DE4340853A1 - Wood preservative containing a copper compound - Google Patents

Description

The application relates to wood preservatives containing at least one copper compound tion, a triazole compound that deals with at least one other fungicide and / or insecticide synergistically supplemented, at least one alkanolamine and given if necessary, an emulsifier.

Wood preservatives based on inorganic copper compounds with alkanolamines as complexing agents are known (EP 89 958). The effectiveness of these remedies against over wood-destroying Basidiomyceten ranges in comparison despite high copper contents to known copper and chromate salts with comparable copper content not from.

Also known are wood preservatives based on copper compounds and Alkanolamines containing a triazole compound and an emulsifier or a Phos contain phonium compound and have activity against wood-destroying basidio mycetes possess (DE 41 12 652 / WO 93/02557 / WO 91/11306).

Also known are synergistic mixtures for the protection of wood based on z. 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 Mix partners.

The aim and object of the present invention was now a wood preservation first of all, to wood discolouring and destroying wood Fungi as well as against wood-damaging insects, especially against wood chips  annoying longhorn beetles (Cerambycidae, Lyctidae, Bostrychidae and Anobiidae) including termites is highly effective and has a good long-term effect, wherein the effectiveness of the fungicide is not affected by the insecticide or vice versa. In addition, the wood preservative should be a good one have penetrating power in wood and wood-based materials.

Furthermore, the occurring in wood and wood materials in contact with the ground should Degradation of the organic drug can be prevented. Because of this degradation of the active ingredient not necessarily caused by wood-destroying and or wood-discolouring fungi, but also of other microorganisms associated with them can, is except the synergistic-acting mixture of z. B. Tebuconazole and another fungicide and / or insecticide, the use of another, biocidal Component necessary to a long-term effect of the organic agents too to reach. According to the invention therefore copper compounds, optionally in Compound with Borderivaten or nitrite-containing salts mixed.

The invention therefore relates to a wood preservative containing in addition to one Copper compound and an alkanolamine, a triazole compound and at least a synergistically complementary, further fungicide and / or insecticide, as well as optionally an emulsifier.

Despite the content of copper compounds in wood preservatives, the two Fungicides when diluted with water are clearly emulsified or dissolved in water. The Advantage of the invention is that z. B. triazole compounds, the are insoluble in water, in the new compositions in the form of aqueous emulsions or clear aqueous concentrates are present. Dilution with water produces clear aqueous liquids.

By adding small amounts of organic solvents for wood preservation medium, z. As alcohols (ethanol, isopropanol), glycols (ethylene glycol, propylene glycol col), glycol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether), Glycol ether esters (butylglycol acetate), dimethylformamide, N-methylpyrrolidone kön homogeneous concentrates are obtained. The solvents have an additional effect Lich as a solubilizer for the fungicides. With the additional use of  Arylcarbonsäuren, Cycloalkylcarbonsäuren or aliphatic C₅-C₂₀ mono- or Dicarboxylic acids or corresponding amine, alkali or copper salts, the Use of solvents, however, must be reduced to a minimum to homogeneous To obtain concentrates. In any case, the mixture or concentrate contains Water as an ingredient.

The copper compounds can be used as water-soluble or water-insoluble verbin used, for. As 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.

An alkanolamine is especially monoethanolamine; the use of other Alka nolamins z. B. isopropanolamine 1,1-, 1,2-diaminoethanol, aminoethylethanolamine, Diethanolamine, triethanolamine, methylethanolamine, N-methylaminoethanol, N-ethylaminoethanol, ethanolhydrazine, N-butylaminoethanol, N-phenylaminoethanol and (2-aminoethoxy) ethanol is possible.

In this case, the amount of alkanolamines added is advantageously such that in the dilute aqueous impregnating solution has a pH of 7 or more, before preferably 8.5 to 10.5, adjusts. The amount of amines is said to complex the Copper suffice (1 g atom of copper requires about 4 mol equivalents of amine).

Synergistic mixtures of triazole compounds such. B. tebuconazole preferably with one or more fungicides from the series:

Azaconazole, Bromuconazole, Cyproconazole, Dichlobutrazole, Diniconazole, Hexa conazole, metconazole, penconazole, epoxyconazole, methyl (E) -methoximino [α- (o-tolyloxy) -o-tolyl)] acetate, methyl (E) -2- {2- [6- (2-cyanophenoxy) -pyimidin-4-yl oxy] phenyl} -3-methoxyacrylate, methfuroxam, carboxin, fenpiclonil, 4 (2,2-difluoro- 1,3-benzodioxol-4-yl) -1H-pyrrole-3-carbonitrile, butenafine, 3-iodo-2-propynyl-n-butyl carbamate (IPBC) and / or polymeric quaternary ammonium borates (known from US Pat EP 355 316 and EP 556454).

As synergistic fungicidal or insecticidal mixing partners are preferably also the the following fungicides or insecticides used.  

triazoles

Amitrole, azocyclotin, bitertanol, fenbuconazole, fenchlorazole, fenethanil, flu quinconazole, flusilazole, flutriafol, imibenconazole, isozofos, myclobutanil, met conazole, epoxyconazole, paclobutrazole, (±) -cis-1- (4-chlorophenyl) -2- (1H-1,2,4- triazol-1-yl) -cycloheptanol, tetraconazole, triadimefon, triadimenol, tri-penthenol, Triflumizole, triticonazole, uniconazole and their metal salts and acid adducts.

imidazoles

Imazalil, pefurazoate, prochloraz, triflumizole, 2- (1-tert-butyl) -1- (2-chlorophenyl) -3- (1,2,4-triazol-1-yl) -propan-2-ol, thiazolecarboxanilides such as 2 ', 6'-dibromo-2-methyl-4- trifluoromethoxy-4'-trifluoromethyl-1,3-thiazoles-5-carboxanilides and their metal salts and acid adducts.

