NZ275812A - Wood preservative comprising at least one copper compound, at least one triazole compound, and one or more alkanolamines - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £7581 £ New Zealand No. 275812 International No. PCT/EP94-/03687 Priority Dst»{s): Complete Specification Rl»d: Claw: (6) 7'6'TOT1997 Publication Date;, P.O. Journal No: NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION Title of Invention: Timber preservative containing a copper compound Name, address and nationality of applicant(s) as in international BAYER*'AKtIbMESELLSCHAFT. company of D 5! 368 Leverkusen, Federal Republic of Germany 27 S%i2 t- Wood preservatives comprising a cornier compound The application relates to wood preservatives comprising at least one copper compound, a triazole compound and at least one alkanolamine.

Wood preservatives based on inorganic copper compounds with alkanolamines as complexing agents have been disclosed (EP 89 958). Despite high copper contents, the activity of these compositions against wood-destroying Basidiomycetes is insufficient in comparison with known copper- and chromate-containing salts with a similar copper content.

Wood preservatives based on copper compounds and alkanolamines which comprise a triazole compound and an emulsifier or a phosphonium compound and which are active against wood-destroying Basidiomycetes have also been disclosed (DE 4 112 652 corresponding to EP-A 514,644 and NZ-A 242,404).

It was the aim and object of the present invention to find a wood preservative which is highly active against wood-discolouring and wood-destroying fungi and, preferably, also against wood-damaging insects, in particular against wood-destroying longhom beetles (Cerambycidae, Lyctidae, Bostrychidae and Anobiidae) including termites and which has a good long-term action, the activity of the fungicide not being adversely affected by the insecticide and vice versa. Moreover, the wood preservative was to have good penetration capacity in wood and in derived timber products.

Furthermore, it was intended to provide a clear formulation which is easy to handle, has a long shelf life and does not comprise additional emulsifier. m 275 8 1 2 Surprisingly, it has now been found that just such wood preservatives can be prepared using suitable alkanolamines or alkanolamine mixtures without employing additional emulsifiers.

The invention therefore relates to a wood preservative comprising, in addition to at least one copper compound, at least one triazole compound and alkanolamines of formula (I), below, or 5 alkanolamine mixtures comprising at least one compound of formula (I) together wife at least one alkanolamine selected from isopropanolamine, aminoethylethanolamine, diethanolamine, triethanolamine, methylethanolamine and monoethyanolamine and, if appropriate, a further fungicide and/or insecticide, and, if appropriate, an emulsifier.

The advantage of the compositions according to the invention is that, for example, triazole compounds which are insoluble in water are present in the new compositions 10 in the form of aqueous emulsions or clear aqueous concentrates despite the copper compound content. Clear aqueous fluids are formed upon dilution with water.

Homogeneous concentrates can be obtained by adding small amounts of organic solvents to the wood preservative, for example alcohols (ethanol, isopropanoi), glycols (ethylene glycol, propylene glycol), glycol ethers (ethylene glycol monomethyl ether, 15 ethylene glycol monoethyl ether), glycol ether esters (butyl glycol acetate), dimethylformamide or N-methylpyrrolidone. The solvents additionally act as solubilizers for the fungicides. However, to obtain homogeneous concentrates, the use of solvents may be reduced to a minimum if arylcarboxylic acids, cycloalkylcarboxylic acids or aliphatic C5-C20-mono- or dicarboxylic acids or corresponding amine, alkali metal or 20 copper salts are additionally used. In any case, one component of the mixture or the concentrate is water.

Copper compounds can be employed as compounds which are soluble or insoluble in water, for example copper sulphate, copper acetate, copper hydroxide, copper oxide, copper borate, copper fluoride, copper hydroxide carbonate, copper chloride or copper 25 phosphate.

Alkanolamines are compounds of the general formula (I) Le A 30 003 - PCT - 2 - 275812 \ .2/ N-R3 R in which R1 denotes optionally substituted alkyl, substituted aryl, substituted alkenyl, alkylcarbonyl, arylcarbonyl, substituted alkenylcarbonyl or alkinylcarbonyl, R2 has the meaning of R1, H or R\ R3 denotes (CHrCH,-0)nH or (CHrCHCH3-0)mH, m denotes 1 to 40.

