MXPA99005872A - Use of aminoisothiazoles as microbicides - Google Patents

Abstract

The invention relates to the use of aminoisothiazoles of formula (I) and to the metal complexes and acid additive salts thereof, wherein R means hydrogen or C1-C4-alkyl and X stands for halogen, NO2, CN and SCN, as microbicides to protect technical materials from infestation with and destruction by microorganisms.

Description

USE OF AMINOISETHAZOLES AS MICROBICIDES The present invention relates to the use of aminoisothiazoles as microbicides to protect industrial materials against attacks and destruction by microorganisms. Furthermore, the invention relates to a method for protecting industrial materials against attacks and destruction by microorganisms. The isothiazoles (US 3,761,488, US 4,105,431, US 4,252,694, US 4,265,899, US 4,279,762, US 5,430,046, EP-A 697 409) and the benzothiophene derivatives (DE-A 44 11 912), and also mixtures of azole-specific derivatives with ammonium compounds (EP-A 533 016), they are known to have microbicidal properties. The preparation of some of these compounds is very complicated and their efficiency, particularly at low application rates, is not always satisfactory. The 5-aminoisothiazoles have been described as coupling components in azo dyes (EP-A 362 708, EP-A 315 898). The 5-aminoisothiazoles (in many cases N-acylated) are also known for their herbicidal activity (EP-A 640 597, DE-A 24 34 922, DE-A 22 49 162, FR 2132691, US 4,032,321, US 4,032,322, ZA 7202352), bactericide and virucide (L. Kuczyns i et al., Pol. J. Pharmacol. Pharm. (1984), 36 (5), 485-491), and because they are useful as intermediates for drugs and protective agents of harvests It is an object of the present invention to provide compounds that they can be used as microbicides for the protection of materials, and they are easily accessible and have a good microbicidal activity. We have found that this object is achieved through the 5-aminoisothiazoles of the formula I, where R is hydrogen or alkyl (C: -C4) and X is halogen, N02, CN or SCN, and metal complexes and acid addition salts thereof which are very suitable for use as microbicides for protection of materials. Preferred are compounds wherein R is (C? -C4) alkyl, particularly methyl. In addition, compounds where X is CN and particularly SCN are preferred. In a particularly preferred embodiment, 3-methyl-4-ciocyanato-5-aminoisothiazole (formula le) is used, and metal complexes and acid addition salts thereof. The compounds I suitable for use according to the present invention are obtained by means of a sequence of reactions known per se from EP-A-640 597 by the conversion of isothiazoles of the general formula II, II the Ib with the aid of a halogenation agent in the halo compound, where Hal is F, Cl, Br, or I, which is then converted, if required, into compound Ib, where X 'is SCN or CN, by reaction with thiocyanates or cyanides. The preparation of the isothiazoles of the general formula II is described, for example, in DE-A-17 70 819. The preparation of 3-methyl-5-aminoisothiazole was described by A. Adams et al. in J. Chem. Soc. 1959, p. 3061. The aminoisothiazoles I, per se or in a formulation, are suitable for the protection of industrial materials H against attacks and destruction by microorganisms. Industrial materials are non-living materials obtained in industrial processes or non-living materials intended for use in industry. Industrial materials a protecting through the active compounds I against alteration or destruction by microbes are, for example, dispersions, adhesives, glues, cosmetics, solutions in starch, emulsions