Methyl (E) -2- [2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl] 3-methoxy-acrylate, methyl (E) -2- [2- [6- (2-thioamidophenoxy) pyimidin-4-yloxy] phenyl] -3-met-hoxyacry late, methyl (E) -2- [2- [6- (2-fluorophenoxy) pyrimidin-4-yloxy] -phenyl] -3-methoxy-xyacrylate, Methyl (E) -2- [2- [6- (2,6-difluorophenoxy) pyimidin-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- (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) pyrrole-1-yl] -3 -methoxyacrylates, methyl (E) -2- [2- (3-methoxyphenoxy) phenyl] -3-methoxyacrylate late, methyl (E) -2- [2- (2-phenylethen-1-yl) phenyl] -3- methoxy acrylates, methyl (E) -2- [2- (3,5-dichlorophenoxy) pyridin-3-yl] -3-methoxyacrylate, methyl (E) -2- (2- (3- (1,1,2, 2-tetrafluoroethoxy) phenoxy) phen yl) -3-methoxyacrylate, methyl (E) -2- (2- [3 (alpha-hydroxybenzyl) phenoxy] phenyl) -3-methoxyacrylate, methyl (E) -2- (2- (4-phenoxypyridine-2 -yloxy) phenyl) -3-methoxyacrylate, methyl (E) -2- [2- (3-n-propyloxyphenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3-isopropyloxyphenoxy) phenyl] 3-methoxyacrylates, methyl (E) -2- [2- [3- (2-fluorophenoxy) phenoxy] phenyl] -3-methoxyacrylate late, methyl (E) -2- [2- (3-ethoxy-phenoxy) -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) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (5-bromopyridin-2-yloxyethyl) 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-dimethylpyra zin-2-yl thyloximinomethyl) phenyl] -3-methoxyacrylate, (E) -methyl-2- {2- [6- (6-methylpyridin-2-yloxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate, (E), (E) methyl-2- {2- (3-methoxyphenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate, (E) methyl-2- {2- [6- (2-azidophenoxy) -pyrimidine 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 late, (E) methyl-2- {2- [6- (2-n-propylphenoxy) -1,3, 5-triazin-4-yloxy] phenyl} -3-methoxyacrylates, (E), (E) methyl-2- {2 - [(3-nitrophenyl) methyloxminomethyl] phenyl} -3-methoxyacrylate;
Succinate dehydrogenase inhibitors such as:
Fenfuram, furcarbanil, cyclafluramide, Furmecyclox, Seedvax, Metsulfovax, pyrocarbolid, oxycarboxin, Shirlan, Mebenil (Mepronil), Benodanil, Flutolanil (Moncut);
Naphthalene derivatives such as:
Terbinafine, naftifine, butenafine, 3-chloro-7- (2-aza-2,7,7-trimethyl-oct-3-en-5-yne);
Sulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet; Captan, Captofol;
Benzimidazoles such as carbendazim, benomyl, furathiocarb, fuberidazole, thiophonate methyl, thiabendazoles or their salts,
Morpholine derivatives such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph; Aldimorph, fenpropidin and their arylsulfonsauren salts, such as. For example, p-toluenesulfonic acid and p-dodecylphenyl-sulfonic acid;
Dithiocarbamates 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 esters, borax;

Formaldehyde and formaldehyde releasing compounds such as benzyl alcohol mono- (poly) -hemiformal, oxazolidines, hexa-hydro-S-triazines, N-methylolchloroacetamide, paraformaldehyde, nitropyrin, oxolinic acid, tecloftalam;
Tris-N- (cyclohexyldiazeniumdioxy) -aluminum, N- (cyclo-hexyldiazeniumdioxy) -tri-butyltin or K-salts, bis-N- (cyclohexyldiazeniumdioxy) -copper.

N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octylisothiazolin-3-one, 4,5-trimethylene -isothiazolinone, 4,5-benzisothiazolinone, N-methylolchloroacetamide;
Aldehydes such as cinnamaldehyde, formaldehyde, glutardialdehyde, β-bromocinnamic aldehyde; Thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate, etc .;
quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethylammonium chloride;
Iodine derivatives such as diiodomethyl-p-tolylsulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargylformal, 3-bromo-2,3-diiodo-2-propenylethylcarbamate, 2,3,3-triiodoallyl alcohol, 3 Bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-butylcarbamate, 3-iodo-2-propynyl-n-hexyl catamate, 3-iodo-2-propynylcyclohexylcarbamate, 3-iodo -2-per-phenylphenylcarbamate;
Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol and their Alkali and alkaline earth metal salts.

