CA2078412A1 - Water-based, solvent- and emulsifier-free, microbicidal active compound combination - Google Patents

Abstract

Water-based, solvent- and emulsifier-free microbicidal active compound combination A b s t r a c t Microbicidal, optionally solvent- and emulsifier-free active compound combinations of known azole and/or benzimidazole fungicides and quaternary ammonium compounds and their use in the preservation of materials are described.

Le A 28 628

Description

2~78~2 ThP present invention relates to new, preferably aqueous, optionally organic solvent- and emulsifier-free micro-bicidal active compound combinations of known azole fungicides and/or benzimidazole derivatives and quater-nary ammonium compounds.

It is known that imidazole or triazole fungicides, such as, for example, ~-[2-(4-chlorophenyl~-ethyl]-~-(1,1-dimethylethyl)-1-H-1,2,4-triazole-1-ethanol (tebucon-azole), 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1,2,3-triazol-l~yl)-propan~2-ol and 1-E[2-(2,~-di-chlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl]-methyl]-1-H
1,2,4-triazole (propiconazole) can be used as such or in the form of their salts for protecting plants and seeds (compare, for example, EP-A 0 040 345 and EP-A 0 052 424).

It is furthermore known that these compounds are also ~,~
suitable for use in the preservation of materials for combating microbes which destroy materials or discolour materials (comparel for example, DE-OS (German Published Specification) 3 621 494 and US 4 07~ 062).

However, the azole fungicides, such as the tebuconazole mentionedj have gaps in their action against some germs relevant to the preservation of materials, such as, for example, Trichoderma cpec.

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, 2~7~12 Furthermore, because of the often low water-solubility of azoles, their use in some fields of application, such as, for example, leather, water-based preservation of wood, disinfection, cooling water treatment, the paper indus-try, metal processing and industrial preservation ofwater-containing products, is limited or impossible.

It is fur~hermore known that b~nzimidazole derivatives, such as methyl benzimidazolecarbamate (BCM, carbendazim), methyl l-(butylcarbamoyl)-2-benzimidazolecarbamate 1~ (benomyl), 2-(2~-furyl)-lH-benzimidazole (uberidazole) and 2-(4'-thiazolyl)-benzimidazole have a fungicidal activity (Farm Chemicals Handbook). These can also be used in the preservation of materials.

Benzimidazole derivatives such as, for example, BCM are sparingly soluble in the customary organic solvents and virtually insoluble in water. They moreover have yaps in ~- their action spectrum, which can make their use in the preservation of materials difficulk because of the breadth of the action spectrum required in that sector.
On the basis of the solubility data, direct use in water-based systems is practically excluded.

Quaternary ammonium salts have been known for a lony time as broad-action microbicides and are used, for example, in disinfection and textile pre~ervation.

Althou~h these active compounds are usually readily water-soluble, they tend to foam severely at the use Le A 28 628 - 2 -, ~ ~ . .. . .

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concentrations, which causes trouble in many fields of use. Because of their cationic properties, they can moreover react with anionic components, such as soaps, surfactants and the like. Their profile of properties can be adversely influenced in this way, or they can become deactivated. It is furthermore known that quaternary ammonium salts are easily deactivated by the presence of protein and dirt.

For many uses in the practice of the preservation of materials it is desirable to employ the active compounds in liquid formulations which are free from organic solvents or in which the corresponding solvent content is reduced drastically.

Water-insoluble solven~s are incompatible with aqueous products, such as leather liquors, emulsion paints, cooling and process waters and disinfectants.
~, ~ ., The users are also often not equipped to handle products in the form of solutions in organic solvents, since particular devices, associated with high investment costs, are required ~or application from the solvent and recovery thereo~, which is essential in order to avoid ecological problems.
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Water-soluble solvents would be suitable in principle as solubilising agents in aqueous systems. However, if they Z5 enter the waste water, they can cause ecological problems. In addition, solvents manifest themselves ::
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2~78~2 adversely in the products to be preserved.

