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WO1995011786A1 - Produit de protection du bois contenant un compose du cuivre - Google Patents

Produit de protection du bois contenant un compose du cuivre 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
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German (de)
English (en)
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/de
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/fr

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

Abstract

La présente demande concerne un produit ou un concentré pour la conservation du bois ou de matériaux à base de bois, contenant un composé du cuivre, un triazole et au moins un autre fongicide et/ou insecticide à action synergique, un aminoalcool et le cas échéant un émulsifiant. Le produit de protection du bois peut également comporter des composés du bore, des ions nitrite ou d'autres auxiliaires.
PCT/EP1994/003370 1993-10-26 1994-10-13 Produit de protection du bois contenant un compose du cuivre WO1995011786A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU78136/94A AU7813694A (en) 1993-10-26 1994-10-13 Timber protecting medium containing a copper compound

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE4336474 1993-10-26
DEP4336474.8 1993-10-26
DEP4340853.2 1993-12-01
DE4340853A DE4340853A1 (de) 1993-10-26 1993-12-01 Holzschutzmittel enthaltend eine Kupferverbindung

Publications (1)

Publication Number Publication Date
WO1995011786A1 true WO1995011786A1 (fr) 1995-05-04

Family

ID=25930722

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/003370 WO1995011786A1 (fr) 1993-10-26 1994-10-13 Produit de protection du bois contenant un compose du cuivre

Country Status (2)

Country Link
AU (1) AU7813694A (fr)
WO (1) WO1995011786A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999037450A1 (fr) * 1998-01-24 1999-07-29 Bayer Aktiengesellschaft Produits de preservation du bois

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0705160A1 (fr) * 1993-06-21 1996-04-10 Bayer Ag Combinaisons de matieres actives fongicides

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0385076A1 (fr) * 1989-03-02 1990-09-05 DESOWAG Materialschutz GmbH Agent ou concentrat de préservation du bois ou des matériaux en bois
WO1991001640A1 (fr) * 1989-07-31 1991-02-21 Chinoin Gyógyszer És Vegyészeti Termékek Gyára Rt Nouvelles compositions combinees de lutte contre les insectes et parasites
EP0514644A2 (fr) * 1991-04-18 1992-11-25 Dr. Wolman GmbH Agent préservatif du bois
WO1993002557A1 (fr) * 1991-08-01 1993-02-18 Hickson International Plc Agents de conservation pour le bois et autres materiaux cellulosiques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0385076A1 (fr) * 1989-03-02 1990-09-05 DESOWAG Materialschutz GmbH Agent ou concentrat de préservation du bois ou des matériaux en bois
WO1991001640A1 (fr) * 1989-07-31 1991-02-21 Chinoin Gyógyszer És Vegyészeti Termékek Gyára Rt Nouvelles compositions combinees de lutte contre les insectes et parasites
EP0514644A2 (fr) * 1991-04-18 1992-11-25 Dr. Wolman GmbH Agent préservatif du bois
WO1993002557A1 (fr) * 1991-08-01 1993-02-18 Hickson International Plc Agents de conservation pour le bois et autres materiaux cellulosiques

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999037450A1 (fr) * 1998-01-24 1999-07-29 Bayer Aktiengesellschaft Produits de preservation du bois

Also Published As

Publication number Publication date
AU7813694A (en) 1995-05-22

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