Activated halogenated microbicides such as chloroacetamide, Bronopol, Bronidox, tectamer such as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane, β-bromo-β-nitrostyrene;
Pyridines such as 1-hydroxy-2-pyridinethione (and its Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrite ion;
Metal soaps such as tin, copper, zinc naphthenate, 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-tetrachloroisophthalodinitrile, disodium cyanodithioimidocarba mat;
Quinolines such as 8-hydroxyquinoline and their Cu salts;
Mucochloric acid, 5-hydroxy-2 (5H) -furanone;
4,5-dichlorodithiazolinone, 4,5-benzdithiazolinone, 4,5-trimethylenedithiazolinone, 4,5-dichloro (3H) -1,2-dithiol-3-one, 3,5-dimethyl-tetrahydro-1,3, 5-thiadiazine-2-thione, N- (2-p-chlorobenzoylethyl) -hexaminium chloride, potassium N-hydroxymethyl-N'-methyl dithiocarbamate,
2-Oxo-2- (4-hydroxy-phenyl) acethydroximsäure chloride,
Phenyl (2-chloro-cyano-vinyl) sulfone,
Phenyl- (1,2-dichloro-2-cyano-vinyl) sulfone;
Ag, Zn or Cu-containing zeolites alone or included in polymeric agents;
Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, α-1 (4-chlorophenyl) -4- (O-ethyl, S-propyl) -phosphoryloxy-pyrazole, chlorpyrifos, coumaphos, demeton, demeton-S-methyl, diazinon, dichlorvos, Dimethoates, Ethoates, Ethoprophos, Etrimfos, Fenitrothion, Fenthion, Heptenophas, Parathion, Parathion-methyl, Phosalone, Phoxim, Pinmiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulfprofos, Triazophos, and Trichlorophone;
Carbamates such as aldicarb, bendiocarb, α-2- (1-methylpropyl) -phenylmethylcarbamate, butocarboxime, butoxycarboxim, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarb;
Organosilicon compounds, preferably dimethyl (phenyl) silyl-methyl-3-phenoxy benzyl ethers such as dimethyl (4-ethoxyphenyl) silylmethyl-3-phenoxybenzyl ether or (dimethylphenyl) silyl-methyl-2-phenoxy-6-pyridylmethyl ether such. For example, dimethyl (9-ethoxy-phenyl) -silylmethyl-2-phenoxy-6-pyridylmethyl ether or [(phenyl) -3- (3-phenoxyphenyl) -propyl] (dimethyl) silanes such. B. (4-ethoxyphenyl) - [3 - (4-fluoro-3-phenoxyphenyl-propyl] -dimethyl-silane, silafluofen;
Pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin, cycloprothrin, cyfluthrin, decamethrin, cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- (2-chloro-2-trifluoro -methylvinyl-) cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerates, flucythrinates, flumethrin, fluvalinates, permethrin, resmethrin and tralomethrin;
Nitroimines and nitromethylenes such as 1 - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-1H-imidazol-2-amine (imidacloprid), N - [(6-chloro-3 -pyridyl) methyl-] N²-cyano-N¹-methylacetamide (NI-25);
Abamectin, AC 303, 630, acephates, acrinathrin, alanycarb, aldoxycarb, aldrin, amitraz, azamethiphos, bacillus thuringiensis, phosmet, phosphamidone, phosphines, prallethrin, propaphos, propetamphos, prothoates, pyraclofos, pyrethrins, pyridaben, pyridafenthione, pyriproxyfen, quinalphos, RH-7988, rotenone, sodium fluoride, sodium hexafluorosilicates, sulfotep, sulfuryl fluoride, tar oils, teflubenzuron, tefluthrin, temephos, terbufos, tetrachlorovphine, tetramethrin, O-2-tert-butyl pyrimidin-5-yl-o-isopropyl phosphorothiate, thiocyclam, thiofanox, thiometone, tralomethrin, triflumuron, trimethacarb, vamidothione, verticillium lacanii, XMC, xylylcarb, benfuracarb, bensultap, bifenthrin, bioallethrin, MERbioallethrin (S) cyclopentenyl isomer, bromophos, bromophos-ethyl, buprofezin, cadusafos, calcium polysulfides , Carbophenothione, cartap, quinomethionate, chlordane, chlorfenvinphos, chlorofluorazuron, chlormephos, chloropicrin, chlorpyrifos, cyanophos, beta-cyfluthrin, alpha-cypermethrin, cyophenot hrine, cyromazine, dazomet, DDT, demeton-S-methylsulphon, diatenthiuron, dialifos, dicrotophos, diflubenzuron, dinoseb, deoxabenzofos, diaxacarb, disulfonot, DNOC, empenthrin, endosulfan, EPN, esfenvalerate, ethiofenecarb, ethion, etofenprox, fenobucarb, fenoxycarb, Fensulfothione, Fipronil, Flucycloxuron, Flufenprox, Flufenoxuron, Fonofos, Formetanate, Formothion, Fosmethilane, Furathiocarb, Heptachlor, Hexaflumuron, Hydramethylnone, Hydrogen Cyanide, Hydroprene, IPSP, Isazofos, Isofenphos, Isoprothiolane, Isoxathion, Iodfenphos, Kadethrin, Lindane, Malathion, Mecarbam , Mephosfolane, mercurous, chloride, metam, metathione, anisopliae, methacrifos, methamidophos, methidathion, methiocarb, methoprene, methoxychloro, methyl isothiocyanate, metholcarb, mevinphos, monocrotophos, naled, neo diprione sertifer NPV, nicotine, omethoate, oxydemeton-methyl, Pentachlorophenol, petroleum oils, phenothrin, phenthoates, phorates;

Particularly preferred mixtures contain as insecticides:
Chlorpyrifos, phoxim, silafluofen, cyfluthrin, cypermethrin, deltamethrin, per methrin, imidacloprid, hexaflunuron, lindane.