Another solubilisation possibility for the preparation of water-based active compound formulations is the use of emulsifiers. In the case of highly water-insoluble compounds, such as azoles and benzimidazole derivatives, large amounts of emulsifier are as a rule required for this, which should be avoided for ecological reasons. The activity of microbicidal active compounds can also ba severely impaired by the use of emulsifiers. Usability for certain systems can also be limited.

The object of the invention was therefore to provide new, preferably water-based, solvent- and emulsifier-free microbicidal act.ive compound formulations which are based on azole fungicides and/or benzimidazole derivatives and can easily be diluted with water and in this form give storage-stable use solutions.

It has now been found ~hat new active compound combina-tions of at least one metal salt and/or at least one acid addition compound of at least one azole fungicide, 20 preferably :
- 1-(4-chlorophenoxy)-3,3-dim~thyl-1-(lH-1,2,4-tri-azol-1-yl)-2-butanone (triadimefon) (4-chlorophenoxy)-~-(l,l~dimethyl-ethyl~-lH-1,2,4-triazole-1-ethanol (triadimenol) Le A 28 628 - 4 -' :

, 2~78~12 [2-(4 chlorophenyl)-ethyl]~ dLmethylethyl)-lH~1,2,4-triazole-1-ethanol (tebuconazole) ; - (RS)-2-(2,4-dichlorophenyl)-1-(lH-1,2,4-triazol-1-~ 5 yl)-hexan-2-ol .: (hexaconazole) - l-(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-dioxolan-2-yl]-methyl]-lH-lj2,4-triazole ~propiconazole~
lo [ 2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl-methyl]-lH-1,2,4-triaxole (azaconazole) wherein, in the cases where the compounds have asymmetric carbon atoms, the isomers and isomer mixtures of the most diverse compositions are also included;

:especially preferably +~-[2-(4-chlorophenyl~-ethyl]-~-(1,1-dimethylethyl)-lH-1j2,4-triazole-1-ethanol ~tebuconazole) ..,~ :
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~: : and/or at least one metal salt and/or at least one acid addition aompound of~at~least one benzimidazole fungi-cide, preferably of the formula (I) ' :
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in which Rl represents carbamic acid ester groups, or furyl or thiazolyl rings which are optionally further substi-- 5 tuted and R2 represents H or carbamic acid ester groups, and at least one preferably fungicidal, quaternary ammonium compound, p~eferably of the formula (II~

~: R1 I
R2_N~_K3 xe (II) : ~: : R4 :~
in which R1, R2, R3 and R4 are identical or different and in each : ` case represent unsubstituted or substituted, ~; straight-chain or branched, saturated or unsaturated alkyl groups having 1 20 carbon atoms, alkylaryl or 15: aralkyl groups:having 5~10 carbon atoms in the aryl part and 1-20 carbon atoms in the alkyl`part or aryl :~ -: groups; having 5-10 carbon atoms, and optionally : ~ mono- or polyalkoxylated derivatlves thereof;
possible substituent3 being halogenl C~-C~-alkyl and C1 C4-alkoxy; and in which 2 or 3 radicals Rl to R4 of :~
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-the quaternary centre, if appropriate with further hetero atoms, can form a saturated or unsaturated 5-, 6- or 7-membered (heterocyclic) ring and X represents an anion which promotes water-solubility, such as, for example, halide, sulphate, alkyl-sulphonate or optionally substituted arylsulphonate, have a particularly high microbicidal activity and at the same time are completely water-soluble and give stable solutions in water.

Such aqueous formulations avoid the abovementioned ecologicaI and use-related disadvantages of solvent-based or emulsifier-mediated formulations and in this respect represent a useful enrichment of the prior art.

~ Benzimidazole derivatives which may be mentioned are, ; ~15 preferably:

methyl benzimidazolylcarbamate (BCM), methyl 1-~butyl-carbamoyl)-2-benzimidazolecarbamate (benomyl), 2-~2'-furyl)-lH-benzimidazole (fuberidazole) an~ 2-(4'-thia-zolyl)benzimidazole (thiabendazole).

:: : 20 Methyl~ benzimidazolylcarbamate lBCM) is particularly preerred. : ~ :
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Quaternary ammonium compounds which may be mentioned are, preferably, ammonium salts ~uch as .

