WO1997018713A1 - Water-based solvant-free and emulsifier-free microbicidal combination of active substances - Google Patents

Abstract

Described are microbicidal, optionally solvent-free and emulsifier-free active-substance combinations or agents made up of prior art azole fungicides, a nitromethylene-type insecticide and quaternary ammonium compounds, plus the use of such combinations in the protection of equipment and materials.

Description

Water-based solvent and emulsifier-free combination of microbicides

The present invention relates to new, in particular aqueous and optionally organic solvent-free and emulsifier-free, microbicidal active substance combinations of known azole fungicides, quaternary ammonium fungicides and an insecticide from the class of the nitromethylenes

It is known that imidazole and triazole fungicides, such as, for example, the α- [2- (4-chlorophenyl) -eΛyl] -α- (l, l-dimethylethyl) -lH-l, 2,4-triazole- l-ethanol (tebuconazole), the

2- (l-chlorocyclopropyl) -l- (2-chlorophenyl) -3- (l, 2,3-triazol-l-yl) propan-2-ol and the 1 - [[2- (2,4- Dichlorophenyl) -4-n-propyl-1, 3-dioxolan-2-yl] -methyl] - 1 H-1, 2,4-triazole (propiconazole) used as such or in the form of its salts for the protection of plants and seeds can be (see e.g. EP-A-0 040 345, EP-A-0 052 424)

Furthermore, it is known that these compounds are also suitable for use in material protection for combating material-destroying or material-coloring microbes (see, for example, DE-OS 3 621 494 and US Pat. No. 4,079,062).

However, the azole finigides, such as the tebuconazole mentioned, have efficacy gaps in some germs relevant to the material, such as Trichoderma spec

Furthermore, due to the often low solubility of azoles, their use in some areas of application, such as leather, water-based wood preservatives, disinfection, cooling water treatment, paper industry, metal processing, technical preservation of water-containing products, is restricted or not possible.

The agonists and antagonists of the nicotinergic acetylcholine receptors are compounds which are known from the following publications

European Patent Application Nos. 664 081, 464 830, 428 941, 425 978, 386 565, 383 091, 375 907, 364 844, 315 826, 259 738, 254 859, 235 725, 212 600, 192 060, 163 855, 154 178 , 136 686, 303 570, 302 833, 306 696 _,

189 972, 455 000, 135 956, 471 372, 302 389, German Offenlegungsschriften No. 3,639,877, 3,712,307;

Japanese Patent Laid-Open No. 03 220 176, 02 207 083, 63 307 857, 63 287 764, 03 246 283, 04 9371, 03 279 359, 03 255 072;

U.S. Patent Nos. 5,034,524, 4,948,798, 4,918,086, 5,039,686, 5,034,404,

PCT applications No. WO 91/17 659, 91/4965,

French application No. 2 611 1 14,

Brazilian application No. 88 03 621

Reference is hereby expressly made to the generic formulas and definitions described in these publications and to the individual compounds described therein

Some of these compounds are summarized under the term nitromethylenes and related compounds

These compounds can preferably be summarized under the general formula (II)

in which

R represents hydrogen, optionally substituted radicals acyl, alkyl, aryl,

Aralkyl, heteroaryl or heteroaryl alkyl,

A represents a monofunctional group from the series hydrogen, acyl, alkyl, aryl or represents a bifunctional group which is linked to the radical Z, E represents an electron-withdrawing residue,

X represents the radicals -CH = or = N-, the radical -CH = instead of an H-

Atom can be linked to the radical Z,

Z for a monofunctional group from the series alkyl, -O-R, -S-R,

/ ^R -N

\

R

represents or represents a bifunctional group which is linked to the radical A or the radical X.