Particularly preferred is the use of synergistic mixtures

• Tebuconazole and cyproconazole and optionally bromoconazole and / or Hexaconazoles and / or propiconazoles and / or tridemorph
• Tebuconazole and metconazole and optionally cyproconazole and / or Hexaconazole and / or tridemorph
• Tebuconazole and hexaconazole and optionally cyproconazole and / or Metconazole and / or Bromoconazole and / or Tridemorph
• Tebuconazole and 1- (2-chlorophenyl) -2- (1-chloro-cycloprop-1-yl) -3- (1,2,4-triazole) 1-yl) -propan-2-ol and optionally cyproconazole and / or metconazole and / or bromoconazole and / or hexaconazole and / or tridemorph
• Tebuconazole and Tridemorph and optionally cyproconazole and / or Propiconazole and / or Bromoconazole and / or Hexaconazole and / or penconazole,  
• Tebuconazole and propiconazole and optionally cyproconazole and / or Bromoconazole and / or hexaconazole and / or metconazole and / or tride morph and / or penconazole and / or 1- (2-chlorophenyl) -2- (1-chlorocycloprop-1-one) yl) -3- (1,2,4-triazol-1-yl) -propan-2-ol
• - Cyproconazole and Bromoconazole and / or Metconazole and / or Hexaconazole and / or tridemorph,
• - hexaconazole and bromoconazole and / or metconazole and / or penconazole and / or tridemorph,
• - penconazole and cyproconazole and / or metconazole and / or bromoconazole and / or tridemorph.

The synergistic effect of the mixtures is in mixing ratios of 99: 1 to 1: 99, preferably from 3: 1 to 1: 3, very particularly preferably in the ratio 1: 1 observed.

The ratio of copper ions to the sum of fungicide mixture should be at least 1: 2.5 to 1000: 1; preferred are mixtures with 5: 1 to 500: 1, completely particularly preferably 10: 1 to 100: 1.

Additive boron salts or boric acid as well as nitrite (as eg sodium nitrite) are related preferably added to the copper ions in the ratio 1: 50 to 50: 1. The exact Quantity is to be oriented in each case on the specific fungicide mixture and is directed as well as the amount of optionally added emulsifier after the Water solubility of the resulting finished mixture.

An emulsifier is, for example, an anionic, cationic or nonionic Emulsifier or a mixture thereof. Nonionic emulsifiers are z. B. Addition products of ethylene oxide (EO) or propylene oxide or mixtures thereof on organic hydroxy compounds, for example alkylphenols, fatty acid, fat alcohols and mixtures thereof. As cationic emulsifiers z. B. quaternary Ammonium compounds and / or salts of fatty amines (eg dimethyl (C₁₂-) C₁₄) alkylamine) find use.

The polymeric quaternary ammonium borates are substances that are obtained by simultaneous reaction of amines of the general formulas I or II

with from 2 to 20, preferably from 3 to 10, moles of ethylene oxide or propylene oxide and from 0.6 to 1.5, preferably 1 mole of boric acid, boric acid esters or salts of boric acid, in each case per mole of nitrogen equivalent, R¹ being C₈-C₂₂-alkyl or C₈- C₂₂ alkenyl or, when R² and R³ are groups of the formula - (C₂H₄O) _x H or - (C₃H₆O) _x H, R¹ may also be C₁-C₄ alkyl, R² is hydrogen, C₁-C₂₂ alkyl or a group of the formulas - (C₂H₄O) _x H, (C₃H₆O) _x H or CH₂CH₂CH₂NH₂, R⁴ and R⁶ C₁-C₄ alkyl or a group of the formulas - (C₂H₄O) _x H or - (C₃H₆O) _x H, R⁵ and R⁷ is a Group of formula - (C₂H₄O) _x H or (C₃H₆O) _x H, A is a group of the formulas - (CH₂) _n -, - (CH₂CH₂OCH₂OH) n or - (CH₂CH₂NHCH₂CH₂) _n -x numbers from 1 to 55 and n is an integer Number from 1 to 20 mean.

As amines of the above formulas, the following are preferred:

• 1. Amides of the formula I, wherein R¹ is C₈-C₂₂-alkyl, R² is C₈-C₂₂-alkyl or C₁-C₄-alkyl and R³ is hydrogen or a group of the formulas - (C₂H₄O) _x H or - (C₃H₆O) _x H.
• 2. Amines of the formula I, wherein R¹ is C₈-C₂₂-alkyl and R² and R³ is hydrogen mean.
• 3. Amines of the formula I, wherein R¹ is C₁-C₄-alkyl or C₈-C₂₂-alkyl and R² and R³ are groups of the formulas - (C₂H₄O) _x H or - (C₃H₆O) _x H, where the sum of the ethylene oxide groups in both radicals R² and R³ is 2 to 20.
• 4. Amines of the formula I, wherein R¹ is C₈-C₂₂-alkyl, R² is hydrogen or a Group of the formula -CH₂CH₂CH₂NH₂ and R³ is a group of the formula Mean -CH₂CH₂CH₂NH₂.  
• 5. Amines of the formula II, where A, R⁴, R⁵, R⁶ and R⁷ are those mentioned above Meanings and where the sum of all ethylene oxide groups 4 to 30 is.

