DE4420522A1 - Bactericidal thiadiazolidinones - Google Patents

Abstract

The use of 2,4-disubstituted 1,2,4-thiadiazolidinone compounds is disclosed for protecting technical materials.

Description

The application relates to the use of 2,4-disubstituted 1,2,4-thia diazolidine-3,5-diones as bactericides in the protection of materials.

2,4-disubstituted 1,2,4-thiadiazolidine-3,5-diones are known and are z. In GB 1 115 350, US 3 301 894, US 3 374240, DD 2 31 070 and US 4 183 816 described. Not yet known is their biocidal use for the protection of technical materials against attack, modification or destruction by micro organisms.

The subject of the present application is therefore the use of Compounds of the formula (I)

in which R¹ and R² are independently C₁-C₆-alkyl or phenyl, as a biocidal component in engineering materials.

Preference is given to using compounds of the formula (I) in which R¹ and R² are independently C₁-C₄ alkyl or phenyl. Especially Preference is given to using compounds of the formula (I) in which R¹ and R² independently of one another represent methyl, ethyl, n-, i-propyl or phenyl.  

Particularly preferred are the following combinations of R¹ and R²

R R (Ia) Me me (Ib) Me et (Ic) Me Ph (Id) Et me (Ie) Et et (If) Et Ph (Ig) Ph me (Ih) Ph et

very particular preference is given to using compounds of the formula (I) in where R¹ = R² = Me.

Surprisingly, the compounds of the formula (I) have a longer duration lasting effect than those known from the prior art structurally nearby compounds Kathon 886 or Dichlorodithiolone.

Surprisingly, compounds of formula (I) show a particularly high microbicidal, in particular bactericidal / bacteriostatic action associated with a broad spectrum of action against microorganisms relevant in the protection of materials. Above all, they are effective against bacteria, both against gram positive as well as gram-negative bacteria, as well as against slime organisms, fungi and algae.

By way of example-without, however, limiting-the following groups of Ark and Eubacteria called:

• - gram-positive cocci z. B. the genera Micrococcus and Staphylococcus such as Micrococcus luteus and Staphylococcus aureus;  
• - gram-negative cocci z. B. the genus Acinetobacter such as Acinetobacter calcoaceticus;
• - gram-positive, non-spore-forming rods z. B. the genus Lacto Bacillus, Lactococcus, Leuconostoc, Streptococcus, Pediococcus;
• - Coryneform bacteria such as representatives of the genera Corynebacterium and Arthrobacter; various actinomycetes in the narrower sense as representatives the genera Nocordia, Actinomyces, Streptomyces, Themoactinomyces;
• - gram-positive, endosporium-forming rods and cocci of the genera Bacillus, sporosarcina. Clostridium and desulfotomaculum such as Bacillus megaterium, Bacillus polymyxa, Bacillus cereus, Bacillus subtilis, Bacillus licheniformis, Bacillus pasteurii and Sporosarcina ureae, Desulfotomaculum nigrificans and Desulfotomaculum orientis, Clostridium pasteurianum, Clostridium butyricum, Clostridium acetobutylicum;
• - gram-negative chopsticks, including representatives of the pseudo family monaceae such as Pseudomonas rubescens, P. aeruginosa, P. stutzeri, P. oleovorans, P. putida, P. fluorescens and representatives of related genera of Gram-negative bacteria such as Alcalignes faecalis and Citrobacter freundii or the vagina known and feared as "sewage fungus" bacterium Sphaerotilus natans;
• - also Gram-negative, facultative anarobal rods from the family Entero bacteriaceae such as Escherichia coli and Salmonella typhimurium, Entero bacter aerogenes and Serratia marescens;
• - Budding and prosthecate bacteria, as well as pedunculated bacteria like Gallionella ferruginea and Nevskia ramosa;
• - Representatives of anaerobic, anoxygenic phototrophic bacteria such as species the genera Rhodospirillum, Rhodopseudomonas and Chromatium;  
• Representatives of cyanobacteria such as species of the genera Nostoc and Anabaena;
• - Sulfate-reducing bacteria such as species of the genera Desulfovibrio, Desulfobacterium, Desulfococcus, Desulfomonas, Desulfobulbus, Desulfosarcina, Archaeoglobus and Desulfotomaculum.