Suitable as the alkanolamine are, in particular, ethoxylated or propoxylated alkanolamines, such as tallow fatty amine * 10 ethylene oxide (E0), coconut fatty amine x 5 E0, tallow fatty alkylpropylenediamine * 5 E0, stearic acid ethanolamide, methylsteaiylamine x 4 E0, alkylaminomethylphenol x 10 E0, and their salts or their propylene oxide analogues. Also of particular interest are mixtures of these alkanolamines with other alkanolamines, such as, for example, isopropanolamine, aminoethylethanolamine, diethanolamine, triethanolamine, methylethanolamine, in particular monoethanolamine.

Preferred alkanolamine mixtures contain 50 to 90 % of monoethanolamine and 5 to 50 % of a further alkanolamine which is an ethoxylated or propoxylated fatty amide or fatty amine. n denotes 1 to 40 and The amount of the alkanolamines added is advantageously chosen such that a pH of 7 or more, preferably 8.5 to 10.5, is established in the dilute aqueous impregnating Le A 30 003 - PCT - 3 - 275812 solution. The amount of the alkanolamines should be sufficient both for complexing the copper and to act as a solubilizer for the triazole compounds.

Triazole compounds which are preferably employed are the following compounds: amitrole, azocyclotin, BAS 480F, bitertanol, difenoconazole, fenbuconazole, fenchlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol, imibenconazole, isozofos, myclobutanil, epoxyconazole, paclobutrazol, penconazole, propiconazole, (±)-cis-l-(4-chlorophenyl)-2-(l H-1,2,4-triazol-1 -yl)-cycloheptanol, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, uniconazole.

The following triazole compounds are very particularly preferred: azaconazole, bromuconazole, cyproconazole, dichlobutrazol, dinicohazole, hexaconazole, metaconazole, penconazole, propiconazole and tebuconazole.

The triazole compounds, such as, for example, tebuconazole, are preferably employed % in combination with further fungicides and/or insecticides which complement each other synergistically. Fungicides which may be mentioned in addition to the triazoles already mentioned are: methyl(E)-methoximino[a-(o-tolyloxy)-o-tolyl)]acetate, methyl(E)-2- {2-[6-(2-cyano-phenoxy)-pyriifiidin-4-yl-oxy]phenyl}-3-methoxyacrylate, methfuroxam, carboxin, fenpiclonil, 4(2,2-difluoro-l ,3-benzodioxol-4-yl)-l H-pyrrole-3-carbonitrile, butenafine and/or 3-iodo-2-propiny 1 n-butylcarbamate.

Synergistic fungicidal or insecticidal components which are also preferably employed are the following fungicides or insecticides. imazaiil, pefurazoate, prochloraz, triflumizole, 2-(l-tert-butyl)-l-(2-chlorophenyl)-3-(l,2,4-triazol-l-yl)-propan-2-ol,thiazolecarboxanilidessuchas 2',6'-dibromo-2-methyl-4-trifluoromethoxy-4,-trifluoromethyl-l,3-thiazole-5-carboxanilides, and their metal salts and acid adducts.