In the alkylene oxide groups of the formulas - (C₂H₄O) _x H and - (C₃H₆O) _x H, the group of the formula - (C₂H₄O) _x H is preferred. Instead of the pure polyoxethylene and polyoxpropylene groups, it is also possible for those radicals which are composed of both ethylene oxide and propylene oxide units to be present.

The reaction of the amines with the boric acid and the alkylene oxide takes place in the Manner that submitted to an autoclave the respective amine and the boric acid and the alkylene oxide is added. 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 addition of the alkylene oxide under These reaction conditions take place over a period of 1 to 5 hours. to After-reaction, the mixture at the indicated pressure for 3 to 12 hours a temperature of 70 to 120 ° C, preferably 70 to 100 ° C held.

Instead of boric acid and their esters, such as. B. Trimethylborsäureester or their salts, for example Na borate can be used. When the reaction arises as by-products water and polyglycols.

The resulting polymeric, quaternary ammonium compounds contain in essence as structural feature groups of the formula

or groups of the formula

when the reaction was made with ethylene oxide. They are as polymeric betaines to watch.

Compounds of the above type and their preparation are described in EP-556 454 and EP 355,316.

A quaternary ammonium compound is z. Example, a compound according to the general formula R¹R²R³R⁴N + Z-, wherein
R¹ represents an alkyl radical having 8 to 20 carbon atoms, in particular an alkyl radical having 12 to 20 carbon atoms or a benzyl radical which is optionally substituted by C₁- to C₂₀-alkyl or halogen,
R² is C₁ to C₆-alkyl, C₃ to C₉-alkoxyalkyl, polymeric ethylene oxide (EO) or propylene oxide (PO) with EO or PO n = 2 to 50,
R³ is C₁ to C₆-alkyl, C₃ to C₄-alkoxy, polymers ethylene oxide (EO) or propylene oxide (PO) with EO or PA n = 2 to 50,
R⁴ C₁ to C₂₀ alkyl
or each two of the radicals R¹ to R⁴ together with the nitrogen atom form a heterocyclic radical containing 4 to 5 C atoms and one, two or three double bonds, wherein the carbon atoms are optionally substituted by C₁- to C₄-alkyl or halogen and Z is an acid radical, e.g. B. halide means.

Aliphatic carboxylic acids can improve the homogeneity of the concentrates be added. Such acids are for. For example, propionic acid, hexanoic acid, heptane acid, branched carboxylic acids such. For example, 2-ethylhexanoic acid, isooctanoic acid, neo carboxylic acids, aliphatic dicarboxylic acids such as. B. sebacic acid, cycloalkylcarbon acids such. For example, cyclohexanoic acid, arylcarboxylic acids such as. B. benzoic acid, 3- or  4-hydroxybenzoic acid or alkoxybenzoic acid, tartaric acid or glycine or the salts acids such as sodium, potassium salts.

When using the abovementioned acids, it is partly advantageous by addition of complexing, polymeric nitrogen compounds such. As polyethyleneimines to improve the wood preservative penetration in large-scale processes.

Polyethyleneimines (PEI, polymine) are known and are formed by polymerization of 1,2-ethyleneimine. In them, the nitrogen is primary (end group), secondary and tertiary (branching). Suitable polyethylenimines with n greater than 10; very good results are achieved when PEI is used with a polymer degree n between 50 and 1000.

The wood preservatives may optionally contain other compounds, e.g. B. Verbindun with a fungicidal anion such as a boron compound (eg, alkali borate, amine borate, boric acid, boric acid esters), fluorides (eg potassium fluoride and / or Salts of fluoroboric acid and / or fluorophosphoric acid and / or difluorophosphorus acid).

By adding further active ingredients, the range of effect of the erfindungsge if appropriate, wood preservatives may be improved. Suitable compounds are z. B. N-Organodiazeniumdioxyverbindungen, organotin compounds, FITS tributyl (TBT) tin compounds, isothiazoline compounds of the following formula

R¹ is hydrogen- an alkyl, alkenyl, alkynyl radical having 1 to 18 carbon atoms, cycloalkyl radical having a C₃ to C₆ ring and having up to 12 carbon atoms, an aralkyl or aryl radical having up to 19 carbon atoms,
R², R³ are independently hydrogen, halogen or C₁ to C₄-alkyl radical or R² and R³ part of an aromatic radical or
R²-R⁶ form -CH₂-CH₂-CH₂-.

