JP2009507797A - Bactericidal and fungicidal mixture for wood protection - Google Patents

Abstract

  A novel synergistic mixture based on triadimephone and / or triadimenol and copper compounds protects industrial materials, in particular wood, from attack, damage and / or destruction by biological plagues, in particular by wood-rotting fungi. Very suitable.

Description

  The present invention relates to novel synergistic fungicidal mixtures comprising triadimephone and / or triadimenol and at least one copper compound, and to a fungicidal composition based on these mixtures, It also relates to the use of these mixtures and compositions for protecting industrial materials, in particular wood, from attack, damage and / or destruction by biological plagues, in particular by wood-rotting fungi.

  Triazimephone ((±) -1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) butan-2-one) and triazimenol (( ±) -1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) butan-2-ol) is produced by fungi Known fungicides for the protection of plants from attack (see (Patent Document 1)), but they have gaps in the spectrum of activity against microorganisms involved in wood protection Since it has (refer (patent document 2)), it cannot use for protection of wood as it is.

Triazimehon or triadimenol are listed as possible mixing partners for various active compounds for the protection of wood in several references (for example (Patent Document 3)), but these prior art mixtures are It still needs improvement in many ways and so far has not played any role in the protection of wood due to the above mentioned active gap. Accordingly, there remains a need for improved active compound mixtures based on triadimephone and / or triadimenol.
DE-A 2552967 EP-A 254857 International Publication No. 00/71314 Pamphlet

  Surprisingly, triazimephone or a combination of triadimenol and a copper compound that is not effective as such acts synergistically against microorganisms involved in wood protection, i.e., the bactericidal and fungicidal activity of the synergistic mixture It has now been found that in an unexpected way, it is higher than the sum of the bactericidal and fungicidal activity of problematic germicides. Thus, an unpredictable synergistic effect exists and is not simply an addition of activity.

  The synergistically enhanced activity not only provides economic benefits, but also an environmental safety risk due to the reduced amount of fungicides that should be used in the wood protection composition according to the present invention. Also has the added advantage of being reduced. Another advantage is that the application rate can be reduced compared to existing systems. Furthermore, the mixture is characterized by the good storage stability of the aqueous wood protection composition system.

  Accordingly, the present invention provides a bactericidal and fungicidal active compound mixture comprising a synergistically effective amount of a) triadimephone and / or triadimenol and b) at least one copper compound.

  The weight ratio of active compound in the active compound mixture can be varied within a relatively wide range. A weight ratio of triadimephone and / or triadimenol to copper compound of 1: 600 to 1: 1, particularly preferably 1: 200 to 1: 2, is preferred.

  Particular preference is given to active compound mixtures comprising a) triadimephone and b) copper compound in a weight ratio of 1:40 to 1: 5.

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

  The copper compound can be used as a water-insoluble compound such as copper sulfate, copper acetate, copper hydroxide, copper oxide, copper borate, copper fluoride or copper hydroxide carbonate. Copper hydroxide carbonate is preferred.

  The claimed synergistic mixture has a particularly fungicidal action, combined with a broad spectrum of activity against microorganisms related to the high microbicidal properties, in particular the protection of materials, which are wood decay It is particularly effective against bacteria. In addition, the mixture has a broad insecticidal and termite action, especially against wood-destroying beetles and termites.

The following microorganisms are exemplified, but are not limited to:
Brown rot fungus (Coniophora puteana), Kawaratake (Coriolus versicolor), Coleophyllum abietinum (Gloeophyllum abetinum), Gloeophyllum trauum (Gloeophyllum trabeum) -Placenta (Poria placenta), Namidatake (Serpula lacrymans), Chiurokotakemodo (Sterum sanguinolentum), Oyuzuratake (Tyromyces palustris).