For mushrooms the following genera are called - without limiting however:
Aspergillus, such as Aspergillus niger,
Chaetomium, such as Chaetomium globosum,
Coniophora, like Coniophora puetana,
Lentinus, like Lentinus tigrinus,
Penicillium, such as Penicillium glaucum,
Polyporus, such as Polyporus versicolor,
Aureobasidium, such as Aureobasidium pullulans,
Sclerophoma, such as Sclerophoma pityophila,
Trichoderma, like Trichoderma viride,
Fusaria, like Fusarium nivale.

Likewise subject of the application are synergistic mixtures of Compounds of the formula (I) with at least one further bactericidal or bacteriostatic agent.

The active ingredients present in the combinations according to the invention (combination partners) are likewise known. The effectiveness of the active ingredients in the following mixtures is greater than the effectiveness of the individual components. Preferred mixing partners are z. For example, the following compounds:
N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octyl-isothiazolin-3-one, 4,5-trimethylene isothiazolinone, 4,5-benzisothiazolinone, benzyl alcohol mono (poly) -hemiformal, N-methylolchloroacetamide;
Aldehydes such as cinnamaldehyde, formaldehyde, glutardialdehyde, β-bromocinnamaldehyde;
Thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate;
quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethylammonium chloride;
Iodine derivatives such as diiodomethyl-p-tolylsulfone, 3-iodo-2-propynyl alcohol, 4-chloro-phenyl-3-iodopropargylformal, 3-bromo-2,3-diiodo-2-propenylethylcarbamate, 2,3,3-triiodoallylalcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-butyl carbamate, 3-iodo-2-propynyl-n-hexyl carbamate, 3-iodo-2-propynylcyclohexylcarbamate, 3 iodo-2-propynyl-phenylcarbamate;
Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol;
Bromo derivatives such as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane , β-bromo-β-nitro styrene;
Pyridines such as 1-hydroxy-2-pyridinethione (and its Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrite ion;
Metal soaps such as tin, copper, zinc naphthenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;
Oxides such as tributyltin oxide, Cu₂O, CuO, ZnO;
Dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetramethylthiuram disulfide, potassium N-methyldithiocarbamate;
Nitriles such as 2,4,5,6-tetrachloroisophthalodinitrile, disodium cyanodithioimidocarba mat;
Quinolines such as 8-hydroxyquinoline and their Cu salts;
Mucochloric acid, 5-hydroxy-2 (5H) -furanone;
4,5-dichlorodithiazolinone, 4,5-benzdithiazolinone, 4,5-trimethylenedithiazolinone, 4,5-dichloro (3H) -1,2-dithiol-3-one, 3,5-dimethyl-tetrahydro-1,3, 5-thiadiazine-2-thione, N- (2-p-chlorobenzoylethyl) -hexaminium chloride, potassium N-hydroxymethyl-N'-methyl-dithiocarbamate,
2-Oxo-2- (4-hydroxy-phenyl) acethydroximsäure chloride,
Phenyl (2-chloro-cyano-vinyl) sulfone,
Phenyl- (1,2-dichloro-2-cyano-vinyl) sulfone;
Ag, Zn or Cu-containing zeolites alone or included in polymeric agents;
Compounds which are formed by reaction of N-substituted propylenediamines with glutamic acid esters according to EP-A 156 275.

By combining compounds of formula (I) with the above active ingredients mixtures produced show a greater than the individual compounds Efficacy, especially when used as a bactericide or bacterio statikum. The mixing ratio of compounds of the formula (I) to the corresponding mixing partners can be easily determined by preliminary experiments and is preferably in the range of 1:99 to 99: 1.

Likewise subject of this application are mixtures of compounds of Formula (I) with at least one fungicide, molluscicide, algicide, insecticide and / or herbicide or mixtures of compounds of the formula with these Substances and additionally at least one other bactericide or Bacteriostatic.