Compounds of the formula (II) in which the radicals have the following meaning are particularly preferred

R represents hydrogen and also optionally substituted radicals from the

Series acyl, alkyl, aryl, aralkyl, heteroaryl, heteroarylalkyl

Formyl, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, (alkyl-) - (aryl-) - phosphoryl, which in turn can be substituted, may be mentioned as acyl radicals

CpC ^ -alkyl, in particular C _] -C ₄ -alkyl, in particular methyl, ethyl, i-propyl, see- or t-butyl, which in turn may be substituted, may be mentioned as alkyl

Phenyl, naphthyl, especially phenyl, may be mentioned as aryl

Phenylmethyl and phenethyl may be mentioned as aralkyl

Heteroaryl with up to 10 ring atoms and N, O,

S, in particular N, as heteroatoms. Thiophenyl, furyl, thiazolyl, imidazolyl, pyridyl, benzthiazolyl may be mentioned individually Heteroaryl alkyl which may be mentioned are heteroarylmethyl, heteroaryl ethyl having up to 6 ring atoms and N, O, S, in particular N, as heteroatoms.

Examples of preferred substituents are:

Alkyl with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methyl, ethyl, n- and i-propyl and n-, i- and t-butyl; Alkoxy with preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methoxy. Ethoxy. n- and i-propyloxy and n- _> i- and t-bufyloxy; Alkylthio with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methylthio, ethylthio, n- and i-propylthio and n-, i- and t-butylthio; Haloalkyl with preferably 1 to 4, in particular 1 or 2_ carbon atoms and preferably 1 to 5, in particular 1 to 3, halogen atoms, the halogen atoms being identical or different and standing as halogen atoms, preferably fluorine, chlorine or bromine, in particular fluorine, such as trifluoromethyl, hydroxy; Halogen, preferably fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine, cyano; Nitro; Amino;

Monoalkyl- and dialkylamino with preferably 1 to 4, in particular 1 or 2 carbon atoms per alkyl group, such as methylamino, methylethylamino, n- and i-propylamino and methyl-n-butylamino; Carboxyl; Carbalkoxy with preferably 2 to 4, in particular 2 or 3, carbon atoms, such as carbomethoxy and carboethoxy; Sulfo (-SO ₃ H); Alkyl sulfonyl with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methyl sulfonyl and ethyl sulfonyl; Arylsulfonyl with preferably 6 or 10 aryl carbon atoms, such as phenylsulfonyl, and also heteroarylamino and heteroaryl alkylamino, such as chloropyridylamino and chloropyridylmethylamino.

A stands for hydrogen and optionally substituted radicals from the series acyl, alkyl, aryl, which preferably have the meanings given above, A furthermore stands for a bifunctional group. Substituted alkylene with 1 to 4, in particular 1 to 2, carbon atoms may be mentioned, where the substituents listed above are mentioned as substituents.

A and Z, together with the atoms to which they are attached, can form a saturated or unsaturated heterocyclic ring. The hetero- Cyclic ring can contain a further 1 or 2 identical or different hetero atoms and / or hetero groups. The heteroatoms are preferably oxygen, sulfur or nitrogen and the hetero groups are N-alkyl, alkyl of the N-alkyl group preferably containing 1 to 4, in particular 1 or 2, carbon atoms. Alkyl, methyl, ethyl, n- and i-

Propyl and n-, i- and t-Butyi called. The heterocyclic ring contains 5 to 7, preferably 5 or 6 ring members. Examples of the heterocyclic ring are pyrrolidine, piperidine, piperazine, hexamethyleneimine, morpholine and N-methylpiperazine

E stands for an electron-withdrawing radical, in particular NO ₂ , CN,

Haloalkylcarbonyl such as 1,5-halogen-C _r C ₄ -carbonyl, in particular COCF ₂ may be mentioned.

X stands for -CH = or -N =.

Z stands for optionally substituted radicals alkyl, -OR, -SR- -NRR, where R and the substituents preferably have the meaning given above.

Z can together with the atom to which it is attached and the rest

= c— form a saturated or unsaturated heterocyclic ring at the position of X. The heterocyclic ring can contain a further 1 or 2 identical or different heteroatoms and / or hetero groups. The hetero atoms are preferably oxygen, sulfur or nitrogen and the hetero groups are N-alkyl, the alkyl or N-alkyl group preferably containing 1 to 4, preferably 1 or 2, carbon atoms. Alkyl, methyl, ethyl, n- and i-propyl and n-, i- and t-butyl may be mentioned. The heterocyclic ring contains 5 to 7, preferably 5 or 6 ring members.