Methyl(E)-2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl]3-methoxyacrylate, Le A 30 003 - PCT - 4 - 275812 methyl(E)-2-[2-[6-(2-thioamidophenoxy)pyrimidin-4-yIoxy]phenyl]-3-rnethoxyacrylate, methyl(E)2-[6-(2-fluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, methyl(E)-2-[2-[6-(2,6-difluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, methyl(E)-2-[2-[3-(pyrimidin-2-yloxy)phenoxy]phenyl]-3-methoxyacrylate, methyl(E)-2-[2-[3-(5-methyIpyrimidin-2-yIoxy)-phenoxy]phenyl]-3-methoxyacrylate, methyl(E)- 2-[2-[3-(phenyl-sulphonyloxy)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-l-yl]-3-niethoxyacrylate, 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-dichloro-phenoxy)pyridin-3-yl]-3-methoxyacrylate, methyl(E)-2-(2-(3-(l ,1,2,2-tetrafluoro-ethoxy)phenoxy)phenyl)-3-methoxyacrylate, methyl(E)-2-(2-[3-(alpha-hydroxyben2yl)-phenoxy]phenyl)-3-methoxyacrylate, methyi(E)-2-(2-(4-phenoxypyridin-2-yloxy)-phenyl)-3-methoxyacrylate,methyl(E)-2-[2-(3-n-propyloxyphenoxy)phenyl]3-methoxy- acrylate, methyl(E)-2-[2-(3-isopropyloxyphenoxy)phenyl]-3-methoxyacrylate, methyl- % (E)-2-[2-[3-(2-fluorophenoxy)pehnoxy]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-cyanophenoxy)-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-methoxyacrylatte, methyl(E)-2-[2-(5-bromopyridin-2-yloxymethyl)phenyl]-3-methoxy-acrylate, methyl(E)-2-[2-(3-(3-iodopyridin-2-yloxy)phenoxy)phenyl]-3-methoxy-acrylate, methyl- (E)-2-[2-[6-(2-chloropyridin-3-yloxy)pyrimidin-4-yloxy]phexiyl]-3-methoxyacrylate, (E),(E)methyl - 2-[2-(5,6-dimethylpyrazin-2-ylmethyloximinomethyl)-phenyl]-3-methoxyacrylate, (E)-methyl - 2-{2-[6-(6-methylpyridin-2-yloxy)-pynmidin-4-yloxy]phenyl}-3-methoxyacrylate, (E),(E)methyl - 2-{2-(3-methoxyphenyl)-methyloximinomethyl]phenyl}-3-methoxyacrylate, (E)methyl - 2-{2-(6-(2-a2ido-phenoxy)pyrimidin-4-yloxy]phenyl}3-methoxyacrylate, (E),(E)methyl -2-{2-[6-phenyl-pyrimidin-4-yl)-methyloximinomethyl]phenyl} -3-methoxyacrylate, (E),(E)-methyl-2-{2-[(4-chlorophenyl)-methyloximinomethyl]phenyl}-3-methoxyacrylate, (E)methyl - 2-{2-[6-(2-n-propylphenoxy)-l,3,5-triazin-4-yloxy]phenyl}-3-methoxyacrylate, (E).(E)-methyl - 2-{2-[(3-nitrophenyl)methyloximinomethyl] phenyl}-3-methoxyacrylate; Le A 30 003 - PCT succinate dehydrogenase inhibitors, such as: 27 5 81 2 fenfuram, furcarbanil, cyclafluramid, 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-ine); sulfenamides, such as dichlofluanid, tolylfluanid, folpet, fluorfolpet, captan, captofol; benzimidazoles, such as carbendazim, benomyl, furathiocarb, fuberidazole, thiophonate-methyl, thiabendazole, or their salts; morpholine derivatives, such as tridemorph, fenpropimorph, falimoiph, dimethomorph, 10 dodemorph; aldimorph, fenpropidin and their arylsulphonate salts such as, for example, p-toluenesulphonic acid and p-dodecylphenyl-sulphonic 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 esters, borax; formaldehyde and formaldehyde-releasing compounds such as benzyl alcohol mono(poly)-hemiformal, oxazolidines, hexa-hydro-S-triazines, N-methylolchloroacetamide, paraformaldehyde, nitropyrine, oxolinic acid, tecloftalam; tris-N-(cyclohexyldiazeniumdioxy)-aluminium, N-(cyclo-hexyldiazeniumdioxy)-tributyltin 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-octyl-isothiazolin-3-one, 4,5-trimethylene-isothiazolinones, Le A 30 003 - PCT -6- 4,5-benzisothiazolinones, N-methylolchloroacetamide; 27 5 812 aldehydes, such as cinnamaldehyde, formaldehyde, glutardialdehyde, P-bromocinnamaldehyde; thiocyanates, such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate, etc; quaternary ammonium compounds, such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethaylammonium chloride; iodine derivatives, such as diiodomethyl p-tolyl sulphone, 3-iodo-2-propinyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenyl ethylcarbamate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propinyl n-hexylcarbamate, 3-iodo-2-propinyl cyclohexylcarbamate, 3-iodo-2-propinyl phenylcarbamate; % phenol derivatives, such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-ben2yl-4-chlorophenol, and their alkali metal and alkaline earth metal salts.