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2~78~12 - C12-cl4-alkYl-benzyl-dimethylammonium chloride - trimethyl-coconut-ammonium chloride - didecyldimethylammonium chloride.

C12-Cl4-Alkyl-benzyl-dimethylammonium chloride is parti-cularly preferred.

The a~ole derivatives and the benzimidazole derivatives lie in each case in the form of their metal salt com-plexes or are present as acid addition salts. Possible metal salts are, preferably, salt~ of metals of main groups II to IV and sub-groups I and II and I~ to VII of the periodic system, coppsr, zinc, manganese, magnesium, tin, iron, calcium, aluminium, lead, chromium, cobalt and nickel being mentioned as examples.
~' Possible anions of ~he salts are those which are prefer-ably dsrived from the followinq acids: hydrogen halide acids, such as, for example, hydrochloric acid and hydrobromic acid, and }urther re phosphoric acid, nitric acid and sulphuric acid or sulphonic acids~

; A combination of tebuconazoles and/or BCM, preferably in ;~ 20 the ~form of their hydxohalides, and C12-C14-alkyl-benzyl-~ dimethylammonium chloride i8 especially preferred.

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The metal salt compIexes can be obtained in a simple manner by customary processes, thus, for example, by dissolving the metal salt in alcohol, for example etha-nol, and adding the solution to the azole derivative or ', - :

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~78~2 ben~imida~oi~ d~rivative. Metal salt complexes can D~
isolated in a ~.nown manner, for example by filtration, and if appropriate purified by recrystallisation.

The following acids are preferably suitable for the preparation of acid addition salts: the hydrogen halide acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, and furthermore phosphoric acid, nitric acid, sulphuric acid, mono- and bifunctional carboxylic acids and hydroxy-carboxylic acids, such as, for example, acetic acid,propionic acid, butyric acid, mandelic acid, oxalic acid, succinic acid, 2 hydroxy-ethane-dicarboxylic acid, maleic acid, fumaric acid, tartaric acid, citric acid, sal:icylic acid, sorbic acid and lactic acid, and sulphonic acids, such as, for example, p-toluenesulphonic acid, 1,5-naphthalenedisulphonic acid and alkanesulphonic acids, and optionally sub~tituted benzoic acids.

The acid addition salts of the compounds can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound in a suitable inert solvent and adding the acid, for example hydrochloric acid, and they can be~isolated in a known manner, for example by filtrationj and if appropriate purified by wa~hing with an inert organic solvent.

The weight ratios of the active compounds in the active compound combinations can be varied within xelatively wide ranges.

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~784:l2 The weight ratio of azole compounds (A) to benzimidazole derivatives (B) can thus be in the range from 1:99 to 99:1, and the weight ratio of A:B is preferably 1~9 to 9:1, especially preferably 1:5 to 5:1. The weight ratio of the compounds ~A) or (~) or of the sum o~ (A)+(B) to the content of quaternary ammonium compounds (C) can be in the range from 1:99 to 99:1, 1:9 to 9:1 being preferred and the weight ratio especially preferably being 1:5 to 5:1.

The active compound combinations according to the inven-tion have a potent action against microorganisms. The : active compound combinations according to the invention are used in the preservation of materials to preserve industrial materials; they are active above all against moulds, wood- and leather-discolouring and wood- and : : leather-destroying fungi and bacteria, and against yeasts, algae and slime organisms. The following genera of microorganisms may be mentioned as examples - but without implying a limitation:

Alternaria, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger and Aspergillus terreus, Aureo-: basidium, such as Aureobasidium pullulans, Chaetomium, ; such as Chaetomium globosum, Cladosporium, such as Cladosporium herbarum, Coniophora, such as Coniophora puteana, Gliocladium, such as Gliocladium virens, . Lentinus, such as Lentinus tigrinus, Paecilomyces, such as Paecilomyces varioti, Penicillium, such as Penicillium Le A 28 628 - 10 ~

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2~7~2 brevicaule, Penicillium glaucum and Penicillium pino-philum, Polyporus, such as Polyporus versicolor, Sclero-phoma, such as Sclerophoma pityophila, Streptoverti-cillium, such as Streptoverticillium reticulum, Tricho-derma, such as Trichoderma viride and Trichophyton, suchas Trichophyton mentagrophytes;

Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonas areuginosa and Staphylococcus, such as Staphylococcus aureus; and Candida, such as Candida albicans.