Examples of the heterocyclic ring include pyrrolidine, piperidine, piperazine, hexamethyleneimine, morpholine and N-methylpiperazine.

The agonists and antagonists of the nicotinergic acetylcholine receptors are particularly preferably compounds of the formula (II) R for

stands, where

n represents 1 or 2,

Subst is one of the substituents listed above, especially halogen, especially chlorine and A, Z, X and E have the meaning given above

Very particularly preferred agonists and antagonists of the nicotinergic acetylcholine receptors are compounds of the following formulas

^J

in particular the compound of the formula

These compounds are also often poorly water-soluble and can only be used to a limited extent or not in water-containing products.

Quaternary ammonium salts have long been known as broadly active microbicides and find e.g. Use in disinfection and textile preservation.

Although these active substances are mostly readily water-soluble, they tend to form strong foams at the application concentrations, which is a problem in many fields of use. In addition, due to their cationic properties, they can react with anionic components such as soaps, surfactants, etc. This allows you to

Property profile can be negatively influenced, or they can be deactivated. Furthermore, it is known that quaternary ammonium salts are easily deactivated by the presence of protein and dirt.

For many applications in the practice of material protection, it is desirable to use the active ingredients in liquid formulations that are free of organic

Are solvents or in which the corresponding solvent is drastically reduced in part.

Water-insoluble solvents are incompatible with aqueous products such as leather liquors, emulsion paints, cooling and process water, disinfectants.

Frequently, the users are also not set up to handle products in the form of solutions in organic solvents, since special devices are required to apply them from the solvent and to recover it, which is indispensable for avoiding ecological problems, and these require high investment costs are connected.

In principle, water-soluble solvents would be suitable as solubilizers in aqueous systems. But if they get into wastewater, they can see problems. In addition, solvents can interfere with the products to be protected.

Another way of imparting solvents for the production of water-based active ingredient formulations is to use emulsifiers. In the case of highly water-insoluble compounds such as azoles, this usually becomes large

Emulsifier narrowly required, which should be avoided for ecological reasons. The effectiveness of microbicidal active substances can likewise be severely impaired by the use of emulsifiers. The replaceability for certain systems can also be limited.

The object of the invention was therefore to provide new, preferably water-based, low-solvent and emulsifier-free microbicidal active ingredient formulations based on azole fungicides and insecticides from the class of the nitromethylenes which can be easily diluted with water and at the same time provide storage-stable use solutions.

It has now surprisingly been found that the combination of at least one azole fungicide is preferred

1 - (4-chlorophenoxy) -3, 3-dimethyl-1 - (1 H-1, 2,4-triazol-1-yl) -2-butanone

(Triadimefon) ß- (4-chlorophenoxy) -α- (l, l-dimethyl-ethyl) -lH-l, 2,4-triazol-l-ethanol (triadimenol)

± α- [2- (4-chlorophenyl) ethyl] -α- (1, 1-dimethylethyl) - 1 H- 1, 2,4-triazole-1 - ethanol

(Tebuconazole)

(RS) -2- (2,4-dichlorophenyl) -l- (lH-l, 2,4-triazol-l-yl) -hexan-2-ol (hexaconazole) l- (N-propyl-N- ( 2- (2,4,6- (trichlorophenoxy) ethyl) carbamoyl) imidazole

(Prochloraz)

2- (l-chlorocyclopropyl) -l- (2-chlorophenyl) -3- (l, 2,4-triazol-l-yl) propan-2-ol l - [[2- (2,4-dichlorophenyl) -4-propyl-l, 3-dioxolon-2-yl] methyl] -lH-l, 2,4-triazole

(Propiconazole) 1- [2- (2,4-dichlorophenyl) -1, 3-dioxolon-2-ylmethyl] -1 H-l, 2,4-triazole