in wax, emulsions in mud, paper, sizing agents, finishes, bathrooms, textiles , leathers, rawhide, gelatin preparations, putty, fillers for joints, wood, paints, plastic made articles, coolers, drilling oils and other materials that can be attacked or decomposed by microorganisms. The compounds are furthermore suitable for use as scavengers in the paper industry, in re-cooling plants and air humidifiers. The aminoisothiazoles I are used particularly preferably in dispersions such as, for example, dispersions of polymers and paints. Microorgan that can cause a decomposition or alteration of industrial materials are, for example, spores, viruses, bacteria, fungi, yeasts, algae and slime organ. The active compounds or the active preparations according to the present invention preferably act against fungi, bacteria and algae. By way of example, the microorgan of the following varieties can be mentioned: Alternate it alternata, Alternarla tenuis, Aspergillus niger, Aureobasidium pullulans, Candida albicans, Chaetomium globosum, Citrobacter freundii, Cladosporium resinae, Coniophora puteana, Desulfovibrio desulfuricans, Escherichia coli, Klebsiella pneumoniae, Lentinus tigrinus, Penicillium expansum, Penicillium funicolosum, Penicillium glaucum, Polyporus versicolor, Proteus mirabilis, Proteus vulgaris, Pseudomonas aeruginosa, Sclerophoma pityophila, Saccharomyces cerevisiae, Staphylococcus aureus, Streptoverticillium rubrireticuli, Trichoderma viride. According to their physical and chemical properties, and according to the desired application, the active compounds of the formula I can be converted into customary formulations, for example solutions, emulsions, powders, pastes or dispersions. These formulations of active compounds are prepared in a conventional manner, for example by mixing the active compounds with suitable extenders or solvents, if required by the use of surfactants, ie, emulsifiers or dispersants. If water is used, organic solvents are generally used as auxiliary solvents. Suitable solvents are, for example, alcohols such as for example methanol, ethanol, propanol, butanol and cyclohexanol, or glycols, such as propylene glycol, 2-phenoxyethanol, phenoxypropanol, or aliphatic, cyclic and aromatic hydrocarbons, such as toluene, xylene, mesitylene, paraffin, tetrahydronaphthalene, naphthalenes alkyls and derivatives thereof, chlorobenzene, dichlorobenzene, or strongly polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone. Suitable emulsifiers are, for example, alkali metal salts, alkali earth metal salts or ammonium salts of aromatic sulfonic acids, for example of lignosulfonic acid, phenolsulfonic acid, naphthalenesphonic acid and dibutylnaphthalenesulfonic acid, and of fatty acids , alkylsulfonates and arylsulfonates, alkyl sulfates, lauryl ether sulfates and alcohol sulphates , fatty, and salts of sulfated hexadecanols, heptadecanoles and octadecanols, as well as condensation products of naphthalene or sulfonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene fatty alcohol ethers, ethers polyoxyethylene octyl phenols, ethoxylated isooctyphenol, ethoxylated octylphenol or ethoxylated nonylphenyl ethers, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ethers, isotridecyl alcohol, alkylaryl polyglycol ethers, ethoxylated castor oil, polyoxyethylene alkyl or polyoxypropylene (sic) ethers, polyglycol ether alcohol acetate lauryl, sorbitol esters; suitable dispersants are, for example, ligno-sulphite residue liquors as well as methylcel-ulose.