Preferred mixing partners are:

triazoles

Amitrole, azocyclotin, BAS 480F, bitertanol, difenoconazole, fenbuconazole, Fenchlorazole, Fenethanil, Fluquinconazole, Flusilazole, Flutriafol, Imiben  conazole, isozofos, myclobutanil, opus, paclobutrazole, penconazole, propio conazole, (±) -cis 1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) -cycloheptanol, Tetra conazole, triadimefon, triadimenol, triapenthenol, triflumizole, uniconazole.

imidazoles

Imazalil, pefurazoate, prochloraz, triflumizole, 2- (1-tert-butyl) -1- (2-chlorophenyl) - 3- (1,2,4-triazol-1-yl) -propan-2-ol, thiazolecarboxanilides such as 2 ', 6'-dibromo-2- methyl-4-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxan-ilide.

Methyl ( E ) -2- [2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl] 3-methoxyacrylate, methyl ( E ) -2- [2- [6- (2-thioamidophenoxy) pyrimidine 4-yloxy] phenyl] -3-methoxy acrylate, methyl ( E ) -2- [2- [6- (2-fluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, methyl ( E ) -2 - [2- [6- (2,6-difluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- [3 (pyrimidin-2-yloxy) phenoxy] phenyl ] -3-methoxyacrylate, methyl ( E ) -2- [2- [3- (5-methylpyrimidin-2-yloxy) phenoxy] phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- [3 - (phenylsulfonyloxy) phenoxy] phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- [3- (4-nitrophenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2 -phenoxyphenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- (3,5-dimethylbenzoyl) pyrrol-1-yl] -3-methoxyacrylate, methyl ( E ) -2- [2- (3-methoxyphenoxy ) phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- (2-phenylethen-1-yl) -phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- (3,5-) dichlorophenoxy) pyridin-3-yl] -3-methoxyacrylate, methyl ( E ) -2- (2- (3- (1,1,2,2-tetra fluoroethoxy) phenoxy) phenyl) -3-methoxyacrylate, methyl ( E ) -2- (2- [3- (alpha-hydroxybenzyl) phenoxy] phenyl) -3-methoxyacrylate, methyl ( E ) -2- (2- (4- phenoxy-pyridin-2-yloxy) -phenyl) -3-methoxy-acrylate, methyl ( E ) -2- [2- (3-n-propyloxy-phenoxy) -phenyl] -3-methoxy-acrylate, methyl ( E ) -2- [2- (3 -isopropyloxyphenoxy) phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- [3- (2-fluorophenoxy) phenoxy] phenyl] -3-methoxy acrylate, methyl ( E ) -2- [2- (3 -ethoxyphenoxy) phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- (4-tert-butylpyridin-2-yloxy) phenyl] -3-methoxyacrylate, methyl ( E ) - [2- [3- (3-cyanophenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl ( E ) - [2- (3-methylpyridin-2-yloxymethyl) phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2-] 6- (2-methylphenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- (5-bromopyridin-2-yloxymethyl) phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- (3- (3-iodopyridin-2-yloxy) phenoxy) phenyl] -3-methoxyacrylate, methyl ( E ) -2- [2- [6- (2-chloropyridin-3-yloxy) pyrimidine -4-yloxy] phenyl] -3-Methox yacrylate, ( E ), ( E ) - methyl-2- [2- (5,6-dimethylpyrazin-2-ylmethyloximinomethyl) phenyl] -3-methoxyacrylate, (E) -methyl-2- {2- [6- ( 6-methylpyridin-2-yloxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate, ( E ), ( E ) methyl-2- {2- (3-methoxyphenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate, ( E ) methyl 2- {2- (6- (2-azidophenoxy) pyrimidin-4-yloxy] phenyl} 3-methoxyacrylate, ( E ), ( E ) methyl-2- {2- [6-phenylpyrimidine-4 -yl) -methyloximinomethyl] phenyl} 3-methoxyacrylate, ( E ), ( E ) methyl-2- {2 - [(4-chlorophenyl) -methyloximinomethyl] phenyl} -3-methoxyacrylate, ( E ) methyl-2- {2- [6- (2-n-propylphenoxy) -1,3,5-triazin-4-yloxy] phenyl} -3-methoxyacrylate, ( E ), ( E ) methyl-2- {2 - [(3 -nitrophenyl) methyloximinomethyl] - phenyl} -3-methoxyacrylate;
Succinate dehydrogenase inhibitors such as:
Fenfuram, furcarbanil, cyclafluramide, Furmecyclox, Seedvax, Metsulfovax, pyrocarbolide, oxycarboxine, Shirlan, Mebenil (Mepronil), Benodanil, Flutolanil (Moncut);
Naphthalene derivatives such as:
Terbinafine, naftifine, butenafine, 3-chloro-7- (2-aza-2,7,7-trimethyl-oct-3-en-5-yne);
Sulfenamides such as dichlorofluidide, tolylfluanid, folpet, fluorfolpet; Captan, Captofol;
Benzimidazole such as carbendazim, benomyl, Furathiocarb, Fuberidazole, Thiopho natmethyl, Thiabendazole or their salts;
Morpholine derivatives such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph; Aldimorph, fenpropidin and their arylsulfonsauren salts, such as. For example, p-toluenesulfonic acid and p-dodecylphenyl-sulfonic acid;
Dithiocarbamate, Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam, Metiram, Thiram Zeneb, Ziram:
Benzothiazoles such as 2-mercaptobenzothiazole;
Quinolines such as 8-hydroxyquinoline and their Cu salts;
Benzamides such as 2,6-dichloro-N- (4-trifluoromethylbenzyl) -benzamide;
Boron compounds such as boric acid, boric acid esters, borax;
Formaldehyde and formaldehyde-releasing compounds such as benzyl alcohol mono- (poly) -hemiformal, oxazolidines, hexa-hydro-S-triazines, N-methylolchloroacetamide, paraformadehyde, nitropyrin, oxolinic acid, tecloftalam;
Tris-N- (cyclohexyldiazeniumdioxy) -aluminum, N- (cyclo-hexyldiazeniumdioxy) tributyltin or K-salts, bis-N- (cyclohexyldiazeniumdioxy) -copper.

