 385.076, EP 413.909, EP 548.759, WO 93/02557), optionally using an insecticide as a mixing partner.
  • the aim and object of the present invention was to find a wood preservative which, first of all, against wood-discoloring and wood-destroying fungi and against wood-damaging insects, in particular against wood-destroying insects.
  • disturbing longhorn beetles (Cerambycidae, Lyctidae, Bostrychidae and Anobiidae) including termites is highly effective and has a good long-term effect, the effectiveness of the fungicide not being impaired by the insecticide or vice versa.
  • the wood preservative should have a good penetration in the wood and in the wood-based materials.
  • the degradation of the organic active substance that occurs in contact with the ground in wood and wood-based materials should be prevented. Since this breakdown of the active ingredient does not necessarily take place through wood-destroying and or wood-staining fungi, but also from other microorganisms associated with them, apart from the synergistic mixture of e.g. Tebuconazole and another fungicide and / or insecticide, the use of a further, biocidal component is necessary in order to achieve a long-term effect of the organic active ingredients.
  • copper compounds are therefore mixed in, if appropriate in conjunction with boron derivatives or nitrite-containing salts.
  • the invention therefore relates to a wood preservative comprising, in addition to a copper compound and an alkanolamine, a triazole compound and at least one further fungicide and / or insecticide, which also complement one another synergistically, and, if appropriate, an emulsifier.
  • the two fungicides are clearly emulsified or dissolved in water when diluted with water.
  • the advantage of the agents according to the invention is that e.g. Triazole compounds which are insoluble in water are present in the new compositions in the form of aqueous emulsions or clear aqueous concentrates. When diluted with water, clear aqueous liquids are formed.
  • organic solvents for example 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 solving agents for the fungicides.
  • the use of solvents can be reduced to a minimum in order to obtain homogeneous concentrates.
  • the mixture or concentrate contains water as an ingredient.
  • the copper compounds can be used as water-soluble or water-insoluble compounds, e.g. Copper sulfate, copper acetate, copper hydroxide, copper oxide, copper borate, copper fluoride, copper hydroxide carbonate, basic copper carbonate, copper nitrate, copper chloride and copper phosphate.
  • Copper sulfate, copper acetate, copper hydroxide, copper oxide, copper borate, copper fluoride, copper hydroxide carbonate, basic copper carbonate, copper nitrate, copper chloride and copper phosphate e.g. Copper sulfate, copper acetate, copper hydroxide, copper oxide, copper borate, copper fluoride, copper hydroxide carbonate, basic copper carbonate, copper nitrate, copper chloride and copper phosphate.
  • alkanolamine is especially monoethanolamine; the use of other alkanolamines e.g. Isopropanolamine 1, 1-, 1,2-diaminoethanol, aminoethylethanolamine, diethanolamine, triethanolamine, methylethanolamine, N-methylaminoethanol, N-ethylaminoethanol, ethanolhydrazine, N-butylaminoethanol, N-phenylaminoethanol and (2-aminoethoxy) ethanol are possible.
  • alkanolamines e.g. Isopropanolamine 1, 1-, 1,2-diaminoethanol, aminoethylethanolamine, diethanolamine, triethanolamine, methylethanolamine, N-methylaminoethanol, N-ethylaminoethanol, ethanolhydrazine, N-butylaminoethanol, N-phenylaminoethanol and (2-aminoethoxy) ethanol are possible.
  • 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 amines should be sufficient to complex the copper (1 g-atom of copper requires approx. 4 mol equivalents of amine).
  • Synergistic mixtures of triazole compounds such as e.g. Tebuconazole, preferably with one or more fungicides from the series:
  • Triazoles The following fungicides or insecticides are also preferably used as synergistic fungicidal or insecticidal mixing partners. Triazoles:
  • Succinate dehydrogenase inhibitors such as:
  • furcarbanil cyclafluramide, furmecyclox, seedvax, metsulfovax, pyrocarbolide, oxycarboxin, shirlan, mebenil (mepronil), benodanil, flutolanil (moncut);
  • 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;
  • Morpho derivatives such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph; Aldimorph, fenpropidine and their aryl sulfonic acid salts, such as, for example, 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, benzyldimethyldodecylaimmonium 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, tetrachlo henol 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chl ⁇ henol 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-acetophenor 2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane, ß-bromo-ß-nitrostyroi;
  • 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, CU2O, 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;
  • 4,5-dichlorodithiazolinone 4,5-benzdithiazolinone, 4,5-trimethylene dithiazolinone, 4,5-dic ⁇ or- (3H) -l, 2-dithiol-3-one, 3,5-dimethyl-tetrahydro-l, 3,5-thiadiazin-2- thione, N- (2-p-CUorbenzoylethyl) hexaminium chloride, potassium N-hydroxymethyl-N'-methyldithiocarba at,
  • Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, ⁇ -l (4-Chl ⁇ henyl) -4- (O-ethyl, S-propyl) phosphoryloxy-pyrazole, Chlo ⁇ yrifos, 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 Trichlo ⁇ hon;
  • 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) silyl-methyl-3- ⁇ henoxy-benzyl 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, ByfenthrirL Cycloprothrin, Cyfluthrin, Decamethrin, Cyhalothrin, Cypermethrin, Deltamethrin, Alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- (2-chloro-2-trif methyl vinyl) 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-lH-imidazol-2-amine (imidacloprid), N - [(6-chloro-3 -pyridyl) methyl-] N2-cyano-Nl-methylacetamide (NI-25);
  • Particularly preferred mixtures contain as insecticides:
  • synergistic mixtures of is particularly preferred
  • 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 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 should be 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 particular fungicide mixture and, like the amount of any emulsifier to be added, depends on the water solubility of the finished mixture obtained.
  • An emulsifier is, for example, an anionic, cationic or nonionic emulsifier or a mixture thereof.
  • Nonionic emulsifiers are, for example, addition products of ethylene oxide (EO) or propylene oxide or mixtures thereof with organic hydroxy compounds, for example alkylphenols, fatty acids, fatty alcohols and mixtures thereof.
  • Quaternary for example, can be used as cationic emulsifiers Ammonium compounds and / or salts of fatty amines (eg dimethyl- (Cj2-C] 4) alkylamine) are used.
  • polymeric quaternary ammonium borates are substances which are obtained by simultaneous reaction of amines of the general formulas I or II
  • K ⁇ - Cg-C22-alkyl or Cg-C22-alkenyl means or, if R 2 and R ⁇ are groups of the formula - (C2H4 ⁇ ) x H or - (C3H ⁇ O) X H, R can also mean Cj-C4-alkyl
  • R 2 is hydrogen, C ⁇ -C22 " Alkyl or a group of the formulas - (C2H 4 O) x H, - (C 3 H ⁇ O) X H or CH2CH2CH2NH2 means R ⁇ and R ⁇ C ⁇ -C4-alkyl or a group of the formulas - (C2H4 ⁇ ) x H or - (C3H ⁇ O) X H
  • R ⁇ and 7 are
  • Amines of formula I wherein R * -C-C4-alkyl or C8-C22-alkyl and R 2 and R ⁇ groups of the formulas - (C2H4 ⁇ ) x H or - (C3K_6 ⁇ ) x H mean, the sum of the ethylene oxide Groups in both radicals R 2 and R ⁇ 2 to 20. 4. Amines of the formula I, where R 'is Cg-C ⁇ alkyl, R 2 is hydrogen or a group of the formula -CH2CH2CH2NH2 and R ⁇ is a group of the formula -CH2CH2CH2NH2.
  • the amines are reacted with the boric acid and the alkylene oxide in such a way that the respective amine and the boric acid are introduced into an autoclave and the alkylene oxide is metered in.
  • the reaction temperature is generally 60 to 130 ° C, preferably 60 to 125 ° C, in particular 60 to 100 ° C.
  • the reaction pressure is 50 to 600 kPa.
  • the alkylene oxide is metered in under these reaction conditions over a period of 1 to 5 hours.
  • the mixture is kept at the temperature entered for 3 to 12 hours at a temperature of 70 to 120 ° C., preferably 70 to 100 ° C.
  • boric acid its esters, e.g. Trimethyl boric acid esters or their salts, for example Na borate, can be used. Water and polyglycols are formed as by-products in the reaction.
  • the polymeric quaternary ammonium compounds obtained essentially contain groups of the formula as a structural feature
  • a quaternary ammonium compound is, for example, a compound corresponding to the general formula R! R 2 R3R 4 N + Z-, where
  • R * denotes an alkyl radical with 8 to 20 carbon atoms, in particular an alkyl radical with 12 to 20 carbon atoms or a benzyl radical which is optionally substituted by C 1 -C 20 -alkyl or halogen,
  • R ⁇ C ⁇ - to Cg-alkyl, C3- to C4-alkoxy, polymer ethylene oxide (EO) or propylene oxide (PO) with EO or PA n 2 to 50,
  • R 4 C 1 to C 2 o-alkyl
  • Aliphatic carboxylic acids can be added to improve the homogeneity of the concentrates.
  • examples of such acids are propionic acid, hexanoic acid, heptanoic acid, branched carboxylic acids such as 2-ethylhexanoic acid, isooctanoic acid, neocarboxylic acids, aliphatic dicarboxylic acids such as sebacic acid, cycloalkylcarboxylic acids such as cyclohexanoic acid, arylcarboxylic acids such as benzoic acid, 3- or 4- Hydroxybenzoic acid or alkoxybenzoic acid, tartaric acid or glycine or the salts of the acids such as sodium, potassium salts.
  • 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.
  • Suitable compounds are e.g. N-organodiazenium dioxy compounds, organotin compounds, particularly tributyl (TBT) tin compounds, isothiazoline compounds of the following formula
  • R1 is hydrogen, an alkyl, alkenyl, alkynyl radical with 1 to 18 carbon atoms, cycloalkyl radical with a C3 to Cg ring and with up to 12 carbon atoms, an aralkyl or aryl radical with up to 19 carbon atoms,
  • R 2 , R ⁇ independently of one another hydrogen, halogen or C] - to C4-alkyl radical or R 2 and R ⁇ part of an aromatic radical or - -
  • R 2 - R 6 form -CH 2 -CH 2 -CH 2 -.