The amount of the active compound combinations employed depends on the nature and the occurrence of the micro organisms, the germ count and on the medium. The optimum amount to be used for the application can be determined in each case by test series. In general, however, it is sufficient to employ 0.001 to 20% by weight, preferably 0.05 to 10% by weight, in particular 0.05 to 2% by weight, of the active compound mixtures, based on the material to be preserved.

- 20 The new active compound combinations can be used as such or in the form of concentrates or generally customary formulations, such as powders, granules, soIutions, suspensions, emulsions or pastes.
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The formulations mentioned can be prepared in a manner which is known per se, for example by mixing the active Le A 28 628 : :
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compounds with a solvents or diluents, emulsifiers, dispersants and/or of a binder or fixing agent, if appropriate siccatives and W stabilisers and if appropriate dyestuffs and pigments, as well as other processing auxiliaries.

Possible solvents and diluents are organochemical sol-vents or solvent mixtures and/or a polar organic solvent or solvent mixtures and/ox an oily or oil-like organo-chemical solvent or solvent mixture and/or water with at least one emulsifier and/or wetting agent. Customary water-insoluble oily or oil-like solvents of low volatil-ity which are used are preferably the particular mineral oils/solvent mixtures containing mineral oils or aromatic fractions thereof. Examples which may be mentioned are white spirit, petroleum or alkylbenzenes, and in addition spindle oil and monochloronaphthalene. The boiling ranges of these solvents or solvent mixtures of low volatility cover the range from about 17~C to not more than 350C.
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The oily or oil-like solvents of low volatility described ahove can be replaced in part by organochemical solvents of higher volatility.

To prepare a wood preservative, some of the solvent or solvent mixture described above is preferably replaced by a polar organochemical solvent or solvent mixture.
Solvents which contain hydroxyl groups, es~er g:roups, ether groups or mixture~ of this functionality are preferably employed here. Examples which may be mentioned .
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2~7~4~2 are esters or glycol ethers. Binders are understood according to the invention as synthetic resins which are water-dilutable or soluble, dispersible or emulsifiable in organochemical solvents, or binding drying oils~ for example based on acrylic resins, vinyl resins, polyester resins, polyurethane resins, alkyl resins, phenolic resins, hydrocarbon resins or silicone resins. The binder used can be employed as a solution, emulsion or dispersion. Mixtures of alkyd resins and drying vegetable oil are preferably used. Alkyd resins having an oil content of between 45 and 70% are particularly preferred.

All or some of the binder mentioned can be replaced by a fixing agent (mixture) or a plasticiser (mixture). These additions are intended to prevent evaporation of the active compounds and crystallisation or precipitation.
They preferably replace 0.01 to 30% of the binder (based on 100~ of the binder employed).
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The plasticisers originate fro~ the chemical classes or phthalic aci~ 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 and amyl stearate, oleates, such as butyl oleate, glycerol ethers or higher molecular weight glycol ethers, glycerol esters and p-toluenesulphonic acid esters.
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` Fixing agents are based chemically on polyvinyl alkyl el:hers, such as, ~or example, polyvinyl methyl ether, or Le A 28 628 - 13 -: . , . ,, :
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2~7~12 ketones, such as benzophenone or ethylbenzophenone.

Possible solvents or diluents are, pre~erably, water, if appropriate mixed with one or more of the abovementioned solvents or diluents, emulsifiers and dispersing agents.

According to the invention, industrial materials are non-living materials which have been prepared for use in industry. Industrial materials which are to be protected by the active compounds according to the invention from microbial change or destruction can be, for example, adhesives, sizes, papers and cardsl textiles, leather wood, paints and articles of plastic, cooling lubricants and other materials which can be attacked or destroyed by microorganisms. Components of production plantsi, for ; example cooling water circulations, which may be impaired by multiplication of microorganisms, may also be men-tion~d in the context of the materials to be preserved.
Preferred industrial materials in the context of the invention are adhesives, sizes, papers and cards, leather wood, paints, cooling lu~ricants, aqueous hydraulic fluids and cooling circulations.
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The active compound combinations, agents and concentrates according to the invention are preferably employed for preserving leather, wood and wood materials against microorganismsj for example against leather- and wood-destroying or leather- and wood-discolouring fungi, in particular in the temporary pxeservation of wood.

