DE19543477A1 - Water-based, solvent and emulsifier-free combination of microbicides - 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

The present invention relates to new, especially aqueous and optionally organic, solvent and emulsifier-free combinations of microbicides from known azole fungicides, quaternary ammonium fungicides and an insect Ticide from the nitromethylene class.

It is known that imidazole and triazole fungicides, such as. B. the α- [2- (4-chlorine phenyl) -ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol (tebuconazole), the 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) -3- (1,2,3-triazol-1-yl) prop-an-2-ol and that 1 - [[2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl] methyl] -1H-1-, 2,4-triazole (Propiconazole) as such or in the form of their salts for the protection of plants and Seeds can be used (cf. e.g. EP-A-0 040 345, EP-A-0 052 424).

It is also known that these compounds are also suitable for use in materials Protection to combat material-destroying or discoloring microbes are suitable (see, for example, DE-OS 36 21 494 and US-4 079 062).

However, the azole finigides, like the tebuconazole mentioned, have gaps in their effectiveness with some germs relevant for material protection, such as B. Trichoderma spec., on.

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

In the agonists and antagonists of the nicotinergic acetylcholine receptors are these compounds that 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. 36 39 877, 37 12 307;
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. 2 611 114;
Brazilian application No. 88 03 621.

The generic formulas and definitions described in these publications NEN, as well as the individual compounds described therein, are hereby made expressly referred.

These compounds are partly called nitromethylenes and there summarized with related connections.

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

in which
R represents hydrogen, optionally substituted radicals acyl, alkyl, aryl, aralkyl, heteroaryl or heteroarylalkyl;
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 group;
X stands for the radicals -CH = or = N-, where the radical -CH = can be linked to the radical Z instead of an H atom;
Z for a monofunctional group from the series alkyl, -OR, -SR,

stands for or a bifunctional group that is associated with the. Rest A or the rest X is linked.

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 and alkyl may be mentioned as acyl radicals sulfonyl, arylsulfonyl, (alkyl -) - (aryl -) - phosphoryl, which in turn substit can be.

As alkyl may be mentioned C₁-C₁₀-alkyl, especially C₁-C im-alkyl, in single NEN methyl, ethyl, i-propyl, sec.- or t.-butyl, which in turn is substituted could be.

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, especially N as heteroatoms. In particular, Thio phenyl, furyl, thiazolyl, imidazolyl, pyridyl, benzthiazolyl.  

Heteroarylmethyl, heteroarylethyl may be mentioned as heteroarylalkyl up to 6 ring atoms and N, O, S, especially N as heteroatoms.

Examples of preferred substituents are:
Alkyl having 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 preferably having 1 to 4, in particular 1 or 2, carbon atoms, such as methoxy, ethoxy, n- and i-propyloxy and n-, i- and t-butyloxy; 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, where the halogen atoms are identical or different and are 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, methyl ethylamino, 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 (-SO₃H); Alkyl sulfonyl preferably having 1 to 4, in particular 1 or 2 carbon atoms, such as methylsulfonyl and ethylsulfonyl; Arylsulfonyl with preferably 6 or 10 aryl carbon atoms, such as phenylsulfonyl and heteroarylamino and heteroarylalkylamino 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. Optionally, substituted alkylene with 1 to 4, in particular 1 to 2, carbon atoms may be mentioned, the substituents listed above being mentioned as substituents.
A and Z, together with the atoms to which they are attached, can form a saturated or unsaturated heterocyclic ring. The heterocyclic 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. As 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 are pyrrolidine, piperidine, piperazine, hexamethyleneimine, morpholine and N-methylpiperazine.
E stands for an electron-withdrawing radical, in particular NO₂, CN, haloalkylcarbonyl such as 1,5-halo-C₁-C₄-carbonyl, in particular COCF₂.
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

X is a saturated or unsaturated heterocyclic Form a ring. The heterocyclic ring can be another 1 or 2 identical or contain different heteroatoms and / or hetero groups. As a straight atoms are preferably oxygen, sulfur or nitrogen and as Hetero groups N-alkyl, the alkyl or N-alkyl group being preferred contains 1 to 4, preferably 1 or 2 carbon atoms. As alkyl may be mentioned methyl, ethyl, n- and i-propyl and n-, i- and t-butyl. Of 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 called.

The agonists and antagonists are particularly preferred nicotinergic acetylcholine receptors around compounds of formula (II)

stands, where
n represents 1 or 2,
Subst. For one of the substituents listed above, especially for halogen, in particular for chlorine, and A, Z, X and E have the meaning given above.