  • N-tridecyl-2,6-dimethylmorpholine Tridemo ⁇ h
  • 4- (3-para-tertiary-butylphenyl) 2-methyl-propyl-2,6-cis-dimethylmo ⁇ holin Frapropi ⁇ morph
  • these active substance combinations have a particularly high, co-microbicidal, in particular fungicidal activity, combined with a broad spectrum of activity against microorganisms and insects relevant in wood preservation; 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:
  • A2 Deuteromycetes: Aspergillus like Aspergillus niger
  • Aureobasidium such as Aureobasidium pullulans
  • Dactylium such as Dactylium fusarioides
  • Penicillium such as Penicillium brevicaule or
  • Penicillium variable Sclerophoma such as Sclerophoma 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
  • Gloeophyllum such as Gloeophyllum abietinum or
  • Lentinus such as Lentinus or cyathiformes
  • Lentinus edodes like Lentinus lepideus or
  • Poria such as Poria monticola or Poria placenta or
  • Chlorophorus pilosis Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus
  • Kaloterm.es flavicollis Cryptotermers brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes 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 active ingredients with a solvent or diluent, emulsifier, dispersant and / or binder or fixative, water repellants, optionally siccatives and UV stabilizers and optionally 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.
  • the organic chemical solvents used are preferably oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C.
  • Corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene, are used as such low-volatility, water-insoluble, oily and oily solvents.
  • Mineral oils with a boiling range of 170 to 220 ° C, white spirit with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C are advantageous.
  • Turpentine oil and the like are advantageous.
  • organic low-volatility oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C can be partially replaced by volatile or ⁇ uttel volatile organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide -Fungicide mixture is soluble or emulsifiable in this 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 organic-chemical binders which are known are water-thinnable and / or synthetic resins which are soluble or dispersible or emulsifiable in the organic-chemical solvents used and / or binding drying oils, in particular binders consisting of or containing an acrylate resin, a vinyl resin. e.g.
  • 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.
  • At least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably contained in the agent or in the concentrate as the organic chemical binder.
  • Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used according to the invention.
  • binder mentioned can be replaced by a fixing agent (mixture) or a plasticizer (mixture). These additions are meant to Prevent volatilization of the active ingredients as well as 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 polyvinyl alkyl ethers such as e.g. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.
  • aids described in EP-383 746, pages 5-6 are preferably also used as a constituent for wood preservatives.
  • Wood which can be protected by the agent according to the invention or mixtures containing it is to be understood as examples: timber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wooden cladding, wooden windows and - Doors, plywood, particle board, carpentry or wood products that are used in general in house construction or in joinery.
  • a particularly effective wood protection is achieved through industrial impregnation processes, e.g. Vacuum, double vacuum or pressure process.
  • 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 ⁇ 0% by weight.
  • the water-thinnable wood preservatives contain - in concentrated form - the copper calculated as metal in general, for example in an amount of 1.0 to 15.0% (weight percent).
  • Suitable concentrates consist of, for example
  • 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 e.g. 0.01 to 1.50% by weight of metal, e.g. 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 agents according to the invention advantageously make it possible to replace the previously available agents with more effective ones. They show good stability and advantageously have a broad spectrum of activity.

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Abstract

The present application relates to a medium or concentrate for preserving timber or timber materials, containing a copper compound, a triazole compound and at least one other synergistically supplemented fungicide and/or insecticide, an alkanol amine and possibly an emulsifier. In addition, the timber protecting medium may contain boron compounds, nitrite ions or other auxiliary agents.

Description

Holzschutzmittel enthaltend eine KupferverbindungWood preservative containing a copper compound
Die Anmeldung betrifft Holzschutzmittel, enthaltend mindestens eine Kupferverbin- düng, eine Triazolverbindung, die sich mit mindestens einem weiteren Fungizid und/oder Insektizid synergistisch ergänzt, mindestens ein Alkanolamin und gegebe¬ nenfalls einen Emulgator.The application relates to wood preservatives containing at least one copper compound, a triazole compound which is synergistically supplemented with at least one further fungicide and / or insecticide, at least one alkanolamine and, if appropriate, an emulsifier.
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 in comparison to known copper- and chromate-containing salts with a comparable copper content.
Ebenfalls bekannt sind Holzschutzmittel auf der Basis von Kupferverbindungen und Alkanolaminen, die eine Triazolverbindung und einen Emulgator oder die eine Phos- phoniumverbindung enthalten und Wirksamkeit gegenüber holzzerstörenden Basidio¬ myceten 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 triazole compound and an emulsifier or which contain a phosphonium compound and are effective against wood-destroying basidio mycetes (DE 4 112 652 / WO 93/02557 / WO 91/11306).
Bekannt sind auch synergistische Mischungen zum Schutz von Holz auf Basis von z.B.: Propiconazole und Tebuconazole (EP 393.746, EP 385.076, EP 413.909, EP 548.759, WO 93/02557), gegebenenfalls unter Verwendung eines Insektizids als Mischpartner.Also known are synergistic mixtures for protecting wood based on, for example: propiconazole and tebuconazole (EP 393.746, EP 385.076, EP 413.909, EP 548.759, WO 93/02557), optionally using an insecticide as a mixing partner.
Ziel und Aufgabe der vorliegenden Erfindung war es nun, ein Holzkonservie¬ rungsmittel zu finden, daß erstens gegenüber holzverfärbenden und holzzerstörenden Pilzen sowie gegenüber holzschädigenden Insekten, insbesondere gegenüber holzzer- störenden Bockkäfern (Cerambycidae, Lyctidae, Bostrychidae und Anobiidae) einschließlich Termiten hochwirksam ist und eine gute Langzeitwirkung aufweist, wobei die Wirksamkeit des Fungizides durch das Insektizid nicht beeinträchtigt wird bzw. umgekehrt. Darüber hinaus sollte das Holzkonservierungsmittel ein gutes Ein- dringvermögen im Holz und in den HolzwerkstofFen aufweisen.The aim and object of the present invention was to find a wood preservative which, first of all, against wood-discoloring and wood-destroying fungi and against wood-damaging insects, in particular against wood-destroying insects. disturbing longhorn beetles (Cerambycidae, Lyctidae, Bostrychidae and Anobiidae) including termites is highly effective and has a good long-term effect, the effectiveness of the fungicide not being impaired by the insecticide or vice versa. In addition, the wood preservative should have a good penetration in the wood and in the wood-based materials.
Weiterhin sollte der bei Holz und HolzwerkstofFen im Bodenkontakt auftretende Abbau des organischen Wirkstoffs verhindert werden. Da dieser Abbau des Wirkstoffs nicht zwangsläufig durch holzzerstörende und oder holzverfarbende Pilze erfolgt, sondern auch von mit ihnen vergesellschafteten anderen Mikroorganismen erfolgen kanri, ist außer der synergistisch wirkenden Mischung von z.B. Tebuconazole und einem weiteren Fungizid und/oder Insektizid die Verwendung einer weiteren, bioziden Komponente notwendig, um eine Langzeitwirkung der organischen Wirkstoffe zu erreichen. Erfmdungsgemäß werden deshalb Kupferverbindungen, gegebenenfalls in Verbindung mit Borderivaten oder Nitrit-haltigen Salzen zugemischt.Furthermore, the degradation of the organic active substance that occurs in contact with the ground in wood and wood-based materials should be prevented. Since this breakdown of the active ingredient does not necessarily take place through wood-destroying and or wood-staining fungi, but also from other microorganisms associated with them, apart from the synergistic mixture of e.g. Tebuconazole and another fungicide and / or insecticide, the use of a further, biocidal component is necessary in order to achieve a long-term effect of the organic active ingredients. According to the invention, copper compounds are therefore mixed in, if appropriate in conjunction with boron derivatives or nitrite-containing salts.
Gegenstand der Erfindung ist daher ein Holzschutzmittel, enthaltend neben einer Kupferverbindung und einem Alkanolamin, eine Triazolverbindung und mindestens ein sich synergistisch ergänzendes, weiteres Fungizid und/oder Insektizid, sowie gegebenenfalls einen Emulgator.The invention therefore relates to a wood preservative comprising, in addition to a copper compound and an alkanolamine, a triazole compound and at least one further fungicide and / or insecticide, which also complement one another synergistically, and, if appropriate, an emulsifier.
Trotz des Gehalts an Kupferverbindungen im Holzschutzmittel werden die beiden Fungizide beim Verdünnen mit Wasser klar in Wasser emulgiert oder gelöst. Der Vorteil der erfindungsgemäßen Mittel liegt darin, daß z.B. Triazolverbindungen, die im Wasser nicht löslich sind, in den neuen Mitteln in Form wäßriger Emulsionen oder klarer wäßriger Konzentrate vorliegen. Beim Verdünnen mit Wasser entstehen klare wäßrige Flüssigkeiten.Despite the content of copper compounds in the wood preservative, the two fungicides are clearly emulsified or dissolved in water when diluted with water. The advantage of the agents according to the invention is that e.g. Triazole compounds which are insoluble in water are present in the new compositions in the form of aqueous emulsions or clear aqueous concentrates. 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), Glykoletherestera (Butylglykolacetat), Dimethylformamid, N-Methylpyrrolidon kön¬ nen homogene Konzentrate erhalten werden. Die Lösungsmittel wirken dabei zusätz- lieh als Lösungsveπnittler für die Fungizide. Bei der zusätzlichen Verwendung von Arylcarbonsäuren, Cycloalkylcarbonsäuren oder aliphatischen C5-C20-Mono- 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, for example 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 solving agents for the fungicides. With the additional use of Arylcarboxylic acids, cycloalkylcarboxylic acids or aliphatic C5-C20 mono- or dicarboxylic acids or corresponding amine, alkali or copper salts, however, 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, basisches Kupfercarbonat, Kupfernitrat, Kupferchlorid und Kupferphosphat.The copper compounds can be used as water-soluble or water-insoluble compounds, e.g. Copper sulfate, copper acetate, copper hydroxide, copper oxide, copper borate, copper fluoride, copper hydroxide carbonate, basic copper carbonate, copper nitrate, copper chloride and copper phosphate.
