WO2007028528A2

WO2007028528A2 - Synergistic mixtures

Info

Publication number: WO2007028528A2
Application number: PCT/EP2006/008443
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: DE102005043139A1; CA2621876A1; RU2008113389A; NO20081741L; JP2009507057A; KR20080042873A; WO2007028528A3; EP1926578A2; AU2006289338A1; CN101258009A

Abstract

The novel synergistic mixtures based on triadimefon and/or triadimenol and known insecticides are highly suitable for protecting commercial materials, in particular timber and wood materials, in addition to wood-plastic composites from being attacked, damaged and/or destroyed by biological pests.

Description

Synergistic mixtures

The present invention relates to new synergistically active mixtures comprising on the one hand triadimefon and / or triadimenol and on the other hand known insecticides, compositions based on these mixtures and the use of these mixtures and compositions for the protection of industrial materials, especially wood and wood-based materials and wood-plastic composites, against infestation, Damage and / or destruction by biological pests.

Basically, the expert distinguishes between a structural destruction of the wood by Basidiomyceten and - if the wood is exposed to a high humidity or earth contact environment - by soft rot fungi, as well as damage to the wood by wood-destroying insects and termites and a visual impairment of the wood by wood discoloring mushrooms. These destructions and impairments of the wood lead among other things to a reduction of the strength and generally to a limited usability of the wood. Consequently, wood and wood products with fungicides and, optionally, insecticides are protected from attack by biological pests, thereby prolonging the usefulness and durability of wood and wood products.

For use in wood preservation against wood-destroying basidiomycetes, triazoles such as tebuconazole (see EP-A 254857) and cyproconazole (see EP-A 554833) are already known whose efficacy in the laboratory test alone is promising, but not always under practical conditions Ensures sufficient protection of the wood, so that these active substances must be combined in the practical application with metals or metal salts, especially copper salts. Thus, in practice, triazole fungicides are frequently mixed with heavy metal-containing compounds, e.g. Copper compounds combined to provide insecticidal protection in addition to the fungicidal finish.

However, the use of wood preservatives containing heavy metals is environmentally questionable. There was therefore still a need for improved wood preservatives based on active ingredients that ensure sufficient protection of wood without the addition of heavy metals.

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). An activity against insects is not reported. Although triadimefon or triadimenol are mentioned in some references (eg WO 00/71314) as possible mixing partners for various active ingredients for the protection of wood, these prior art blends still need to be improved in many respects and have hitherto not played any role in wood preservation due to the aforementioned effectiveness gaps Role. There was therefore still a need for an improved active ingredient mixture based on triadimefon and / or triadimenol.

Surprisingly, it has been found that the combination of the alone inactive triadimone or triadimenol with certain insecticides has a synergistic increase in activity against biological pests that are relevant in wood preservation.

The present invention relates to mixtures comprising synergistically effective amounts of triadimefon and / or triadimenol and at least one insecticide, preferably from the series of phosphoric esters, carbamates, ureas, pyrethroids, pyrroles, phenylpyrazoles, diphenyl ethers, diacylhydrazines and nitromethylenes.

The mixtures according to the invention exhibit synergistic activity against biological pests which are relevant in wood preservation, ie. H. the potency of the synergistic mixtures is unexpectedly higher than the sum of the potency of the respective active ingredients alone. There is thus an unpredictable synergistic effect and not just an effect supplement.

Another object of the present invention is the use of synergistic mixtures according to the invention for the protection of wood, wood materials and Holzplastikverbundstof- fen against relevant in wood protection biological pests, especially against wood-destroying bark beetles and termites.

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.

Preference is given to mixtures comprising triadimefon and / or triadimenol and at least one insecticide from the series:

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. Very particular preference is given to mixtures comprising triadimefon and / or triadimenol and at least one insecticide from the series:

Bifenthrin, chlorfenapyr, chlorpyrifos, clothianidin, cyfluthrin, cypermethrin, deltamethrin, etofenprox, fipronil, flufenoxuron, imidacloprid, permethrin, thiacloprid, thiamethoxam.

Particular preference is given to mixtures comprising triadimefon and / or triadimenol and at least one insecticide from the series:

Bifenthrin, Chlorfenapyr, Clothianidin, Cyfluthrin, Cypermethrin, Deltamethrin, Imidacloprid, Permethrin, Thiacloprid.