(Azaconazole) (R », R _* ) -α- (4-chlorophenyl) -α- (1 -cyclopropylethyl) 1 H- 1, 2,4-triazole-1 - ethanol (cyproconazole)

where the compounds in which the compounds have asymmetric carbon atoms also include the isomers and isomer mixtures of the most varied compositions;

very particularly preferably ± α- [2- (4-chloro-phenyl) -ethyl] -α- (l, l-dimethylethyl) -lH-1,2,4-triazole-l -ethanol (tebuconazole e) and / or propiconazole

and at least one insecticide from the class of the nitromethylenes, preferably of the formulas (Ila) to (Hh), in particular the compound (Ih),

and at least one quaternary ammonium fungicide, preferably of the formula

(III)

R ¹

R ² N ⁺ - R ³ _X - (HI)

R ⁴

in which

R ¹ , R ² , R ³ , R ^{4 are the} same or different and each is unsubstituted or substituted, straight-chain or branched, saturated or unsaturated

Alkyl groups with 1 to 20 carbon atoms, alkylaryl and aralkyl groups with 5 to 10 carbon atoms in the aryl part and 1 to 20 carbon atoms in the alkyl part or aryl groups with 5 to 10 carbon atoms, as well as optionally single or multiple alkoxylated derivatives thereof, where as substituents Halogen, C, -C ₄ alkyl, C _] -C ₄ -

Alkoxy come into question, and where 2 or 3 radicals R ¹ to R ⁴ at the quaternary center can optionally form a saturated or unsaturated 5-, 6- or 7-membered (hetero) cycle with further heteroatoms and

X for an anion which requires solubility in water, e.g. halide, sulfate,

Alkyl sulfonate or optionally substituted aryl sulfonate, stable aqueous solutions or emulsions can be produced which have a particularly high microbicidal and insecticidal activity.

Such aqueous formulations avoid the above-mentioned ecological and application-related disadvantages of solvent-based or emulsifier-mediated formulations and in this respect represent a valuable addition to the prior art

Technology.

Preferred quaternary ammonium compounds are ammonium salts such as

C ₁₂ -C _{] 4-} Alkyl-benzyl-dimethylammonium chloride called trimethylcocosammonium chloride - didecyldimethylammonium chloride.

Didecyldimethylammonium chloride (DDAC) is particularly preferred.

A combination of tebuconazole and / or propiconazole and imidacloprid and didecyldimethylammonium chloride is very particularly preferred.

The weight ratios of the active substances in the active substance combinations can be varied within relatively large ranges. They are generally dependent on the area of application and on the active ingredients used in each case. However, these weight ratios can easily be determined in test series by simply mixing the components.

The weight ratio of quaternary ammonium fungicide to azole fungicide to the insecticide is preferably 400: 20: 1 to 50: 10: 1.

For the preparation of aqueous formulations, the active ingredients are used individually or as a combination of active ingredients, e.g. in the form of powders, granules, pastes or concentrated solutions, suspensions or emulsions by simple mixing in water and are then in the form of an aqueous suspension, solution or emulsion.

The aqueous solutions or emulsions preferably contain more than 20% by weight, in particular more than 40% by weight, of water and can be diluted with water to the application concentration as desired. It goes without saying / 18713 PCΪ7EP96 / 04919

- 1 1 -

lent also possible to directly the active ingredients or combinations of active ingredients in the form of concentrates, solutions, suspensions, emulsions, powders, granules or pastes in the amounts required for the application, e.g. by stirring to incorporate into the application agent.

The microbicidal compositions contain the active ingredient combination in a concentration of 0.001 to 95% by weight, in particular 0.01 to 60% by weight and, if appropriate, 0.001 to 30% by weight, in particular 0.1 to 20% by weight. %, very particularly 0.05 to 10% by weight of a suitable further fungicide, insecticide or another active substance.

