DE4320495A1 - Fungicidal active substance combinations - Google Patents

Abstract

The present application relates to novel active substance combinations composed, on the one hand, of alpha -butyl- alpha -(2,4-dichlorophenyl)-1H-1,2,4-triazole-1-ethanol (hexaconazole), which is known, and, on the other hand, of other known active substances and which are highly suitable for the protection of industrial materials.

Description

The present application relates to new combinations of active ingredients resulting from the known α-butyl-α- (2,4-dichlorophenyl) -1H-1,2,4-triazole-1-ethanol (hexacon azoles) on the one hand and other known active ingredients on the other hand exist and very are well suited for protecting technical materials.

It is already known that α-butyl-α- (2,4-dichlorophenyl) -1H-1,2,4-triazole-1-ethanol (Hexaconazole) has fungicidal properties.

Mixtures of hexaconazoles are also already known (cf. EP 415.569, GB 2.119.653, EP 95.242, EP 289.356, EP 287.346).

The blends are used in plant and material protection.

But wood preservatives have requirements that go beyond pure fungicidal efficacy go beyond.

The aim and object of the present invention was therefore to provide a wood preservation means to find that against wood-discoloring and wood-destroying fungi as well against wood-damaging insects, especially against wood-destroying ones Longhorn beetles (Cerambycidae, Lyctidae, Bostrychidae and Anobiidae) including  Termite is highly effective and has a good long-term effect the fungicide is not impaired by the insecticide or vice versa returns. In addition, the wood preservative should penetrate well have assets in wood and wood-based materials.

According to the invention it was found that these goals and tasks are a means or concentrate for preserving wood and wood-based materials 0.01 to 25% by weight of α-butyl-α- (2,4-dichlorophenyl) -1H-1,2,4-triazole-1-ethanol (Hexaconazole) in a mixture of 0.1 to 99.9 wt .-% with at least one further azole and 0.00001 to 10% by weight of at least one insecticide and more than 40% by weight of a mixture of solvent and / or diluent and / or organic chemical binders or fixatives, processing agents, Contains dye, pigment, dye or pigment mixture.

Preferred azoles as mixing partners are:

Azaconazole:
1 - {[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl} 1-H-1,2,4-triazole
Propiconazole:
1- [2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-yl] methyl-1-H-1-, 2-, 4-triazoles
Tebuconazole:
1-p-chlorophenyl-4,4-dimethyl-3 (1H-1,2,4-triazol-1-yl-methyl) pentan-3-ol
Cyproconazole:
2- (4-chlorophenyl) -3-cyclopropyl-1- (1H-1,2,4-triazol-1-yl) butan-2-ol-
2- (1-chloro-cyclopropyl) -1- (2-chlorophenyl) -3- (1H-1,2,4-triazol-1yl) propan-2-ol
2- (tert-butyl) -1- (2-chlorophenyl) -3- (1H-1,2,4-triazol-1-yl) propan-2-ol

The following are preferably added as insecticides:

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, Dimethoate, Ethoate, Ethoprophos, Etrimfos, Fenitrothion, Fenthion, Heptenophos, Parathion, Parathion-methyl, Phosalone, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofosm Prothiofos, Sulfprofos, Triazophos and Trichlorphone;
Carbamates such as aldicarb, bendiocarb, α-2- (1-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-phenoybenzyl ether such as dimethyl- (4-ethoxyphenyl) -silylmethyl-3-phenoxybenzyl ether or
(Dimethylphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether such as e.g. B. Dimethyl- (9-ethoxy-phenyl) -silylmethyl-2-phenoxy-6-pyridylmethyl ether or [(phenyl) - 3- (3-phenoxyphenyl) propyl] (dimethyl) -silanes such as. B. (4-Ethoxyphenyl) - [3- (4-fluoro-3-phenoxyphenylpropyl] dimethylsilane, sila fluofin
Pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin, cycloprothiin, cyfluthrin, decamethrin, cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- (2-chloro-2-trifluoro-2-trifluoromethyl) -methylvin-yl) cyclopro pancarboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, 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, Acephate, Acrinathrin, Alanycarb, Aldoxycarb, Aldrin, Ammoniumbifluoride, Amitraz, Azamethiphos, Bacillus thuringiensis, Phosmet, Phosphamidon, Phosphine, Prallethrin, Propaphos, Propetamphos, Prothoate, Pyrethridos, Pyrethridospy, Pyridhridos, Pyrethridos, Pyrethridos, Pyrethridos RH-7988, Rotenone, Sodium fluoride, Sodium hexafluorosilicate, Sulfotep, Sulfuryl fluoride, Tar Oils, Teflubenzuron, Tefluthrin, Temephos, Terbufos, Tetrachlorvinphos, Tetramethrin, O-2-tert.-Butyl-pyrimidin-5-yl-o-isopropyl -phosphorothiate, thiocyclam, thiofanox, thiometone, tralomethrin, triflumuron, trimethacarb, vamidothio, verticillium lacanii, XMC, xylylcarb, benfuracarb, bensultap, bifenthrin, bioallethrin, MERbioomercyclos, bromophosphate, bromine, cyclophosphate, bromophosphorus Calcium Polysulfide, Carbophenothion, Cartap, Chinomethionate, Chlordane, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chloropicrin, Chlorpyrifos, Cyanophos, Beta-Cyfluthrin, Alpha-cyper methrin, cyophenothrin, cyromazine, Dazomet, DDT, Demeton-S-methylsulphone, diafenthiuron, Dialifos, Dicrotophos, Diflubenzuron, Dinoseb, Dioxabenzofos, Diaxacarb, Disulfoton, DNOC, Empenthrin, Etosulffenofenx, Fenos, Oxeniobium, EPN Fenoxycarb, Fensulfothion, Fipronil, Flucycloxuron, Flufenprox, Flufenoxuron, Fonofos, Formetanate, Formothion, Fosmethilan, Furathiocarb, Heptachlor, Hexaflumuron, Hydramethylnon, Hydrogen Cyanide, Hydroprene, IPSP, Isazofos, Isothionion, Iodophone Iodine, Iodophone Iodine, Iodine Phonophone, Isothionophone, Iodophone Iodine, Iodine Phonophone , Mecarbam, Mephosfolan, Mercurous, chloride, Metam, Metarthician, anisopliae, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methoprene, Methoxychlor, Methyl isothiocyanate, Metholcarb, Mevinphos, Monocrotophos, Naled, Neodiprion, methyl oxine, Oxif, NPV Pentachlorophenol, petroleum oils, phenothrin, phenthoates, phorates;

The mixtures according to the invention produced in this way show activity not only against fungi but also against material-destroying insects.

In order to achieve further increased effects against wood-destroying fungi, the following fungicides can also be added.

Triazoles:

Amitrole, Azocyclotin, BAS 480F, Bitertanol, Difenoconazole, Fenbuconazole, Fenchlorazole, Fenethanil, Fluquinconazole, flusilazole, flutriafol, imibenconazole, isazofos, myclobutanil, opus, paclobutrazole, Penconazole, propioconazole, (±) -cis-1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) -cycloheptanol, tetraconazole, Triadimefon, triadimenol, triapenthenol, triflumizole, uniconazole;  

Imidazole:

Imazalil, pefurazoate, prochloraz, triflumizole, 2- (1-tert-butyl) -1- (2-chlorophenyl) -3- (1,2,4-triazol-1-yl) - propan-2-ol, thiazole carboxanilides such as 2 ′, 6′-dibromo-2-methyl-4-trifluoromethoxy-4′-trifluoromethyl-1,3- thiazole-5-carboxanilide.

Copper salts:

Copper, sulfate, carbonate, chloride, ammonia complexes, amine complexes.

Zinc salts:

Zinc sulfate, carbonate, chloride.