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By wood which can be preserved by the mixtures accordin~
to the invention there is to be understood, for example:
building timber, wood~n beams, railway sleepers, bridge components, boat jetties, wooden vehicles, crates, pallets, containers, telephone poles, wooden fences, wood panelling, wooden windows and doors, plywood, chipboard, joinery work or timber products which are used quite generally in house construction or building joinery.

Particularly effective preservation of wood is achieved by large-scale industrial impregnation processes, for example vacuum, double vacuum or pressure process~s.

The activity and the action spectrum of the active compound combination according to the invention and the agents, concentrates or quite generally formulations which can be prepared therefrom is increased if, as appropriate, other antimicrobially active substances, fun~icides, insecticides or other acti~e compounds are added to increase the active compound spectrum or achieve particular effects, such as, for example, the additional protection against insects. Particularly favourable mixing partners are, for example, the following compounds:

sulphenamides, such as dichlofluanid (Euparen), tolyl-fluanid ~Methyleuparen), folpet and fluorofolpet; thio-cyanates, ~uch as thiocyanatomethylthiobenzothiazole(TCMTB) and methylene bisthiocyanate (MBT); morpholine derivatives,suchasCll-Cl4-4-alkyl-2,6-dimethylmorpholine Le A 28 628 - 15 - -.

2~7~2 homologues(tridemorph),(+)-cis-4-[3-tert.-butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine (fenpropimorph) and falimorph; phenols, such as o-phenylphenol, halogen~
ated cresols, tribromophenol, tetrachlorophenol, penta-chlorophenol and 3-methyl~4-chlorophenol; dichlorophen;
iodopropargyl derivatives, such as iodopropargyl butyl-carbamate (IPBC) t chlorophenyl formal, phenylcarbamate, hexylcarbamate and cyclohexylcarbamate; isothiazolinones, such as N-methylisothiazolin-3-one, 5-chloro-N-methyl-isothiazolin-3-one, 4,5-dichloro-N~octylisothiazolin-3-one and N-octylisothiazolin-3-one (octhilinone); pyrid-ines, such as 1-hydroxy-2-pyridinethione (and its Na, Fe, Mn and Zn salts) tetrachloro-4-methyl-sulphonylpyridine and tetrachloro-4-methyl-sulphonylpyridine; metal soaps, such as tin, copper or zinc naphthenate, octoate, 2-ethylhexanoate, olete, phosphate, benzoate or oxide;
zinc salts of dialkyldithiocarbamates; tetramethyldiuram disulphite (TMTD); 2,4,5,6-tetrachloroisophthalonitrile (chlorthalonil); benzothiazoles, such as 2-mercapto-benzothiazole; thiazolyl-benzimidazole; quinolines, such as ~-hydroxyquinoline; benzyl alcohol mono(poly)hemi-formal; tris-N-(cyclohexyldiazeniumdioxy)-aluminium and N-(cyclohexyldiaæeniumdioxy)-tributyl tin.

: Insecticides which are preferably added are:

phosphoric acid esters, such as azinphos-ethyl, azinphos-: methyl, 1-(4-chlorophenyl)-4-(0-ethyl r S-propyl)phos-phoryloxypyrazole (TIA-230), chlorpyrifos, coumaphos, demeton, demeton S-methyl, Diazinon, dichlorvos and Le A 28 628 - 16 -... , . . , . . ~ . . . . :

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2~7~12 dimethoate, and carbamate~, such as aldicarb, bendiocarb, BPMC (2-(1-methylpropyl)phenyl methylcarbamate), buto-carboxim, butoxycarboxim, carbaryl, carbofuran, carbo-sulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pyrimicarb, promecarb, propoxur and thiodicarb;

pyrethroids, such as allethrin, alphamethrin, biores-methrin, byfenthrin (FMC 54 800), cycloprothrin, cyflu-thrin, decamethrion, cyhalcthrin, cypermethrin, delta-methrin, alpha-cyano-3-phenyl-2-methylbenzyl 2,2-dimeth-yl-3 (2-chloro-2-trifluoromethylvinyl)cyclopropane-carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin and resmethrin; and nitroimides, such as 1-[(6-chloro-3~
pyridinyl)-methyl]-4,5-dihydro-N-nitro-lH-imidazol-2-anine (imidacloprid).