Ein Alkanolamin ist insbesondere Monoethanolamin; der Einsatz von anderen Alka¬ nolaminen z.B. Isopropanolamin 1, 1-, 1,2-Diaminoethanol, Aminoethylethanolamin, Diethanolamin, Triethanolamin, Methylethanolamin, N-Methylaminoethanol, N- Ethylaminoethanol, Ethanolhydrazin, N-Butylaminoethanol, N-Phenylaminoethanol und (2-Aminoethoxy)ethanol ist möglich.An alkanolamine is especially monoethanolamine; the use of other alkanolamines e.g. Isopropanolamine 1, 1-, 1,2-diaminoethanol, aminoethylethanolamine, diethanolamine, triethanolamine, methylethanolamine, N-methylaminoethanol, N-ethylaminoethanol, ethanolhydrazine, N-butylaminoethanol, N-phenylaminoethanol and (2-aminoethoxy) ethanol are possible.
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 Amine soll zur Komplexbildung des Kupfers ausreichen (1 g-Atom Kupfer benötigt ca. 4 mol Äquivalente Amin).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 amines should be sufficient to complex the copper (1 g-atom of copper requires approx. 4 mol equivalents of amine).
Synergistische Mischungen von Triazolverbindungen wie z.B. Tebuconazole, ergeben sich vorzugsweise mit einem oder mehreren Fungiziden aus der Reihe:Synergistic mixtures of triazole compounds such as e.g. Tebuconazole, preferably with one or more fungicides from the series:
Azaconazole, Bromuconazole, Cyproconazole, Dichlobutrazol, Diniconazole, Hexa- conazole, Metconazole, Penconazole, Epoxyconazole, Methyl-(E)-methoximino[α- (o-tolyloxy)-o-tolyl)]acetate, Methyl-(E)-2-{2-[6-(2-cyanphenoxy)-pyrimidin-4-yl- oxy]phenyl}-3-methoxyacrylat, Methfuroxam, Carboxin, Fenpiclonil, 4(2,2-Difluoro- l,3-benzodioxol-4-yl)-lH-pyrrol-3-carbonitril, Butenafine und oder polymere, quar- täre Ammoniumborate (bekannt aus EP 355 316 und EP 556 454).Azaconazole, bromuconazole, cyproconazole, dichlobutrazole, diniconazole, hexaconazole, metconazole, penconazole, epoxyconazole, 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-oil, 3-benzodioxol-4- yl) -lH-pyrrole-3-carbonitrile, butenafine and or polymeric quaternary ammonium borates (known from EP 355 316 and EP 556 454).
Als synergistische fungizide bzw. insektizide Mischpartner werden bevorzugt auch die folgenden Fungizide bzw. Insektizide eingesetzt. Triazole:The following fungicides or insecticides are also preferably used as synergistic fungicidal or insecticidal mixing partners. Triazoles:
Amitrole, Azocyclotin, Bitertanol, Fenbuconazole, Fenchlorazole, Fenethanil, Flu- quinconazole, Flusilazole, Flutriafol, Imibenconazole, Isozofos, Myclobutanil, Met- conazole, Epoxyconazole, Paclobutrazol, (+)-cis-l-(4-chlorphenyl)-2-(lH- 1,2,4- triazol-l-yl)-cycloheptanol, Tetraconazole, Triadimefon, Triadimenol, Triapenthenol, Triflumizole, Triticonazole, Uniconazole sowie deren Metallsalze und Säureaddukte.Amitrole, Azocyclotin, Bitertanol, Fenbuconazole, Fenchlorazole, Fenethanil, Fluquinconazole, Flusilazole, Flutriafol, Imibenconazole, Isozofos, Myclobutanil, Met- conazole, Epoxyconazole, Paclobutrazol, (+) - cisphenyl- (-2) (lH-1,2,4-triazol-l-yl) cycloheptanol, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, triticonazole, uniconazole and their metal salts and acid adducts.
Imidazole:Imidazole:
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-methoxyacr late, methyl(E)-2-[2- phenoxyphenyl] -3 -methoxyacrylate, methyl(E)-2-[2-(3,5-dimethylbenzoyl)pyrrol-l- yl] -3 -methoxyacrylate, 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-(l,l,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-methoxyacrylate, 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(E)-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, ιB),(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;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-methoxyacrylate, methyl (E) -2- [2- [6- (2-fluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, 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-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-methoxyacrylate, 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- (l, l, 2,2-tetrafluoroethoxy) phenoxy) phenyl) -3-methoxyacrylate, methyl (E) -2- (2- [3- (alpha-hydroxybenzyl) phenoxy] phenyl) -3-methoxyacrylate, methyl (E) -2- (2- (4th -phenoxypyridine- 2-yloxy) phenyl) -3-methoxyacrylate, methyl (E) -2- [2- (3-n-propyloxyphenoxy) - phenyl] 3 -methoxyacrylate, methyl (E) -2- [2- (3rd -isopropyloxyphenoxy) phenyl] -3 -meth¬ oxyacrylate, 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-methoxyacrylate, methyl (E) -2- [2- (3-methylpyridin-2-yloxymethyl) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [6- (2-methylphenoxy) pyrimid-4-yloxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (5-bromopyridin-2-yloxymethyl) phenyl] -3-methoxyacrylate, methyl ( E) -2- [2- (3- (3-iodopyridin-2-yloxy) phenoxy) phenyl] -3-methoxyacrylates, methyl (E) -2- [2- [6- (2-chloropyridin-3- yloxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, (E), (E) methyl-2- [2- (5, 6-dimethylpyrazin-2-yl-methyloximinomethyl) phenyl] -3-methoxyacrylate, ( E) -methyl-2- {2- [6- (6-methylpyridin-2-yloxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylates, ι B), (E) methyl-2- {2- ( 3-methoxyphenyl) 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-methoxyacrylate, (E) me thyl-2- {2- [6- (2-n-propylphenoxy) 1,3,5-triazin-4-yloxy] phenyl} -3-methoxyacrylates, (E), (E) methyl-2- {2 - [(3 -nitrophenyl) methyloximinomethyl] phenyl} -3 - methoxyacrylate;
Succinat-Dehydrogenase Inhibitoren wie: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-2,8,8-trimethyl-non-4-en-6- in)benzothiophen-3-en-5-in);Terbinafine, naftifine, butenafine, 3-chloro-7- (2-aza-2,8,8-trimethyl-non-4-en-6-in) benzothiophene-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;
Morphoünderivate wie Tridemorph, Fenpropimorph, Falimorph, Dimethomorph, Dodemorph; Aldimorph, Fenpropidin und ihre arylsulfonsauren Salze, wie z.B. p- Toluolsulfonsäure und p-Dodecylphenyl-sulfonsäure; Dithiocarbamate, Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam, Metiram, Thiram Zeneb, Ziram;Morpho derivatives such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph; Aldimorph, fenpropidine and their aryl sulfonic acid salts, such as, for example, p-toluenesulfonic acid and p-dodecylphenyl sulfonic acid; Dithiocarbamate, Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam, Metiram, Thiram Zeneb, Ziram;
Benzthiazole wie 2-Mercaptobenzothiazol;Benzothiazoles such as 2-mercaptobenzothiazole;
Benzamide wie 2,6-Dichloro-N-(4-trifluoromethylbenzyl)-benzamide; Borverbindungen wie Borsäure, Borsäureester, Borax;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-isothiazolinone, 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-isothiazolinone, 4,5-benzisothiazolinone, N-methylolchloroacetamide;
Aldehyde wie Zimtaldehyd, Formaldehyd, Glutardialdehyd, ß-Bromzimtaldehyd; Thiocyanate wie Thiocyanatomethylthiobenzothiazol, Methylenbisthiocyanat, usw;Aldehydes such as cinnamaldehyde, formaldehyde, glutardialdehyde, β-bromocinnamaldehyde; Thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate, etc;
quartäre Ammoniumverbindungen wie Benzyldimethyltetradecylammoniumchlorid, Benzyldimethyldodecylaimmoniumchlorid, Didecyldimethaylämmoniumchlorid;quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylaimmonium 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, Tetrachlo henoL 3-Methyl-4-chloφhenol, 3,5- Dimethyl-4-chlorphenol, Phenoxyethanol, Dichlorphen, o-Phenylphenol, m-Phenyl- phenol, p-Phenylphenol, 2-Benzyl-4-chlθφhenol und deren Alkali- und Erdalkali- metallsalze. Mikrobizide mit aktivierter Halogengruppe wie Chloracetamid, Bronopol, Bronidox. Tectamer wie 2-Brom-2-nitro-l,3-propandiol, 2-Brom-4'-hydroxy-acetophenor 2,2- Dibrom-3-nitril-propionamid, 1 ,2-Dibrom-2,4-dicyanobutan, ß-Brom-ß-nitrostyroi;Phenol derivatives such as tribromophenol, tetrachlo henol 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlθφhenol 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-acetophenor 2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane, ß-bromo-ß-nitrostyroi;
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, CU2O, 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;Quinolines such as 8-hydroxyquinoline and their Cu salts;
Mucochlorsäure, 5 -Hydroxy-2(5H)-furanon;Mucochloric acid, 5-hydroxy-2 (5H) -furanone;
4,5-Dichlorodithiazolinon. 4,5-Benzdithiazolinon, 4,5-Trimethylendithiazolinon, 4,5- Dicωor-(3H)-l,2-dithiol-3-on, 3,5-Dimethyl-tetrahydro-l,3,5-thiadiazin-2-thion, N-(2-p-CUorbenzoylethyl)-hexaminiumchlorid, Kalium-N-hydroxymethyl-N'-methyl- dithiocarba at,4,5-dichlorodithiazolinone. 4,5-benzdithiazolinone, 4,5-trimethylene dithiazolinone, 4,5-dicωor- (3H) -l, 2-dithiol-3-one, 3,5-dimethyl-tetrahydro-l, 3,5-thiadiazin-2- thione, N- (2-p-CUorbenzoylethyl) hexaminium chloride, potassium N-hydroxymethyl-N'-methyldithiocarba at,
2-Oxo-2-(4-iιydroxy-phenyl)acethydroximsäure-chlorid,2-oxo-2- (4-iιydroxy-phenyl) acethydroximic acid chloride,
