WO2007028526A2

WO2007028526A2 - Fungicidal mixtures for the protection of timber

Info

Publication number: WO2007028526A2
Application number: PCT/EP2006/008441
Authority: WO
Inventors: Rainer Bruns; Martin Kugler; Thomas Jaetsch
Original assignee: Lanxess Deutschland Gmbh
Priority date: 2005-09-10
Filing date: 2006-08-29
Publication date: 2007-03-15
Also published as: DE102005043138A1; JP2009507797A; NO20081740L; AU2006289336A1; WO2007028526A3; EP1926579A2; CN101378659A

Abstract

The novel synergistic mixtures based on triadimefon and/or triadimenol and copper compounds are highly suitable for protecting commercial materials, in particular timber, from being attacked, damaged and/or destroyed by biological pests, in particular by timber-blighting fungi.

Description

Fungicidal mixtures for wood protection

The present invention relates to novel synergistic fungicidal mixtures containing Triadime- fon and / or triadimenol and at least one copper compound, and fungicidal compositions based on these mixtures and the use of these mixtures and agents for the protection of technical see materials, especially wood, against infestation, damage and / or destruction by biological pests, in particular by wood-destroying fungi.

Triadimefon ((+) 1 - (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -butan-2-one) and triadimenol ((±) 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -butan-2-ol) are known fungicides for protecting plants against attack by fungi ( see DE-A 2552967), which, however, can not be used alone in wood preservation, since the spectrum of activity is incomplete against the microorganisms relevant to wood preservation (cf EP-A 254857).

Although triadimefon or triadimenol is mentioned in some references (eg WO 00/71314) as a possible mixing partner for various active substances for the protection of wood, these prior art mixtures still need to be improved in many respects and play a protective role due to the mentioned efficacy gaps so far no role. There was therefore still a need for an improved active ingredient mixture based on triadimefon and / or triadimenol.

Surprisingly, it has now been found that the combination of the alone inactive triadimone or triadimenol with copper compounds acts synergistically against microorganisms relevant in wood preservation, ie. H. the fungicidal potency of the synergistic mixtures is unexpectedly higher than the sum of the fungicidal potency of the respective fungicides alone. There is thus an unpredictable synergistic effect and not just an effect supplement.

Due to the synergistic increase in activity, there is the additional advantage that the smaller amount of fungicide to be used in a wood preservative according to the present invention not only provides an economic advantage, but also reduces the safety risk for the environment. Furthermore, there is the advantage that the application rate can be reduced compared to existing systems. In addition, the mixture is characterized by a good storage stability of the aqueous wood preservative systems.

The present invention therefore fungicidal active substance mixtures containing a synergistically effective amount of a) triadimefon and / or triadimenol and b) at least one copper compound. The weight ratios of the active ingredients in the active ingredient mixture can be varied within a relatively wide range. Preference is given to weight ratios of triadimefon and / or tri-maleol to the copper compound of from 1: 600 to 1: 1, more preferably from 1: 200 to 1: 2.

Particular preference is given to mixtures of active substances which contain a) triadimefon and b) the copper compound in a weight ratio of from 1:40 to 1: 5.

Very particular preference is given to mixtures of active substances which contain a) triadimenol and b) the copper compound in a weight ratio of 1:25 to 1: 5.

The copper compounds can be used as water-insoluble compounds, e.g. Copper sulfate, copper acetate, copper hydroxide, copper oxide, copper borate, copper fluoride or copper hydroxide carbonate. Preference is given to copper hydroxide carbonate.

The claimed synergistic mixtures show a particularly high microbicidal, in particular fungicidal action, combined with a broad spectrum of action against microorganisms relevant in the protection of materials, they are especially effective against wood-destroying fungi. Furthermore, the mixtures show a broad insecticidal and termiticidal action, in particular against wood-destroying beetles and termites.

By way of example-without, however, limiting-the following microorganisms may be mentioned:

Coniophora puteana, Coriolus versicolor, Gloeophyllum abietinum, Gloeophyllum trabeum, Lentinus tigrinus, Poria monticola, Poria placenta, Serpula lacrymans, Stereum sanguinolentum, Tyromyces palustris

By way of example-without, however, limiting-the following wood-destroying insects are mentioned:

Beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Ahobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec, Tryptodendron spec , Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec., Dinoderus minutus;

Hymenoptera such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur;

Termites such as Kalotermes flavicollis, Crypotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucilugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus. Optionally, the synergistic mixtures according to the invention can be mixed with a further microbicidal compound c) to increase the activity spectrum or to achieve particular effects.