Microbicides having an activated halogen group, such as chloroacetamide, bronopol, bronidox, tectamers, such as 2-bromo-2-nitro-l,3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3-nitrile-propionamide, l ,2-dibromo-2,4-dicyanobutane, P-bromo- p-nitrostyrene; pyridines, such as l-hydroxy-2-pyridinethione (and their Na, Fe, Mn and Zn salts), tetrachloro-4-methylsulphonylpyridine, pyrimethanol, mepanipyrim, dipyrithione; metal soaps, such as tin napthtenate, tin octoate, tin 2-ethylhexanoate, tin oleate, tin phosphate, tin benzoate, copper naphtenate, copper octoate, copper 2-ethylhexanoate, copper oleate, copper phosphate, copper benzoate, zinc naphtenate, zinc octoate, zinc 2-ethylhexanoate, zinc oleate, zinc phosphate or zinc benzoate; Le A 30 003 - PCT - 7 - 27 S 81 L metal salts, such as sodium dichromate, potassium dichromate, potassium chromate, copper borate, zinc fluorosilicate or copper fluorosilicate.

Oxides, such as tributyltin oxide, Cu20, CuO, ZnO; dialkyldithiocarbamates, such as Na and Zn salts of dialkyldithiocarbamates, 5 tetramethylthiuram disulphide, potassium N-methyl-dithiocarbamate; nitriles, such as 2,4,5,6-tetrachloroisophthalodinitrile, disodium cyano-dithioimidocarbamate; 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)-l ,2-dithiol-3-one, 3,5-dimethyl-tetrahydro-l ,3,5-thiadiazine-2-thione, N-(2-p-chlorobenzoylethyl)-hexaminium chloride, potassium N-hy droxymethy 1-N-methyldithiocarbamate, 2-oxo-2-(4-hydroxy-phenyl)acethydroximoyl chloride, phenyl 2-chloro-cyano-vinyl sulphone, phenyl l,2-dichloro-2-cyano-vinyl sulphone; Ag-, Zn- or Cu-containing zeolites alone or included in polymeric active compounds; phosphoric esters, such as azinphos-ethyl, azinphos-methyl, a -1 (4-chlorophenyl)-4-(0-ethyl, S-propyl)phosphoryloxy-pyrazole,chlorpyrifos, coumaphos, demeton, demeton-S-20 methyl, diazinon, dichlorvos, dimethoate, ethoate, ethoprophos, etrimfos, fenitrothion, fenthion, heptenophas, parathion, parathion-methyl, phosalone, phoxim, pirimiphos-ethyl, pirimiphos-methyl, profenofos, prothiofos, sulfprofos, triazophos and trichlorphon; carbamates, such as aldicarb, bendiocarb, a-2-(l -methylpropyl)-phenylmethylcarbamate, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, cloethocarb, Le A 30 003 - PCT - 8 - 27 5 81Z isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarb; organosilicon compounds, preferably dimethyl(phenyl)silyl-methyl 3-phenoxybenzyl ethers, such as dimethyl-(4-ethoxyphenyl)-silylmethyl 3-phenoxybenzyl ether or (dimethylphenyl)-silyl-methyl-2-phenoxy-6-pyridylmethyl ethers, such as, for example, dimethyl-(9-ethoxy-phenyl)-silylmethyl-2-phenoxy-6-pyridylmethyither,or [(phenyl)-3-(3-phenoxyphenyl)-propyl](dimethyl)-silanes such as, for example, (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)-cyclopropanecarboxylate, 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-N'-methylacetamide (NI-25); abamectin, AO 303 630, acephate, acrinathrin, alanycarb, aldoxycarb, aldrin, amitraz, azamethiophos, 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, 0-2-tert-butyl-pyrimidin-5-yl o-isopropyl phosphorothiate, thiocyclam, thiofanox, thiometon, tralomethrin, triflumuron, trimethacarb, vamidothion, Verticillium Lacanii, XMC, xylylcarb, benfuracarb, bensultap, bifenthrin, bioallethrin, MERbioallethrin (S)-cyclopentenyl isomer, bromophos, bromophos-ethyl, buprofezin, cadusafos, calcium polysulfide, carbophenothion, cartap, quinomethionate, chlordane, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorpyrifos, cyanophos, beta-cyfluthrin, alpha-cypermethrin, cyophenothrin, cyromazine, dazomet, DDT, demeton-S methylsulphone, diafenthiuron, Le A 30 003 - PCT 27 5812 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, 5 hydramethylnon, hydrogen cyanide, hydroprene, IPSP, isazophos, .isofenphos, isoprothiolane, isoxathion, iodofenphos, kadethrin, lindane, malathion, mecarbam, mephosfolan, mercurous, chloride, metam, Metarthizium, anisopliae, methacrifos, methamidophos, methidathion, methiocarb, methoprene, methoxychlor, methyl isothiocyanate, metholcarb, mevinphos, monocrotophos, naled, Neodiprion sertifer NPV, 10 nicotine, omethoate, oxydemeton-methyl, pentachlorophenol, petroleum oils, phenothrin, phenthoate, phorate; acypetacs, 2-aminobutane, ampropylfos, anilazine, bcnalaxyl, bupirimate, quinomethionate, chloroneb, chlozolinate, cymoxanil, dazomet, diclomezine, dichloram, diethofencarb, dimethirimol, diocarb, dithianon, dodine, drazoxolon, edifenphos, ethirimol, etridiazole, fenarimol, fenitropan, fentin acetate, fentin hydroxide, ferimzone, * fluazdnam, fluromide, flusulfamide, flutriafol, fosetyl, fthalide, furalaxyl, guazatine, hymexazol, iprobenfos, iprodione, isoprothiolane, metalaxyl, methasulfocarb, nitrothal-isopropyl, nuarimol, ofurace, oxadiyl, perflurazoate, pencycuron, phosdiphen, pimaricin, piperalin, procymidone, propamocarb, propineb, pyrazophos, pyrifenox, pyroquilon, 20 quintozene, tar oils, tecnazene, thicyofen, thiophanate-methyl, tolclofos-methyl, triazoxide, trichlamide, tricyclazole, triforine, vinclozolin.