Aliphatic carboxylic acids can be added in order to improve the homogeneity of the concentrates. Such acids are for example propionic acid, hexanoic acid, heptanoic acid, branched carboxylic acids such as for example 2-ethylenehexanoic acid, isooctanoic acid, neocarboxylic acids, aliphatic dicarboxylic acids such as sebacic acid, cycloalkylcarboxylic acids, such as cyclohexanoic acid, arylcarboxylic acids, such as benzoic acid, 3- or 4-hydroxybenzoic acid. Paints or precursors for the preparation of paints include plastic dispersions, dispersion paints for the paint industry, starch solutions, suspensions of other raw materials, such as pigments or dyes or filler suspensions, such as kaolin, carbonate calcium, silicic acids, silica gels, silicate, talc, limestone, lime, chalk, fine clayey earth, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, or ground plastic . The activity and spectrum of activity of the active compounds of the formula I or of the compositions, intermediates or formulations that can be prepared therefrom can be increased by the addition of optionally active antimicrobial compounds, bactericides, fungicides, herbicides, insecticides, or other compounds assets to expand the spectrum of activity or to obtain special effects. In many cases, this results in synergistic effects, that is, the spectrum of activity of the mixture is superior to the activity of the individual components. Particularly beneficial mixing partners are, for example: microbicides: 2- (thiocyanatomethylthio) benzothiazole, 1- [2- (2,4-dichlorophenyl) -2- (2-propenyl-oxy) ethyl] -IH-imidazole, bisthiocyanate methylene 2,4,5,6-tetrachloroisophthalodinitrile, tributyltin oxide, tributyltin naphthenate, tributyltin benzoate, tributyltin salicylate, mercaptobenzothiazole, 1,2-benzisothiazolone and its alkali metal salts, alkali metal compounds of N 'oxide -hydroxy-N-cyclohexyldiazene, 2- (methoxycarbonylamino) enzimidazole, 2-methyl-3-oxo-5-chlorothiazolin-3-one, trihydroxymethylnitro ethane, glutaraldehyde, chloroacetamide, polyhexamethylenebisguanides, 5-chloro-2-methyl-4-isothiazolin -3-one + magnesium salts, 2-methyl-4-isothiazolin-3-one, 3,5-dimethyltetrahydro-1,3,4-2H-thiadiazin-2-thione, hexahydrotriazine, N, N-methylolchloroacetamide, 2-n-octyl-4-isothiazolin- 3-one, oxazolidines, bisoxazolidines, -dihydro-2, 5-dialkoxy-2, 5-dialkylfurans, diethyldodecylbenzylammonium chloride, dimethyloctadecyldimethylbenzylammonium chloride, dimethyldidecylammonium chloride, dimethyldidodecylammonium chloride, trimethyltetradecylammonium chloride, benzyldimethylalkyl- (C 2 -C 8) - ammonium, dichlorobenzyldimethyldodecylammonium chloride, cetylpyridinium chloride, cetylpyridinium bromide, cetyl rimethylammonium chloride, laurylpyridinium chloride, laurylpyridinium bisulfate, benzyldodecyldi (beta-oxyethyl) ammonium chloride, dodecylbenzyltrimethylammonium chloride, n-alkyldimethylbenzylammonium chloride (radical alkyl: 40% C12, 50% C? 4/10% Cie), lauryl dimethyl ethyl ammonium sulfate, n-alkyldimethyl (1-naphthylmethyl) ammonium chloride (alkyl radical: 98% C? 2, 2% C) ?), cetyl dimethylbenzylammonium chloride, lauryldimethylbenzylammonium chloride, Bactericides: bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, casugamycin, octylinone, furancarbox acid Ionic, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations, Fungicides: sulfur, dithiocarbamates and their derivatives, as well as iron (III) dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbate, manganese ethylene bisdithiocarbamate, zinc manganese ethylene diamine bis-dithiocarbamate, tetramethylthiuram disulfides [sic], ammoniacal zinc (N, N-ethylene-bis-dithiocarbamate) complex, ammonia complex of zinc (N, NT-propylene-bis-dithiocarbamate), zinc (N, N-propylenebisdithiocarbamate), N, N'-polypropylenebis (thiocarbamoyl) disulfide; nitro derivatives, such as dinitro- (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate, 2-sec-butyl-4,6-dinitrophenylisopropyl carbonate , 5-nitroisophthalate diisopropyl; heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, 0.0-diethyl phthalimidophosphothioate, 5-amino-1- [bis ( dimethylamino) phosphinyl] -3-phenyl-l-2,4-triazole, 2,3-dicyan-l, 4-dithioanthraquinone, 2-thio-l, 3-dithiolo [4, 5-b] quinoxaline, methyl 1- (butylcarbamoyl) -2-benzimidazolcarbamate, 2-methoxycarbonylaminobenzimidazole, 2- (furyl- (2)) benzimidazole, 2- (thiazolyl- (4)) benzimidazole, N- (1,1,2, 2 -tetrachloroethylthio) tetrahydroftalimide, N -trichloromethylthiotetrahydroftalimide, N-trichloromethylthiophthalimide, diamide of N-dichlorofluoromethylthio-N ', N' -dimethyl-N-phenylsulfuric acid, 5-ethoxy-3-trichloromethyl-l, 2,3-thiadiazole, 2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline or its copper salts , 2, 3-dihydro-5-carboxanilido-6-methyl-l, 4-oxatiine, 2,3-dihydro-5-carboxanilido-6-methyl-l, 4-oxazine-4, 4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2-methyl-furan-3-carboxanilide, 2,5-dimethyl-furan-3-carboxanilide, 2,4 , 5-trimethyl-furan-3-carboxanilide, cyclohexyl-2, 5-dimethyl-furan-3-carboxamide, N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, N-formyl -N-morpholine 2, 2, 2-trichloroethylacetal, piperazin-1,4-diylbis- (1- (2, 2, 2-trichloroethyl) formamide [sic], 1- (3,4-dichloroanilino) -l-formylamino -2, 2, 2-trichloroethane, 2,6-dimethyl-N-tridecylmorpholine or its salts, 2, β-dimethyl-N-cyclododecylmorpholine or its salts, N- [3- (p-tert-butylphenyl) - 2-methylpropyl] -cis-2,6-dimethylmorpholine, N- [3- (p-tert-butylphenyl) -2-methylpropyl] piperidine, 1- [2- (2,4-dichlorophenyl) -4-ethyl-1 , 3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, 1- [2- (2, 4-dichlorophenyl) -4-n-propyl-l, 3-dioxolan-2-ylethyl ) -1 HOUR- 1, 2, 4-triazole, N- (n-propyl) -N- (2, 4,6-trichlorofenoxyethyl) -N'-imidazolylurea, 1- (4-chlorophenoxy) -3,3-dimethyl-l- (1H-1, 2,4-triazol-1-yl) -2-butanone, (2-chlorophenyl) - (4-chlorophenyl) -5-pyrimidine-methanol, 5-butyl-2-dimethylamino-4-hydroxy- 6-methylpyrimidine, bis (p-chlorophenyl) -3-piridinme'tanol, 1, 2-bis (3-ethoxycarbonyl-2-thioureido) benzene, 1, 2-bis (3-methoxycarbonyl-2-thioureido) benzene, [ 2- (4-chlorophenyl) ethyl] - (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol, 1- [3- (2-chlorophenyl) -1- (4-fluorophenyl) oxirane-2-ylmethyl] -1H-1,2,4-triazole, and various fungicides, such as dodecylguanidine acetate, 3- [3- (3, 5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, N- (2, 6-dimethylphenyl) -N- (2-furoyl) -DL-alaninate, methyl ester DL-N- (2,6-dimethylphenyl) -N- (2'-metoxiacetil) alanine , N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2-aminobutyrolactone, methyl ester of DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine, 5-met il-5-vinyl-3- (3, 5-dichlorophenyl) -2,4-dioxo-l, 3-oxazolidine, 3- [3,5-dichlorophenyl (-5-methyl-5-methoxymethyl) -1,3 oxazolidin-2, 4-dione [sic], 3- (3, 5-diclorohenil) -1-iso-propylcarbamoyl-hydantoin [sic], N- (3, 5-dichlorophenyl) -1,2-dimethylcyclopropane-1 , 2-dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] acetamide, 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1, 2,4-triazole, 2,4-difluoro- alcohol a- (1H-1, 2,4-triazolyl-1-methyl) benzhydryl [sic], N- (3-chloro-2,6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3-chloro- 2- aminopyridine, 1- ((bis- (4-fluorophenyl) methylsilyl) methyl) -1H-1,2,4-triazole.