Very particular preference is given to mixtures of compounds of the formula (I) with
Azaconazole, bromuconazole, cyproconazole, dichlobutrazole, diniconazole, hexaconazole, metaconazole, penconazole, propiconazole, tebuconazole, methyl (E) -methoximino [α- (o-tolyloxy) -o-tolyl)] acetate, methyl (E) -2 - {2- [6- (2-cyanophenoxy) -pyrimidin-4-yl-oxy] phenyl} -3-methoxyacrylate, methfuroxam, carboxin, fenpiclonil, 4- (2,2-difluoro-1,3-benzodioxole -4-yl) -1H-pyrrole-3-carbonitrile, butenafine, imazalil, N -methyl-isothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, N-octylisothiazolin-3-one, benzisothiazolinone, N- (2-hydroxypropyl) amino methanol, benzyl alcohol (hemi) formal, glutaraldehyde, omadine, dimethyl dicarbonate, and / or 3-iodo-2-propynyl-n-butyl carbamate.

Surprisingly, the effect of these drug combinations is essential higher than the sum of the effects of the individual active ingredients. So it's on unpredictable true synergistic effect before and not just one Addition of activities.

When the active ingredients in the active ingredient combinations according to the invention in certain weight ratios are present, the synergistic Effect particularly clear. However, the weight ratios of the active ingredients be varied in the drug combinations in a relatively wide range.  

Furthermore, also effective mixtures of compounds of the Formula (I) prepared with the following active ingredients:

fungicides

Acypetacs, 2-aminobutane, ampropylfos, anilazine, benalaxyl, bupirimate, Quinomethionate, chloroneb, chlozolinates, cymoxanil, dazomet, diclomezine, Dichloram, Diethofencarb, Dimethirimol, Diocab, Dithianone, Dodine, Drazoxolone, Edifenphos, Ethirimol, Etridiazole, Fenarimol, Fenitropan, Fentin acetate, Fentin Hydroxides, ferimzone, fluazinam, fluromides, flusulfamides, flutriafol, fosetyl, Fthalides, Furalaxyl, Guazatine, Hymexazole, Iprobenfos, Iprodione, Isoprothiolanes, Metalaxyl, methasulfocarb, nitrothal-isopropyl, nuarimol, ofurace, oxadiyl, Perflurazoate, pencycuron, phosphodiphene, pimaricin, piperaline, procymidone, Propamocarb, Propineb, Pyrazophos, Pyrifenox, Pyroquilon, Quintozene, Tar Oils, Tecnazene, thicyofen, thiophanate-methyl, tolclofos-methyl, triazoxide, Trichlamides, tricyclazoles, triforines, vinclozolin.

molluscicides

Fentinacetate, Metaldehyde, Methiocarb. Niclosamide, thiodicarb, trimethacarb.

