WO1997039865A1 - Process for treating wood against infection by moulds harmful to wood - Google Patents

Abstract

In a process for treating wood against the infection by moulds which are harmful to wood, the wood is treated with a mixture which contains (a) fenpropimorph and (b) a triazole compound, with the exception of epoxyconazol, in a synergistically effective amount against said moulds.

Description

 Process for treating wood against infestation by wood-damaging fungi

5 Description

The present invention relates to a method for treating wood against infestation by wood-damaging fungi.

^ _Q The fungicidal activity of fenpropimorph (4- [3- {4-tert-butylphenyl} -2-methylpropyl] -2,6-cιs-dimethylmorpholm) is generally known (cf. DE-A 26 56 747).

It is also known to include tnazole compounds in wood preservation

15 [Propiconazole: US-A 4,079,062; Tebuconazole: EP-A 40 345 or EP-A 52 424; Cyproconazole: EP-A 131 684 or EP-A 555 186].

WO-A 95/16349 discloses fungicidal mixtures and agents for crop protection containing them, which contain fenpropimorph and a tnazole compound as active substances.

20th

The synergistic effect of a mixture of fenpropimorph and prochloraz against phytopathogenic fungi is known from EP-A 72 156.

25 Synergistic mixtures of tnazole compounds are also common in wood preservation [propiconazole + tebuconazole: EP-A 393 746].

DE-A 43 40 853 teaches a synergistic mixture for use in wood protection which, in addition to a copper compound and an alkanolamine, contains a tazole compound and a further fungicide, for example fenpropimorph.

Furthermore, the synergistic effect of a mixture of fenpropimorph and epoxiconazole against harmful fungi 35 on materials is known from EP-A 425 857.

Fenpropimorph, the tnazole compounds and the known synergistic mixtures which contain these active ingredients, however, do not have a satisfactory effect against wood-damaging, wood-fungal fungi.

The object of the present invention was therefore to remedy this deficiency.

5

CONFIRMATION COPY Accordingly, a method for treating wood against infestation by wood-damaging fungi has been found, wherein the wood is mixed with a mixture which

a) fenpropimorph and

b) a triazole compound with the exception of epoxiconazole

contains in an amount synergistically effective against these fungi.

The term "wood" is also intended to include wood secondary products such as woodcuts, cellulose and other technical products or materials containing cellulose that are susceptible to fungal attack, e.g. Intermediates in papermaking and woody annual plants (bar alley, rapeseed) are included.

The active substances mentioned here, in particular fenpropimorph and the triazole compounds, are known to the person skilled in the art (cf. e.g.

"The Pesticide Manual", 10th Edition, The British Crop Protection Council, Farnham, UK).

Examples of suitable triazole compounds are: 2- (1-chlorocyclopropyl-1- (2-chlorophenyl) -3- (1,2,4-triazol-1-yl) propan-2-ol, 1-butyl-1 - (2, 4-dichlorophenyl) -2- (1,2, 4-triazol-l-yl) ethanol (hexaconazole), 1- (2-chlorophenyl) methyl) -l- (1, 1- dimethyl) -2- (1,2, 4-triazol-l-ylethanol, 1- (4-fluorophenyl) -1- (2-fluorophenyl) -2- (1,2,4-triazol-l-yl) ethanol (Flutriafol), (RS) -4- (4-chlorophenyl) -2-phenyl-2- (1H-1,2,4-triazol-l-yl-methyl) butyronitrile, 1- (2 RS, 4 RS; 2 RS, 4 SR) -4-bromo-2- (2,4-dichlorophenyl) tetrahydrofurfuryl) -1H-1,2,4-triazole, 3- (2,4-dichlorophenyl) -2- (1H-1,2,4-triazol-l-yl) quinazolin-4 (3H) -one, (RS) -2,2-dimethyl-3- (2-chlorobenzyl) -4- (1H -1,2,4-triazol-l-yl) butan-3-ol, bitertanol, Triadime¬ fon, triadimenol, cyproconazole, dichlobutrazole, difenoconazole, diniconazole, etaconazole, flusilazole, penconazole, tetraconazole, bromoconazole, metconazole, fenconazole, fen , 1- (2- (2, 4, -Dichlorophenyl) -1, 3-dioxolan-2-yl-methyl) -lH-l, 2,4-tπazole (Azaco nazole), 1- (2- (2,4-dichlorophenyl) -4-propyl-l, 3-dioxolan-2-yl-methyl) -1H-1,2,4-triazole (propi-conazole), (RS) -lp-chlorophenyl-4,4-dimethyl-3- (1H-1,2,4-triazol-1-ylmethyl) pentan-3-ol (tebuconazole) and mixtures thereof.