An addition of other fungicides or insecticides is possible, for. B. in emulsified form, such as
N-tridecyl-2,6-dimethymorpholine (tridemorph) and / or
4- (3-para-tertiary-butylphenyl) 2-methyl-propyl-2,6-cis-dimethylmorpholine (Fenpropi morph) and / or
aldimorph,
chlorinated phenols
Tetrachlorisophthalsäure-dinitrile,
N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide,
N-dimethyl-N'-phenyl- (N-fluoromethylthio) -sulphamide,
N, N-dimethyl-N'-tolyl (N-fluoromethylthio) -sulphamide,
Benzimidazole-2-carbamate methylester,
2-thiocyanomethyl-thiobenzothiazole,
2-Iodbenzoesäureanilid,
1- (1 ', 2', 4'-triazolyl-1 ') - (1- (4'-chlorophenoxy) -3,3-dimethyl-butan-2-one,
1- (1 ', 2', 4'-triazolyl-1 ') - (1- (4'-chlorophenoxy) -3,3-dimethyl-butan-2-ol,
hexachlorocyclohexane,
0,0Diethyl-dithio-phosphoryl-methyl-6-chlorobenzoxazolone,
2- (1,3-thiazol-4-yl) -benzimidazole,
N-trichloromethylthio-3,6,7,8-tetrahydrophthalimide,
N- (1,1,2,2-tetrachloroethylthio) -3,6,7,8-tetrahydrophthalimide,
N-trichloromethylthiophthalimide.
3-Iodo-2-propylbutylcarbamat,
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-diethyl-O- (α-cyanbenzyliden-amino) -thiophosphate,
6,7,8,9,10-hexachloro, 1,5,5a, 6,9,9a-hexahydro-6,9-methanol-2,3,4-benzoedioxothiepien-3-oxide,
(4-ethoxyphenyl) - (dimethyl) - (3- (4-fluoro-3-phenoxy-phenyl) -propyl-si-lane,
2-sec-butyl-phenyl-N-methylcarbamate,
2-1-propoxyphenyl N-methylcarbamate,
N-methyl-1-naphthyl-carbamate,
Norbornene dimethanohexa-chlorcyclosulfit,
1- (4-chlorophenyl) -3- (2,6-di-fluorobenzoyl) -urea.

Acypetacs, 2-aminobutane, ampropylfos, anilazine, benalaxyl, bupirimate, Quinomethionate, chloroneb, chlozolinates, cymoxanil, dazomet, diclomezine, Dichloram, Dietholtcarb, Dimethirimol, Diocab, Dithianone, Dodine, Drazoxolone, Edifenphos, Ethirimol, Etridiazole, Fenarimol, Fenitropan, Fentin acetate, Fentin Hydroxides, ferimzone, fluazinam, fluromides, flusulfamides, flutriafol, fosetyl, Fthalides, Furalaxyl, Guazatine, Hymexazole, Iprobenfos, Iprodione, Isoprothiolanes, Metalaxyl, methasulfocarb, nitrothal-isopropyl, nuarimol, ofurace, oxadiyl, Perflurazoate, pencycuron, phosphodiphene, pimaricin, piperaline, procymidone, Propamocarb, Propineb, Pyrazophos, Pyrifenox, Pyroquilon, Quintozene, Tar Oils, Tecnazene, thicyofen, thiophanate-methyl, tolclofos-methyl, triazoxide, Trichlamides, tricyclazoles, triforines, vinclozolin.

Surprisingly, these drug combinations show a particularly high, mitcrobicidal, in particular fungicidal action, combined with a broad action spectrum against microorganisms and insects relevant in wood preservation; they are ahead all effective against molds, wood-discolouring and wood-destroying fungi and Insects. By way of example but without limitation, the following groups of Called microorganisms:

• A: Wood discoloring mushrooms:
  • A1: Ascomycetes:
    Ceratocystis such as Ceratocystis minor
  • A2: Deuteromycetes:
    Aspergillus as Aspergillus niger
    Aureobasidium such as Aureobasidium pullulans
    Dactylium such as Dactylium fusarioides
    Penicillium such as Penicillium brevicaule or
    Penicillium variabile
    Sclerophoma like Sclerophoma pithyophila
    Acopularia like Scopularia phycomyces
    Trichoderma like Trichoderma viride or
    Trichoderma lignorum
  • A3: Zygomycetes:
    Mucor like Mucor spinorus
• B: Wood-destroying mushrooms:
  • B1: Ascomycetes:
    Chaetomium like Chaetomium globosum or
    Chaetomium alba-arenulum
    Humicola like Humicola grisea
    Petriella as Petriella setifera
    Trichurus like Trichurus spiralis
  • B2: Basidiomycetes:
    Coniophora like Coniophora puteana
    Coriolus like Coriolus versicolor
    Donkioporia like Donkioporia expansa
    Glenospora as Glenospora graphii
    Gloeophyllum such as Gloeophyllum abietinum or
    Gloeophyllum adoratum or Gloeophyllum protactum or
    Gloeophyllum sepiarium or Gloeophyllum trabeum
    Lentinus such as Lentinus cyathiformes or
    Lentinus edodes such as Lentinus lepideus or
    Lentinus grinus or Lentinus squarrolosus
    Paxillus like Paxillus panuoides
    Pleurotus such as Pleurotus ostreatus
    Poria like Poria monticola or Poria placenta or
    Poria vaillantii or Poria vaporaria
    Serpula like Serpula himantoides or
    Serpula lacrymans
    Stereum like Stereum hirsutum
    Tyromyces such as Tyromyces palustris
  • B3: Deuteromycetes:
    Alternaria like Alternaria tenius
    Cladosporium like Cladosporium herbarum
    Alternaria tenuis
• C. Wood-destroying insects like
  • C1: Beetle
    Hylotrupes bajulus. Chlorophorus pilosis, Anobium punctatum, Xesto bium 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 minutus
  • C2: Hymenoptera
    Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur
  • C3: termites
    Kalotermes flavicollis, Cryptotermers brevis, Heterotermes indicola, Reti culitermes flavipes, Reticulitermes santonensis, Reticulitermes lucilugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formo sans.