Particularly preferred wood preservatives contain , as insecticides, chlorpyrifos, phoxim, silafluofen, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, hexaflumuron, lindane.

Particularly preferred is the use of synergistic mixtures of tebuconazole and propiconazole and/or bromoconazole and/or hexaconazole, cyproconazole and bromoconazole and/or metaconazole and/or hexaconazole, hexaconazole and bromoconazole and/or metaconazole and/or penconazole, penconazole and cyproconazole and/or metaconazole and/or bromoconazole, propiconazole and 30 cyproconazole and/or hexaconazole and/or penconazole.

Le A 30 003 - PCT 275812 i The synergistic action of the mixtures is observed at mixing ratios of 99:1 to 1:99f preferably from 3:1 to 1:3, very particularly preferably in a ratio of 1:1.

The ratio of copper ions to the fungicide or to the total of the fungicide mixture should be at least 1:2.5 to 1000:1; mixtures with a ratio of 5:1 to 500:1 are preferred and 5 those with a ratio of 10:1 to 100: 1 are very particularly preferred.

Additional boron salts or boric acid and nitrite (for example in the form of sodium nitrite) are preferably to be added in a ratio of 1:50 to 50:1 based on the copper -"otfs. The exact amount is to be adapted in each case to the specific fungicide or fim^icide mixture and, just as the amount of emulsifier optionally to be added, depends on the 10 solubility in water of the resulting finished mixture.

Aliphatic carboxylic acids may 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, for example, 2-ethylenehexanoic acid, isooctanoic acid, neocarboxylic acids, aliphatic dicarboxylic acids, such as, for example, scbacic 15 acid, cycloalkylcarboxylic acids, such as, for example, cyclohexanoic acid, arylcarboxylic acids, such as, for example, benzoic acid or 3- or 4-hydroxybenzoic acid.

When using the abovementioned acids, it is advantageous in some cases to improve the penetration of the wood preservative in large-scale processes by adding complexing, polymeric nitrogen compounds, such as, for example, polyethyleneimines.