Algicide

Coppersulfates, Dichlororphs, Endothal, Fentinacetate, Quinoclamine.  

herbicide

The weight ratios of the active ingredients in the active substance combinations can be in be varied in relatively large areas.

The active substance combinations preferably contain compounds of the formula (I) from 0.1 to 99.9%, in particular from 1 to 75%, particularly preferably from 5 to 50%, the remainder being 100% by one or more of the above Mixture partner is filled.

The active ingredient of the formula (I) and the active compound combinations according to the invention have a strong microbicidal action and can be used to combat be used practically undesirable microorganisms. The active ingredients of Formula (I) and the active compound combinations according to the invention are for protection of technical materials against infestation and destruction by unwanted Microorganisms suitable.

Among technical materials in the present context are non-living Understand materials that have been prepared for use in the art  they are. For example, technical materials that can be invented by fiction appropriate agents protected against microbial change or destruction who adhesives, glues, paper and cardboard, textiles, leather, wood, to coating materials and plastic articles, coolants and other materials, which can be attacked or decomposed by microorganisms. As part of the to be protected materials were also parts of production facilities, at For example, cooling water circuits, called by multiplication of Mikroor organisms can be affected. In the context of the present invention As technical materials are preferably adhesives, glues, papers and Cartons, leather, wood, paints, coolants and heat transfer liquids.

Particular preference is given to technical materials containing or on water Water-based or processed with water.

Preference is given to the compounds of the formula (I) in cooling lubricants, in Pot preservation of emulsion paints, in adhesives, glues or in Cooling water circuits used. Here is the given long-term stability of particularly high economic benefit, since so by one-time low Dosing adequate protection for many weeks is guaranteed. Next The low consumption of active ingredient may additionally be the otherwise required continuous analysis of the active substance content is omitted. Ultimately, too ecological advantages, since the compounds of the prior art chlorine in the Molecule contained in the material (eg., Cooling lubricant) by Enriching decomposition and then has to be disposed of separately. The in the Pot preservation or active ingredients used in adhesives have to have single-dose sufficient effectiveness, since in these appl post-dosing is not possible.

The active ingredient of the formula (I) and the active compound combinations according to the invention depending on their respective physical and / or chemical Properties are converted into common formulations, such as solutions, Emulsions, suspensions, powders, foams, pastes, granules, aerosols and Very fine encapsulation in polymeric substances.  

These formulations are prepared in a known manner, for. B. by Mixing the active ingredients with extenders, so liquid solvents, under Pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or Dispersants and / or foaming agents. In case of use of water as an extender z. As well as organic solvents as an auxiliary solvents are used. As liquid solvents come in wesent in question: aromatics, such as xylene, toluene, alkylnaphthalenes, chlorinated flavor or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethyl lene, or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or Paraffins, e.g. As petroleum fractions, alcohols such as butanol or glycol and their Ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or Cyclohexanone, strongly polar solvents such as dimethylformamide or dimethyl sulfoxide, as well as water; with liquefied gaseous diluents or carriers Substances are meant liquids which are at normal temperature and are gaseous under atmospheric pressure, for. B. aerosol propellants, such as halogen coals hydrogens as well as butane, propane, nitrogen and carbon dioxide; as solid Carriers come into question: z. As natural minerals, such as kaolin, clay earth, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and ground synthetic minerals such as fumed silica, alumina and silicates; As solid carriers for granules are: z. Broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours, and Granules of organic material such as sawdust, coconut shells, corn on the cob and. Tobacco stalks; come as emulsifying and / or foam-producing agents in question: z. Nonionic and anionic emulsifiers, such as polyoxyethylene grease acid ester, polyoxyethylene fatty alcohol ether, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; as a dispersant mediums are suitable: z. B. Ligninsulfitablaugen and methyl cellulose.