Very particularly preferred agonists and antagonists of nicotinic acetyl Choline receptors are compounds of the following formulas:

in particular the compound of the formula

These compounds are also often poorly water-soluble and only limited or cannot be used in water-based products.

Quaternary ammonium salts have long been used as broadly effective microbicides knows and find z. B. Use in disinfection and textile preservation.

Although these active ingredients are mostly readily water-soluble, they tend to tend to be application concentrations to excessive foaming, which in many fields of application disturbs. In addition, due to their cation-active properties, they can also be used anionic components such as soaps, surfactants, etc. react. This allows you to Property profile can be negatively influenced, or they can be deactivated. Furthermore, it is known that quaternary ammonium salts by the presence of Protein and dirt can be easily deactivated.

For many applications in the practice of material protection, it is desirable use the active ingredients in liquid formulations that are free of organic Solvents are or in which the corresponding proportion of solvent drastically reduced is adorned.

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

Often, users are not in shape when handling products set up of solutions in organic solvents because of the application the solvent and for its recovery, which to avoid ecological problems is indispensable, special devices are required that work with high investment costs are associated.

Water-soluble solvents would act as solubilizers in aqueous systems basically suitable. But if they get into the wastewater, they can be ecological  cause problems. In addition, solvents can be in the to be protected Make products noticeable.

Another way of mediation for the production of water-based Active ingredient formulations consist in the use of emulsifiers. With strong Water-insoluble compounds such as azoles are usually large for this Amounts of emulsifier are required, which should be avoided for ecological reasons. Likewise, the effectiveness of microbicidal agents can be strongly influenced by the ver use of emulsifiers. Likewise, the usability limited for certain systems.

The object of the invention was therefore to provide new, preferably water based, low-solvent and emulsifier-free microbicidal active ingredient formulation on the basis of azole fungicides and insecticides from the class of Nitromethylenes that can be easily diluted with water and stored in the process deliver stable solutions for use.

It has now surprisingly been found that the combination of at least an azole fungicide preferably

• - 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone- (Triadi phone)
• - β- (4-chlorophenoxy) -α- (1,1-dimethyl-ethyl) -1H-1,2,4-triazole-1-ethanol (Triadimenol)
• - ± α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1- ethanol (Tebuconazole)
• - (RS) -2- (2,4-dichlorophenyl) -1- (1H-1,2,4-triazol-1-yl) hexan-2-ol (Hexaconazole)
• - 1- (N-propyl-N- (2- (2,4,6- (trichlorophenoxy) ethyl) carbamoyl) imidazole - (Prochloraz)
• - 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) -3- (1,2,4-triazol-1-yl) prop-an-2-ol
• - 1 - [[2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolon-2-yl] methyl] -1H-1,2-, 4- triazole (Propiconazole)
• - 1- [2- (2,4-dichlorophenyl) -1,3-dioxolon-2-ylmethyl] -1H-1,2,4-triazole (Azaconazole)  
• - (R *, R *) - α- (4-chlorophenyl) -α- (1-cyclopropylethyl) 1H-1,2,4-triazole-1- ethanol (cyproconazole)

where in the cases where the compounds have asymmetric carbon atoms, the isomers and isomer mixtures of the most varied compositions are also included;
very particularly preferably ± α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol (tebuconazole) and / or propiconazole
and at least one insecticide from the class of the nitromethylenes, preferably of the formulas (IIa) to (IIh), in particular the compound (Ih),
and at least one quaternary ammonium fungicide, preferably of the formula (III)

in which
R¹, R², R³, R⁴ 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, alkylaryl and Ar alkyl 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, and optionally single or multiple alkoxylated derivatives thereof; where halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy are suitable as substituents; and where 2 or 3 radicals R¹ to R⁴ 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 promoting water solubility such as B. halide, sulfate, alkyl sulfonate or optionally substituted aryl sulfonate, stable aqueous solutions or emulsions can be prepared which have a particularly high microbicidal and insecticidal activity.

Such aqueous formulations avoid the aforementioned ecological and application-related disadvantages of solvent-based or emulsifier-mediated Formulations and thus represent a valuable addition to the state of the Technology.

Preferred quaternary ammonium compounds are ammonium salts such as

• - C₁₂-C₁₄-alkyl-benzyl-dimethylammonium chloride
• Trimethyl cocosammonium chloride
• - called Didecyldimethylammoniumchlorid.

Didecyldimethylammonium chloride (DDAC) is particularly preferred.

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

The weight ratios of the active ingredients in the active ingredient combinations can be in relatively large areas can be varied. They are generally dependent on the area of application and the active ingredients used. This weight However, conditions can be checked in test series by simply mixing the compo can be easily identified.