Mixed salts:

Copper / boron mixtures, copper / chrome / boron mixtures, copper / chrome / arsenic mixtures.
methyl ( E ) -2- [2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- [6 - (- 2-thioamidophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- [6- (2-fluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylic acid, methyl ( E ) -2- [2- [6- (2,6difluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylates, methyl ( E ) -2- [2- [3- (pyrimidin-2-yloxy) phenoxy ] phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- [3- (5-methylpyrimidin-2-yloxy) phenoxy] phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- [3- (phenylsulfonyloxy) phenoxy] phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- [3- [4-nitrophenoxy] phenoxy] phenyl] -3-methoxyacrylate, methyl ( E ) -2 - [2-phenoxyphenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- (3,5-dimethylbenzoyl) pyrrol-1-yl] -3-methoxyacrylate, methyl ( E ) -2- [2- ( 3-methoxyphenoxy) phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- (2-phenylethen-1-yl) - phenyl] -3-methoxyacrylate, methyl ( E ) -2- (2- [3 , 5-dichlorophenoxy] pyridin-3-yl) -3-methoxyacrylate, methyl ( E ) -2- (2- (3- ( 1,1,2,2-tetrafluoroethoxy) phenoxy) phenyl) -3-methoxyacrylate, methyl ( E ) -2- (2- [3- ( alpha - hydroxybenzyl) phenoxy] phenyl) -3-methoxyacrylate, methyl ( E ) -2- (2- (4-phenoxypyridin-2-yloxy) phenyl) -3- methoxyacrylate, methyl ( E ) -2- [2- (3-n-propyloxyphenoxy) phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- (3- iso propyloxyphenoxy) phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- [3- (2-fluorophenoxy) phenoxy] phenyl] -3-methoxy acrylate, 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- methoxyacrylates, 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-bromopyridine-2 - yloxymethyl) phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- (3- (3-iodopyridin-2-yloxy) phenoxy) phenyl] -3- methoxyacrylate, methyl ( E ) -2- [2 - [6- (2-chloropyridin-3-yloxy ) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, ( E ), ( E ) -methyl 2- [2- (5,6-dimethylpyrazin-2-ylmethyloximinomethyl) phenyl] -3-methoxy-crylate, ( 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) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate, ( E ), ( E ) -methyl 2- {2- [6-phenylpyrimidin-4-yl) - methyloximinomethyl] phenyl} -3-methoxyacrylate, ( E ), ( E ) -methyl 2- {2 - [(4-chlorophenyl) - methyloximinomethyl] phenyl} -3-methoxyacrylate, ( E ) -methyl 2- {2- [6- (2-n-propylphenoxy) -1,3,5-triazin-4-yloxy] phenyl} -3-methoxyacrylate, ( E ), ( E ) -methyl 2- {2 - [(3-nitrophenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate,

Succinate dehydrogenase inhibitors such as:

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-in)

Sulfenamides such as dichlorfluanide, tolylfluanid, folpet, fluorfolpet; Captan, Captofol,
Benzimidazoles such as Carbendazim, Benomyl, Furathiocarb, Fuberidazole, Thio phonatmethyl, Thiabendazole or their salts;
Thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthlocyanate;
quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecyclammonium chloride, didecyldimethylammonium chloride,
Morpholine derivatives such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph; Aldimorph, fenpropidine and their arylsulfonic salts, such as. B. p-toluenesulfonic acid and p-dodecylphenyl sulfonic acid,
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, 6-iodo-3-oxo-hex-5-in-ol butyl carbamate, 6-iodo-3-oxo-hex-5-in-ol-phenyl carbamate, 3- Iodine-2-propynyl-n-hexyl carbamate, 3-iodine-2-propynyl-cyclohexyl carbamate, 3-iodine-2-propynyl-phenyl carbamate;
Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenyl, di chlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol;
Glutaraldehyde;
Bromine derivatives such as 2-bromo-2-nitro-1,3-propanediol;
Isothiazolinones such as N-methylisothiazolin-3-one, 5-chloro-N-methyl-isothiazolin-3-one, 4,5-dichlorod-N-octylisothiazolin-3-one, N-octyl-isothiazolin-3-one;
Benzisothlazolinone, 4,5-trimethylene-isothiazolinone;
Pyridines or pyrimidines such as 1-hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine, pyrimethanil, mepanipyrim, dipyrithione;
Metal soaps such as tin, copper, zinc naphthenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;
Oxides such as tributyltin oxide, Cu₂O, CuO, ZnO;
Dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetra methylthiuram disulfide;
Dithiocarbamate, Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam, Metiram, Thiram Zineb, Ziram:
Nitriles such as 2,4,5,6-tetrachloroisophthalonitrile, 2,3,5,6-tetrafluoroterephthalalo dinitrile;
Benzothiazoles such as 2-mercaptobenzothiazole;
Quinolines such as 8-hydroxyquinoline and their Cu salts;
Benzamides such as 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide (XRD-563); 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, paraformaldehyde, nitropyrin, oxolinic acid, tecloftalam;
Tris-N- (cyclohexyldiazeniumdioxy) aluminum, N- (cyclohexyldiazeniumdioxy) tributyltin or K salts, bis-N- (cyclohexyldiazeniumdioxy) copper.