Possible other active compounds are algicides, mollusci-cides, and active compounds against "sea animals" which colonise, for example, paint films on ships' bottoms.

The microbicidal agents or concentrates used for preser-vation of the industrial materials comprise the active compound combinations according to the invention in a concentration of 0.01 to 95~ by weight, in particular 0.01 to 60~ by weight, and in addition if approp:riate ~ 0.001 to 10% by weight of a suitable further fungicide, : 25 insecticide or a further active compound as mentioned above.

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The active compound combinations or agents according to the invention advantageously allow the microbicidal agents hitherto available to be replaced by more effec-tive and more environmentally compatible agents. They exhibit a good stability and advantageously have a broad action spectrum.

The following examples serve to illustrate the invention, without limiting it thereto. Parts and percentage data denote parts by weight and percentages by weight.

Example 1 Microbicidal mixture based on tebuconazole, BCM and Cl2/Cl4-alkyl-benzyldimethyl-a~monium chloride 21.6 g of C12/C14-alkyl-benzyl-dimethylammonium ch:Loride are initially dissolved in 845 ml of water. 34 g of concentrated hydrochloric acid are added, while stirring.
80 g of tebuconazole and 20 g of BCM are added to this mixture. Ater the mixture has been stirred at 65-70C
for 2 hours, a clear, st~ble aqueous formulation of the active compou~d mixture which can be further diluted with water as desired is obtained.

, Example 2 Microbicidal activity of the active compound mixtures according to the invention !

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~7~2 This activity can be documented with the aid of the MIC
(minimum inhibitory concentration) values.

~etermination of the MIC values:

To demonstrate the activity against fungi, yeasts and bacteria, the minimum inhibitory concentrations (MIC) of mixtures according to the invention were determined:

Active compounds according to the invention are added in concentrations of 0.1 mg/l to 5000 ml/l to an agar prepared by beer wort and peptone. After the agar has solidified, it is contaminated with pure cultures of the test organisms shown in the table. After storage at 28C
and 60 to 70% relative atmospheric humidity for 2 weeks, the MIC is determined. The MIC is the lowest concentration of active compound at which no growth at all of the species of microbe used takes place; it is shown in the following Table l.

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~7~ 2 Table 1 MIC values of the mxiture against moulds, yeasts and bacteria Test germsMixture according toExample 1 MIC values in mgfl Penicillium brevic. 50 Chaetomium globosum 10 Aspergillus niger 50 Lentius tigrinus 5 Sclerophoma pityoph. 5 Trichoderma viride 75 Cladosporium herb. 5 Alternaria tenuis 400 Aureobasidum pull. 5 Escherichia coll 800 Pseudomonas fluorescens >800 Bacillus subtilis 50 Aeromonas punctata 100 Proteus mirabilis >800 Aerobacter Aerogenes250 Bacillus mycoides 75 Leuconostoc mesenteroides 100 Staphylococc. aureus 50 Pseudomonas aerug. >800 Rhodotorula mucilaginosa 100 Candida albicans 75 Candida krusel 35 Saccharomyces bailil7.5 Torula rubra lO0 Saccharomyces cerivisiae 250 Torula utilis 35 Example 3 Preservation of leather The activity of the mixture according to Example 1 in preserving damp chrome leather (wet-blue) is tested. The mixture according to Example 1 is added during chrome he A 28 628 - 20 -.;. ..