Phenyl-(2-chlor-cyan-vinyl)sulfon-Phenyl- (2-chloro-cyan-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-Chlθφhenyl)-4-(O- ethyl, S-propyl)phosphoryloxy-pyrazol, Chloφyrifos, 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 Trichloφhon;Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, α-l (4-Chlθφhenyl) -4- (O-ethyl, S-propyl) phosphoryloxy-pyrazole, Chloφyrifos, 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 Trichloφhon;
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 -φhenoxy- benzylether wie Dimethyl-(4-ethoxyphenyl)-silylmethyl-3-phenoxybenzylether oderOrganosilicon compounds, preferably dimethyl (phenyl) silyl-methyl-3-φhenoxy-benzyl 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, ByfenthrirL 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, ByfenthrirL Cycloprothrin, Cyfluthrin, Decamethrin, Cyhalothrin, Cypermethrin, Deltamethrin, Alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- (2-chloro-2-trif methyl vinyl) 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-lH-imidazol-2-amin (Imidacloprid), N-[(6-Chlor-3-pyridyl)methyl-]N2-cyano- Nl-methylacetamide (NI-25);Nitroimines and nitromethylenes such as l - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-lH-imidazol-2-amine (imidacloprid), N - [(6-chloro-3 -pyridyl) methyl-] N2-cyano-Nl-methylacetamide (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, Thiofiieton, 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, IPSP, Isazofos, Isofenphos, Isoprothiolane, Isoxathion, Iodfenphos, 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;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, thiofiieton, tralomethrin, triflumuron, trimethacarb, vamidothione, verticillium lacanii, XMC, Xylylcarb, Benfuracarb, Bensultap, Bifenthrin, Bioallethrin, MERbioallethrin (S) - cyclopentenyl isomer, Bromophos, Bromophos-ethyl, Buprofezin, Cadusafos, Calcium Polysulfide, Carbophenothion, Cartap, Chinomethionate, Chlordane, Chlorfenazonophenyl, Chlorphurosphonophenyl, Chlorfluorosinophenyl , Beta-Cyfluthrin, Alpha-cypermethrin, Cyophenothrin, Cyromazine, Dazomet, DDT, Demeton-S-methylsulphone, Diafenthiuron, Dialifos, Dicrotophos, Diflubenzuron, Dinoseb, Deoxabenzofos, Diaxacarb, Endosulfonofen, DNulphonoentin, DN , Ethion, Etofenprox, Fenobucarb, Fenoxycarb, Fensulfothion, Fipronil, Flucycloxuron, Flufenprox, Flufenoxuron, Fonofos, Formetanate, Formothion, Fosmethilan, Furathiocarb, Heptachlor, Hexaflumuron, Hydramethylnon, Hydrogen CyanideSP, Isophonophone, Hydroaz Iodfenphos, Kadethrin, Lindane, Malathion, Mecarbam, Mephosfolan, Mercurous, chloride, Metam, Metarthician, anisopliae, M ethacrifos, methamidophos, methidathione, methiocarb, methoprene, methoxychloro, methyl isothiocyanate, metholcarb, mevinphos, monocrotophos, naled, neodiprion sertifer NPV, nicotine, omethoate, oxydemeton-methyl, pentachlorophenol, petroleum phentate, phenothrine
Besonders bevorzugte Mischungen enthalten als Insektizide:Particularly preferred mixtures contain as insecticides:
Chlorpyrifos, Phoxim, Silafluofen, Cyfluthrin, Cypermethrin, Deltamethrin, Per- methrin, Imidacloprid, Hexaflunuron, Lindan.Chlorpyrifos, phoxim, silafluofen, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, hexaflunuron, lindane.
Besonders bevorzugt ist der Einsatz von synergistischen Mischungen ausThe use of synergistic mixtures of is particularly preferred
- Tebuconazole und Cyproconazole und gegebenenfalls Bromoconazole und/oder Hexaconazole und oder Propiconazole und/oder Tridemoφh- Tebuconazole and cyproconazole and optionally bromoconazole and / or hexaconazole and or propiconazole and / or Tridemoφh
- Tebuconazole und Metconazole und gegebenenfalls Cyproconazole und/oder Hexaconazole und/oder Tridemoφh- Tebuconazole and Metconazole and optionally Cyproconazole and / or Hexaconazole and / or Tridemoφh
- Tebuconazole und Hexaconazole und gegebenenfalls Cyproconazole und/oder Metconazole und/oder Bromoconazole und/oder Tridemoφh- Tebuconazole and Hexaconazole and optionally Cyproconazole and / or Metconazole and / or Bromoconazole and / or Tridemoφh
- Tebuconazole und l-(2-Chlθφhenyl)-2-(l-chlor-cycloprop-l-yl)-3-(l,2,4-triazol- l-yl)-propan-2-ol und gegebenenfalls Cyproconazole und/oder Metconazole und/oder Bromoconazole und/oder Hexaconazole und/oder Tridemoφh - Tebuconazole und Tridemorph und gegebenenfalls Cyproconazole und/oder Propiconazole und/oder Bromoconazole und/oder Hexaconazole und/oder Penconazole,- Tebuconazole and l- (2-Chlθφhenyl) -2- (l-chloro-cycloprop-l-yl) -3- (l, 2,4-triazol-l-yl) propan-2-ol and optionally cyproconazole and / or Metconazole and / or Bromoconazole and / or Hexaconazole and / or Tridemoφh Tebuconazole and tridemorph and optionally cyproconazole and / or propiconazole and / or bromoconazole and / or hexaconazole and / or penconazole,
- Tebuconazole und Propiconazole und gegebenenfalls Cyproconazole und/oder Bromoconazole und/oder Hexaconazole und/oder Metconazole und/oder Tride¬ morph und/oder Penconazole und/oder l-(2-Chlorphenyl)-2-(l-chlorcycloprop-l- yl)-3-( 1 ,2,4-triazol- 1 -yl)-propan-2-ol- Tebuconazole and propiconazole and optionally cyproconazole and / or bromoconazole and / or hexaconazole and / or metconazole and / or Tride morph and / or penconazole and / or l- (2-chlorophenyl) -2- (l-chlorocycloprop-l-yl ) -3- (1, 2,4-triazol-1-yl) propan-2-ol
- Cyproconazole und Bromoconazole und/oder Metconazole und/oder Hexaconazole und/oder Tridemoφh, - Hexaconazole und Bromoconazole und/oder Metconazole und/oder Penconazole und/oder Tridemorph,- Cyproconazole and Bromoconazole and / or Metconazole and / or Hexaconazole and / or Tridemoφh, - Hexaconazole and Bromoconazole and / or Metconazole and / or Penconazole and / or Tridemorph,
- Penconazole und Cyproconazole und/oder Metconazole und/oder Bromoconazole und/oder Tridemoφh.- Penconazole and cyproconazole and / or metconazole and / or bromoconazole and / or tridemoφh.
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 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 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 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 (e.g. sodium nitrite) should be 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 particular fungicide mixture and, like the amount of any emulsifier to be added, depends on the water solubility of the finished mixture obtained.
Ein Emulgator ist beispielsweise ein anionischer, kationischer oder nichtionischer Emulgator oder eine Mischung davon. Nichtionische Emulgatoren sind z.B. Additionsprodukte von Ethylenoxid (EO) oder Propylenoxid oder deren Mischungen an organischen Hydroxyverbindungen, beispielsweise Alkylphenole, Fettsäure, Fett¬ alkohole und deren Mischungen. Als kationische Emulgatoren können z.B. quateraäre Ammoniumverbindungen und/oder Salze von Fettaminen (z.B. Dimethyl-(Cj2- C]4)alkylamin) Verwendung finden.An emulsifier is, for example, an anionic, cationic or nonionic emulsifier or a mixture thereof. Nonionic emulsifiers are, for example, addition products of ethylene oxide (EO) or propylene oxide or mixtures thereof with organic hydroxy compounds, for example alkylphenols, fatty acids, fatty alcohols and mixtures thereof. Quaternary, for example, can be used as cationic emulsifiers Ammonium compounds and / or salts of fatty amines (eg dimethyl- (Cj2-C] 4) alkylamine) are used.
Die polymeren quartären Ammoniumborate sind Substanzen, die erhalten werden , durch gleichzeitige Umsetzung von Aminen der allgemeinen Formeln I oder IIThe polymeric quaternary ammonium borates are substances which are obtained by simultaneous reaction of amines of the general formulas I or II
R2 R6 R 2 R 6
D l / \ / D l / \ /
R—N (l). N — A— N (H),R-N (l). N - A - N (H),
\ 3 / \ 7\ 3 / \ 7
R3 R5 R R 3 R 5 R
mit 2 bis 20, vorzugsweise 3 bis 10, Mol Ethylen- oder Propylenoxid und 0,6 bis 1,5, vorzugsweise 1 Mol Borsäure, Borsäureester oder Salzen der Borsäure, jeweils pro Mol Stickstoffäquivalent, wobei K→- Cg-C22-Alkyl oder Cg-C22-Alkenyl bedeutet oder, wenn R2 und R^ Gruppen der Formel -(C2H4θ)xH oder -(C3HÖO)XH darstellen, R auch Cj-C4-Alkyl bedeuten kann, R2 Wasserstoff, Cι -C22"Alkyl oder eine Gruppe der der Formeln -(C2H4O)xH, -(C3HÖO)XH oder CH2CH2CH2NH2 bedeutet, R^ und R^ Cι-C4-Alkyl oder eine Gruppe der Formeln -(C2H4θ)xH oder -(C3HÖO)XH bedeuten, R^ und 7 eine Gruppe der Formel -(C2H4θ)xH oder -(C3H6O)xH, A eine Gruppe der Formeln -(CH2)n-, -(CH2CH2OCH2OH)n- oder -(CH2CH2NHCH2CH2)n-x Zahlen von 1 bis 55 und n eine ganze Zahl von 1 bis 20 bedeuten.with 2 to 20, preferably 3 to 10, moles of ethylene or propylene oxide and 0.6 to 1.5, preferably 1 mole of boric acid, boric acid ester or salts of boric acid, in each case per mole of nitrogen equivalent, where K → - Cg-C22-alkyl or Cg-C22-alkenyl means or, if R 2 and R ^ are groups of the formula - (C2H4θ) x H or - (C3HÖO) X H, R can also mean Cj-C4-alkyl, R 2 is hydrogen, Cι -C22 " Alkyl or a group of the formulas - (C2H 4 O) x H, - (C 3 HÖO) X H or CH2CH2CH2NH2 means R ^ and R ^ Cι-C4-alkyl or a group of the formulas - (C2H4θ) x H or - (C3HÖO) X H, R ^ and 7 are a group of the formula - (C2H4θ) x H or - (C 3 H 6 O) x H, A is a group of the formulas - (CH 2 ) n -, - (CH2CH 2 OCH 2 OH) n - or - (CH2CH 2 NHCH 2 CH2) n -x numbers from 1 to 55 and n is an integer from 1 to 20.