Polyethyleneimines (PEI, polymine) are known and formed by polymerization of 1,2-ethyleneimine. The nitrogen is present in primary form (terminal group), secondary form and tertiary form (branching). Suitable polyethyleneimines are those where n is greater than 10; very good results are achieved by using PEI with a degree of polymerization n of between 50 and 1000.

If appropriate, Lhe wood preservatives may contain other compounds, for example compounds having a fungicidal anion, such as, for example, a boron compound (for example alkali metal borate, amine borate, boric acid, boric esters), fluorides (for Le A 30 003 - PCT LI 00 I L example potassium fluoride and/or salts of fliioroboric acid and/or fluorophosphoric acid and/or difluorophosphoric acid).

Surprisingly, these combinations of active compounds have a particularly powerful microbicidal, in particular fungicidal, activity combined with a wide spectrum of action 5 against microorganisms and insects which are relevant in the preservation of wood; they are especially active against moulds, wood-discolouring and wood-destroying fungi and insects. The following groups of microorganisms may be mentioned by way of example but not by way of limitation.

A: Wood-discolouring fungi: Al: Ascomycetes Ceratocystis, such as Ceratocystis minor % A2: Deuteromycetes: Aspergillus, such as Aspergillus niger, Aureobasidium, such as Aureobasidium pullulans, 15 Dactylium, such as Dactylium fusarioides, Penicillium, such as Penicillium brevicaule or Penicillium variabile, Sclerophoma, such as Sclerophoma pithyophila . Acopularia, such as Scopularia phycomyces 20 Trichoderma, such as Trichoderma viride or Trichoderma lignorum A3: Zygomycetes: Mucor, such as Mucor spinorus B: Wood-destroying fungi: Bl: Ascomycetes: Chaetomium, such as Chaetomium globosum or Le A 30 003 - PCT - 12 - Chaetomium alba-arenulum Humicola, such as Humicola grisea Petriella, such as Petriella setifera Trichurus, such as Trichurus spiralis B2: Basidiomycetes: Coniophora, such as Coniophora puteana Coriolus, such as Coriolus versicolor Donkioporia, such as Donkioporia expansa Glenospora, such as Glenospora graphii Gloeophyllum, such as Gloeophyllum abietinum or Gloeophyllum adoratum or Gloeophyllum protactum Gloeophyllum sepiarium or Gloeophyllum trabeum Lentinus, such as Lentinus cyathiformes or Lentinus edodes, such as Lentinus lepideus or * Lentinus grinus or Lentinus squarrolosus Paxillus, such as Paxillus panuoides Pleurotus, such as Pleurotus ostreatus Poria, such as Poria monticola or Poria placenta or Poria vaillantii or Poria vaporaria Serpula, such as Serpula himantoides or Serpula lacrymans Stereum, such as Stereum hirsutum Tyromyces, such as Tyromyces palustris B3: Deuteromycetes Alternaria, such as Alternaria tenius Cladosporium, such as Cladosporium herbarum Alternaria tenuis C. Wood-destroying insects, such as CI: Beetles Le A 30 003 - PCT 275812 Hylotrupes bajulus. Chlordphorus pilosis, Anobium punctatum, XfcStobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Emobius 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: Dermapterans Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur C3: Termites Kalotermes flavicollis, Cryptotermers brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucilugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.

The amount of the compositions or concentrates employed depends on the species and the occurrence of the insects, microorganisms, the cell count and the medium. The optimum amount used can be determined in each case upon application by means of test series. Howevef, in general, it suffices to employ 0.001 to 20 % by weight, preferably 0.05 to 10 % by weight, of the mixture of active compounds, based on the material to be protected.

The insecticides are generally present at a use 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, for example by mixing the components, if appropriate with addition of a solvent or diluent, dispersant and/or binder or fixative, water repellent, if appropriate desiccants and UV stabilizers and, if appropriate, colourants and pigments and other processing auxiliaries.

Besides water, the solvent and/or diluent used is, if appropriate, an organic-chemical Le A 30 003 - PCT - 14 - 275812 solvent or solvent mixture and/or an oily or oil-like organic-chemical solvent or solvent mixture of low volatility and/or a polar organic-chemical solvent or solvent mixture.