Preference is given to mixtures with one or more of the following microbicidal active compounds c): dichlorofluanide, tolylfluanid, carbendazim, thiabendazoles, benzalkonium chloride, fenpropimorph, bethoxazine, 4,5-dichloro-N-octylisothiazolin-3-one, N-octylisothiazolin-3-one, Benzisothiazolinone, thiocyanato-methylthiobenzothiazole, 3-iodo-2-propynyl-n-butylcarbamate, o-phenylphenol, N- (3-aminopropyl) -N-dodecylpropane-1,3-diamine, acetamiprid, allethrin, alpha-cypermethrin, beta cyfluthrin, bifenthrin, bioallethrin, 4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridyl) methoxy] -3 (2H) -pyridazinone (CAS-RN: 120955 -77-3), chlorfenapyr, chlorpyrifos, clothianidin, cyfluthrin, cyhalothrin, cypermethrin, deltamethrin, etofenprox, fenoxycarb, fipronil, flufenoxuron, hexaflumuron, imidacloprid, nitenpyram, permethrin, pyriproxifen, silafluofen, tebufenozide, thiacloprid, thiamethoxam, tralomethrin, triflumuron.

Particular preference is given to mixtures according to the invention which contain as further active ingredient c) tolylfluanid, bethoxazine, benzalkonium chloride, 3-iodo-2-propynyl-butylcarbamate, bifenthrin, chlorfenapyr, clothianidin, cyfluthrin, cypermethrin, deltamethrin, imidacloprid, permethrin, thiacloprid or a mixture of these components ,

The mixtures according to the invention generally contain 0.005 to 2.5% by weight of triadimefon and / or triadimenol, 0.5 to 30% by weight of copper compound and optionally 0.001 to 20% by weight of one or more active substances c).

The mixtures according to the invention preferably contain 0.01-10% by weight of triadimefon and / or triadimenol, 1.0-15% by weight of copper compound and 0.005-10% by weight of tolylfluanid, bethoxazine, benzalkonium chloride, 3-iodo-2-propynyl-butylcarbamate, Bifenthrin, Chlorfenapyr, Clothianidin, Cyfluthrin, Cypermethrin, Deltamethrin, Imidacloprid, Permethrin, Thiacloprid or mixtures thereof.

Another object of the present invention is the use of the erfϊndungsgemäßen drug mixtures for the protection of industrial materials, in particular of wood, wood-based materials and wood plastic composites against infestation, damage and / or destruction by biological pests.

Depending on their respective physical and / or chemical properties, the active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and very fine encapsulations in polymeric substances. The present invention further provides microbicidal compositions containing a synergistically effective amount of a) triadimefon and / or triadimenol and b) at least one copper compound and at least one diluent or solvent, optionally further auxiliaries and additives and optionally one or more further fungicidal components c ).

The formulations are prepared in a known manner, e.g. by mixing the active compounds with extenders, that is to say liquid solvents, liquefied gases under pressure and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as an extender, e.g. also organic solvents can be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols such as butanol or glycol such as ethylene glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide, and water. By liquefied gaseous diluents or carriers are meant those liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: e.g. ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates. Suitable solid carriers for granules are: e.g. Cracked and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks. Suitable emulsifiers and / or foam-formers are: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates. Suitable dispersants are: e.g. Lignin-sulphite liquors and methylcellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex polymers may be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids. Other additives may be mineral and vegetable oils. Dyes such as inorganic pigments such as iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

As an additional constituent of the formulation, an alkanolamine, e.g. Monoethanolamine can be used. In this case, the amount of alkanolamines added is advantageously such that a pH of 7 or more, preferably between 8.5 and 10.5, is established in the dilute aqueous impregnating solution. The amount of amines should be sufficient to complex the copper.

The formulations generally contain between 0.5 and 50 percent by weight of active ingredient combination, preferably between 1.0 and 25%.

The microbicidal agents or concentrates used to protect the technical materials contain the active ingredient or combination of active ingredients in a concentration of 0.05 and 35% by weight, in particular 0.2 to 20% by weight.

The use concentrations of the active substances or the active ingredient combinations to be used depends on the type and occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimum amount used can be determined by test series. In general, the use concentrations are in the range of 0.001 to 5 wt .-%, preferably from 0.01 to 1.5 wt .-%, based on the material to be protected.

The active compound combinations or compositions according to the invention advantageously make it possible to replace the previously available microbicidal agents with more effective ones. They show good stability and advantageously have a broad spectrum of activity.

Under wood, which can be protected by the erf Wirkstoffndungsgemäßen drug mixtures or these agents contained, is to be understood by way of example: timber, wooden beams, railway sleepers, bridge parts, boat jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wood panels, wooden windows and doors , Plywood, MDF, Particle Board, Oriented Strand Board (OSB), Waferboard, Laminated Veneer Lumber (LVL) or wood products commonly used in house building or carpentry, as well as wood-plastic composites. In particular, the active substance mixture to be used according to the invention and agents containing it serve to protect solid wood and wood products produced therefrom.

In the inventive use of the drug mixtures, the drug mixtures can be used as such or in the form of their individual active ingredients. It is possible to convert the active substance mixtures or the individual active substances contained therein beforehand into formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, pastes, soluble powders.

By dissolving the copper salts, optionally with heat input, in the alkanolamines, if appropriate with the addition of acid, water or solvent, and then adding the emulsifier and the triazole compound, highly concentrated pastes, liquid concentrates or else multiphase systems are obtained which after dilution can be used with water to impregnate wood. They also give a clear, storage-stable liquid at high drug concentration in water.

