DE102005043138A1 - Fungicidal mixtures for wood protection - Google Patents

Abstract

The new synergistic mixtures based on triadimefon and / or triadimenol and copper compounds are outstandingly suitable for protecting industrial materials, in particular wood, against attack, damage and / or destruction by biological pests, in particular by wood-destroying fungi.

Description

The The present invention relates to novel synergistic fungicidal mixtures containing triadimefon and / or triadimenol and at least one Copper compound, and fungicidal compositions based on these mixtures as well as the use of these mixtures and means of protection of technical materials, in particular wood, against infestation, damage and / or destruction by biological pests, especially by wood-destroying Mushrooms.

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 the protection of plants against attack by Fungi (see DE-A 2552967), but not used alone in wood preservation can be since the spectrum of activity against the wood protection relevant microorganisms incomplete is (see EP-A 254857).

Even though Triadimefon or triadimenol in some references (e.g. WO 00/71314) as possible Mixing partner for various agents for the protection of wood is called, these are previously known mixtures still in many ways in need of improvement and play in wood preservation due to the mentioned effectiveness gaps so far not matter. There was therefore still the 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 is not effective Triadimefons or Triadimenols with copper compounds against in wood preservation relevant microorganisms act synergistically, d. H. the fungicides potency The synergistic mixtures are unexpectedly higher than that Sum of fungicidal potency the respective fungicides alone. There is thus an unpredictable synergistic Effect and not just an effect supplement.

By the synergistic increase in effect results in the additional Advantage that by applying less amount of fungicide in a wood preservative according to the present invention Invention not only an economic one Advantage, but also the safety risk to the environment is reduced. Furthermore, there is the advantage that the application rate can be reduced compared to existing systems. moreover the mixture is characterized by a good storage stability of the aqueous Wood preservative systems.

object The present invention therefore fungicidal drug mixtures containing a synergistically effective amount of a) triadimefon and / or Triadimenol and b) at least one copper compound.

The weight ratios The active ingredients in the drug mixture can be in a relatively large range be varied. Preferred are weight ratios of triadimefon and / or Triadimenol to the copper compound of 1: 600 to 1: 1, more preferably from 1: 200 to 1: 2.

Especially Active substance mixtures are preferably the a) triadimefon and b) the Copper compound in weight ratio from 1:40 to 1: 5.

All Particular preference is given to mixtures of active substances which are a) triadimenol and b) the copper compound in a weight ratio of 1:25 to 1: 5 included.

The Copper compounds can as water-insoluble Compounds are used, 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, associated with a broad spectrum of activity against microorganisms relevant in the protection of materials, Above all, they are effective against wood-destroying fungi. Continue to show the mixtures have a broad insecticidal and termiticidal action, especially against wood-destroying Beetle and Termites.

By way of example-without limiting, however-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.

The synergistic according to the invention Mixtures can optionally with a further microbicidal compound c) Magnification of the Spectrum of action or achievement of special effects are mixed.

Prefers are mixtures with one or more of the following microbicides Active ingredients c): Dichlofluanid, Tolylfluanid, Carbendazim, Thiabendazole, 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-pyridinyl) 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.

Especially preference is given to mixtures according to the invention which 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 - 2.5 % By weight of triadimefon and / or triadimenol, 0.5-30% by weight of copper compound and optionally 0.001 - 20 % By weight of one or more active substances c).

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

Another The present invention is the use of the drug mixtures according to the invention for the protection of technical materials, in particular wood, wood-based materials and wood plastic composites from infestation, damage and / or destruction by biological pests.

The Active ingredients can dependent on from their respective physical and / or chemical properties in the usual Formulations are transferred, like solutions, Emulsions, suspensions, powders, foams, pastes, granules, aerosols and finest encapsulations in polymeric substances.

Another The present invention relates to microbicidal agents 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, for example by mixing the active compounds with extenders, ie liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as extender For example, organic solvents may also be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example 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 dimethyl sulfoxide, and water. By liquefied gaseous diluents or carriers are meant those liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for example 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. As solid carriers for granules are: for example, broken 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: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates. Suitable dispersants are: for example lignin-sulphite liquors and methylcellulose.

It can in the formulations adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-shaped Polymers such as gum arabic, polyvinyl alcohol, Polyvinyl acetate, as well as natural Phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Further Additives can mineral and vegetable oils be.

It can Dyes such as inorganic pigments, e.g. 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 are used.

When another component of the formulation may optionally be Alkanolamine, e.g. Monoethanolamine can be used. This is the amount of added alkanolamines advantageously such that yourself in the diluted one aqueous Impregnation solution pH of 7 or more, preferably between 8.5 and 10.5. The amount of amines should be sufficient to complex the copper.

The Formulations generally contain between 0.5 and 50 weight percent Active substance combination, preferably between 1.0 and 25%.

The Microbicides used to protect engineering materials Agents or concentrates contain the active ingredient or combination of active ingredients in a concentration of 0.05 and 35 wt .-%, in particular 0.2 to 20% by weight.

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

The active compound combinations according to the invention or allow funds advantageously, the previously available microbicidal agents to replace with more effective ones. They show good stability and have in advantageously a broad spectrum of activity.