The amount of agents or concentrates used is of the type and Occurrence of insects, microorganisms, germ count and medium dependent. The optimal amount can be used in each case by Test series are determined. In general, however, it is sufficient to 0.001 to 20 wt .-%, preferably 0.05 to 10 wt .-%, of the active ingredient mixture, based on the to be protected material to use.  

The insecticides are generally in an application concentration of 0.00001% to 10%, preferably 0.00001% to 5%, more preferably 0.001% to 1% before.

The formulations mentioned can be prepared in a manner known per se, z. B. by mixing the active ingredients with a solvent or diluent, Emulsifier, dispersing and / or binding or fixing agent, water repellent, optionally siccative and UV stabilizers and optionally dyes and Pigments and other processing aids.

As solvent and / or diluent is optionally used in addition to water organic-chemical solvent or solvent mixture and / or an oily or oleaginous volatile organic-chemical solvent or solution medium mixture and / or a polar organic-chemical solvent or Lö solvent mixture.

As organic-chemical solvents are preferably oily or oil-like Lö agent with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C used. As such low-volatility, water insoluble, oily and oily solvents are corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably Example, white spirit, petroleum and / or alkylbenzene used.

Advantageously, mineral oils having a boiling range of 170 to 220 ° C., White spirit with a boiling range of 170 to 220 ° C, spindle oil with a boiling point range from 250 to 350 ° C, petroleum or aromatics of the boiling range from 160 to 280 ° C, turpentine oil and the like are used.

In a preferred embodiment, liquid aliphatic hydrocarbons substances with a boiling range of 180 to 210 ° C or high-boiling mixtures of aromatic and aliphatic hydrocarbons having a boiling range of 180 to 220 ° C and / or spindle oil and / or monochloronaphthalene, preferably α-monochloronaphthalene used.

The organic low volatility oily or oily solvents with a Ver Evaporation rate above 35 and a flash point above 30 ° C, preferably above  45 ° C, can partially by slightly or medium-volatile organic chemical Lö be replaced with the proviso that the solvent mixture also an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture in this solution medium mixture is soluble or emulsifiable.

According to a preferred embodiment, hydroxyl and / or ester and / or aliphatic organochemical solvents containing ether groups such as glycol ethers, esters or the like. For use.

As organic-chemical binders are used in the context of the present invention the known water-dilutable and / or in the used organic chemical solvents soluble or dispersible or emulsifiable synthetic resins and / or binding drying oils, in particular binders consisting of or containing an acrylate resin, a vinyl resin, e.g. B. polyvinyl acetate, polyester resin, Polykondensations- or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin preferably with medium oil length, phenolic resin, Hydrocarbon resin such as indene cumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders on the base a natural and / or synthetic resin used.

The resin used as a binder may be in the form of an emulsion, dispersion or solution can be used. As binders can also bitumen or bitumi nous substances are used up to 10 wt .-%. In addition, in itself can known dyes, pigments, water repellents, odorants and Inhibitors or corrosion inhibitors and the like. Be used.

It is preferred according to the invention as organic-chemical binder at least an alkyd resin or modified alkyd resin and / or a drying vegetable oil contained in the middle or in the concentrate. Preferred according to the invention Alkyd resins having an oil content of more than 45% by weight, preferably 50 to 68 wt .-%, used.

The mentioned binder can be wholly or partly by a fixation medium (mixture) or a plasticizer (mixture) are replaced. These additives should  volatilization of the active ingredients and crystallization or precipitation prevent. Preferably, they 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, Adipinsäureester such as di (2-ethylhexyl) adipate, stearates such as butyl stearate or Amyl stearate, oleates such as butyl oleate, glycerol ethers or higher molecular weight glycol ethers, Glycerol ester and p-toluenesulfonic acid ester.

Fixing agents are chemically based on polyvinyl alkyl ethers such. For example, polyvinylmethyl ethers or ketones such as benzophenone, ethylene benzophenone.

In addition to these aids are preferably also in EP-383 746, pages 5-6 used as a component for wood preservatives.

Under wood, which by the agent according to the invention or this containing Mi is to be understood as exemplary: lumber, wooden beams, Railway sleepers, Bridge parts, Jetties, Wooden vehicles, Crates, Pallets, Con tainer, telephone poles, wooden cladding, wooden windows and doors, plywood, Particleboard, carpentry or wood products, generally used in house building or use in the joinery.

A particularly effective wood protection is achieved by large-scale impregnation, z. As vacuum, double vacuum or printing process achieved.

The water-dilutable wood preservatives contain - in concentrated form - the Triazole / fungicide or insecticide mixture generally in amounts of 0.01 to 95 wt .-%, in particular 0.01 to 60 wt .-%.

The water-dilutable wood preservatives contain - in concentrated form - the Copper is calculated as metal in general, e.g. In an amount of 1.0 to 15.0% (Weight percent).  

Suitable concentrates consist for. B. off
0.50 to 45% copper compounds
From 5.00 to 50% alkanolamine
0.25 to 15% synergistic triazole / fungicide or insecticide mixture
0.5 to 30% of an emulsifier and / or a phosphonium compound and / or tridemorph or aldimorph
0 to 40% compound with a fungicidal inorganic or organic anion
0 to 40% organic solvents
0 to 40% of an aliphatic mono- or dicarboxylic acid and / or cycloalic acid and / or cycloarylcarboxylic acid and / or boric acid or a borate
0 to 15% of a complexing, polymeric nitrogen compound
wherein the sum each gives 100 wt .-%, and optionally minor amounts of other ingredients, such as. As ammonia, corrosion inhibitors, complexing acids (eg., Nitrilotriacetic acid, ethylenediaminetetraacetic acid when using water with higher degrees of hardness) and, if necessary, water, the proportion of which, however, can be kept low in general and the handling wesent union serves.