The active substance combinations or agents according to the invention have a strong

Action against microorganisms. They are used in the material to protect technical materials: they are particularly effective against mold, wood-staining and wood-destroying fungi and bacteria, and against yeasts, algae and slime organisms. The following types of microorganisms may be mentioned by way of example, but without limitation:

Alternaria such as Alternaria tenuis, Aspergillus such as Aspergillus niger and Aspergillus terreus, Aureobasidium such as Aureobasidium pullulans, Chaetomium such as Chatomatium globosum, Cladosporium like Cladosporium herbarum, Coniophora like Coniophora puteana, Gliocladium like Liocentinilominusces, such as Liocentinigrincesinces Penicillium such as Penicillium brevicaule, Penicillium glaueum and Penicillium pinophilum, Polyporus such as Polyporus versicolor, Sclerophoma such as Sclerophoma pityophila, Streptoverticillium such as Streptoverticillium reticulum, Trichoderma such as Trichoderma viride and Trichyophyton;

Escherichia such as Escherichia coli, Pseudomonas such as Pseudomonas areuginosa,

Staphylococcus such as Staphylococcus aureus;

Candida like Candida aibicans.

The active compound combinations according to the invention are particularly suitable for protecting technical materials, in particular wood, even from infestation by wood-destroying insects, such as, for example 1. Beetle

Hylotrupes bajulus, Chlorophorus pilosis, Anabium punctatum, Xestobium rufovillosum, Ptilinus pecticomis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearesces, Lyctus pubis linearis, Lyctus pubis linearis, specie

Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus

2. Skin wing

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur

3. Termites

Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucilugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.

The active ingredient combinations according to the invention can generally be incorporated into all wood preservatives or formulations, e.g. by mixing the

Active ingredients with solvents or diluents, emulsifiers, dispersants and / or binders or fixatives, water repellants, optionally siccatives and UV stabilizers and optionally dyes and pigments as well as other processing aids or as an additive to any other wood preservation formulations.

An organic-chemical solvent or solvent mixture and / or an oily or oil-like low-volatility organic-chemical solvent or solvent mixture and / or a polar organic-chemical solvent or solvent - mixture and / or water and at least one emulsifier and / or wetting agent or consists thereof.

Easily or moderately volatile organic chemical solvents are preferably used as organic chemical solvents. The readily or moderately volatile organic chemical solvents can be partially replaced by organic, non-volatile, oily or oil-like solvents, with the proviso that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture

According to a preferred embodiment, aliphatic organic chemical solvents containing hydroxyl and / or ester and / or ether groups, such as alcohols, glycol ethers, esters or the like, are used

In the context of the present invention, the known organic-chemical binders are the water-dilutable synthetic resins and / or synthetic resins soluble or dispersible or emulsifiable in the organic chemical solvents used and / or binding drying oils, in particular binders consisting of or containing an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders the basis of a natural and / or synthetic resin used

The synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances up to 10% by weight can also be used as binders. In addition, dyes, pigments, water-repellents, odor control agents known per se Gentien and inhibitors or corrosion protection agents and the like are used

According to the invention, at least one acrylate resin or modified acrylate resin and / or a drying alkyl resin is preferably contained in the agent or in the concentrate as the organic chemical binder

All or part of the binder mentioned can be replaced by a fixative (mixture) or a plasticizer (mixture). These additives are intended to prevent volatilization of the active ingredients and crystallization or precipitation). They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used) The plasticizers come from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate or glycerol, glycerol - Kolether, glycerol ester and p-toluenesulfonic acid ester

Fixing agents are chemically based on polyvinyl alkyl ethers such as polyvinyl methyl ether or ketones such as benzophenone, ethyl enbenzophenone, amines such as alkanolamines such as monoethanolamine or ammonia

According to the invention, technical materials are non-living materials which have been prepared for use in technology. For example, technical materials which are to be protected against microbial change or destruction by active substances according to the invention, adhesives, glues, paper and cardboard, textiles, leather, wood, Coating agents and plastic articles, cooling lubricants and other materials that can be attacked or decomposed by microorganisms are also within the scope of the materials to be protected

Parts of production plants, for example cooling water circuits, which can be impaired by the multiplication of microorganisms. Preferred technical materials for the purposes of the invention are adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants, aqueous hydraulic fluids and cooling circuits