Strobilurins, such as methyl E-methoximino- [α- (o-tolyloxy) -o-tolyl] acetate (sic), E-2- { 2- [6- (2-cyanophenoxy) pyridimin-4-yloxy ] methyl phenyl.} - 3-methoxy-acrylate, methyl-E-methoximino- [a- (2-phenoxyphenyl)] acetamide [sic], methyl-E-methoximino- [α- (2,5-dimethylphenoxy) -o- [tolyl] acetamide [sic]. Anilinopyrimidines, such as N- (4,6-dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline, N- (4-methyl- 6-) cyclopropylpyrimidin-2-yl) aniline. Phenylpyrroles, such as 4- (2, 2-difluoro-l, 3-benzodioxol-4-yl) pyrro1-3-carbonitrile. Cinnamamides, such as 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) acryloylmorpholide. (2RS, 3SR) -1- [3- (2-chlorophenyl) -2- [4-fluorophenyl) oxiran-2-ylmethyl] -1H-1, 2,4-triazole. Insecticides: abamectin, acephate, acrinatrine, alanicarb, aldicarb, alphamethrin, amitraz, avermectin, azadirachtin, azinphos A, azinphos M, azocyclotin, thuringiensis bacillus, bendiocarb, benfuracarb, bensultap, beta-cilutrina, bifenthrin, BPMC, brofenprox, bromophos A, butencarb [sic], buprofezin, butocarboxina [sic], butylpyridaben, cadusafor [sic], carbaryl, carbofuran, carbophenothione, carbosulfan, cartap, cloetocarb, chloretoxyphos, chlorfenvinphos, chlorfluazurone, chloromus, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocitrin, clofentezin, cyanophos, cycloprothrine, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cipromazine, deltamethrin, demeton M, demeton S, demeton-S-methyl, diafentiuron, diazinone, diclofenthione, dichlorvos, diclifos, dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos, dioxationa, disulfotone, edifenfos, emamectin, esfenvalerate, etiofencarb, etion, etofenprox, ethoprofos, etrimfos, fenamifos, fenazaquina, fenbutatin oxide, fenitrotion, fenobucarb, phenothiocarb, fenoxicarb, fenpropatrina, fenpirad, fenpir oximate, fention, fenvalerate, fipronil, fluazinam, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonofos, formotion, fosthiazate, fubfenprox, furathiocarb, HC, heptenophos, hexaflumuron, hexythiazox, imidacloprid, iprobenfos, isazofos, isofenfos, isoprocarb, isoxationa, ivemectin, lamda-cyhalothrin, lufenuron, malathion, mecarbam, mervinfos, mesulfenfos, metaldehyde, methacryphs, methamidophos, methidathione, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, naled, nitenpyram, ometoate, oxamyl, oxidemetone M, oxideprofos, parathion A, parathion M, permethrin, phenoate, phorate, fosalone, fosmet, fosfamdona, phoxim, piri icarb, pirimiphos M, primiphos A, profenofos, promecarb, propafos, propoxur, protiofos, protiofos [sic] ], protoate, pymetrozine, pyraclofos, pydamphenone, piresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxyfen, quinalphos, salithione, sebufos, silafluofen, sulfotep, sulprofos, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzurona, tefluthrin, temephos, terbam, terbufos, tetrachlorvinfos, thiafenox, thiodicarb, thiofanox, thiometone, thionazine, thuringiensine, tralometrine, triaratena, triazophos, triazurone, trichlorfonone, triflu urone, trimetacarb, vamidothione, XMC, xylilcarb, zetamethrin. Additional suitable mixing partners are algicides, molluscicides, and active compounds against marine animals that colonize, for example, ship paints. Examples of such preparations are: 1. Examples of formulations in dispersion paints or plastic dispersions: a) 1000 parts by weight of a polyacrylate-based polymer dispersion are initially introduced and mixed under stirring with 0.25 parts by weight of a suspension concentration at 20% by weight of 3-methyl-4-thiocyanato-5-aminoisothiazole in propylene carbonate. b) It is possible to add the active compound powder to the dispersion already prepared. c) A 3% by weight solution of 3-methyl-4-thiocyanato-5-aminoisothiazole in propylene glycol, dipropylene glycol, phenoxyethanol, phenoxypropanol or polyethylene glycol is suitable for incorporation into aqueous dispersions and plastic dispersions containing solvents. d) A water or glycol-based paste containing 20 to 50% by weight of 3-methyl-4-thiocyanato-5-aminoisothiazole is suitable for incorporation into plastic dispersions containing solvents and aqueous. e) A solution of 90 parts by weight of 3-methyl-4-thiocyanato-5-aminoisothiazole and 10 parts by weight of N-methylpyrrolidone is suitable for incorporation into plastic dispersions containing solvents and aqueous. f) An aqueous dispersion of 20 parts by weight of 3-methyl-4-thiocyanato-5-aminoisothiazole, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction with a boiling point of 210-280. ° C and 10 parts by weight of the addition product of 40 moles of ethylene oxide to 1 mole of castor oil. The mixture of this dispersion with 100,000 parts by weight of an aqueous paint dispersion comprises 0.02% of the g) active compound. 