However, the invention extends next to the wood preservatives (concentrates) glei so to speak, to the producible by dilution of the concentrates with water Impregnating solutions correspondingly lower individual concentration. The application concentration is z. B. 0.01 to 1.50 wt .-% metal, for. As copper, in the aqueous Impregnating solution, depending on the type of impregnation and the degree of risk of impregnating wood.

By dissolving the copper salts, optionally with heat, into the alkanol amines, optionally with addition of acid, water or solvent, and on closing addition of the emulsifier, the triazole compounds and the syner gistic mixing partner produces highly concentrated pastes, liquid concentrates or also two-phase mixtures, which after dilution with water to Im  can be used to accentuate wood. They also result in high Concentrate in water a clear liquid.

The application of impregnating solution to protect wood can be done by craft Liche procedures such as spraying, brushing, diving, trough or through large-scale processes such as boiler pressure processes, alternating pressure processes, Double vacuum process done. Under "wood" are both solid wood and To understand wood-based materials such as chipboard, plywood; here may be the Wood preservatives are also introduced in Leimeuntermischverfahren.

The copper fixation of the wood preservatives of the invention is high when used for Large-scale process is more than 90%.

The concentrates or solutions may be emulsified by water or in water gable dyes and / or pigment preparations are colored.

An addition of wax, paraffin and / or acrylate dispersions to obtain a water repellent effect or improvement of fixation is possible.

Optionally, the concentrates may also be used in binder-containing water thinnable systems (primers, glazes) are incorporated.

The compositions of the invention advantageously allow the previously available to replace funds with more effective ones. They show good stability and have in advantageously a broad spectrum of activity.

Examples example 1

A concentrate Wt .-% Monoethanolamine 23.1 xylene 3.8 process oil 4.0 boric acid 16.9 Copper carbonate, basic 10.9 tebuconazole 0.14 cyproconazole 0.10 emulsifier 1.2 permethrin 0.7 Water, ad 100

Example 2

A concentrate Wt .-% xylene 50 cyclohexanone 30 Castor oil polyglycol ether (36 mol ethylene oxide) 4 dodecylbenzenesulfonates 3 Octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3 tebuconazole 5 cyproconazole 4

Example 3

use solution Wt .-% boric acid 0.8 ammonia 0.6 sodium nitrite 1.3 lactic acid 2.15 Copper sulfate · 5 H₂O 1.18 cypermethrin 0.05 tebuconazole 0.02 metconazole 0.02 emulsifier 0.10 Water, ad 100

Example 4

concentrate Wt .-% permethrin 0.6 Monoethanolamine 33.5 Copper carbonate, basic 14.0 boric acid 7.5 propionic 6.0 Nonylphenol, ethanilated (about 10 moles of ethylene oxide) 10 propylene glycol 6 tebuconazole 2 bromoconazole 1.5 Water, ad 100

Example 5

concentrate Wt .-% Monoethanolamine 35 benzoic acid 21 Copper carbonate, basic 14 tebuconazole 2.5 hexaconazole 1.5 propylene glycol 6 Nonylphenol, ethoxylated 10 Water, ad 100

Example 6

use solution Wt .-% boric acid 1 sodium nitrite 1.5 benzoic acid 1.5 Copper sulfate · 5 H₂O 1.3 cyfluthrin 0.06 tebuconazole 0.03 cyproconazole 0.01 emulsifier 0.14 ammonia 0.7 Water, ad 100

Example 7

use solution Wt .-% Zinkoctanat 3 sodium nitrite 1.0 2-ethylhexanoic 2.0 Copper carbonate, basic 1.1 cyfluthrin 0.03 tebuconazole 0.01 cyproconazole 0.02 emulsifier 0.17 ammonia 0.7 Water, ad 100

Example 8

concentrate Wt .-% Copper carbonate, basic 12.4 ethanolamine 27.3 2-ethylhexanoic 2.5 tebuconazole 0.9 Wocosan (88% propiconazole) 1.0 Cyflutrin 0.02 tridemorph 7.0 Water, ad 100

Example 9

use solution Wt .-% Zinkoctanat 3 sodium nitrite 1.0 2-ethylhexanoic 2.0 Copper carbonate, basic 1.1 cyfluthrin 0.03 cyproconazole 0.04 emulsifier 0.17 ammonia 0.7 Water, ad 100

Example 10

concentrate Wt .-% Copper carbonate, basic 12.4 ethanolamine 27.3 2-ethylhexanoic 2.5 cyproconazole 2.9 Cyflutrin 0.02 tridemorph 7.0 Water, ad 100

Claims (2)

1. Wood preservative containing in addition to at least one copper compound and at least one alkanolamine, a triazole compound and at least one another fungicide and / or insecticide that complement each other synergistically, as well as optionally an emulsifier. 2. Use of an agent containing at least one copper compound, at least one alkanolamine, a triazole compound and at least one synergistically complementary further fungicide and / or insecticide for the protection of Wood and wood materials.