Other fungicidal mixing partners are very particularly preferably:

Azaconazole, bromuconazole, cyproconazole, dichlobutrazole, diniconazole, hexa conazole, metaconazole, penconazole, propiconazole, tebuconazole, methyl- (E) methoximino [α- (o-tolyloxy) -o-tolyl)] acetate, methyl- (E) -2- {2- [6- (2-cyanphenoxy) pyrimidin-4-yl-oxy] phenyl} -3-methoxyacrylate, methfuroxam, carboxin, fenpiclo nil, 4 (2,2-difluoro-1,3-benzodioxol-4-yl) -1H-pyrrole-3-carbonitrile, butenafine and / or 3-iodo-2-propynyl-n-butyl carbamate.

If the active ingredients in the active ingredient combinations according to the invention in certain ten weight ratios are mixed, synergistic effects are shown. The weight ratios of the active ingredients in the active ingredient combinations can can be varied within a relatively large range.

Furthermore, there are also effective mixtures with the following active ingredients manufactured:

Fungicides
Acypetacs, 2-aminobutane, ampropylfos, anilazine, benalaxyl, bupirimate, quinomethionate, chloroneb, chlozolinate, cymoxanil, dazomet, diclomezine, dichloram, diethofencarb, dimethirimol, dinocab, dithianon, dodonidolololol, dolonolimololol, dolonimololol, dolonimololol, doline, dolinololol, doline, phenolol, dolimidolol, dolonimolol, dolonimolol, dolonimololol, dolonimolol, phenol, dolimidolol, dolonimolol, dolonimolol, dolonol, zolimolol, dolimidololol, dolimidolol, phenol, zolimolol, dolimidolol, dolimidolol, dolimidololol, dolimidolol, dolimidolol, phenol, dolimidol, phenol, dolimidol fentin acetate, fentin hydroxide, Ferimzone, fluazinam, Fluromide, flusulfamide, flutriafol, fosetyl, Fthalide, furalaxyl, guazatine, hymexazol, iprobenfos, iprodione, isoprothiolane, metalaxyl, methasulfocarb, nitro Thal-isopropyl, nuarimol, ofurace, Oxadiyl, Perflurazoate, pencycuron, Phosdiphen, Pimaricin, Piperalin, Procymidone, Propamocarb, Propineb, Pyrazophos, Pyrifenox, Pyroquilon, Quintozene, Tar Oils, Tecnazene, Thicyofen, Thiophanate-methyl, Tolclofos-methyl, Triazoxide, Trichlamide, Tricyclazole, Triforoline.

Particularly preferred mixtures contain as azoles in addition to hexaconazole, Tebu conazole, propiconazole, cycproconazole and / or 2- (1-chloro-cyclopropyl) - 1- (2-chlorophenyl) -3-1H- (1,2,4-triazol-1-yl) propan-2-ol, preferably in one Weight ratio to hexaconazole from 1: 9 to 9: 1.

Particularly preferred mixtures contain as insecticides:

Chlorpyrifos, Phoxim, Silafluofen, Cyfluthrin, Cypermethrin, Deltamethrin, Permethrin, Imidacloprid, Hexaflunuron, lindane.

The insecticides are generally in a dosage of 0.00001% to 10%, preferably 0.0001% to 5%, particularly preferably 0.001% to 1%.