Propiconazole, penconazole, cyproconazole, hexaconazole, tebuconazole and mixtures thereof are used with particular advantage as the triazole compound. Fenpropimorph and the triazole compounds can each be in the form of the free base or in the form of a metal salt complex or as an acid addition salt.

The salts are produced by reacting the respective active ingredient with the corresponding acids, e.g. Halogenwasserstoffsäu¬ ren cloth acid such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydriodic acid, or sulfuric acid, phosphoric acid, phosphorous acid, nitric acid or organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, Propions¬ acid, glycolic acid, lactic acid, succinic acid, citric acid, malic acid, tartaric acid, Benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid and 1,2-naphthalene disulfonic acid.

The metal complexes are produced from fenpropimorph or the underlying triazole compound and an inorganic or organic metal salt, for example the halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates and benzoates of the metals of the second main group of the periodic table such as calcium and magnesium and the third and fourth main group such as aluminum, tin or lead and the first to eighth subgroups such as chromium, manganese, iron, cobalt, nickel, copper, zinc. The sub-group elements of the 4th period and in particular copper are preferred. The metals can be present in the various valences which they can assume. The metal complexes can contain one or more organic molecular moieties as ligands.

For the purposes of the present invention, particular preference is given to the use of a mixture of fenpropimorph and propiconazole, in each case in the form of the free base.

The mixing ratio of fenpropimorph and triazole compound in the mixtures used according to the invention is between 0.25: 1 to 5: 1, in particular 1: 1 to 4: 1 parts by weight.

The mixtures of fenpropimorph and one or more triazole compounds are generally formulated with conventional formulation auxiliaries to form wood preservatives before they are used. Liquid wood preservatives are preferably produced because of the better handling. The mixture is used in such a way that the wood to be protected is treated with fenpropimorph and one or more triazole compounds simultaneously, together or separately, or in succession.

The mixture of fenpropimorph and one or more triazole compounds is preferably used in an amount of 0.05 to 5 kg per cubic meter of wood.

The mixtures used according to the invention are partly liquid. Regarding their use in wood protection, they are preferably formulated in liquid form, for example

a) as a solution in an organic solvent, ready for use or as a dilutable preconcentrate,

b) as an additive to wood preservatives which are formulated in organic solvents and which can be used as such or after the addition of further organic solvents, or

c) in water-thinnable wood preservatives which contain organic solvents and, if appropriate, water (emulsion concentrates).

Water and solvents serve to improve the handling of the mixtures or the agents by facilitating the setting of the viscosity and / or accelerating the dissolution of the emulsion concentrates in water. The organic solvents are partly at the same time required to dissolve the triazole compounds. The emulsion concentrates can be in liquid, homogeneous form, but also in paste form in solid form.

Preferred organic solvents for such formulations 5 are water-soluble or water-miscible polar solvents, e.g. Glycols (ethylene glycol, propylene glycol), glycol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, phenylglycol), glycol ether acetates (butylglycol acetate), lactic acid esters (lactic acid ethyl ester, lactic acid propyl ester), N-alkylpyrrolidone-0-nolonol-n-acetone, methyl-n-acetone hol, dimethylformamide, diethylformamide, dimethyl sulfoxide, N, N'-dimethylpropyleneurea and mixtures thereof.