Als Amine der obigen Formeln sind folgende bevorzugt:The following are preferred as amines of the above formulas:
1. Amide der Formel I, wobei R1 Cg-C22-Alkyl, R2 Cg-C22-Alkyl oder C1-C4- Alkyl und R Wasserstoff oder eine Gruppe der Formeln -(C2H4θ)xH oder -(C3HöO)xH bedeuten.1. Amides of the formula I, where R 1 is Cg-C22-alkyl, R 2 Cg-C22-alkyl or C1-C4-alkyl and R is hydrogen or a group of the formulas - (C2H4θ) x H or - (C3HöO) x H mean.
2. Amine der Formel I, wobei R Cg-C22-Alkyl und R2 und R^ Wasserstoff bedeuten.2. Amines of the formula I, where R is Cg-C22-alkyl and R 2 and R ^ are hydrogen.
3. Amine der Formel I, wobei R* Cι-C4-Alkyl oder C8-C22-Alkyl und R2 und R^ Gruppen der Formeln -(C2H4θ)xH oder -(C3K_6θ)xH bedeuten, wobei die Summe der Ethylenoxid-Gruppen in beiden Resten R2 und R^ 2 bis 20 beträgt. 4. Amine der Formel I, wobei R' Cg-C^-Alkyl, R2 Wasserstoff oder eine Gruppe der Formel -CH2CH2CH2NH2 und R^ eine Gruppe der Formel -CH2CH2CH2NH2 bedeuten.3. Amines of formula I, wherein R * -C-C4-alkyl or C8-C22-alkyl and R 2 and R ^ groups of the formulas - (C2H4θ) x H or - (C3K_6θ) x H mean, the sum of the ethylene oxide Groups in both radicals R 2 and R ^ 2 to 20. 4. Amines of the formula I, where R 'is Cg-C ^ alkyl, R 2 is hydrogen or a group of the formula -CH2CH2CH2NH2 and R ^ is a group of the formula -CH2CH2CH2NH2.
5. Amine der Formel II, wobei A ^, R~\ R^ und R^ die oben genannten Bedeutungen haben und wobei die Summe aller Ethylenoxid-Gruppen 4 bis 30 beträgt.5. Amines of formula II, wherein A ^, R ~ \ R ^ and R ^ have the meanings given above and wherein the sum of all ethylene oxide groups is 4 to 30.
Bei den Alkylenoxid-Gruppen der Formeln -(C2H4Ü)XH und -(C3HöO)xH ist die Gruppe der Formel -(C2H4θ)xH bevorzugt. Anstelle der reinen Polyoxethylen- und Polyoxpropylen-Gruppen können auch solche Reste vorhanden sein, die sowohl aus Ethylenoxid- als auch aus Propylenoxid-Einheiten aufgebaut sind.In the case of the alkylene oxide groups of the formulas - (C2H4Ü) X H and - (C3HöO) x H, the group of the formula - (C2H4θ) x H is preferred. Instead of the pure polyoxethylene and polyoxpropylene groups, there may also be residues which are composed of both ethylene oxide and propylene oxide units.
Die Umsetzung der Amine mit der Borsäure und dem Alkylenoxid erfolgt in der Weise, daß ion einem Autoklaven das jeweilige Amin und die Borsäure vorgelegt und das Alkylenoxid zudosiert wird. Die Reaktionstemperatur beträgt im allgemeinen 60 bis 130°C, vorzugsweise 60 bis 125°C, insbesondere 60 bis 100°C. Der Reaktionsdruck beträgt 50 bis 600 kPa. Die Zudosierung des Alkylenoxides unter diesen Reaktionsbedingungen erfolgt über einen Zeitraum von 1 bis 5 Stunden. Zur Nachreaktion wird das Gemisch bei dem eingegebenen Druck 3 bis 12 Stunden auf einer Temperatur von 70 bis 120°C, vorzugsweise 70 bis 100°C, gehalten.The amines are reacted with the boric acid and the alkylene oxide in such a way that the respective amine and the boric acid are introduced into an autoclave and the alkylene oxide is metered in. The reaction temperature is generally 60 to 130 ° C, preferably 60 to 125 ° C, in particular 60 to 100 ° C. The reaction pressure is 50 to 600 kPa. The alkylene oxide is metered in under these reaction conditions over a period of 1 to 5 hours. For the after-reaction, the mixture is kept at the temperature entered for 3 to 12 hours at a temperature of 70 to 120 ° C., preferably 70 to 100 ° C.
Anstelle der Borsäure können auch deren Ester, wie z.B. Trimethylborsäureester oder deren Salze, beispielsweise Na-Borat eingesetzt werden. Bei der Reaktion entstehen als Nebenprodukte Wasser und Polyglykole.Instead of boric acid, its esters, e.g. Trimethyl boric acid esters or their salts, for example Na borate, can be used. Water and polyglycols are formed as by-products in the reaction.
Die erhaltenen polymeren, quartären Ammoniumverbindungen enthalten im wesent¬ lichen als Strukturmerkmal Gruppen der FormelThe polymeric quaternary ammonium compounds obtained essentially contain groups of the formula as a structural feature
Figure imgf000014_0001
Figure imgf000014_0001
bzw. Gruppen der Formel f oG or groups of the formula fo G
— N-A-N-(CH2CH20)χ— B— (OCH2CH2)-0-B-(OCH2CH2)z R5 - NAN- (CH 2 CH 2 0) χ - B— (OCH 2 CH 2 ) -0-B- (OCH 2 CH 2 ) z R 5
wenn die Reaktion mit Ethylenoxid gemacht wurde. Sie sind als polymere Betaine anzusehen.if the reaction was done with ethylene oxide. They are to be regarded as polymer betaines.
Verbindungen obengenannten Typs und deren Herstellung werden in der EP-556 454 und EP-355 316 beschrieben.Compounds of the above type and their preparation are described in EP-556 454 and EP-355 316.
Eine quateraäre Ammoniumverbindung ist z.B. eine Verbindung entsprechend der allgemeinen Formel R!R2R3R4N + Z- , wobeiA quaternary ammonium compound is, for example, a compound corresponding to the general formula R! R 2 R3R 4 N + Z-, where
R* einen Alkylrest mit 8 bis 20 Kohlenstoffatomen, insbesondere einen Alkylrest mit 12 bis 20 Kohlenstoffatomen oder einen Benzylrest bedeutet, der gegebenenfalls durch Cj- bis C20-Alkyl oder Halogen substituiert ist,R * denotes an alkyl radical with 8 to 20 carbon atoms, in particular an alkyl radical with 12 to 20 carbon atoms or a benzyl radical which is optionally substituted by C 1 -C 20 -alkyl or halogen,
R2 Ci- bis Cg-Alkyl, C3- bis C9-Alkoxyalkyl, Polymeres Ethylenoxid (EO) oder Propylenoxid (PO) mit EO bzw. PO n = 2 bis 50,R 2 Ci to Cg alkyl, C3 to C9 alkoxyalkyl, polymeric ethylene oxide (EO) or propylene oxide (PO) with EO or PO n = 2 to 50,
R^ C\- bis Cg-Alkyl, C3- bis C4-Alkoxy, Polymers Ethylenoxid (EO) oder Propylenoxid (PO) mit EO bzw. PA n = 2 bis 50,R ^ C \ - to Cg-alkyl, C3- to C4-alkoxy, polymer ethylene oxide (EO) or propylene oxide (PO) with EO or PA n = 2 to 50,
R4 C1- bis C2o-AlkylR 4 C 1 to C 2 o-alkyl
bedeutet oder je zwei der Reste R* bis R4 zusammen mit dem Stickstoffatom einen heterocyclischen Rest bilden, der 4 bis 5 C-Atome und eine, zwei oder drei Doppel¬ bindungen enthält, wobei die Kohlenstoffatome gegebenenfalls durch C]- bis C4- Alkyl oder Halogen substituiert sind und Z einen Säurerest, z. B. Halogenid, bedeutet.means or each two of the radicals R * to R 4 together with the nitrogen atom form a heterocyclic radical which contains 4 to 5 carbon atoms and one, two or three double bonds, the carbon atoms being optionally by C] - to C4-alkyl or halogen are substituted and Z is an acid residue, e.g. B. halide means.
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-Ethylhexansäure, Isooctansäure, Neo- carbonsäuren, aliphatische Dicarbonsäuren wie z.B. Sebacinsäure, Cycloalkylcarbon- säuren wie z.B. Cyclohexansäure, Arylcarbonsäuren wie z.B. Benzoesäure, 3- oder 4- Hydroxybenzoesäure oder Alkoxybenzoesäure, Weinsäure oder Glycin oder die Salze der Säuren wie Natrium, Kaliumsalze.Aliphatic carboxylic acids can be added to improve the homogeneity of the concentrates. Examples of such acids are propionic acid, hexanoic acid, heptanoic acid, branched carboxylic acids such as 2-ethylhexanoic acid, isooctanoic acid, neocarboxylic acids, aliphatic dicarboxylic acids such as sebacic acid, cycloalkylcarboxylic acids such as cyclohexanoic acid, arylcarboxylic acids such as benzoic acid, 3- or 4- Hydroxybenzoic acid or alkoxybenzoic acid, tartaric acid or glycine or the salts of the acids such as sodium, potassium salts.