The following wood-destroying insects are exemplified, but are not limited to:
For example, Hairotorupesu-Bajurusu (Hylotrupes bajulus), Kurorohorusu-Piroshisu (Chlorophorus pilosis), Obiumu-Pankutatamu (Ahobium punctatum), Kisesutobiumu-Rufobirosumu (Xestobium rufovillosum), Puchirinusu-Pekuchikorunisu (Ptilinus pecticornis), Dendrobium Peruchinekkusu (Dendrobium pertinex) , Ernobius mollis, Priobium carpini, Lyctus bruneus, African larva, Lyctus africanus Lyctus pnicense, Lyctus linearis, Lyctus pubecens, Trogoxylon aequile, Trogylon aequile (Tryptendron spec.), Apate monachus, Bostrichus capcins, Heterobostrus bruneus, Sinoxyn sp. Beetles, such as Shinkuimushi (Dinoderus minutus);
For example, membrane insects such as Corix wasp (Sirex juvencus), Prunus wasp (Urocerus gigas), Urocerus gigas taignus, Urocerus augur;
For example, Carotermes flavicollis, Crypotermes brevis, Heterotermes indicola, Heterotermes radis genus, Reticulis genus Termites such as Reticulitermes lucillus, Mastotermes darwiniensis, Zotermopsis nevadensis, Copttermes formosanus Li.

  The synergistic mixtures according to the invention can be mixed with further microbicidal compounds c), if appropriate, in order to broaden the activity spectrum or to achieve specific effects.

  Mixtures with one or more of the following microbicidal active compounds c) are preferred: dicloflurane, tolylfluanid, carbendazim, thiabendazole, benzalkonium chloride, fenpropimorph, besoxazine, 4,5-dichloro- N-octylisothiazolin-3-one, N-octylisothiazolin-3-one, benzisothiazolinone, thiocyanatomethylthiobenzothiazole, 3-iodo-2-propynyl n-butylcarbamate, o-phenylphenol, N- ( 3-aminopropyl) -N-dodecylpropane-1,3-diamine, acetamiprid, allethrin, alpha-cypermethrin, beta-cyfluthrin, bifenthrin, bioaresulin, 4-chloro-2- (2-chloro-2-methylpropyl) ) -5-[( -Iodo-3-pyridinyl) methoxy] -3 (2H) -pyridazinone (CAS Registry Number: 120955-77-3), chlorfenapyr, chlorpyrifos, clothianidin, cyfluthrin, cyhalothrin, cypermethrin, deltamethrin, etofenprox, phenoxycarb, Fipronil, flufenoxuron, hexaflumuron, imidacloprid, nitenpyram, permethrin, pyriproxyfen, silafluophene, tebufenozide, thiacloprid, thiamethoxam, tralomethrin, triflumurone.

  Further active compounds c) include tolylfluanid, besoxazine, benzalkonium chloride, 3-iodo-2-propynylbutylcarbamate, bifenthrin, chlorfenapyr, clothianidin, cyfluthrin, cypermethrin, deltamethrin, imidacloprid, permethrin, thiacloprid or their compounds Particular preference is given to mixtures according to the invention comprising a mixture of

  The mixtures according to the invention are generally from 0.005 to 2.5% by weight of triadimephone and / or triadimenol, from 0.5 to 30% by weight of copper compound and, where appropriate, from 0.001 to 20% by weight. One or more active compounds c).

  Preferably, the mixture according to the invention comprises 0.01 to 10% by weight of triazimephone and / or triadimenol, 1.0 to 15% by weight of a copper compound and 0.005 to 10% by weight of tolylfluanid, besoxazine. Benzalkonium chloride, 3-iodo-2-propynylbutylcarbamate, bifenthrin, chlorfenapyr, clothianidin, cyfluthrin, cypermethrin, deltamethrin, imidacloprid, permethrin, thiacloprid or mixtures thereof.

  The invention further provides the use of the active compound mixtures according to the invention for protecting industrial materials, in particular wood, woodwork products and wood / plastic composites, from attack, damage and / or destruction by biological plagues.

  Depending on their specific physical and / or chemical properties, the active compounds are customary such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and microcapsules with polymeric substances. Can be converted to a formulation.

  The invention further provides a synergistically effective amount of a) triadimephone and / or triadimenol, b) at least one copper compound and also at least one diluent or solvent, if appropriate further auxiliaries and additives. Also, where appropriate, a microbicidal composition is provided comprising one or more additional sterilizing and fungicidal components c).