Suitable, mostly as such ready-losungsmittelhal- _c term wood preservatives containing eg 0.1-5% by weight of the fenpropimorph / triazole compound mixture, preferably 0.25-2.5% by weight and especially 0.5-2% by weight,

0-10% by weight of organic solvent, if appropriate for dissolving the triazole compound and / or as a penetration aid, the remainder being 100% by weight of aliphatic and / or aromatic hydrocarbons.

Suitable water-thinnable wood preservatives (emulsion concentrates) exist e.g. out

1 - 90% by weight of an emulsifier, 1 - 50% by weight of the fenpropimorph / triazole compound mixture, preferably 5 - 40 and especially 10 to 35% by weight, 0 - 60% by weight. % of an organic solvent and

0 - 60% by weight water,

the proportions of the components of these agents should add up to 100% by weight.

Non-ionic, cationic and anionic emulsifiers can be used as emulsifiers. Quaternary ammonium compounds and alkoxylated, especially ethoxylated: fatty alcohols, oxo alcohols and oils (castor oil, fish oil) are preferred.

Very particularly advantageous fatty amines have been found as an emulsifier, which are alkoxylated with from 2 to 25 moles of ethylene oxide, such as Ethomen ^® C 15, Ethomen® T23 or S20 Ethomen® (Akzo Chemicals GmbH, Duren 52355, Germany).

The water-dilutable emulsion concentrates form clear to opaque emulsions when diluted in water.

To improve the fungicidal activity, it may be advantageous that these wood preservatives also contain piperidine derivatives and / or further morpholine derivatives, preferably one or more of the fungicidal active substances from the group fenpropidine, (N- (3 (4-tert.-Bu- tylphenyl) -2-methylpropyl) piperidine, tridemorph (N-tridecyl-2, 6-dimethylmorpholine) or their salts.

To increase the spectrum of activity or to achieve special effects, for example additional protection against insects, including termites, the above-mentioned solvent-containing formulations or emulsion concentrates can be used with teren active ingredients are combined, which in the latter case are incorporated with suitable additional emulsifiers.

Suitable mixture partners include the following compounds _:

Fenulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet;

Benzimidazoles such as carbendazim, benomyl, fuberidazole, thiabendazole or their salts;

Thiocyanates such as thiocyanatomethylthiobenzothiazol, methylene bisthiocyanate

quaternary ammonium compounds such as benzyldimethyletradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethylammonium chloride;

quaternary phosphonium compounds;

Iodine derivatives such as diiodomethyl p-tolysulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2, 3-di-iodo-2-propenylethyl carbonate, 2,3, 3-triiodallyl alcohol, 3-bromo-2, 3-di-iodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-butyl carbamate, 3-iodo-2-propynyl-n-hexyl carbamate, 3-iodo-2-propi nyl-cyclohexyl carbamate, 3-iodo-2-propynylphenyl carbamate, 0-1- (6-iodo-3-oxo-hex-5-ynyl) butyl carbamate, 0-1- (6-iodo-3-oxo-hex -5-inyl) phenyl carbamate, napcocide;

- Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol;

Bromine derivatives such as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-2-bromomethyl-glutaronitrile;

Isothiazolinones such as N-methylisothiazolin-3-one, 5-chloro-N-methyl-isothiazolin-3-one, 4,5-dichloro-N-octylisothiazoline-3-one, N-octyl-isothiazolin-3- on;

Benzisothiazolinones such as 4, 5-trimethylisothiazol-3-one;

Pyridines such as l-hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine; Metal soaps such as tin, copper, zinc naphthenate, octate, 2-ethylhexanoate, oleate, phosphate, benzoate.