2. A mixture of 14 parts by weight of Cu (OH) 2CuC03, 33 parts by weight of monoethanolamine, 22 parts by weight of benzoic acid, 11 parts by weight of water, 4 parts by weight of 3-methyl-4-thiocyanate -5-aminoisothiazole, 10 parts by weight of ethoxylated nonylphenol and 6 parts by weight of propylene glycol is particularly suitable for impregnating wood. The microbicidal compositions or concentrates that are employed for the protection of industrial materials comprise the active compound or the combination of active compounds in a concentration of 0.01 to 95, preferably 0.1 to 50% by weight. The concentration of application of the active compounds to be used depends on the species and the occurrence of the microorganisms to be controlled, and also depends on the composition of the material to be protected. Application concentrations are usually within the range of 0.001 to 5% by weight, preferably 0.05 to 1% by weight, based on the material to be protected. The following examples illustrate the invention: Biological examples: 1. Microtiter dish test - 1000, 500 and 250 ppm The active compound was dissolved in acetone. 1000 μl of a culture medium was placed in the wells of plates of microtiter and aliquots of the active compound stock solution were pipetted to provide the desired test concentration. The final concentration of acetone was 10%. The test microorganisms used were (bacterium) Citrobacter freundii, Escherchia [sic] coli, Proteus mirabilis, Pseidonomas [sic] aeruginosa and Staphylococcus aureus (yeast) Candida albicans and Saccharomyces cerevisiae, and (fungi) Alternarla alternata, Aspergillus niger and Penicillium funciculosum [sic] The inoculated dishes were incubated at a temperature of 23 ° C (yeast and fungi) or at 30 ° C (bacteria). The growth of the microorganisms was evaluated after 2 days (bacteria), 3 days (yeast) or 5 days (fungi): Test organism Concentration of active substance in ppm (s.a.) 000 500 250 Citrobacter freundii 0 0 0 0 5 Escherchia [sic] coli 0 0 0 0 H Proteus mirabilis 00 00 0 Pseidomonas [sic] Aeruginosa 00 00 0 Staphylococcus aureus HH HH H Candida albicans 0 0 H Saccharamoyces (sic) 0 0 H cerevisiae Alternating alternata, 0 0 0 Aspergillus niger 0 0 0 Penicillium funiculosum 0 0 0 Control 5 5 5 O = absence of growth H = inhibition of growth 5 = no action, growth as in the control. 2. Conservation test with inoculation in a polymer dispersion based on polyacrylate. In-depth tests were carried out on a polyacrylate-based polymer dispersion. The active compound was dissolved in acetone and mixed with the dispersion in concentrations of 500, 250 and 100 ppm of active substance. The dispersions were then inoculated ("stressed") with a mixture of microorganisms. The mixture contained the microorganisms mentioned in point 1. The experiments were incubated at a temperature of 23 ° C and inoculated again every 7 days. After 6 cycles, the microorganism content of the dispersion was determined. It was found that the polymer dispersion could be kept free of microorganisms through the use of an application concentration of 250 ppm of active substance.

Claims (1)

CLAIMS 1. The use of aminoisothiazoles of the formula I where R is hydrogen or alkyl (Ci-Ci) and X is halogen, N02, CN or SCN, and metal complexes and acid addition salts thereof as microbicides for the protection of industrial materials against attacks and destruction by microorganisms. 2. The use according to claim 1, wherein R is alkyl (C? ~ C4), and X is CN and SCN. 3. The use according to claim 1, wherein R is methyl. 4. The use according to claim 1, wherein X in formula I is thiocyanate. 5_. The use according to claim 1, wherein X / x employs 3-methyl-4-thiocyanato-5-aminoisothiazole (formula le) A method for the protection of industrial materials against attack and destruction by microorganisms, said method comprises the treatment of industrial materials with microbicidally active amounts of aminoisothiazoles of the formula I according to claim

1. The method according to the claim 6, wherein the microbicide employed is 3-methyl-4-thiocyanato-5-aminoisothiazole of the formula I according to claim 3 in microbicidally active amounts. A process for the preparation of microbicidal compositions, comprising the mixture of aminoisothiazoles of the formula I with an inert carrier material and, if appropriate, surfactant compounds.