  The formulations are prepared in a known manner, for example with the active compound as a bulking agent, ie liquid solvent, pressurized liquefied gas and / or solid carrier and, where appropriate, surfactants, ie emulsifiers and / or dispersants and / or foam formation. It is prepared by mixing with the agent. If the extender used is water, it is also possible, for example, to use organic solvents as auxiliary solvents. Suitable liquid solvents are essentially aromatic compounds such as xylene, toluene or alkylnaphthalene, cyclohexane or paraffins, aliphatic hydrocarbons such as mineral oil fractions, alcohols such as butanol or glycols such as ethylene glycol, and also Their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide, and also water. Liquefied gas extender or carrier is understood to mean liquids that are gaseous at ambient temperature and atmospheric pressure, for example aerosol high pressure gases such as halogenated hydrocarbons, and also butane, propane, nitrogen and carbon dioxide. Should. Suitable solid carriers are, for example, natural fine minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and fine synthetic minerals such as finely divided silica, alumina and silicates. Suitable solid carriers for the granules are, for example, crushed and separated natural minerals such as calcite, marble, pumice, sepiolite, dolomite and also inorganic and organic coarse granules and also sawdust, coconut shells, corn ears With granules of organic materials such as shafts and tobacco stems. Suitable emulsifiers and / or foam formers are, for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers such as alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and also protein hydrolysates. Nonionic and anionic emulsifiers. Suitable dispersants are for example lignosulfite waste liquors and methylcellulose.

  Tackifiers such as powders, granules and carboxymethylcellulose and natural and synthetic polymers in the form of latex such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or other natural and synthetic phospholipids such as kephalin and lecithin Can be used in the formulation. Other possible additives are mineral and vegetable oils.

  Colorants such as inorganic pigments such as iron oxide, titanium oxide and Prussian blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and iron, manganese, boron, copper, cobalt, molybdenum and zinc It is possible to use trace amounts of nutrients such as salt.

  As a further component of the formulation, it is possible to use alkanolamines, for example monoethanolamine, where appropriate. Here, the amount of alkanolamine added is advantageously such that the pH generated in the diluted aqueous impregnating liquid is 7 or higher, preferably 8.5 to 10.5. The amount of amine should be sufficient to form a complex with copper.

  The formulations generally comprise between 0.5 and 50% by weight, preferably between 1.0 and 25% by weight of the active compound combination.

  The microbicidal composition or concentrate used to protect industrial materials comprises the active compound or a combination of active compounds in a concentration of 0.05 to 35% by weight, in particular 0.2 to 20% by weight.

  The application concentration of the active compound or combination of active compounds to be used depends on the nature and development of the microorganism to be controlled and the composition of the material to be protected. The optimal amount to be used can be determined by the test series. In general, the application concentration is in the range of 0.001 to 5% by weight, preferably 0.01 to 1.5% by weight, based on the material to be protected.

  By using the active compound combinations or compositions according to the invention, it is possible to replace previously available microbicidal compositions with more effective compositions in an advantageous manner. The composition according to the invention has good stability and, advantageously, a broad spectrum of activity.

  The wood that can be protected by the active compound mixtures according to the invention or the compositions containing them is, for example, building timber, wood beams, railway sleepers, bridge components, piers, wooden vehicles, boxes, pallets, containers, utility poles , Wood insulation, wooden windows and doors, plywood, medium density fiberboard (MDF), cardboard, oriented strand board (OSB), wafer board, very commonly used in the construction of home or building construction Veneer laminates (LVL) or laminated woodworking products, and also wood / plastic composites. The active compound mixtures to be used according to the invention and the compositions comprising them are used in particular for the protection of non-hollow wood and wood products produced therefrom.

  With the use according to the invention of active compound mixtures, the active compound mixtures can be used as such or in the form of their individual active compounds. Here, the active compound mixture or the individual active compounds contained therein can be converted beforehand into formulations or use forms prepared therefrom such as solutions, suspensions, pastes, soluble powders, etc. that can be used at any time. Is possible.

  If appropriate, add acid, water or solvent, and then add emulsifiers and triazole compounds to dissolve the copper salt in alkanolamine, if appropriate, by heating to a high concentration paste, liquid outlet. Even rate or multiphase systems are formed, which can be used to impregnate wood after dilution with water. They give a clear, colorless, storage-stable liquid and also at high active compound concentrations in water.

  The use according to the invention for protecting wood is generally carried out in the light of known methods for the treatment of wood, for example by spraying, painting, dipping and industrial impregnation methods, such as vacuum, double vacuum or pressure methods. .

  Particularly effective protection of wood is achieved by industrial impregnation methods such as vacuum, double vacuum or pressure methods.