It can in the formulations adhesives such as carboxymethylcellulose, natural Liche and synthetic, powdery, granular or latex-shaped polymers used such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural Phospholipids such as cephalins and lecithins and synthetic phospholipids. Other additives may be mineral and vegetable oils.  

It can dyes such as inorganic pigments, eg. For example, iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, Copper, cobalt, molybdenum and zinc are used.

The microbicidal agents used to protect the technical materials or Concentrates contain the active substance or the active ingredient combination in one Concentration of 0.1 and 95 wt .-%, in particular 1.0 to 60 wt .-%.

The use concentrations of the invention to be used Wirk fabric or the drug combinations depends on the type and Occurrence of the microorganisms to be controlled and after the together tion of the material to be protected. The optimal amount can be through Test series are determined. In general, the Anwendungskonzentra tions in the range of 0.001 to 5 wt .-%, preferably from 0.01 to 1.0 wt .-%, based on the material to be protected.

The agents according to the invention advantageously make it possible to date available microbicidal agent to replace it with more effective. They show a good one Stability and have advantageously a broad spectrum of activity.

The following examples serve to illustrate the invention. The Invention is not limited to the examples.

example 1 Determination of effectiveness in a cooling lubricant emulsion

The investigation is carried out with a mineral oil-based coolant leads. The concentrate is diluted with water such that a 5% emulsion results. In this formulation, the substances to be tested in the angege incorporated concentration range. The samples obtained are then with Inoculated bacteria and a mixture of molds and yeasts (ge separated approaches). After one week at room temperature, a sample is taken to determine the number of surviving microorganisms. In connection it is vaccinated again, then a guard waited and as described proceed. The experiment is stopped as soon as the growth of the micro organisms by the respectively added amount of the microbicide no longer is controlled.

The determination of surviving microorganisms occurs for bacteria Standard germ count agar, for molds and yeasts on malt extract agar, wherein in each case duplicate determinations are carried out.

The inoculating microorganisms include the following representatives:

bacteria
Pseudomonas aeruginosa
Pseudomonas fluorescens
Pseudomonas oleovorans
Pseudomonas rubescens
Pseudomonas stutzeri
Alcaligenes faecalis
Citrobacter freundii
Corynebacterium sp.

molds
Acremonium strictum
Fusarium solani
Geotrichum

yeasts
Rhodotorula rubra

The results are shown in the following table:

Table 1

The number of colony-forming units per ml (CFU / ml) is given. Active substance concentration: 200 ppm

As Table 1 shows, the addition of the compound of the invention already in low concentration to an effective suppression of microbes growth, with this effect lasting several weeks, after only additive, stops (long-term stability). Thus, the Ver invention Compounds significantly more stable than the structurally close compounds such as Kathon 886 or dichlorodithiolone

Kathon 886 substance mixture 1: 3

Dichlorodithiolon
which degrade under comparable conditions after a short time and thus are ineffective. For the degradation of Kathon 886 (see also Paul "Microbicides for the protection of materials", Chapman & Hall, 1993, pp. 322-323).

Claims (8)

1. Use of compounds of the formula (I) in the
R¹ and R² independently of one another are C₁-C₆-alkyl or phenyl,
for the protection of technical materials against microorganisms. 2. Use of compounds of the formula (I) according to claim 1, in where R¹ and R² independently of one another are methyl, ethyl, n-, i-propyl or phenyl are against the protection of technical materials Microorganisms. 3. Use of compounds of the formula (I) according to claim 1, in where R¹ and R² are methyl for the protection of technical Materials against microorganisms. 4. Use of compounds of formula (I) according to claim 1 to 3 as Bactericides or bacteriostats for the protection of technical materials. 5. Use according to one of claims 1 to 4, characterized that as technical materials cooling lubricants, emulsion paints, Adhesives, glues and heat transfer fluids are protected. 6. Method of protecting technical materials against attack, Alteration or destruction by microorganisms, thereby marked  records that the technical materials with compounds of Formula (I) according to claim 1 added or treated. 7. Microbicidal agents for the protection of technical materials against attack, Altered or destroyed by microorganisms by a content of at least one compound of the formula (I) Claim 1. 8. Technical materials containing at least one compound of the formula (I) according to claim 1 as a microbicide.