Surprisingly, these combinations of active ingredients show a particularly high, microbicidal, especially fungicidal, combined with a broad Spectrum of action against microorganisms and insects relevant to material protection; They are particularly effective against mold, wood-staining and wood-cutting annoying fungi and insects. Exemplary - but without limitation - are the the following groups of microorganisms:

A: Wood-staining fungi:

A1: Ascomycetes
Ceratocystis such as Ceratocystis minor;

A2: Deuteromycetes:
Aspergillus such as Aspergillus niger,
Aureobasidium such as Aureobasidium pullulans,
Dactylium such as Dactylium fusarioides,
Penicillium such as Penicillium brevicaule or
Penicillium variabile,
Sclerophoma such as Sclerophoma pithyophila,
Scopularia like Scopularia phycomyces,
Trichoderma like Trichoderma viride or
Trichoderma lignorum;

A3: Zygomycetes:
Mucor such as Mucor spinorus;

B: Wood-destroying mushrooms:

B1: Ascomycetes:
Chaetomium like Chaetomium globosum or
Chaetomium alba arenulum,
Humicola like Humicola grisea,
Petriella like Petriella setifera,
Trichurus such as Trichurus spiralis;

B2: Basidiomycetes:
Coniophora like Coniophora puteana,
Coriolus like Coriolus versicolor,
Donkioporia like Donkioporia expansa,
Glenospora like Glenospora graphii,
Gloeophyllum such as Gloeophyllum abietinum or
Gloeophyllum adoratum or Eq. protactum or
Gloeophyllum sepiarium or Gl. trabeum,
Lentinus such as Lentinus or cyathiformes
Lentinus edodes like Lentinus lepideus or
Lentinus grinus or L. 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 like Stereum hirsutum,
Tyromyces such as Tyromyces palustris;

B3: Deuteromycetes

Alternaria such as Alternaria tenius,
Cladosporium such as Clasdosporium herbarum;

C. Wood-destroying insects like

C1: Beetle
Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearesces, Lyctus pubis linearis, Lyctus pubis linearis, speculum Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus;

C2: Skin wing
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 agents or concentrates used depends on the type and the Occurrence of insects, microorganisms, the number of germs and of the medium dependent. The optimal amount can be used in each case Test series can be determined. In general, however, it is sufficient from 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 active ingredient mixture can be used as such, in the form of concentrates or in general usual formulations such as powders, granules, solutions, suspensions, emul sions or pastes.

The formulations mentioned can be prepared in a manner known per se be, e.g. B. by mixing the active ingredients with at least one solution or Diluents, emulsifiers, dispersants and / or binders or fixatives, Water repellants, possibly desiccants and UV stabilizers and optionally dyes and pigments and other processing aids average.

An organic chemical is used as the solvent and / or diluent Solvent or solvent mixture and / or an oily or oily heavy volatile organic chemical solvent or solvent mixture and / or a polar organic chemical solvent or solvent mixture and / or water and at least one emulsifier and / or wetting agent or consists of it.

The organic chemical solvents used are preferably oily or oily ones Solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, used. As such volatile, water-insoluble, oily and oily solvents become corresponding mine ral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene used.  

Mineral oils with a boiling range of 170 to 220 ° C are advantageous, test petrol with a boiling range of 170 to 220 ° C, spindle oil with a boil range from 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 up to 280 ° C, turpentine oil and the like.

In a preferred embodiment, liquid aliphatic coals Hydrogen with a boiling range of 180 to 210 ° C or high-boiling Mixtures of aromatic and aliphatic hydrocarbons with one Boiling range from 180 to 220 ° C and / or spindle oil and / or monochlomaphthalene, preferably α-monochlomaphthalene used.

The organic non-volatile oily or oily solvents with a Evaporation rate above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be caused in part by easily or moderately volatile organic chemical solvents are replaced, provided that the solvent mix also 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.

According to a preferred embodiment, part of the organic chemical Solvent or solvent mixture or an aliphatic polar orga niche chemical solvent or solvent mixture replaced. Preferably come aliphatic containing hydroxyl and / or ester and / or ether groups organic chemical solvents such as glycol ether, ester or the like. to use.

As an organic chemical binder in the present Er finding the known water-dilutable and / or in the used organic chemical solvents soluble or dispersing or emul gable synthetic resins and / or binding drying oils, especially binders consisting of or containing an acrylic resin, a vinyl resin, e.g. B. polyvinyl acetate, Polyester resin, polycondensation or polyaddition resin, polyurethane resin, Alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as  Inden-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or Resin used.

The synthetic resin used as a binder can be in the form of an emulsion, dispersion or solution. Bitumen or bitumi can also be used as binders nous substances up to 10 wt .-% can be used. In addition, in itself known dyes, pigments, water repellants, odor correctors and Inhibitors or anticorrosive agents and the like are used.