Organotin compounds e.g. Tributyl (TBT) tin compounds, dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetramethylthiuram disulfide;

Nitriles such as 2,4, 5, 6-tetrachloroisophthalonitrile;

- benzothiazoles such as 2-mercaptobenzothiazole;

Quinolines such as 8-hydroxyquinoline and their Cu salts;

Tris-N- (cyclohexyldiazeniumdioxy) aluminum, N- (cyclohexyldiazeniumdioxy) tributyltin or K-salt, bis-N- (cyclohexyldiazenium dioxide) copper;

Morpholine derivatives such as aldemorph.

The following are preferably added as insecticides:

Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl,

1- (4-chlorophenyl) -4- (o-ethyl, S-propyl) phosphoryloxypyrazole,

Chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, Diazinon, Dichlorvos, Dimethoate, Ethoprophos, Etrimfos, Fenitro¬ thion, Fenthion, Heptenophos, Parathion, Parathion-methyl, Phosalone, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Pro fenofos, prothiofos, sulfprofos, triazophos and trichlorone; Carbamates such as aldocarb, bendiocarb, 2- (1-methylpropyl) phenylmethylcarbamate, butocarboxime, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, primicarb, promecarb, propoxur and thiocarb;

Organosilicon compounds, preferably dimethyl (phenyl) silylmethyl-3-phenoxybenzyl ether such as dimethyl (4-ethoxyphenyl) silylmethyl-3-phenoxybenzyl ether or (dimethylphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether such as dimethyl ⁽ 9-ethoxy -phenyl ⁾ silylmethyl-2-phenoxy-6-pyridylmethyl ether or (phenyl-3- (3-phenoxyphenyl (propyl) dimethylsilane such as (4-ethoxyphenyl) - (3- (4-fluoro-3-phenoxyphenyl-propyl) di- methylsilane;

Pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin, cycloprothin, cyfluthrin, decamethrin, cyhalothrin, cypermethrin, deltamethrin, a-cyno-3-phenyl-2-methyl-ben-zyl-2,2-dimethyl-3- (2 -chlor-2-trifluoromethylvinyl) cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flu- cythrinate, flumethrin, fluvalinate, permethrin, resemethrin and tralomethrin;

Nitroimines and nitromethylenes such as 1- ((6-chloro-3-pyridinyl ⁾ methyl) -4, 5-dihydro-N-nitro-lH-imidazol-2-amine (midacloprid ⁾ , N- ⁽⁽ 6- Chloro-3-pyridyl ⁾ methyl ⁾ -N'-cyano-N'-methylacetamide;

Slough inhibitors like Flurox and Farox.

Adding water-insoluble acids to the mixtures or wood preservatives can also improve the effectiveness of the active substances fenpropimorph and triazole compound. Suitable water-soluble organic acids are e.g. 8-hydroxyquinoline, or an aliphatic or aromatic mono- or polycarboxylic acid, e.g. an aliphatic unbranched monocarboxylic acid with 5 to 20 carbon atoms such as hexanoic acid, heptanoic acid, octane acid, nonanoic acid and decanoic acid, or an aliphatic branched monocarboxylic acid with 5 to 20 carbon atoms such as 2-ethylpentanoic acid, 2-ethylhexanoic acid, 2-ethylheptanoic acid, isooonanoic acid, isooonanoic acid and versatic acid, or neocarboxylic acid (more strongly branched monocarboxylic acids), or an aliphatic dicarboxylic acid with 5 to 20 carbon atoms such as sebacic acid and decanedicarboxylic acid, or an aromatic or aromatic / aliphatic carboxylic acid such as naphthenic acid and benzoic acid.

The solvent-containing wood preservatives or aqueous dilutions of the emulsion concentrates can additionally contain binders, e.g. ollosable or water-thinnable alkyd resins, acrylate dispersion, or in the case of primers, which contain approx. 2 to 10% by weight of solid resin or glazes, which contain approx. 10 to 25% solid resin, also inorganic or organic pigment preparations, water-based and olless dyes, "water repellants" such as metal stearates or waxes and / or other auxiliaries such as dryers, wetting agents and penetration aids are added.