In a preferred embodiment, aliphatic organic-chemical solvents containing hydroxyl and/or ester and/or ether groups are used, such as, for example, glycol ethers, esters or 5 the like.

Organic-chemical binders which can be employed within the scope of the present invention are the binding drying oils and/or synthetic resins known per se which can be diluted with water and/or are soluble, dispersible or emulsifiable in the organic chemical solvents employed, in particular binders composed of, or containing, an 10 acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenol resin, hydrocarbon resin, such as indene-coumarone resin, silicone resin, drying vegetable oils and/or drying oils and/or physically drying binders based on a natural and/or synthetic resin.

IS The synthetic resin used as the binder can be employed in the form of an emulsion, dispersion or solution. Binders which can also be used are bitumen or bituminous substances in amounts of up to 10 % by weight. Colourants, pigments, water repellents, odour-masking* agents and inhibitors or anticorrosives which are known per se and the like can additionally be employed.

All or some of the binder mentioned can be replaced by a fixative (mixture) or a plasticizer (mixture). These additives are intended to prevent volatilization of the active compounds and crystallization or precipitation. They preferably replace 0.01 to 30 % of the binder (based on 100 % of binder employed).

The plasticizers are from the chemical classes of phthalic esters, such as dibutyl 25 phthalate, dioctyl phthalate or benzylbutyl phthalate, the phosphoric esters, such as tributyl phosphate, the adipic esters, such as di-(2-ethylhexyl) adipate, the stearates, such as butyl stearate or amyl stearate, the oleates, such as butyl oleate, the glycerol ethers or higher-molecular-weight glycol ethers, the glycerol esters and the p-toluenesulphonic Le A 30 003 - PCT 275812 esters.

Fixatives are based chemically on polyvinyl alkyl ethers, such as, for example, polyvinyl methyl ether, or ketones, such as benzophenone and ethylenebenzophenone.

Wood which can bo preserved by the composition according to the invention or 5 mixtures containing this composition is to be understood as meaning, for example, construction timber, wooden beams, railway sleepers, bridge components, jetties, vehicles made of wood, boxes, pallets, containers, telegraph poles, wood lagging, windows and doors made of wood, plywood, particle boards, joiner's work, or wood products which, quite generally, are used in house-building or building joinery.

Particularly effective protection of wood is achieved by large-scale impregnating processes, for example vacuum, double-vacuum or pressure processes.

\ The wood preserveeves - in concentrated form - which can be diluted with water generally contain the triazole/fungicide or insecticide mixture in amounts of 0.01 to 95 % by weight, in particular 0.01 to 60 % by weight.

The wood preservptives - in concentrated form - which can be diluted with water preferably contain the copper, calculated as metal, in an amount of 1.0 to 15.0 % (per cent by weight).

Suitable concentrates consist, for example, of 0.50 to 45 % of copper compounds 20 5.00 to 50 % of alkanolamines according to the invention 0.25 to 4 % of triazole or triazole/fungicide or insecticide mixture 0.5 to 30 % of other alkanolamines 0 to 40 % of a compound having a fungicidal inorganic or organic anion 0 to 40 % of organic solvents 25 0 to 40 % of an aliphatic mono- or dicarboxylic acid and/or cycloalkylcarboxylic acid and/or cycloarylcarboxylic acid and/or boric acid or a borate Le A 30 003 - PCT - 16 - 275812 0 to 15 % of a complexing, polymeric nitrogen compound the total in each case amounting to 100 % by weight, and, if appropriate, minor amounts of other components, such as, for example, ammonia, anticorrosives, complexing acids (for example nitrilotriacetic acid, ethylenediaminetetraacetic acid when using water with a substantial degree of hardness) and, if required, water, the content of which may, however, generally be kept low, which is essentially for handling purposes.

However, the invention extends not only to the wood preservatives (concentrates), but, equally, also to the impregnating solutions which can be prepared by diluting the concentrates with water and which have a correspondingly lower individual concentration. The use concentration is, for example, 0.01 to 1.50% by weight of metal, for example copper, in the aqueous impregnating solution, depending on the type of impregnation and the degree of potential damage to the wood to be impregnated.