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

For the preparation of aqueous formulations, the active ingredients are used individually or as an active ingredient combination z. B. in the form of powders, granules, pastes or con centered solutions, suspensions or emulsions by simply mixing in Water incorporated and are then in the form of an aqueous suspension, solution or emulsion before.

The aqueous solutions or emulsions preferably contain more than 20% by weight, in particular more than 40% by weight, of water and can be mixed with Water should be diluted to the application concentration. It goes without saying  Lich also possible, the active ingredients individually or combinations of active ingredients in the form of concentrates, solutions, suspensions, emulsions, powders, granules or Pastes directly in the amounts required for the application, e.g. B. by Rüh to work into the application materials.

The microbicidal agents contain the active ingredient combination in a concentra tion of 0.001 to 95 wt .-%, in particular 0.01 to 60 wt .-% and in addition ge optionally 0.001 to 30% by weight, in particular 0.1 to 20% by weight, very particularly 0.05 to 10 wt .-% of a suitable further fungicide, insecticide or another active ingredient.

The active substance combinations or agents according to the invention have a strong Action against microorganisms. They are in material protection for protection technical materials used: they are especially effective against mold fungi, wood discoloring and destroying fungi and bacteria, as well as against yeasts, Algae and slime organisms. Exemplary - but without limitation - are the named following types of microorganisms:

Alternaria such as Alternaria tenuis, Aspergillus such as Aspergillus niger and Aspergillus terreus, Aureobasidium such as Aureobasidium pullulans, Chaetomium such as Chae tomium globosum, Cladosporium herbarum, Coniophora such as Coniophora puteana, Gliocladium such as Lientusinomidiosilinces such as Liocusinomidililces, Pa like Penicillium brevicaule, Penicillium glaucum and Penicillium pinophilum, Polyporus like Polyporus versicolor, Sclerophoma like Sclerophoma pityophila, Streptoverticillium like Streptoverticillium reticulum, Trichoderma like Trichoderma viride, Trichophyton like Trichytesy;
Escherichia such as Escherichia coli, Pseudomonas such as Pseudomonas areuginosa, Staphylococcus such as Staphylococcus aureus;
Candida like Candida albicans.

The active substance combinations according to the invention are particularly suitable excellent for protecting technical materials, especially wood infestation by wood-destroying insects, such as  

1. Beetle

Hylotrupes bajulus, Chlorophorus pilosis, Anabium 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.

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 substance combinations according to the invention can generally be used in all wood Protective agents or formulations are incorporated e.g. B. by mixing the Active ingredients with solvents or diluents, emulsifiers, dispersants and / or Binders or fixatives, water repellants, possibly siccatives and UV Stabilizers and optionally dyes and pigments and others Processing aids or as an addition to any other wood protection formulations.

An organic chemical is used as the solvent and / or diluent Solvent or solvent mixture and / or an oily or oily difficultly volatile 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 of it.

The organic chemical solvents used are preferably light or medium volatile organic chemical solvents used.  

The easily or moderately volatile organic chemical solvents can partly wisely replaced by organic non-volatile oily or oily solvents with the proviso that the insecticide-fungicide mixture in this Solvent mixture is soluble or emulsifiable.

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

As organic-chemical binders in the context of the present invention dung known per se and / or in the used organic chemical solvents soluble or dispersing or emulsifying Resins and / or binding drying oils, especially binders consisting of or containing an acrylic resin, a vinyl resin, e.g. B. 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 based on a natural and / or Resin used.

The synthetic resin used as a binder can be in the form of an emulsion, disper sion or solution. Bitumen or bituminous substances up to 10 wt .-%, are used. In addition, you can dyes, pigments, water-repellants, odor correction known per se Gentien and inhibitors or corrosion protection agents and the like. Be used.

According to the invention, preference is given to organic chemical binders least an acrylic resin or modified acrylic resin and / or a drying one Alkyl resin contained in the medium or in the concentrate.

The binder mentioned can be wholly or partly by a fixing agent. (mixture) or a plasticizer (mixture) can be replaced. These additions are meant to volatilization of the active ingredients and crystallization or precipitation prevent. They preferably replace 0.01 to 30% of the binder (based on to 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, glycerol ether or higher molecular weight Gly kolether, glycerol ester and p-toluenesulfonic acid ester.

Fixing agents are chemically based on polyvinyl alkyl ethers such as. B. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone, amines such as e.g. B. alkanolamines such as monoethanolamine or ammonia.