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 triadimenol to at least one of said insecticides in the range from 1000: 1 to 1: 1, more preferably from 100: 1 to 2: 1.

Particular preference is given to mixtures of active substances according to the invention containing the triadimefon and / or triadimenol and at least one of the said insecticides in a weight ratio of 50: 1 to 5: 1.

The synergistic mixtures according to the invention exhibit a particularly high biocidal, in particular fungicidal and insecticidal and termiticidal action, combined with a broad spectrum of activity against biological pests which are relevant in the protection of materials. Above all, they are effective against wood destroying basidiomycetes and insects, especially wood-destroying beetles and termites.

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

Chaetomium globosum, Glenospora graphii, Humicola gisea, Petriella setifera, Trichurus spiralis and Lecythophora mutabilis, and Trichoderma viride, Stachybotrys cartarum, Chephalosporium sp. and Acremonium sp.

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, Urocenis gigas taignus, Urocerus augur;

Termites such as e.g. Kalotermes flavicollis, Crypotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucilugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.

In addition to soft rot fungi, under humid conditions bacteria such as e.g. Caldocellulosiruptor sp., Anaerocellum sp., Clostridium species such as Clostridium cellulovorans, Clostridium aldrichii, Cellulomonas species, Streptomycetes, Micromonospora sp., Thermomonospora sp., Microbispora sp. Cytophaga and Sporocytophaga species contribute significantly to the degradation of cellulose.

The synergistic mixtures according to the invention can be combined with at least one further microbicidal active ingredient in order to increase the spectrum of action or to achieve special effects. In particular, the synergistic mixture may contain at least one further active ingredient from the series of fungicides and antibacterial compounds.

Particularly preferred are mixtures with one or more of the following microbicidal components: dichlofluanid, tolylfluanid, carbendazim, fenpropimorph, bethoxazine, thiocyanato-methylthiobenzothiazole, 3-iodo-2-propynyl-n-butylcarbamate, zinc pyrithione, copper pyrithione, N- (3 aminopropyl) -N-dodecylpropane-1,3-diamine, tebuconazole, propiconazole, cyproconazole and copper salts.

Particular preference is given to mixtures according to the invention which comprise, as further component, dichlorofluanide, tolylfluanid, bethoxazine, 3-iodo-2-propynyl-butylcarbamate, zinc or copper pyrithione, tebuconazoles, propiconazoles, cyproconazoles, copper salts or a mixture of these components.

Likewise preferred are mixtures with one or more of the following bactericidal components:

Benzyl alcohol mono- (poly) -hemiformal, ethylene glycol hemiformal, N- (2-hydroxypropyl) amino methanol, N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-benzisothiazole linone, formaldehyde, glutardialdehyde, benzalkonium chloride, benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, 3-methyl-4-chlorophenol and 2-benzyl-4-chlorophenol and their alkali metal and alkaline earth metal salts, p-hydroxybenzoic acid esters and o-phenylphenol and their alkali metal and alkaline earth metal salts, Bronopol, 2,2-dibromo-3-nitrile propionamide and silver compounds. Preference is given to erf Wirkstoffndungsgemäße drug combinations with the following bactericides:

Benzyl alcohol mono- (poly) -hemiformal, N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-benzisothiazolinone, glutaric dialdehyde, benzalkonium chloride, bronopol, 3-methyl-4-chlorophenol and 2-Benzyl-4-chlorophenol and the alkali and alkaline earth salts, o-phenylphenol and their alkali and alkaline earth salts and silver compounds.

Very particular preference is given to active ingredient combinations with the following bactericides:

Benzyl alcohol mono- (poly) -hemiformal, 4,5-benzisothiazolinone, benzalkonium chloride, bronopol, 3-methyl-4-chlorophenol and 2-benzyl-4-chlorophenol and their sodium and potassium salts, o-phenylphenol and the sodium and potassium salts and silver (I) compounds.

The mixtures according to the invention generally contain 0.01-85 percent by weight of triadimefon and / or triadimenol, 0.001-15 percent by weight of at least one of said insecticides and optionally 0.01-80 percent by weight of at least one further microbicidal active compound, in particular from the series of the abovementioned active compounds.