Bei Verwendung der obengenannten Säuren ist es teilweise von Vorteil, durch Zusatz von komplexbildenden, polymeren StickstoffVerbindungen wie z.B. Polyethyleniminen die Holzschutzmitteleindringung bei großtechnischen Verfahren zu verbessern.When using the acids mentioned above, 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 Fluorophosphorsäure 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).
Durch den Zusatz weiterer Wirkstoffe kann die Wirkungsbreite der erfindungsge¬ mäßen Holzschutzmittel gegebenenfalls verbessert werden. Geeignete Verbindungen sind z.B. N-Organodiazeniumdioxyverbindungen, Organozinnverbindungen, beson¬ ders Tributyl(TBT)zinnverbindungen, Isothiazolinverbindungen der folgenden FormelThe range of action of the wood preservatives according to the invention can optionally be improved by the addition of further active ingredients. Suitable compounds are e.g. N-organodiazenium dioxy compounds, organotin compounds, particularly tributyl (TBT) tin compounds, isothiazoline compounds of the following formula
Figure imgf000016_0001
Figure imgf000016_0001
Rl ist Wasserstoff, ein Alkyl-, Alkenyl-, Alkinylrest mit 1 bis 18 Kohlenstoff¬ atomen, Cycloalkylrest mit einem C3- bis Cg-Ring und mit bis zu 12 Kohlen¬ stoffatomen, einem Aralkyl- oder Arylrest mit bis zu 19 Kohlenstoffatomen,R1 is hydrogen, an alkyl, alkenyl, alkynyl radical with 1 to 18 carbon atoms, cycloalkyl radical with a C3 to Cg ring and with up to 12 carbon atoms, an aralkyl or aryl radical with up to 19 carbon atoms,
R2, R^ unabhängig voneinander Hydrogen-, Halogen- oder C]- bis C4-Alkylrest bzw. R2 und R^ Teil eines Aromatenrestes oder - -R 2 , R ^ independently of one another hydrogen, halogen or C] - to C4-alkyl radical or R 2 and R ^ part of an aromatic radical or - -
R2 - R6 bilden -CH2-CH2-CH2- .R 2 - R 6 form -CH 2 -CH 2 -CH 2 -.
Auch ein Zusatz weiterer Fungizide oder Insektizide ist möglich, z.B. in emulgierter Form, wieIt is also possible to add other fungicides or insecticides, e.g. in emulsified form, like
N-Tridecyl-2,6-dimethylmorpholin (Tridemoφh) und/oder 4-(3-para-tertiär-butylphenyl)2-methyl-propyl-2,6-cis-dimethylmoφholin (Fenpropi¬ morph) und/oderN-tridecyl-2,6-dimethylmorpholine (Tridemoφh) and / or 4- (3-para-tertiary-butylphenyl) 2-methyl-propyl-2,6-cis-dimethylmoφholin (Fenpropi¬ morph) and / or
Aldimoφh, chlorierte PhenoleAldimoφh, chlorinated phenols
Tetrachlorisophthalsäure-dinitril, N-Cyclohexyl-N-methoxy-2,5-dimethyl-fur_m-3-carbonsäureamid,Tetrachloroisophthalic acid dinitrile, N-cyclohexyl-N-methoxy-2,5-dimethyl-fur_m-3-carboxamide,
N-Dimethyl-N'-phenyl-(N-fluormethylthio)-sulfamid,N-dimethyl-N'-phenyl- (N-fluoromethylthio) sulfamide,
N,N-Dimethyl-N'-toluyl-(N-fluormethylthio)-sulfamid,N, N-dimethyl-N'-toluyl- (N-fluoromethylthio) sulfamide,
Benzimidazol-2-carbaminsäure-methylester,Benzimidazole-2-carbamic acid methyl ester,
2-Thiocyanomethyl-thiobenzothiazol, 2-Iodbenzoesäureanilid,2-thiocyanomethyl-thiobenzothiazole, 2-iodobenzoic acid anilide,
Figure imgf000017_0001
Figure imgf000017_0001
Hexachlorcyclohexan,Hexachlorocyclohexane,
0,0-Diethyl-dithio-phosphoryl-methyl-6-chlorbenzoxazolon- 2-(l,3-Thiazol-4-yl)-benzimidazol,0,0-diethyl-dithio-phosphoryl-methyl-6-chlorobenzoxazolone-2- (1,3-thiazol-4-yl) benzimidazole,
N-Trichlormethylthio-3 , 6, 7, 8-tetrahydrophthalimid,N-trichloromethylthio-3, 6, 7, 8-tetrahydrophthalimide,
N-(l,l,2,2-Tetrachlorethylthio)-3,6,7,8-tetrahydrophthaliπ_id,N- (l, l, 2,2-tetrachloroethylthio) -3,6,7,8-tetrahydrophthaliπ_id,
N-Trichlormethylthiophthalimid.N-trichloromethylthiophthalimide.
O,O-Dimethyl-S-(2-methylamino-2-oxoethyl)-dithiophosphat, O,O-Dimethyl-O-(3,5,6-trichlor-2-pyridyl)-thiophosphat,O, O-dimethyl-S- (2-methylamino-2-oxoethyl) dithiophosphate, O, O-dimethyl-O- (3,5,6-trichloro-2-pyridyl) thiophosphate,
O,O-Dimethyl-S-(N-phthalimido)-methyldithiophosphat,O, O-dimethyl-S- (N-phthalimido) methyldithiophosphate,
O,O-Diethyl-O-(α-cyanbenzyliden-amino)-thiophosphat,O, O-diethyl-O- (α-cyanobenzylidene-amino) thiophosphate,
6,7,8,9,10-Hexachlor,l,5,5a,6,9,9a-hexahydro-6,9-methanol-2,3,4- benzoedioxothiepien-3 -oxid, (4-Ethoxyphenyl)-(dimethyl)-(3 -(4-fluoro-3 -phenoxy-pher_yl)-propyl-silane,6,7,8,9,10-hexachlor, l, 5,5a, 6,9,9a-hexahydro-6,9-methanol-2,3,4-benzoedioxothiepien-3-oxide, (4-ethoxyphenyl) - (dimethyl) - (3 - (4-fluoro-3-phenoxy-pher_yl) propyl silanes,
2-sek.-Butyl-p0henyl-N-methylcarbamat,2-sec-butyl-phenyl-N-methylcarbamate,
2-1-Propoxyphenyl-N-methyl-carbamat, N-Methyl-1-naphthyl-carbamat,2-1-propoxyphenyl-N-methyl-carbamate, N-methyl-1-naphthyl carbamate,
Norbonen-dimethanohexa-chlorcyclosulfit, l-(4-Chlorphenyl)-3-(2,6-di-fluorbenzoyl)-harnstoff.Norbonen-dimethanohexa-chlorocyclosulfite, l- (4-chlorophenyl) -3- (2,6-di-fluorobenzoyl) urea.
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, Isoprbthiolane, Metälaxyl, 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.Acypetacs, 2-aminobutane, ampropylfos, anilazine, benalaxyl, bupirimate, quinomethionate, chloroneb, chlozolinate, cymoxanil, dazomet, diclomezine, dichloram-diethofencarb, dimethirimol, diocab, dithianon, dodonidimololol, ethodololol, phenolimololol, dolonimololol, phenolimolol, dolonimolol, phenolol, dolonimolol, dolonimolol, phenolol, phenol, dolimidolol, phenol, dolimidolol, dolonimolol, dolonimolol, dolonimolol, dolonimolol, dolonimolol, phenol, dolimidolol, phenol, dolimidolol, dolimidolol, phenol, dolimidol, phenol, dolimidolol, phenol, dolimidol, phenol, dolimidol, phenol, dolimidol Fentin acetate, Fentin Hydroxide, Ferimzone, Fluazinam, Fluromide, Flusulfamide, Flutriafol, Fosetyl, Fthalide, Furalaxyl, Guazatine, Hymexazol, Iprobefos, Iprodione, Isoprbthiolane, Metälaxyl, Methasulfocarb, Nitrothalimimidolate, Peroxalcimidazolate, Peroxalcimidazurate, Peroxalcimidazolate, Peroxalcimidazolate, Peroxalcimidazolate, Peroxalcimidazolate, Peroxalcimidazolate, Peroxalcimidate Phosdiphen, Pimaricin, Piperalin, Procymidone, Propamocarb, Propineb, Pyrazophos, Pyrifenox, Pyroquilon, Quintozene, Tar Oils, Tecnazene, Thicyofen, Thiophanate-methyl, Tolclofos-methyl, Triazoxide, Trichlamide, Tricyclazole, Triforoline.