The application for protecting the wood can e.g. depending on the risk to the wood:

a) by spraying the wood with the impregnation solution,

b) by dipping the wood into the impregnation solution (short dives to trough tendrils),

c) by impregnating the wood with the aid of pressure differences, for example boiler pressure or double vacuum drinking, d) by painting the wood or flooding.

The concentration of the fungicidal mixture in the respective wood preservative mostly depends on the degree of danger to the wood to be treated by the fungi and, in addition, on the selected application method. For wood secondary products and cellulose, for example, mostly undiluted concentrates are used (e.g. plywood, chipboard, bagasse panels).

The success of the treatment with the fungicidal mixtures or the ready-to-use wood preservatives, especially with the emulsion concentrates, usually depends on the application procedure.

The mixtures and wood preservatives used in accordance with the invention provide particularly effective protection against wood-discoloring fungi, in particular blue fungi and, in particular, Aureobasidium pullulans and Sclero phoma pityophila, which are included in the Ascomycetes.

It has also been found that the mixtures and wood preservatives also protect wood well

a) Basidiomycetes (e.g. Serpula lacrymans, Coniophora puteana) and

b) other ascomycetes such as mold (e.g. Aspergillus niger) and mold rot (e.g. Chaetomium globosum).

Examples

Pine sapwood blocks measuring 40 x 15 x 4 mm ³ were impregnated by vacuum impregnation with fungicide solutions in one concentration row. For this, the test blocks were 30 min. exposed to a vacuum of 30 mbar in a drinking vessel. The fungicide solution was then sucked into the drinking container by means of the vacuum, and the test blocks secured against floating were flooded in this way. After pressure equalization, the test blocks were then left under the solution for 1 h.

The amount of solution taken up by the test blocks was determined by weighing the blocks before and after the drinking, and from this the uptake of active substance or formulation was then calculated.

After an evaporation and fixing time of 2 weeks, the test blocks were soaked with water by vacuum impregnation and washed out with a 5-fold volume of water for 1 week. One water change was carried out per day. After drying again and sterilizing the blocks were then in the Clean room bank placed in petri dishes on agar culture medium and inoculated with a spore mixture of the blue fungi Aureobasidium pullulans and Sclerophoma pityophila (test fungi according to EN 152).

5 The Petri dishes with the test blocks were then installed in the test room at 20 ° C and approx. 70% humidity for 6 weeks. After this period, the growth on the surface of the block and after splitting the block, the discoloration (blueing) inside the block was determined visually. 0

The evaluation of the growth (outside) by the fungus was based on the following scale:

0

0

The fogging was assessed on the inside using the following scale:

0

Each test was carried out three times and then the mean for fouling or bluing in these three tests was formed.

5 The test results are summarized in the following two tables A and B. "Contribution amount" means the amount of the solutions or formulations (unit [kg / m ']) absorbed by the wood.

«The emulsifier Ethomen ^® C 15 is a coconut fatty amine alkoxylated with an average of 5 moles of ethylene oxide from Akzo Chemicals GmbH, 52355 Duren, Germany.

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Claims

claims 1. A method of treating wood against infestation by wood-damaging fungi, characterized in that the wood with a mixture which a) fenpropimorph and b) a triazole compound with the exception of epoxiconazole contained in a synergistically effective amount against these fungi. 2. The method according to claim 1, characterized in that propiconazole is used as the triazole compound (b). 3. The method according to claim 1 or 2, characterized in that the weight ratio of fenpropimorph (a) to the triazole compound (b) is 1: 1 to 4: 1. 4. The method according to claims 1 to 3, characterized gekennzeich¬ net that fenpropimorph (a) and the triazole compound (b) at the same time, namely together or separately, or in succession. 5. The method according to claims 1 to 4, characterized gekennzeich¬ net that one uses the mixture according to claim 1 in an amount of 0.05 to 5 kg per cubic meter of wood. 6. Use of mixtures containing Tnazole with the exception of epoxiconazole and fenpropimorph for the treatment of wood against wood-damaging fungi.