The active substance combinations, compositions or concentrates according to the invention are preferably used to protect wood and wood-based materials against microorganisms, for example against wood-destroying or wood-staining fungi, in particular in tropical wood preservation

Wood, which can be protected by the active substance mixture according to the invention or agents containing it, is to be understood, for example, as construction timber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone masts, wooden cladding, wooden windows and doors, plywood, chipboard , Carpentry or wood products that are generally used in house building or in carpentry

A particularly effective wood protection is achieved by large-scale impregnation processes, eg vacuum, double vacuum or printing processes The amount of the active ingredient combinations used depends on the type and the occurrence of the microorganisms, the number of bacteria, the insects and on the medium. The optimum amount used can be determined in each case by test series. In general, however, it is sufficient to use 0.001 to 20% by weight, preferably 0.05 to 10% by weight, of the active compound mixtures, based on the material to be protected.

The insecticidal compositions or concentrates used to protect wood and wood-based materials contain the active ingredient combination in a concentration of 0.001 to 95% by weight, in particular 0.001 to 60% by weight.

The new active ingredient combinations can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.

Water is preferably used as the solvent or diluent, if appropriate in a mixture with one or more of the abovementioned solvents or diluents, emulsifiers and dispersants.

The effectiveness and the spectrum of activity of the combination of active substances according to the invention or of the agents, concentrates or very general formulations which can be produced therefrom is increased if further antimicrobial substances, fungicides, insecticides or other active substances are used to enlarge the spectrum of active substances or to achieve particular ones Effects such as additional protection against insects. In many cases, additional synergisms have to be considered. Particularly favorable mix partners are e.g. the following connections:

Sulfenamides such as dichlofluanid (Euparen), tolylfluanid (Methyleuparen), Folpet, Fluorfolpet; Benzimidazoles (optionally in the form of their salts) such as carbendazim

(MBC), Benomyl, Fuberidazole, Thiabendazole; Thiocyanates such as thiocyanatomethylthiobenzothiazole (TCMTB), methyl enbisthiocyanat (MBT); Morpholine derivatives such as C _j pC _j ^ alkyl ^ ό-dimethylmorpholine homologue (tridemorph), (+) - cis-4- [3- (tert-butylphenyl) -2-methylpropyl] -2,6-dimethylmorpholine (fenpropimorph) , Falimorph; Phenols such as o-phenylphenol, halogenated cresols, tribromophenol,

Tetrachlorophenol, pentachlorophenol, 3-methyl-4-chlorophenol, dichlorophen; Iodine propargyl derivatives such as iodopropargyl butyl carbamate (IPBC), chlorophenyl formal, -phenyl carbamate, -hexyl carbamate, -cycl ohexyl carbamate, isothiazolinones such as N-methylisothiazolin-3-one, 5-chloro-N-methyl-isothiazolin-3-one, 4,5-dichloro-N-octyhsothiazolιn- 3-one, N-octylιsothiazolin-3-one (octhilinones), pyridines such as l-hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methyl-sulfonyl-pyπdin , Tetrachloro-4-methyl-sulfonylpyridine, metal soaps such as tin, copper,

Zinc naphthenate, octoate, -2-ethylhexanoate, oleate, phosphate, benzoate, oxide, zinc salts of dialkyldithiocarbamates, tetramethyldiuram disulfite (TMTD), 2,4,5,6-tetrachloπsophthalonitrile (chlorothaloleole such as 2-chloro-halonilil), benzol Mercapto-benzothiazole, thiazolyl-benzimidazole, quinone such as γ-hydroxyquinoline, benzyl alcohol mono (poly) hemiformal, tris-N- (cyclohexyl-dazazione-doxy) -aluminum, N-

(Cyciohexyldιazenιumdioxy) -tributyltin

Preferred insecticides are added

Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, l- (4-chlorophenyl) -4- (O-ethyl, S-propyl) -phosphoryloxypyrazole (TIA-230), Chlorpyπfos, Coumaphos, Demeton, Demeton-S-methyl , Diazinon, Dichlorvos, Dimethoate, Ethoprophos, Etπm- fos, Fenitrothion, Fention, Heptenophos, Parathion, Parathion-methyl, Phosalone, Phoxion, Pinmiphos-ethyl, Piπmiphos-methyl, Profenofos, Prothiofos, Sulprofos, Tπazophon, and Trichlorophos, and Trichlorophos