The present invention further provides a synergistically effective amount of a) triadimethone and / or triadimenol and b) at least one copper compound and at least one diluent or solvent by vacuum, double vacuum, pressure or dipping methods; Provided is a method for protecting wood, wherein the wood is impregnated with further auxiliaries and additives, if appropriate, and, if appropriate, with one or more fungicidal components c).
[Example]

Biological Examples Various concentrations of triazimephone and a mixture of two active compounds referred to as copper sulfate were tested against the wood decay basidiomycete polya placenta. Mycelium pieces were punched out from a colony of wood-rotting organisms and cultured at 26 ° C. on an agar medium containing malt extract and peptone. Subsequently, the radial growth of fungal and mold pieces with and without the addition of active compound was compared. The lowest inhibitory concentration stated was the lowest concentration of the series of active compounds that completely prevented radial growth.

  Synergism was then followed by Kull et al. (FC Kull, PC Eismann, HD Sylvestrowicks (H.C. D. Sylvestroicz), RL Mayer, Applied Microbiology 9 (1961), pages 538-541). Here the following relationship applies:

Ｘ＝１は加法性を意味する。
Ｘ＞１は拮抗作用を意味する。
Ｘ＜１が相乗作用を意味する。
Ｑａ＝ＭＩＣに対応する物質Ａの濃度
Ｑｂ＝ＭＩＣに対応する物質Ｂの濃度
ＱＡ＝微生物増殖を抑えるＡ／Ｂの濃度における物質Ａの濃度
ＱＢ＝微生物増殖を抑えるＡ／Ｂの濃度における物質Ｂの濃度

X = 1 means additivity.
X> 1 means antagonism.
X <1 means synergy.
Qa = concentration of substance A corresponding to MIC Qb = concentration of substance B corresponding to MIC QA = concentration of substance A at the concentration of A / B suppressing microbial growth QB = substance B at the concentration of A / B suppressing microbial growth Concentration of

  Based on the measured index data, it can be concluded that the combined triazimephone / copper sulfate has significant synergism.

Formulation Example Example 1 (Concentrate):
0.5% triazimephone, 0.3% sodium rhizinolate / sodium dodecylbenzenesulfonate formulation, 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% triazimephone, 4.0% benzalkonium chloride, 7.5% copper hydroxide carbonate, 20% ethanolamine, 68.1% water

Example 3 (Composition for impregnation)
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)

  A mixture comprising a synergistically effective amount of a) triadimephone and / or triadimenol and b) at least one copper compound.   The mixture according to claim 1, wherein the copper compound is selected from the group consisting of copper sulfate, copper acetate, copper hydroxide, copper oxide, copper borate, copper fluoride and copper hydroxide carbonate. .   The mixture according to claim 1, wherein the copper compound is copper hydroxide carbonate.   Mixture according to any one of claims 1 to 3, characterized in that the weight ratio of triadimephone and / or triadimenol to copper compound is from 1: 600 to 1: 1.   5. Mixture according to any one of claims 1 to 4, characterized in that it comprises at least one further active compound c) from the group of fungicides and fungicides.   Further active compounds c) from the group consisting of tolylfluanid, besoxazine, benzalkonium chloride, 3-iodo-2-propynylbutylcarbamate, bifenthrin, chlorfenapyr, clothianidin, cyfluthrin, cypermethrin, deltamethrin, imidacloprid, permethrin, thiacloprid A mixture according to any one of the preceding claims, characterized in that it comprises at least one compound.   0.005 to 2.5% by weight of triadimethone and / or triadimenol, 0.5 to 30% by weight of copper compound and, where appropriate, 0.001 to 20% by weight of at least one further active compound The mixture according to claim 1, characterized in that it comprises c).   A synergistically effective amount of a) triadimethone and / or triadimenol; b) at least one copper compound; at least one diluent or solvent, if appropriate further auxiliaries and additives; A microbicidal composition comprising a bactericidal and fungicidal agent and at least one further active compound c) from the group of antibacterial active compounds.   8. Active compound mixtures or claims according to any one of claims 1 to 7 for protecting industrial materials, in particular wood, woodwork products and wood / plastic composites from attack, damage and / or destruction by biological plague. Item 9. Use of the composition according to item 8.   A) synergistically effective amounts of a) triadimethone and / or triadimenol and b) at least one copper compound and at least one diluent or solvent, by painting, spraying, vacuum, double vacuum, pressure or dipping methods, as appropriate Characterized in that the wood is impregnated with further auxiliaries and additives and, if appropriate, with one or more fungicidal or insecticidal active compounds c) How to protect wood products.   An industrial material comprising a synergistically effective amount of a) triadimephone and / or triadimenol and b) at least one copper compound.