Überraschenderweise zeigen diese Wirkstoffkombinationen eine besonders hohe, mitkrobizide, insbesondere fungizide Wirkung, verbunden mit einem breiten Wirk¬ spektrum 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:Surprisingly, these active substance combinations have a particularly high, co-microbicidal, in particular fungicidal activity, combined with a broad spectrum of activity against microorganisms and insects relevant in wood preservation; 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: Holzverfarbende Pilze:A: Wood-colored mushrooms:
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 pullulansAureobasidium such as Aureobasidium pullulans
Dactylium wie Dactylium fusarioidesDactylium such as Dactylium fusarioides
Penicillium wie Penicillium brevicaule oderPenicillium such as Penicillium brevicaule or
Penicillium variabile Sclerophoma wie Sclerophoma pithyophila Acopularia wie Scopularia phycomyces Trichoderma wie Trichoderma viride oder Trichoderma lignorumPenicillium variable Sclerophoma such as Sclerophoma pithyophila Acopularia 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 expansaDonkioporia like Donkioporia expansa
Glenospora wie Glenospora graphiiGlenospora such as Glenospora graphii
Gloeophyllum wie Gloeophyllum abietinum oderGloeophyllum such as Gloeophyllum abietinum or
Gloeophyllum adoratum oder Gloeophyllum protactum oder Gloeophyllum sepiarium oder Gloeophyllum trabeumGloeophyllum adoratum or Gloeophyllum protactum or Gloeophyllum sepiarium or Gloeophyllum trabeum
Lentinus wie Lentinus cyathiformes oderLentinus such as Lentinus or cyathiformes
Lentinus edodes wie Lentinus lepideus oderLentinus edodes like Lentinus lepideus or
Lentinus grinus oder Lentinus squairolosusLentinus grinus or Lentinus squairolosus
Paxillus wie Paxillus panuoides Pleurotus wie Pleurotus ostreatusPaxillus like Paxillus panuoides Pleurotus like Pleurotus ostreatus
Poria wie Poria monticola oder Poria placenta oderPoria such as Poria monticola or Poria placenta or
Poria vaillantii oder Poria vaporariaPoria vaillantii or Poria vaporaria
Seφula wie Seφula himantoides oderSeφula like Seφula himantoides or
Seφula lacrymans Stereum wie Stereum hirsutum Tyro yces wie Tyromyces palustrisSeφula lacrymans Stereum and Stereum hirsutum Tyro yces like Tyromyces palustris
B3: DeuteromycetenB3: Deuteromycetes
.Alternaria wie Alternaria tenius Cladosporium wie Cladosporium herbarum Alternaria tenuis.Alternaria such as Alternaria tenius Cladosporium such as Cladosporium herbarum Alternaria tenuis
C. Holzzerstörende Insekten wieC. Wood-destroying insects like
CI : KäferCI: Beetle
Hylotrupes bajulus. Chlorophorus pilosis, Anobium punctatum, Xesto- bium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, LyctusHylotrupes bajulus. Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus
Planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec, Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutusPlanicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec, Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus
C2: HautflüglerC2: Skin wing
Sirex juvencus, Urocerus gigas, Urocerus gigas taignus. Urocerus augurSirex juvencus, Urocerus gigas, Urocerus gigas taignus. Urocerus augur
C3 : TermitenC3: termites
Kaloterm.es flavicollis, Cryptotermers brevis, Heterotermes indicola, Reti- culitermes flavipes, Reticulitermes santonensis, Reticulitermes lucilugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formo- sanus.Kaloterm.es flavicollis, Cryptotermers brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes 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 Wirkstoffmischung, bezogen auf das zu schützende Material, einzusetzen. Die Insektizide liegen im allgemeinen in einer Anwendungskonzentration von 0,00001 % bis 10 %, bevor.zugt 0,00001 % bis 5 %, besonders bevorzugt 0,001% bis 1 % vor.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%.
Die genannten Formulierungen können in an sich bekannter Weise hergestellt werden, z.B. durch Vermischen der Wirkstoffe mit einem Lösungs- bzw. Verdünnungsmittel, Emulgator, 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 active ingredients with a solvent or diluent, emulsifier, dispersant and / or binder or fixative, water repellants, optionally siccatives and UV stabilizers and optionally 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.
Als organisch-chemische Lösungsmittel werden vorzugsweise ölige oder ölartige Lö¬ sungsmittel mit einer Verdunstungszahl über 35 und einem Flammpunkt oberhalb 30°C, vorzugsweise oberhalb 45°C, eingesetzt. Als derartige schwerflüchtige, wasser¬ unlösliche, ölige und ölartige Lösungsmittel werden entsprechende Mineralöle oder deren Aromatenfral tionen oder mineralölhaltige Lösungsmittelgemische, vorzugs¬ weise Testbenzin, Petroleum und/oder Alkylbenzol verwendet.The organic chemical solvents used are preferably oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C. Corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene, are used as such low-volatility, water-insoluble, oily and oily solvents.
Vorteilhaft gelangen Mineralöle mit einem Siedebereich von 170 bis 220°C, Testbenzin mit einem Siedebereich von 170 bis 220°C, Spindelöl mit einem Siede¬ bereich von 250 bis 350°C, Petroleum bzw. Aromaten vom Siedebereich von 160 bis 280°C, Terpentinöl und dergl. zum Einsatz.Mineral oils with a boiling range of 170 to 220 ° C, white spirit with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C are advantageous. Turpentine oil and the like.
In einer bevorzugten Ausfuhrungsform werden flüssige aliphatische Kohlenwasser¬ stoffe mit einem Siedebereich von 180 bis 210°C oder hochsiedende Gemische von aromatischen und aliphatischen Kohlenwasserstoffen mit einem Siedebereich von 180 bis 220°C und/oder Spindelöl und/oder Monochlornaphthalin, vorzugsweise α- Monochlornaphthalin, verwendet.In a preferred embodiment, liquid aliphatic hydrocarbons with a boiling range from 180 to 210 ° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range from 180 to 220 ° C. and / or spindle oil and / or monochloronaphthalene, preferably α-monochloronaphthalene, used.
Die organischen schwerflüchtigen öligen oder ölartigen Lösungsmittel mit einer Ver¬ dunstungszahl über 35 und einem Flammpunkt oberhalb 30°C, vorzugsweise oberhalb 45°C, können teilweise durch leicht oder πuttelflüchtige organisch-chemische Lö¬ sungsmittel ersetzt werden, mit der Maßgabe, daß das Lösungsmittelgemisch ebenfalls eine Verdunstungszahl über 35 und einen Flammpunkt oberhalb 30°C, vorzugsweise oberhalb 45°C, aufweist und daß das Insektizid-Fungizid-Gemisch in diesem Lösungs- mittelgemisch löslich oder emulgierbar istThe organic low-volatility oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C, can be partially replaced by volatile or πuttel volatile organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide -Fungicide mixture is soluble or emulsifiable in this solvent mixture
Nach einer bevorzugten Ausfuhrungsform 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 werden 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 bevorzugt πrt mittlerer Öllänge, Phenolharz, Kohlenwasserstoffharz wie Inden-Cumaronl___rz, Siliconharz, trocknende pflanzliche und/oder trocknende Öle und/oder physikalisch trocknende Bindemittel auf der Basis eines Natur- und/oder Kunstharzes verwende:In the context of the present invention, the organic-chemical binders which are known are water-thinnable and / or synthetic resins which are soluble or dispersible or emulsifiable in the organic-chemical solvents used and / or binding drying oils, in particular binders consisting of or containing an acrylate resin, a vinyl resin. e.g. Polyvinyl acetate, polyester resin, polycondensation or polyaddition resin-polyurethane resin, alkyd resin or modified alkyd resin, preferably medium-length oil, phenolic resin, hydrocarbon resin such as Inden-Coumaronl ___ rz, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or synthetic resin use:
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.
Bevorzugt ist gemäß der Erfindung als organisch-chemische Bindemittel mindestens ein Alkydharz bzw. modifiziertes Alkydharz und/oder ein trocknendes pflanzliches Öl im Mittel oder im Konzentrat enthalten. Bevorzugt werden gemäß der Erfindung Alkydharze mit einem Ölgehalt von mehr als 45 Gew.-%, vorzugsweise 50 bis 68 Gew.-%, verwendet.According to the invention, at least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably contained in the agent or in the concentrate as the organic chemical binder. Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used according to the invention.
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 additions are meant to Prevent volatilization of the active ingredients as well as 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 Polyvinylalkylethern wie z.B. Polyvinylmethyl- ether oder Ketonen wie Benzophenon, Ethylenbenzophenon.Fixing agents are chemically based on polyvinyl alkyl ethers such as e.g. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.
Neben diesen Hilfsmitteln werden vorzugsweise auch die in der EP-383 746, Seiten 5- 6 beschriebenen Hilfsmittel als Bestandteil für Holzschutzmittel verwendet.In addition to these aids, the aids described in EP-383 746, pages 5-6 are preferably also used as a constituent for wood preservatives.
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.Wood which can be protected by the agent according to the invention or mixtures containing it is to be understood as examples: timber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wooden cladding, wooden windows and - Doors, plywood, particle board, carpentry or wood products that are used in general in house construction or in joinery.
Ein besonders effektiver Holzschutz wird durch großtechnische Imprägnierverfahren, z.B. Vakuum, Doppelvakuum oder Druckverfahren, erzielt.A particularly effective wood protection is achieved through industrial impregnation processes, e.g. Vacuum, double vacuum or pressure process.
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 ^0 Gew.-%.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 ^ 0% by weight.
Die wasserverdünnbaren Holzschutzmittel enthalten - in konzentrierter Form - das Kupfer berechnet als Metall im allgemeinen, z.B. in einer Menge von 1,0 bis 15,0 % (Gewichtsprozent) . Geeignete Konzentrate bestehen z.B. ausThe water-thinnable wood preservatives contain - in concentrated form - the copper calculated as metal in general, for example in an amount of 1.0 to 15.0% (weight percent). Suitable concentrates consist of, for example
0,50 bis 45 % Kupferverbindungen0.50 to 45% copper compounds
5,00 bis 50 % Alkanolamin5.00 to 50% alkanolamine
0,25 bis 15 % synergistischer Triazol/Fungizid- bzw. Insektizid-Mischung0.25 to 15% synergistic triazole / fungicide or insecticide mixture
0,5 bis 30 % eines Emulgators und/oder einer Phosphoniumverbindung und/oder Tridemoφh oder Aldimoφh 0 bis 40 % Verbindung mit einem fungiziden anorganischen oder organi¬ schen Anion0.5 to 30% of an emulsifier and / or a phosphonium compound and / or Tridemoφh or Aldimoφh 0 to 40% compound with a fungicidal inorganic or organic anion
0 bis 40 % organische Lösungsmittel0 to 40% organic solvents
0 bis 40 % e ner aliphatischen Mono- oder Dicarbonsäure und/oder Cycloal- kylcarbonsäure und/oder Cycloarylcarbonsäure und/oder Bor¬ säure oder eines Borates0 to 40% e ner 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 Stickstoffverbindung0 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.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 e.g. 0.01 to 1.50% by weight of metal, e.g. Copper, in the aqueous impregnation solution, depending on the type of impregnation and the degree of hazard of the wood to be impregnated.