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~, 2û7~12 tanning of cattle hideO Circular samples (~ 3 cm) are then taken ~rom the resulting wet-blue and are placed on contaminated agar in Petri dishes in the agar diffusion test in accordance with the Swiss test standard SNV 195 921. The test germs Aspergillus niger, Trichoderma viride and Penicillium glaucum are used for the contamination.
The samples are stored in an incubating cabinet at 28C/80-100% atmospheric humidity. The period over which the wet-blue sample~ remain unattacked by mould is tested.

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2 ~ 1 2 ) 14.4% of tebuconazole 1.0% of BCM

3.3% of dodecylbenzenesulphonic acid 61.3~ of propylene glycol mono-methyl ether 20.0% of ethoxylated nonylphenol (about 10 mol of ethylene oxide) b~ ) alkyl (C12JC14)-benzyldimethyl-ammonium chloride The results demonstrate the outstanding activity of the microbicide mixture of Example 1 according to the invention.

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Claims (11)

1. Active compound combination of at least one metal salt and/or at least one acid addition compound of at least one azole derivative and/or at least one metal salt and/or at least one acid addition com-pound of at least one benzimidazole derivative and at least one quaternary ammonium compound.

2. Active compound 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-(triadimefon) - .beta.-(4-chlorophenoxyl-.alpha.-(1,1-dimethyl-ethyl)-1H-1,2,4-triazoles-1-ethanol - ?,2-(4-chlorophenyl)-ethyl]-.alpha.-(1,1-dimethyl-ethyl)-lH-1,2,4-triazole-1-ethanol - (RS)-2-(2,4-dichlorophenyl)-1-(1H-1,2,4-tri-azol-1-yl)-hexan-2-ol - 1-(N-propyl-N-(2-(2,4,6-(trichlorophenoxy)-ethyl)-carbamoyl)-imidazole - 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-dioxo-lan-2-yl]~methyl]-1H-1,2,4-triazole (propicon-azole) - 1-[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl-methyl]-1H-1,2,4-triazole (azaconazole) Le A 28 628 - 24 -and/or at least one benzimidazole fungicide of the formula (I) (I) in which R1 represents carbamic acid ester groups, or furyl or thiazolyl rings which are optionally further substituted and R2 represents H or carbamic acid ester groups, and at least one quaternary ammonium compound, of the formula (II) (II) in which R1, R2, R3 and R4 are identical or different and in each case represent unsubstituted or substi-tuted, straight-chain or branched, saturated or unsaturated alkyl groups having 1-20 carbon atoms, alkylaryl or aralkyl groups each having 5-10 carbon atoms in the aryl part and 1-20 carbon atoms in the alkyl part or aryl group having 5-10 carbon atoms, and optionally Le A 28 628 - 25 -mono or polyalkoxylated derivatives thereof;
possible substituents being halogen, C1-C4-alkyl and C1-C4-alkoxy; and in which 2 or 3 of the substituents of the quaternary centre, if appropriate with further hetero atoms, can form a saturated or unsaturated 5-, 6- or 7-membered (heterocyclic) ring and X represents an anion which promotes water-solubility.

3. Active compound combination according to Claim 1 characterised in that the salts are in the form of the hydrogen halide acid, phosphoric acid/ nitric acid and/or sulphuric acid anions.

4. Active compound combination according to Claim 1, comprising tebuconazole and/or BCM and C12-C14-alkyl-benzyldimethyl-ammonium chloride in the form of their hydrohalides.

5. Microbicidal agents for the preservation of mater-ials, comprising an active compound combination according to Claim 1, solvents or diluents and if appropriate processing auxiliaries and if approp-riate other active compounds.

6. Microbicidal agents according to Claim 5, comprising water.

7. Microbicidal agents according to Claim 5, for Le A 28 628 - 26 -preservation of leather and wood.

8. Method of combating microorganisms, characterised in that the active compound combination according to Claim 1 is allowed to act on microbes or their environment.

9. Use of the active compound combination according to Claim 1 as a microbicide for the preservation of industrial materials.

10. Use according to Claim 9, as a fungicide for the preservation of leather and wood.

11. Use of the active compound combination according to Claim 1 for the preparation of stable, optionally organic solvent- and emulsifier-free aqueous micro-bicidal agents, Le A 28 626 - 27 -