Carbamates such as aldicarb, bendiocarb, BPMC (2- (l-methylpropyl) phenylmethyl carbamate), butocarboxime, butoxy carboxime, carbaryl, carbofuran, carbosulfane,

Cloethocarb, isoprocarb, methomyl, oxamyl, pimicarb, promecarb, propoxur and thiodicarb,

Pyrethroids such as Allethnn, Alphamethπn, Bioresmethπn, Byfenthnn (FMC 54 800), Cycloprothrin, Cyfluthrin, Decamethπon, Cyhalothπn, Cypermethnn, Deltamethπn, Alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl chloro-2-tπ- fluoromethylvιnyl) cyclopropane carboxylate, fenpropathπn, fenfluthπn, fenvalerate, flucythπnate, flumethrin, fluvalinate, permethrin and resmethπn, nitroimides such as l - [(6-chloro-3-pyπdιnyl) methyl] -4,5-dehydro N-nιtro-lH-ιmιdazol-2-anιn (Imida-clopπd)

Algicides, molluscicides, active substances against "sea animals" which, for example, settle on ship's floor paints come into consideration as other active substances The combinations of active substances or agents according to the invention advantageously make it possible to replace the previously available biocidal agents with more effective and more environmentally compatible ones. They show good stability and advantageously have a broad spectrum of activity

The following example serves to explain the invention, without restricting it to parts and percentages mean parts by weight or percentages by weight

example 1

Test methods and results

Checking the storage stability

50-, 75-, 100- and 200-fold dilutions of the test sample in water are in closed polyethylene bottles at 2 ° C and 40 ° C for 3

Months stored Then the dilutions are poured into a 1 000 ml

Beaker poured, on change of appearance as well as on formation of

Crystals and precipitates are patterned and evaluated according to the following criteria

A clear solution, no precipitation

B low turbidity, but no sediment formation

C clear turbidity with sediment formation

D obviously destroyed with the formation of crystals and sediments The following stabilities are found

Wood permeability test

50-, 75-, 100- and 200-fold aqueous dilutions of the test sample are made

Test specimens measuring 2 cm x 2 cm x 12 cm are cut out of Cryptomeria sapwood, all surfaces except for one end face are sealed with epoxy resin from these test specimens

After each weighing, 10 test specimens are stored in a 1,000 ml beaker in such a way that floating is not possible. After storage for 2 hours under vacuum (60 mm Hg), the dilutions are introduced and the test specimens in at normal pressure for 22 hours kept immersed in the dilutions Then the test specimens are removed from the dilutions and weighed back to determine the amount taken up (kg / m ³ )

The treated test specimens are cut open at a distance of 2 cm and 8 cm from the unclosed front end for analysis of the active substances DDAC, tebuconazole and imidcloprid after they have been stored under a polyethylene film at 26 ° C. for 1 month The following results have been achieved

1 number 2 cm from the face, 2 number 8 cm from the

End face removed

Retention ratio 2 cm 8 cm

The result is considered acceptable if the value is above 50%

Examination of fungus resistance

For the tests, 50, 75, 100 and 200-fold aqueous dilutions of the test sample are prepared. The controls used are 1.0%, 0.7%, 0.5% and 0.3% DDAC in water 2 1 described test samples, which are stored for 3 months at 2 ° C

Test specimens with the dimensions 2 cm x 2 cm x 10 cm are cut out of Cryptomeria sapwood each 5 of these test specimens are stored in a 1,000 ml beaker in such a way that floating is not possible After storage for 2 hours under vacuum (60 mm Hg) the dilutions are introduced and the test specimens are kept immersed in the dilutions for 2 hours at normal pressure. The test specimens are then removed from the dilutions and stored individually for 21 days under a polyethylene film The treated and untreated test specimens are alternately stored in wood-destroying soil at 26 ° C and 90% relative atmospheric humidity for 6 months, as described in standard ENV 807 parts 1 and 2. After 6 months, protection against wood-destroying fungi is assessed as follows

A without Angπff

B colors

C partial destruction

D complete destruction

Claims

claims

1. Active ingredient combination of at least one azole fungicide, at least one insecticide from the class of nitromethylenes and at least one quaternary ammonium fungicide.