According to the invention, industrial materials are non-living materials which are suitable for the use has been prepared in the art. For example technical materials that are active against microbial by active ingredients according to the invention Change or destruction should be protected, adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials that are infested with microorganisms or can be decomposed. Also within the scope of the materials to be protected Parts of production facilities, such as cooling water circuits, called can be impaired by the multiplication of microorganisms. Preferred Technical materials in the sense of the invention are adhesives, glues, papers and cartons, leather, wood, paints, coolants, aqueous hydraulics liquids and cooling circuits.

The active substance combinations, agents or concentrates according to the invention are preferably to protect wood and wood-based materials against microorganisms, e.g. B. against wood-destroying or wood-staining fungi, especially in tropical Wood protection, can be used.

Under wood, which by the active ingredient mixture according to the invention or this can be protected, is to be understood as an example: construction timber, Wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, Pallets, containers, telephone poles, wooden cladding, wooden windows and doors, Plywood, particle board, carpentry or wood products, all in general used in house building or in carpentry.

A particularly effective wood protection is provided by industrial impregnation drive, e.g. B. vacuum, double vacuum or printing process.  

The amount of active ingredient combinations used depends on the type and the type come from the microorganisms, the number of germs, the insects and from the medium dependent. The optimal amount can be used by testing rows can be determined. In general, however, it is sufficient from 0.001 to 20 wt .-%, preferably 0.05 to 10 wt .-% of the active ingredient mixtures, based on the material to be protected.

The insecticidal agents used to protect wood and wood-based materials or concentrates 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 drug combinations can be used as such, in the form of concentrates or general formulations such as powders, granules, solutions, suspensions sions, emulsions or pastes.

Water is the preferred solvent or diluent, ge optionally in a mixture with one or more of the above-mentioned solutions or diluents, emulsifiers and dispersants.

The effectiveness and spectrum of action of the active ingredient according to the invention combination or the means, concentrates or very general producible therefrom my formulations, will be increased if necessary further antimicrobial active substances, fungicides, insecticides or other active substances for enlargement the spectrum of active ingredients or to achieve special effects, such as. B. the additional protection against insects. Then in many cases additional synergisms to consider. Particularly cheap mix partners are z. B. 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 thiocyanato methylthiobenzothiazole (TCMTB), methylene bisthiocyanate (MBT); Morpholinderi vate such as C₁₁-C₁₄-4-alkyl-2,6-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, -cyclohexyl carbamate; Isothiazolinones such as N-Me thylisothiazolin-3-one, 5-chloro-N-methyl-isothiazolin-3-one, 4,5-dichloro-N-octyliso thiazolin-3-one, N-octylisothiazolin-3-one (octhilinones); Pyridines such as 1-hydroxy-2- pyridinthione (and its Na, Fe, Mn, Zn salts), tetrachloro-4-methyl-sulfonyl pyridine, tetrachloro-4-methylsulfonylpyridine; 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-tetrachloroisophthalonitrile (chlorothalonil); Benzothiazoles such as 2-mercapto benzothiazole; Thiazolyl benzimidazole; Quinolines such as γ-hydroxyquinoline; Benzyl alcohol mono (poly) hemiformal; Tris-N- (cyclohexyldiazeniumdioxy) aluminum, N- (Cyclohexyldiazeniumdioxy) tributyltin.

The following are preferably added as insecticides:
Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, 1- (4-chlorophenyl) -4- (O-ethyl, S-propyl) -phosphoryloxypyrazole (TIA-230), chlorpyrifos, Coumaphos, Dem eton, Demeton-S-methyl, Diazinon, Dichlorvos, Dimethoate, Ethoprophos, Etrim fos, Fenitrothion, Fention, Heptenophos, Parathion, Parathion-methyl, Phosalone, Phoxion, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulprofos, Triazophos and Trichlorphon;
Carbamates such as aldicarb, bendiocarb, BPMC (2- (1-methylpropyl) phenylmethyl carbamate), butocarboxime, butoxicarboxim, carbaryl, carbofurann, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and
Pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin (FMC 54 800), cycloprothrin, cyfluthrin, decamethrione, cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- ( chloro-2-tri fluoromethylvinyl) cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethnn, fluvalinate, permethrin and resmethrin, nitroimides such as 1 - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N -nitro-1H-imidazol-2-a-nine (Imida cloprid).

Algicides, molluscicides and active substances come into consideration as other active substances against "sea animals", which z. B. settle on ship floor paints.  

The active substance combinations or agents according to the invention enable in front some way, the previously available biocidal agents through more effective and order to replace more environmentally compatible. They show good stability and have an advantage hard way a wide range of effects.