The use according to the invention for the protection of wood is carried out in the usual way in the context of known wood treatment methods, e.g. by spray, brush, dip and large scale impregnation methods, e.g. Vacuum, double vacuum or pressure method.

Particularly effective wood protection is provided by large scale impregnation methods, e.g. Achieved vacuum, double vacuum or printing process.

The present invention further provides a process for the protection of wood wherein the wood with a synergistically effective amount of a) triadimefon and / or triadimenol and b) at least one copper compound and at least one diluent or solvent, optionally other auxiliaries and additives and optionally one or more fungicidal components c) is impregnated by means of vacuum, double vacuum, pressure or dipping method.

Biological example:

Various concentrations of triadimefon, copper sulphate and mixtures of the two active substances mentioned were tested against the wood destroying basidiomycete Poria placenta. Mycelium pieces were punched out of a colony of the wood destructor and incubated on a Maize extract peptone containing nutrient agar at 26 ° C. Subsequently, radial hyphae growth was compared with and without added active substance. The minimum inhibitory concentration was given as the lowest active ingredient concentration in succession, which completely suppresses the radial growth.

According to the KuIl et al. (F.C. Kull, P.C. Eismann, H.D. Sylvestrowicz, R. L. Mayer, Applied Microbiology 9, 538-541, 1961) the synergism was then determined. The following relationships apply:

QA QB + = X (synergistic index)

Qa Qb X = I means additivity

X> 1 means antagonism

X <1 means synergism

Qa = concentration of substance A, which represents the MIC

Qb = concentration of substance B, which represents the MIC

QA = Concentration of substance A at the concentration of A / B that inhibits microbial growth

QB = Concentration of substance B at the concentration of A / B that inhibits microbial growth

From the index data obtained, it can be concluded that the combination triadimphone / copper sulphate has pronounced synergism.

Examples of formulations

Example 1 (Concentrate):

0.5% triadimefon, 0.3% sodium hydrazolate / sodium dodecylbenzenesulfonate preparation, 2.7% fatty acid polyethylene glycol ether ester, 6.5% Texanol, 10% copper hydroxide carbonate (basic copper carbonate), 22% ethanolamine, 58% water

Example 2 (concentrate):

0.4% triadimefon, 4.0% benzalkonium chloride, 7.5% copper hydroxide carbonate, 20% ethanolamine, 68.1% water

Example 3 (impregnating agent):

0.1% Triadimenol, 1.0% Ethoxylated Castor Oil, 1.0% Texanol, 0.75% Copper Hydroxide Carbonate, 0.9% Ammonium Hydroxide, 0.45% Ammonium Bicarbonate, 95.8% Water

Claims

claims

1. Mixtures comprising a synergistically effective amount of a) triadimefon and / or triadimenol and b) at least one copper compound.

2. Mixtures according to claim 1, characterized in that the copper compound is selected from the series copper sulfate, copper acetate, copper hydroxide, copper oxide, copper borate, copper fluoride or copper hydroxide.

3. Mixtures according to at least one of claims 1 and 2, characterized in that the copper compound is copper hydroxide carbonate.

4. Mixtures according to at least one of claims 1 to 3, characterized in that the weight ratio of triadimefon and / or triadimenol to the copper compound is 1: 600 to 1: 1.

5. Mixtures according to at least one of claims 1 to 4, characterized in at least one further active ingredient c) from the series of fungicides and antibacterial compounds is contained.

6. Mixtures according to at least one of claims 1 to 5, characterized as further active ingredient e) at least one compound from the series Tolylfluanid, Bethoxazine, benzalkonium chloride, 3-iodo-2-propynyl-butylcarbamate, bifenthrin, Chlorfenapyr, Clothianidin, Cyfluthrin, Cypermethrin , Deltamethrin, imidacloprid, permethrin, thiacloprid.

7. Mixtures according to at least one of claims 1 to 6, characterized in that they 0.005 - 2.5 wt .-% triadimefon and / or triadimenol, 0.5 - 30 wt .-% copper compound and optionally 0.001 - 20 wt .-% of at least one further active ingredient c) contains.

8. A microbicidal composition containing a synergistically effective amount of a) triadimefon and / or triadimenol and b) at least one copper compound,

and at least one diluent or solvent, optionally further auxiliaries and additives and optionally at least one further active ingredient c) from the series of fungicides and antibacterial compounds.

9. Use of an active compound mixture according to at least one of claims 1 to 7 or of an agent according to claim 8 for the protection of technical materials, in particular Of wood, wood materials and wood plastic composites against infestation, damage and / or destruction by biological pests.

10. A method for the protection of wood and wood-based materials, characterized in that the wood with a synergistically effective amount of a) triadimefon and / or Triadimeno! and b) at least one copper compound and at least one diluent or

Solvent, optionally further auxiliaries and additives and optionally one or more fungicidal or insecticidal active ingredients c) is impregnated by means of coating, spray, vacuum, double vacuum, pressure or dipping method.

11. Technical materials containing synergistically effective amounts of a) triadimefon and / or triadimenol and b) at least one copper compound.