2. Active ingredient combination according to claim 1, comprising at least one of the following azole fungicides:

l- (4-chlorophenoxy) -3,3-dimethyl-l- (lH-l, 2,4-triazol-l -yl) -2-butanone (triadimphone) ß- (4-chlorophenoxy) -α- (l , l-dimethyl-ethyl) -lH-l, 2,4-triazole-l-ethanol (triadimenol)

± α- [2- (4-chlorophenyl) ethyl] -α- (l, 1-dimethylethyl) - 1 H- 1, 2,4-triazole-

1-ethanol (tebuconazole)

(RS) -2- (2,4-dichlorophenyl) -l- (lH-l, 2,4-triazol-l-yl) hexan-2-oI

(Hexaconazole) - l- (N-propyl-N- (2- (2,4,6- (trichlorophenoxy) ethyl) carbamoyl) - imidazole (Prochloraz)

2- (l-chlorocyclopropyl) - l- (2-chlorophenyl) -3- (l, 2,4-triazol-l -yl) - propan-2-ol l - [[2- (2,4-dichlorophenyl) -4-propyl-l, 3-dioxolon-2-yI] methyl] -lH- 1, 2,4-triazole (propiconazole) l- [2- (2,4-dichlorophenyl) -l,

3-dioxolon-2-yl-methyl] -IH-l, 2,4-triazole

(Azaconazole)

(R _* , R -,) - α- (4-chlorophenyl) -α- (1 -cyclopropyl ethyl 1 H- 1, 2,4-triazole-1 - ethanol (cyproconazole)

and at least one insecticide of the formula

in particular the compound of the formula

and at least one quaternary ammonium fungicide of the formula (II)

R ¹

I.

R ² N ⁺ - R ³ x (m)

R ⁴

in which

R ¹ , R ² , R ³ , R ^{4 are the} same or different and each represents unsubstituted or substituted, straight-chain or branched, saturated or unsaturated alkyl groups with 1 to 20 carbon atoms, alkyl aryl and aralkyl groups with 5 to 10 carbon atoms in the aryl part and 1 to 20 carbon atoms in the alkyl or aryl groups having 5 to 10 carbon atoms and optionally mono- or multiply alkoxylated Deπvate thereof, wherein ₄ alkoxy, suitable substituents are halogen, C _j -C ₄ alkyl, C _τ -C in question, and where 2 or 3 radicals R ¹ to R ⁴ at the quaternary center can optionally form a saturated or unsaturated 5-, 6- or 7-ghedπgen (hetero) cycle with further heteroatoms and

X for an anion demanding lack of water

stands

Active ingredient combination according to claim 1, containing tebuconazole and / or propiconazole and imidaclopπd and C _{] 2} -C ₁₄ -alkyl-benzyl-dimethyl-ammonium chloride and / or trimethyl-cocosammonium chloride and / or

Didecyldimethylammonium chloride

4. Microbicidal agent for protecting the material, comprising an active ingredient combination according to claim 1, solution and diluent and, if appropriate, processing aids and, if appropriate, further active ingredients.

5. Microbicidal composition according to claim 4, containing water.

6 microbicidal agents according to claim 4 for the protection of wood and leather

7 A method of combating microorganisms, characterized in that the active compound combination according to claim 1 is allowed to act on microbes or their habitat

8 Use of the active ingredient combination according to claim 1 as a microbicide for protecting industrial materials

9 Use according to claim 8 as a fungicide for protecting leather and wood

10 Use of the active ingredient combination according to claim 1 for the preparation of stable, optionally organic, solvent and emulsifier-free aqueous microbicidal agents.