Durch Auflösen der Kupfersalze, gegebenenfalls unter Wärmezufuhr, in den Alkanol¬ aminen, gegebenenfalls unter Säure-, Wasser- oder Lösungsmittelzugabe, und an¬ schließender Zugabe des Emulgators, der Triazolverbindungen und des syner¬ gistischen Mischpartners entstehen hochkonzentrierte Pasten, flüssige Konzentrate oder auch Zwei-Phasen-Mischungen, die nach dem Verdünnen mit Wasser zum Im- prägnieren von Holz verwendet werden können. Sie ergeben auch bei hoher Konzentration in Wasser ein klare Flüssigkeit.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 then adding the emulsifier, the triazole compounds and the synergistic mixing partner, highly concentrated pastes, liquid concentrates or two are formed -Phase mixtures which, after dilution with water, impregnate wood can be used. 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 verfug¬ baren Mittel durch effektivere zu ersetzen. Sie zeigen eine gute Stabihtät und haben in vorteilhafter Weise ein breites Wirkungsspektrum. The agents according to the invention advantageously make it possible to replace the previously available agents with more effective ones. They show good stability and advantageously have a broad spectrum of activity.
BeispieleExamples
Beispiel 1example 1
Ein Konzentrat:A concentrate:
Gew.-%% By weight
Monoethanolamin 23,1Monoethanolamine 23.1
Xylol 3,8Xylene 3.8
Prozeßöl 4,0Process oil 4.0
Borsäure 16,9Boric acid 16.9
Kupfercarbonat, basisch 10,9Copper carbonate, basic 10.9
Tebuconazole 0,14Tebuconazole 0.14
Cyproconazole 0,10Cyproconazole 0.10
Emulgator 1,2Emulsifier 1,2
Permethrin 0,7Permethrin 0.7
Wasser ad 100Water ad 100
Beispiel 2Example 2
Ein Konzentrat:A concentrate:
Gew.-%% By weight
Xylol 50Xylene 50
Cyclohexanon 30Cyclohexanone 30
Castoröl-Polyglycolether (36 mol Ethylenoxid) 4Castor oil polyglycol ether (36 mol ethylene oxide) 4
Dodecylbenzolsulfonate 3Dodecylbenzenesulfonates 3
Octylphenolpolyethylenglykolether (4-5 mol Ethylenoxid) 3Octylphenol polyethylene glycol ether (4-5 mol ethylene oxide) 3
Tebuconazole 5Tebuconazole 5
Cyproconazole 4 Beispiel 3Cyproconazole 4 Example 3
Gebrauchslösung:Use solution:
Gew.-%% By weight
Borsäure 0,8Boric acid 0.8
Ammoniak 0,6Ammonia 0.6
Natriumnitrit 1,3Sodium nitrite 1.3
Milchsäure 2, 15Lactic acid 2, 15
Kupfersulfat • 5 H2O 1,18Copper sulfate • 5 H 2 O 1.18
Cypermethrin 0,05Cypermethrin 0.05
Tebuconazole 0,02Tebuconazole 0.02
Metconazole 0,02Metconazole 0.02
Emulgator 0,10Emulsifier 0.10
Wasser ad 100Water ad 100
Beispiel 4Example 4
Konzentrat:Concentrate:
Gew.-% Permethrin 0,6% By weight permethrin 0.6
Monoethanolamin 33,5Monoethanolamine 33.5
Kupfercarbonat, basisch 14,0 Borsäure 7,5Copper carbonate, basic 14.0 boric acid 7.5
Propionsäure 6,0Propionic acid 6.0
Nonylphenol, ethaniliert (ca. 10 Mol Ethylenoxid) 10 Propylenglykol 6Nonylphenol, ethanolized (approx. 10 moles of ethylene oxide) 10 propylene glycol 6
Tebuconazole 2Tebuconazole 2
Bromoconazole 1,5Bromoconazole 1.5
Wasser ad 100 Beispiel 5Water ad 100 Example 5
Konzentrat:Concentrate:
Gew.-%% By weight
Monoethanolamin 35Monoethanolamine 35
Benzolsäure 21Benzene acid 21
Kupfercarbonat, basisch 14Copper carbonate, basic 14
Tebuconazole ,5Tebuconazole, 5th
Hexaconazol 1,5Hexaconazole 1.5
Propylenglykol 6Propylene glycol 6
Nonylphenol, ethoxiliert 10Nonylphenol, ethoxylated 10
Wasser ad 100Water ad 100
Beispiel 6Example 6
Gebrauchslösung:Use solution:
Gew.-%% By weight
Borsäure 1Boric acid 1
Natriumnitrit 1,5Sodium nitrite 1.5
Benzolsäure 1,5Benzene acid 1.5
Kupfersulfat • 5 H O 1,3Copper sulfate • 5 HO 1.3
Cyfluthrin 0,06Cyfluthrin 0.06
Tebuconazole 0,03Tebuconazole 0.03
Cyproconazole 0, 01Cyproconazole 0.01
Emulgator 0,14Emulsifier 0.14
Ammoniak 0,7 Wasser ad 100 Beispiel 7Ammonia 0.7 water ad 100 Example 7
GebrauchslösungWorking solution
Gew.-%% By weight
Zinkoctanat 3Zinc octanate 3
Natriumnitrit 1,0Sodium nitrite 1.0
2-Ethylhexansäure 2,02-ethylhexanoic acid 2.0
Kupfercarbonat, basisch 1,1Copper carbonate, basic 1.1
Cyfluthrin 0,03Cyfluthrin 0.03
Tebuconazole 0,01Tebuconazole 0.01
Cyproconazole 0,02Cyproconazole 0.02
Emulgator 0,17Emulsifier 0.17
Ammoniak 0,7Ammonia 0.7
Wasser ad 100Water ad 100
Beispiel 8Example 8
Konzentratconcentrate
Gew.-%% By weight
Kupfercarbonat, basisch 12,4Copper carbonate, basic 12.4
Ethanolamin 27,3Ethanolamine 27.3
2-Ethylhexansäure 2,52-ethylhexanoic acid 2 , 5
Tebuconazole 0,9Tebuconazole 0.9
Wocosan (88 % Propiconazole) 1,0Wocosan (88% propiconazole) 1.0
Cyflutrin 0,02Cyflutrin 0.02
Tridemoφh 7,0Tridemoφh 7.0
Wasser i id 100 Beispiel 9Water i id 100 Example 9
GebrauchslösungWorking solution
Gew.-%% By weight
Zinkoctanat 3Zinc octanate 3
Natriumnitrit 1,0Sodium nitrite 1.0
2-Ethylhexansäure 2,02-ethylhexanoic acid 2.0
Kupfercarbonat, basisch 1 , 1Copper carbonate, basic 1, 1
Cyfluthrin 0,03Cyfluthrin 0.03
Cyproconazole 0,04Cyproconazole 0.04
Emulgator 0, 17Emulsifier 0.17
Ammoniak 0,7Ammonia 0.7
Wasser ad 100Water ad 100
Beispiel 10Example 10
Konzentratconcentrate
Gew.-%% By weight
Kupfercarbonat, basisch 12,4Copper carbonate, basic 12.4
Ethanolamin 27,3Ethanolamine 27.3
2-Ethylhexansäure 2,52-ethylhexanoic acid 2.5
Cyproconazole 2,9Cyproconazole 2.9
Cyflutrin 0,02Cyflutrin 0.02
Tridemoφh 7,0Tridemoφh 7.0
Wasser ad 100 Water ad 100

Claims

Patentansprüche claims
1. Holzschutzmittel, enthaltend neben mindestens einer Kupferverbindung und mindestens einem Alkanolamin, eine Triazolverbindung und mindestens ein weiteres Fungizid und/oder Insektizid, die sich synergistisch ergänzen, sowie gegebenenfalls einen Emulgator.1. Wood preservative comprising, in addition to at least one copper compound and at least one alkanolamine, a triazole compound and at least one further fungicide and / or insecticide, which complement one another synergistically, and, if appropriate, an emulsifier.
2. Verwendung eines Mittels, enthaltend mindestens eine Kupferverbindung, mindestens ein Alkanolamin, eine Triazolverbindung und mindestens ein sich synergistisch ergänzendes weiteres Fungizid und/oder Insektizid, zum Schutz von Holz und Holzwerkstoffen. 2. Use of an agent containing at least one copper compound, at least one alkanolamine, a triazole compound and at least one synergistically complementary fungicide and / or insecticide, for protecting wood and wood-based materials.
PCT/EP1994/003370 1993-10-26 1994-10-13 Timber protecting medium containing a copper compound WO1995011786A1 (en)

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DE4336474 1993-10-26
DEP4336474.8 1993-10-26
DEP4340853.2 1993-12-01
DE4340853A DE4340853A1 (en) 1993-10-26 1993-12-01 Wood preservative containing a copper compound

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999037450A1 (en) * 1998-01-24 1999-07-29 Bayer Aktiengesellschaft Wood preservation agents

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CA2165560A1 (en) * 1993-06-21 1995-01-05 Lutz Heuer Fungicidal active-substance combination

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EP0385076A1 (en) * 1989-03-02 1990-09-05 DESOWAG Materialschutz GmbH Agent or concentrate for the preservation of wood or wooden materials
WO1991001640A1 (en) * 1989-07-31 1991-02-21 Chinoin Gyógyszer És Vegyészeti Termékek Gyára Rt Novel combined compositions for combatting pests
EP0514644A2 (en) * 1991-04-18 1992-11-25 Dr. Wolman GmbH Wood preservative
WO1993002557A1 (en) * 1991-08-01 1993-02-18 Hickson International Plc Preservatives for wood and other cellulosic materials

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Publication number Priority date Publication date Assignee Title
EP0385076A1 (en) * 1989-03-02 1990-09-05 DESOWAG Materialschutz GmbH Agent or concentrate for the preservation of wood or wooden materials
WO1991001640A1 (en) * 1989-07-31 1991-02-21 Chinoin Gyógyszer És Vegyészeti Termékek Gyára Rt Novel combined compositions for combatting pests
EP0514644A2 (en) * 1991-04-18 1992-11-25 Dr. Wolman GmbH Wood preservative
WO1993002557A1 (en) * 1991-08-01 1993-02-18 Hickson International Plc Preservatives for wood and other cellulosic materials

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WO1999037450A1 (en) * 1998-01-24 1999-07-29 Bayer Aktiengesellschaft Wood preservation agents

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