Preferably, the mixtures according to the invention contain 0.1-40% by weight of triadimenone and / or triadimenol, 0.01-5% by weight of at least one of said insecticides and optionally 0.05-30% by weight of at least one further microbicidal active ingredient, in particular from the series of the abovementioned active substances.

The mixtures according to the invention can be prepared in a known manner, for example by grinding and / or mixing and / or granulating the active ingredients in a suitable apparatus. It is likewise possible for the active compounds to be used individually or jointly in a suitable solvent, if appropriate with addition of further auxiliaries and additives, such as, for example, To dissolve emulsifiers, to disperse or emulsify and if necessary to precipitate out of this by addition of a further solvent or optionally distill the solvent to dryness.

Another object of the present invention is the use of the active compound mixtures according to the invention 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, in particular by fungi and insects.

Depending on their respective physical and / or chemical properties, the active compounds as well as the active substance mixtures can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and ultrafine encapsulations in polymeric substances. Another object of the present invention are microbicidal compositions containing a synergistically effective amount of triadimefon and / or triadimenol and at least one of said insecticides and at least one diluent or solvent, optionally further auxiliaries and additives and optionally at least one further mentioned active ingredient.

The formulations can be 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, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide 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, 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, alkyl sulfonates, alkyl sulfates, aryl sulfonates 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, 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.

The formulations generally contain between 0.1 and 95 percent by weight of active ingredient combination, preferably between 0.5 and 50 percent by weight. The microbicidal agents or concentrates used for the protection of the technical materials contain the active substance or the active ingredient combination in a concentration of 0.005 and 95 percent by weight, in particular 0.1 to 50 percent 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 10 weight percent, preferably from 0.01 to 5 weight percent, 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.

By wood, wood materials and wood plastic composites, which can be protected by the active substance mixtures according to the invention or these agents, 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 paneling, wooden windows and doors, plywood, medium density fibreboard (MDF), chipboard, 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.

The active compounds can be used individually or as a finished mixture, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use solutions, suspensions, pastes, soluble powders. The application is done in the usual way by treating the technical material with the individual active ingredients or the finished mixture or with a formulation or application form prepared therefrom. When the materials to be protected are wood, wood-based materials or wood-plastic composites, application is by conventional methods, e.g. by spray, brush, dip, large scale impregnation, e.g. Vacuum, double vacuum or pressure method and by adding to the glue or by adding via the compounder or mixer as well as over Materbatches.

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

The present invention furthermore relates to a method for protecting wood and wood-based materials, the wood or the wood-based material containing a synergistically effective amount of triadimefon and / or triadimenol and at least one of said insecticides and at least one diluent or solvent, optionally further auxiliary substances. and additives and, where appropriate, at least one other active substance by means of coating, spraying, Vacuum, double vacuum, pressure or dipping process is impregnated. The active substances triadimefon and / or triadimenol and at least one of said insecticides can be used either individually or as a ready-mixed mixture.

Biological examples

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

QA / Qa + QB / Qb = SI

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

SI = synergistic index

SI = 1 means additivity

SI> 1 means antagonism

SI <1 means synergism

Example 1:

Various concentrations of chlorfenapyr (A), triadimefon (B) and mixtures of the two drugs were tested against the wood destroying basidiomycete Gloeophyllum trabeum. Mycelium pieces were punched out of a colony of the wood destructor and incubated on a malt 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.

From the index data determined, it appears that the inventive combination of triadimefon with Chlorfenapyr has a pronounced synergism over a wide range.

Example 2:

Various concentrations of permethrin (A), triadimefon (B) and mixtures of the two active substances mentioned were tested against the wood destroying basidiomycete Lentinus tigrinus. Mycelium pieces were punched out of a colony of the wood destructor and incubated on a malt 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.

It emerges from the index data determined that the combination of permethrin with triadimefon according to the invention has pronounced synergism over a wide range.

Example 3:

Various concentrations of thiacloprid (A), triadimefon (B) and mixtures of the two active substances mentioned were tested against the wood destroying basidiomycete Poria placenta. From a colony of Holzdestruenten mycelium pieces were punched out and incubated on a malt extract peptone-containing nutrient agar at 26 ⁰ C. Subsequently, radial hyphae growth was compared with and without addition of active ingredient. The minimum inhibitory concentration was given as the lowest active ingredient concentration in succession, which completely suppresses the radial growth.