According to the invention, preference is given to at least one organic chemical binder an alkyd resin or modified alkyd resin and / or a drying vegetable Contain oil in the medium or in the concentrate. Are preferred according to the invention Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight.

The binder mentioned can be wholly or partly by a fixation medium (mixture) or a plasticizer (mixture) can be replaced. These additions should volatilize the active ingredients and crystallize or Preventing precipitates, preferably replacing 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 Dibutyl, 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, glycerol ether or higher molecular weight Gly kolether, glycerol ester and p-toluenesulfonic acid ester.

Fixing agents are chemically based on polyvinyl alkyl ethers such as. B. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.  

Water is also suitable as a solvent or diluent, if appropriate in mixture with one or more of the above-mentioned organic chemical Solvents or diluents, emulsifiers and dispersants.

Under wood, which by the agent according to the invention or containing it Mixtures that can be protected are to be understood as examples: construction timber, wood 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, all in general used in house building or in carpentry.

A particularly effective wood preservation is through industrial impregnation procedure, e.g. B. vacuum, double vacuum or printing process.

The microbicidal agents used to protect wood and wood-based materials or concentrates contain the active ingredient combination in a concentration of 0.01 to 95% by weight, in particular 0.01 to 60% by weight.

Preferred agents (ready-to-use agents) preferably contain 0.2 to 3 wt .-%, in particular 0.5 to 2 wt .-% of hexaconazole in a mixture with the further azole, 0.005 to 1% by weight, preferably 0.01 to 0.5% by weight of the Insecticides and at least one organic chemical solvent or Solvent mixture and / or an oily or oily low volatile organic chemical solvent or solvent mixture and / or a polar organic chemical solvent or solvent mixture and / or Water and emulsifier and / or wetting agent and optionally 0 to 5% by weight, preferably 0.1 to 3 wt .-% fixative and / or other additives than Residual component.

Particularly preferred (ready-to-use) agents contain 2 to 30% by weight preferably 5 to 22% by weight, calculated as a solid, of a synthetic resin binder, preferably an alkyd resin and / or a drying vegetable oil as well at least one organic chemical solvent or solvent mixture  and / or an oily or oily semi-volatile organic chemical Solvent or solvent mixture and / or a polar organic chemical solvent or solvent mixture and / or water and Emulsifier and / or wetting agent and optionally desiccants, dyes, Color pigments, anti-settling agents and / or UV stabilizers as a residual component.

Concentrates for preserving wood and wood-based materials preferably contain example, 0.2 to 25 wt .-%, preferably 3 to 8 wt .-% of hexaconazole in Mixture with the further azole, 0.05 to 5 wt .-%, preferably 0.5 to 1% by weight of the insecticide, 5 to 40% by weight, preferably 10 to 30% by weight (calculated as a solid) of at least one organic chemical binder and / or fixative or plasticizer and additionally an organic chemical solvent or solvent mixture and / or an oily or oily semi-volatile organic chemical solvent or solution mixed agent and / or a polar organic chemical solvent or Solvent mixture and / or a penetration aid and / or water and contains an emulsifier and / or wetting agent as a residual component.

In particularly preferred concentrations, the further azoles are from 0 up to 50% by weight, preferably from 0.5 to 25% by weight (based on 100% by weight) contain used hexaconazoles.

The agents according to the invention advantageously enable the previously ver to replace available microbicidal agents with more effective ones. You show a good one Stability and advantageously have a broad spectrum of activity.

Claims (9)