The following example serves to explain the invention, without going to it limit. Parts and percentages mean parts by weight or Ge weight percent.  

example 1

Test methods and results 1. Checking the storage stability

50, 75, 100 and 200-fold dilutions of the test sample in water are stored in closed polyethylene bottles at 2 ° C and 40 ° C for 3 months. The dilutions are then poured into a 1,000 ml beaker, checked for changes in appearance and for the formation of crystals and precipitates, 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:

2. Wood permeability test

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

Cryptomeria sapwood becomes test specimens with dimensions 2 cm × 2 cm × 12 cm cut out; of these test specimens all surfaces with the exception of one end face with epoxy resin locked.

After weighing, 10 test specimens are put into a 1,000 ml beaker camps that floating is not possible. After storage for The dilutions are taken in for 2 hours under vacuum (60 mm Hg) brings and the test specimens at normal pressure for 22 hours in the ver dives kept immersed. Then the test specimens are removed from the Dilutions taken and to determine the intake amount (kg / m³) weighed out.

The treated test specimens are placed at a distance of 2 cm and 8 cm from the unclosed forehead for analysis of the active substances DDAC, Tebuconazole and Imidcloprid cut open after being used for 1 month have been stored under a polyethylene film at 26 ° C.  

The following results were achieved:

3. Examination of fungus failure

For the tests, 50, 75, 100 and 200 times aqueous are Dilutions of the test sample are made. 1.0% serve as control, 0.7%, 0.5% and 0.3% DDAC in water. In addition, as in 2.1 described test samples prepared, which are stored at 2 ° C for 3 months.

Cryptomeria sapwood becomes test specimens with dimensions Cut out 2 cm × 2 cm × 10 cm. 5 of these test specimens are in a 1,000 ml beaker stored so that floating does not is possible. After storage for 2 hours under vacuum (60 mm Hg) the dilutions are introduced and the test specimens at normal pressure kept immersed in the dilutions for 2 hours. After that the test specimens are removed from the dilutions and individually for 21 days stored under polyethylene film.  

The treated and untreated test specimens are alternately stored in wood-destroying soil at 26 ° C and 90% relative air 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 attack
B: discoloration
C: partial destruction
D: complete destruction

Claims (11)

1. Active ingredient combination of at least one azole fungicide, at least an 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:

• - 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone (triadimphone)
• - β- (4-chlorophenoxy) -α- (1,1-dimethyl-ethyl) -1H-1,2,4-triazd-1-ethanol (triadimenol)
• - ± α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol (tebuconazole)
• - (RS) -2- (2,4-dichlorophenyl) -1- (1H-1,2,4-triazol-1-yl) hexan-2-ol (hexaconazole)
• - 1- (N-Propyl-N- (2- (2,4,6- (trichlorophenoxy) ethyl) carbamoyl) imidazole (Prochloraz)
• - 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) -3- (1,2,4-triazol-1-yl) propan-2-ol
• - 1 - [[2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolon-2-yl] methyl] -1H- 1,2,4-triazole (propiconazole)
• - 1- [2- (2,4-dichlorophenyl) -1,3-dioxolon-2-yl-methyl] -1H-1,2,4-triazole (azaconazole)
• - (R *, R *) - α- (4-chlorophenyl) -α- (1-cyclopropylethyl1H-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) in which
R¹, R², R³, R⁴ are the same or different and each for 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 part or aryl groups with 5 to 10 carbon atoms, and optionally single or multiple alkoxylated derivatives thereof; where halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy are suitable as substituents; and where 2 or 3 radicals R¹ to R⁴ at the quaternary center can optionally form a saturated or unsaturated 5-, 6- or 7-membered (hetero) cycle with further heteroatoms and
X stands for an anion which promotes water solubility. 3. Active ingredient combination according to claim 1, containing tebuconazole and / or propiconazole and imidacloprid and C₁₂-C₁₄-alkyl-benzyl-dime thylammonium chloride and / or trimethylcocosammonium chloride and / or Didecyldimethylammonium chloride.   4. Microbicidal agents for material protection, containing an active ingredient com combination according to claim 1, solvent and diluent and counter if necessary, processing aids and possibly other active ingredients. 5. Microbicidal composition according to claim 4, containing water. 6. Microbicidal agents according to claim 4 for protecting wood and leather. 7. A method of combating microorganisms, characterized in that that the active ingredient combination according to claim 1 on microbes or whose habitat has an impact. 8. Use of the active ingredient combination according to claim 1 as a microbicide to protect technical 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, possibly organic, solvent and emulsifier free aqueous microbicidal agents.