% Highly-concentrated pastes, liquid concentrates or two-phase mixtures which, after dilution with water, can be used for impregnating wood are formed by dissolving the copper salts in the alkanolamines, if appropriate with heating, if appropriate with addition of acid, water or solvent, and, if appropriate, with subsequent addition of the emulsifier, the^ triazole compounds and the synergistic component. They give a clear liquid, even at high concentrations in water.

Impregnation solution for the protection of wood can be applied by manual processes, such as spraying, brushing on, immersing, soaking in vats, or by large-scale processes, such as boiler pressure processes, alternating-pressure processes, or double-vacuum processes. "Wood" is to be understood as meaning solid wood, but also derived timber products, such as particle boards or. plywood; for these, the wood preservative may also be incorporated by admixing it to the adhesive, if appropriate..

The degree of copper fixation of the wood preservatives according to the invention is high; it is over 90 % when used for large-scale processes.

Le A 30 003 - PCT 275812 The concentrates or solutions can be coJoured by colourants and/or pigment preparations which are soluble or emulsifiable in water.

It is possible to add wax dispersions, paraffin dispersions and/or acrylate dispersions to achieve a water-repellent action or to improve fixation.

If appropriate, the concentrates can also be incorporated into binder-containing systems (base coats, varnishes) which can be diluted with water.

The compositions according to the invention advantageously allow the compositions available to date to be replaced by more effective ones. They show good stability and advantageously have a broad spectrum of action.

Le A 30 003 - PCT 275812 Examples Example 1 43.5 % of alkanolamine mixture composed of % of ethoxylated tallow fatty amine 75 % of monoethanolamine 14.0% of Cu(OH)2CuCo3 7.5 % of boric acid 6.0 % of propionic acid 19.0 % of water 10 4.0 % of propiconazole 6.0 % of propylene glycol F/xnmple 2 43.5 % of alkanolamine mixture composed of % of ethoxylated coconut fatty amine 15 75 % of monoethanolamine 14.0% of Cu(OH)2CuCo3 22.0 % of benzoic acid 10.5 % of water 1.0 % of tebuconazole 20 9.0 % of propylene glycol Example 3 43.5 % of alkanolamine mixture composed of % of ethoxylated methylstearylamine 75 % of monoethanolamine 25 14.0 % of Cu(OH)2CuCo3 22.0 % of benzoic acid 10.5% of water Le A 30 003 - PCT - 19 -

Claims (4)

275812 2.5 % of propiconazole 1.5 % of tebuconazole .0 % of propylene glycol Le A 30 003 - PCT - 20 - 27 5 8 1 2 Patent Claims

1. Wood preservative comprising at least one copper compound in addition to, at least one triazole compound and at least one alkanolamine compound of general formula (I) in which R1 denotes optionally substituted alkyl, substituted aryl, substituted jlkenyl, alkylcarbonyl, arylcarbonyl, substituted alkenylcarbonyl or alkinylcarbonyl, R2 has the meaning of R', H or R\ R3 denotes (CH:-CH2-0)„H or (CH2-CHCH3-0)mH, n denotes 1 to 40 and m denotes 1 to 40,, or alkanolamine mixture wherein said mixture comprises at least one alkanolamine of formula (I) together with at least one alkanolamine selected from isopropanolamine, aminoethylethanolamine, diethanolamine, triethanolamine, methylethanolamine and monoethyanolamine and, if appropriate, other fungicides and/or insecticides.

2. Process for the protection of wood, characterized in that the wood is treated with an effective amount of a combination of at least one copper compound with at least one triazole compound ar.d at least one alkanolamine compound of formula (I) according to claim 1 or alkanolaniine mixtures comprising at least one alkanolamine of formula (I) according to claim 1 together with at least one alkanolamine selected from isopropanolamine, aminoethylethanolamine, diethanolamine, triethanolamine, methylethanolamine and monoethyanolamine and, if appropriate, other fungicides and/or insecticides.

3. A wood preservation according to claim 1 substantially as herein described or exemplified.

4. A process according to claim 2 substantially as he T.e A 30 003 - PCT or exemplified. END OF CLAIMS -21 -