1. Agent or concentrate for preserving wood and wood-based materials based on or with the use of α-butyl-α- (2,4dichlorophenyl) -1H-1,2,4-triazole-1-ethanol (hexaconazole) and / or whose acid addition salts and metal salt complexes and at least one solvent, diluent and / or additive, characterized in that the agent or concentrate 0.01 to 25 wt .-% of hexaconazoles in a mixture of 0.1 to 99.9 wt .-% with at least one other azole and / or their acid addition salts and metal salt complexes, 0.00001 to 10 wt .-% of at least one insecticide and more than 40 wt .-% of a mixture of solvent and / or diluent and / or contains organic chemical binder and / or fixative, processing agent, dye, pigment, dye or pigment mixture. 2. Agent or concentrate according to claim 1, characterized in that the Solvent and / or diluent is an organic chemical solution medium or solvent mixture and / or an oily or oily semi-volatile organic chemical solvent or solvent mixture and / or polar organic chemical solvent or Solvent mixture and / or water and at least one emulsifier and / or contains or consists of wetting agents. 3. agent or concentrate for preserving wood and wood-based materials according to claims 1 or 2, characterized in that it is as azole
Azaconazole:
1 - {[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl} 1-H-1,2,4triazole
Propiconazole:
1- [2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-yl] methyl-1-H-1,2,4-triazoles
Tebuconazole:
1-p-chlorophenyl-4,4-dimethyl-3 (1H-1,2,4-triazol-1-yl-methyl) pentan-3-ol
Cyproconazole:
2- (4-chlorophenyl) -3-cyclopropyl-1- (1H-1,2,4-triazol-1-yl) butan-2-ol-
2- (1-chloro-cyclopropyl) -1- (2-chlorophenyl) -3-1H- (1,2,4-triazole-1yl) propan-2-ol
2- (tert-butyl) -1- (2-chlorophenyl) -3-1H- (1,2,4-triazol-1-yl) propan-2-ol
and or
contains. 4. Means for preserving wood and wooden materials according to one or several of claims 1 to 3, characterized in that the agent (ready-to-use agents) 0.2 to 3% by weight of the azoles, 0.005 to 1 wt .-%, preferably 0.01 to 0.5 wt .-% of the insecticide and min an organic chemical solvent or solvent mixture and / or an oily or oily semi-volatile organic chemical Solvent or solvent mixture and / or a polar organic chemical solvent or solvent mixture and / or water and Emulsifier and / or wetting agent and optionally 0 to 5% by weight, preferably as 0.1 to 3 wt .-% fixative and / or other additives than Contains residual ingredient. 5. Means for preserving wood and wood-based materials according to one or several of claims 1 to 3, characterized in that the agent (ready-to-use agents) 0.2 to 3 wt .-%, preferably 0.5 to 2% by weight of the azoles, 0.005 to 1% by weight, preferably 0.01 to 0.5% by weight of the insecticide, 2 to 30% by weight, preferably 5 to 22% by weight, calculated as a solid, of a synthetic resin binder  preferably an alkyd resin and / or a drying vegetable oil and at least one organic chemical solvent or solvent mixture and / or an oily or oily semi-volatile organic chemical solvent or solvent mixture and / or a polar organic chemical solvent or solvent mixture and / or Water and emulsifier and / or wetting agent and optionally desiccants, Dyes, color pigments, anti-settling agents and / or UV stabilizers as Contains residual ingredient. 6. Concentrate for preserving wood and wood-based materials after one or more of claims 1 to 3, characterized in that the Concentrate 0.2 to 25% by weight, preferably 3 to 8% by weight of the azoles, 0.05 to 5 wt .-%, preferably 0.5 to 1 wt .-% of the insecticide, 5 to 40% by weight, preferably 10 to 30% by weight (calculated as a solid) at least one organic chemical binder and / or fixation by means of or plasticizer as well as an organic chemical Solvent or solvent mixture and / or an oily or oily semi-volatile organic chemical solvent or solvent mixture and / or a polar organic chemical solvent or Solvent mixture and / or a penetration aid and / or water and contains an emulsifier and / or wetting agent as a residual component. 7. Medium or concentrate for preserving wood and wood-based materials according to one or more of claims 1 to 6, characterized in that that the further azoles from 0 to 50 wt .-%, preferably from 0.5 to 25% by weight (based on 100% by weight of hexaconazole used) are. 8. Medium or concentrate for preserving wood and wood-based materials according to one or more of claims 1 to 7, characterized in that that the agent or concentrate is free from aromatic oxy alcohols.   9. Medium or concentrate for preserving wood and wood-based materials according to one or more of claims 1 to 8, characterized in that that part of the organic chemical solvent or solution medium mixture through an aliphatic polar organic chemical Solvent or solvent mixture, preferably a hydroxy and / or aliphatic containing ester and / or ether groups organic chemical solvent or solvent mixture is replaced.