Under Wood, which by the active substance mixtures according to invention or this contained means protected is to be understood by way of example: lumber, wooden beams, Railway sleepers, Bridge parts, Jetties, Wooden vehicles, crates, pallets, containers, telephone poles, wood paneling, Wooden windows and doors, Plywood, Medium Density Fiberboard (MDF), Particle Board, Oriented Strand Board (OSB), Wafer Board, Laminated Veneer Lumber (LVL) or Wood products, generally used in house building or in joinery Find use as well as wood plastic composites. Especially serves the invention to be used Active substance mixture and compositions containing them for the protection of solid wood and wood products made 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, the Wirkstoff mix gene or the individual active substances contained therein previously in formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, pastes to transfer soluble powders.

By Dissolve the copper salts, optionally with the addition of heat, in the alkanolamines, optionally under acid, Water or solvent addition, and subsequently Addition of the emulsifier and the triazole compound form highly concentrated Pastes, liquid Concentrates or multiphase systems which after dilution with Water to impregnate of wood can be used. They also give a high concentration of active ingredient in water clear, storage-stable liquid.

The erfindungsgemäge Use for the protection of wood is done in the usual way in the context of known Wood treatment process, e.g. by spraying, brushing, dipping and large-scale impregnation, e.g. Vacuum, double vacuum or pressure method.

One particularly effective wood protection is achieved by large-scale impregnation e.g. Achieved vacuum, double vacuum or printing process.

object The present invention further provides a method of protection of wood wherein the wood comes in with a synergistically effective amount a) triadimefon and / or triadimenol and b) at least one copper compound and at least one dilution or solution center, optionally further auxiliaries and additives and optionally one or more fungicidal components c) by means of vacuum, double vacuum, Pressure or immersion impregnated becomes.

Biological example:

Various Concentrations of triadimefon, copper sulfate and mixtures of Both of these agents were against the wood destroying Basidiomycetes Poria placenta tested. From a colony of Holzdestruenten mycelium pieces were gouged out and incubated on a malt extract peptone containing nutrient agar at 26 ° C. As a result, radial hyphae growth with and without additive was observed compared. The minimum inhibitory concentration became the lowest Concentration of active substance indicated in a row, showing the radial growth completely suppressed.

X = 1

bedeutet Additivität

X > 1

bedeutet Antagonismus

X < 1

bedeutet Synergismus

Qa

= Konzentration von Substanz A, welche die MHK darstellt

Qb

= Konzentration von Substanz B, welche die MHK darstellt

QA

= Konzentation von Substanz A in der Konzentration von A/B, die das Mikrobenwachstum unterbindet

QB

= Konzentation von Substanz B in der Konzentration von A/B, die das Mikrobenwachstum unterbindet

After the Kull et al. (FCKull, PC Eismann, HDSylvestrowicz, RLMayer, Applied Microbiology 9, 538-541, 1961) the synergism was then determined. The following relationships apply:

X = 1

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 in the concentration of A / B that inhibits microbial growth

QB

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

Out the determined index data can be concluded that the combination Tridimefon / copper sulfate has a 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 (11)

Mixtures containing a synergistically effective Amount of a) triadimefon and / or triadimenol and b) at least one Copper compound. 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 carbonate. Mixtures according to at least one of the claims 1 and 2, characterized in that the copper compound is copper hydroxide carbonate is. Mixtures according to at least one of the claims 1 to 3, characterized in that the weight ratio of Triadimefon and / or triadimenol to copper compound 1: 600 to 1: 1. Mixtures according to at least one of the claims 1 to 4, characterized at least one further active ingredient c) from the series of fungicides and antibacterial compounds is included. Mixtures according to at least one of the claims 1 to 5, characterized as further active ingredient c) at least a compound from the series tolylfluanid, bethoxazine, benzalkonium chloride, 3-iodo-2-propynyl-butylcarbamate, Bifenthrin, Chlorfenapyr, Clothianidin, Cyfluthrin, Cypermethrin, Deltamethrin, imidacloprid, permethrin, thiacloprid is included. Mixtures according to at least one of the claims 1 to 6, characterized in that they 0.005 - 2.5 wt .-% triadimefon and / or Triadimenol, 0.5 - 30 % By weight of copper compound and optionally 0.001 to 20% by weight contains at least one further active ingredient c). Microbicidal agent containing a synergistic effective amounts of a) triadimefon and / or triadimenol and b) at least a copper compound and at least one dilution or solvent, if appropriate other auxiliaries and additives and optionally at least another active ingredient c) from the range of fungicides and antibacterial effective compounds. Use of an active ingredient mixture according to at least one of the claims 1 to 7 or an agent according to claim 8 for the protection of technical materials, in particular wood, Wood materials and wood plastic composites against infestation, damage and or destruction by biological pests. A process for the protection of wood and wood-based materials, characterized in that 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 or insecticidal active substances c) by means of a coating, Spray, vacuum, double vacuum, pressure or dipping method is impregnated. Technical materials containing synergistic effective amounts of a) triadimefon and / or triadimenol and b) at least a copper compound.