It can be concluded from the determined index data that the combination of thiacloprid with triadimefon has a pronounced synergism over a wide range.

Formulation Examples: Example 1 (Technical Concentrate):

10% triadimefon, 0.5% permethrin, 24.5% texanol, 15% ethoxylated castor oil, 15% sodium hydohydolate / sodium dodecylbenzenesulfonate preparation, 35% dimethyl fatty acid amide

Example 2 (Technical Concentrate):

15% triadimefon, 0.5% chlorfenapyr, 22.5% texanol, 13% sodium hydrazolate / sodium dodecylbenzenesulfonate preparation, 14% fatty acid polyethylene glycol ether ester, 35% dimethyl fatty acid amide

Example 3 (Technical Concentrate):

7.5% Triadimenol, 0.25% Bifenthrin, 16.25% Sodium Rhizinolate / Sodium Dodecyl Benzenesulfonate Preparation, 27% Ethoxylated Castor Oil, 49% Texanol

Example 4 (Emulsifiable concentrate):

5.0% Triadimefon, 0.1% Thiacloprid, 2.9% Sodium Rhizinolate / Sodium Dodecyl Benzenesulfonate Preparation, 27% Fatty Acid Polyethylene Glycol Ether Ester, 65% Texanol Example 5 (impregnating agent):

0.3% Triadimenol, 0.01% Deltamethrin, 15% Worleesol 31A (Concentrate Concentrate), 0.8% Additol VXW 4940, 3.0% Ethoxylated Castor Oil, 3.0% Texanol, 77.89% Water

Example 6 (impregnating agent):

0.4% triadimefon, 0.01% Cyfluthrin, 4.0% alkyd resin, 4.0% Dowanol DPM, 91.59% white spirit

Example 7 (Primer):

0.2% triadimefon, 0.2% tebuconazole, 0.4% tolylfluanid, 0.05% cypermethrin, 6% dowanol DPM, 10% alkyd resin, 83.2% white spirit

Claims

claims

1. Mixtures containing synergistically effective amounts of triadimefon and / or triadimol and at least one insecticidal active ingredient.

2. Mixtures according to claim 1, characterized in that the insecticidal active ingredient is selected from the series of phosphoric esters, carbamates, ureas, pyrethroids,

Pyrroles, phenylpyrazoles, diphenyl ethers, diacylhydrazines and nitromethylenes.

3. Mixtures according to at least one of claims 1 and 2, characterized in that the insecticidal active ingredient is selected from the series: 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.

4. Mixtures according to at least one of claims 1 to 3, characterized in that the insecticidal active ingredient is selected from the series: bifenthrin, chlorfenapyr, chlorpyrifos, clothianidin, cyfluthrin, cypermethrin, deltamethrin, etofenprox, fipronil, flufenoxuron, imidacloprid, permethrin, thiacloprid , Thiamethoxam.

5. Mixtures according to at least one of claims 1 to 4, characterized in that the weight ratio of triadimefon and / or triadimenol to insecticidal active ingredient

1000: 1 to 1: 1.

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

7. Mixtures according to at least one of claims 1 to 6, characterized in that they 0.01 to 85 weight percent triadimefon and / or triadimenol, 0.001 to 15 weight percent of at least one insecticidal active ingredient and optionally 0.01 to 80 weight percent of at least one further microbicidal active ingredient from the series of fungicides and antibacterial compounds.

8. A microbicidal composition containing a synergistically effective amount of triadimefon and / or triadimenol and at least one insecticidal active ingredient and at least one diluent or solvent, optionally other auxiliaries and additives and optionally at least one further active ingredient 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 an agent according to claim 8 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.

10. A method for the protection of wood and wood-based materials, characterized in that the wood or the wood material with synergistically effective amounts of triadimefon and / or triadimenol and at least one insecticidal active ingredient and at least one diluent or solvent, optionally other auxiliaries and additives, and optionally at least one further active ingredient from the series of fungicides and antibacterial compounds, impregnated by means of coating, spraying, vacuum, double-vacuum, pressure or dipping method.

11. Technical materials containing synergistically effective amounts of triadimefon and / or triadimenol and at least one insecticidal active ingredient.