AU749071B2 - Use of mixtures of polymers and aminonisothiazols as biocides - Google Patents

Description

0050/48325 Use of mixtures of polymers and aminoisothiazoles as biocide.

The invention relates to the use of mixtures of A) polymers containing in copolymerized form from 0.1 to 100 mol% of vinylamine or ethyleneimine units, from 0 to 99.9 mol% of units of at least one monomer from the group consisting of N-vinylcarboxamides of the formula I R1

CH

2 =CH N CO-- R 2 vinyl formate, vinyl acetate, vinyl propionate, vinyl alcohol, C 1 to C 6 alkyl vinyl ethers, monoethylenically unsaturated C 3 to C 8 carboxylic acids, their esters, nitriles, amides and anhydrides, N-vinylurea, N-vinylimidazoles and N-vinylimidazolines, and from 0 to 5 mol% of units of monomers having at least two ethylenically unsaturated double bonds, and B) aminoisothiazoles of the formula V 3 0 R

X

V

NS NH 2 where R is hydrogen or C 1

-C

4 alkyl and X is halogen, NO 2 CN and SCN, and their metal complexes and acid addition salts, as biocides.

Z. Chem., Volume 27, 1 (1987) discloses specifically functionalized polyvinyl alcohols, polyacrylates and polyethyleneimines for immobilizing antimicrobially active substances. The active substances are released in a controlled manner when such systems are employed. The antimicrobial activity 0050/48325 2 is based, however, according to the information in the publication, on the release of the biocidal active compounds.

SU-A-1 071 630 discloses that copolymers of diallyldimethylammonium chloride and sodium acrylate have a bacteriocidal activity. EP-A-0 331 528 discloses copolymers of ethylene and dialkylaminoacrylamides having biocidal activity.

Antimicrobially active polymers containing vinylphosphonium and vinylsulfonium groups were reported in J. Polym. Sci. Part A: Polym. Chem., Volume 31, 335, 1441, 1467 and 2873 (1993) and in Arch. Pharm. (Weinheim) 321, 89 (1988). Biocidally active copolymers of N-vinylpyrrolidone and vinylamines are known from Makromol. Chem., Suppl. Volume 9, 25 (1985).

Microbicidal properties of 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 benzothiophene derivatives (DE-A 44 11 912), and of mixtures of individual azole derivatives with ammonium compounds (EP-A 533 016), are known. The preparation of these compounds is in some cases very complex and, especially at low application rates, their action is not always satisfactory.

have already been described as coupling components in azo dyes (EP-A 362 708, EP-A 315 898). For (often N-acylated) 5-aminoisothiazoles, herbicidal (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), bacteriocidal and virucidal activity (L.

Kuczynski et. al., Pol. J. Pharmacol. Pharm. (1984), 36(5), 485-491), and their suitability as intermediates for drugs and crop protection agents, are likewise known.

It is an object of the present invention to provide new biocidal compositions.

We have found that this object is achieved in accordance with the invention by the use of the mixtures, defined at the outset, as biocides.

The polymers present as component A) in the mixtures to be used in accordance with the invention are known from the prior art; cf. EP-B-0 071 050 and EP-B-0 216 387. The polymers containing vinylamine units are obtainable, for example, by polymerizing mixtures which polymerized [sic] from 0.1 to 100 mol% of open-chain N-vinylcarboxamides of the above formula I, 0050/48325 3 from 0 to 99.9 mol% of at least one monomer from the group consisting of vinyl formate, vinyl acetate, vinyl propionate,

C

1 to C 6 alkyl vinyl ethers, monoethylenically unsaturated C 3 to C 8 carboxylic acids, their esters, nitriles, amides and anhydrides, N-vinylimidazoles and N-vinylimidazolines, and from 0 to 5 mol% of at least one monomer having at least two ethylenically unsaturated double bonds, and subsequently subjecting the group C- R2 II

(II),

O

where R 2 is as defined in formula I, to partial or complete elimination from the copolymerized monomers of the formula I.

Examples of open-chain N-vinylcarboxamides of the formula I are N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-methylpropionamide and N-vinylpropionamide. The open-chain vinylcarboxamides can be used alone or in a mixture for the polymerization. From this group of monomers it is preferred to use N-vinylformamide.

The polymers containing ethyleneimine units are polyethyleneimines which are obtainable by polymerizing ethyleneimine in the presence of acids, Lewis acids or acid-donating catalysts such as alkyl halides, e.g. methyl chloride, ethyl chloride, propyl chloride, methylene chloride, trichloromethane, carbon tetrachloride or tetrabromomethane. The polyethyleneimines have molecular masses Mw of from 300 to 1,000,000, for example. Also suitable are those polymers containing ethyleneimine units that are obtainable by grafting polyamidoamines with ethyleneimine or by grafting polymers of open-chain N-vinylcarboxamides of the formula I with ethyleneimine. Grafted polyamidoamines are known, for example, from US-A-4 144 123.

The polymers to be used in accordance with the invention contain as component from 0.1 to 100, preferably from 10 to 90 mol% of vinylamine or ethyleneimine units. Of the polymers containing 0050/48325 4 ethyleneimine units, it is preferred to use polyethyleneimine having molecular masses of from 500 to 500,000.

Polymers containing vinylamine units can be modified by copolymerizing the monomers of the formula I with other monomers.

The monomers in question include vinyl formate, vinyl acetate, vinyl propionate, C 1 to C 6 alkyl vinyl ethers, monoethylenically unsaturated C 3 to C 8 carboxylic acids, their esters, nitriles, amides and, where available, the anhydrides, N-vinylurea, N-vinylimidazoles and N-vinylimidazolines. Examples of said monomers of group are vinyl esters of saturated carboxylic acids having from 1 to 6 carbon atoms, such as vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate, monoethylenically unsaturated C 3 to C 8 carboxylic acids, such as acrylic acid, methacrylic acid, dimethylacrylic acid, ethacrylic acid, crotonic acid, vinylacetic acid, allylacetic acid, maleic acid, fumaric acid, citroconic acid and itaconic acid and also their esters, anhydrides, amides and nitriles. Examples of anhydrides used with preference are maleic anhydride, citraconic anhydride and itaconic anhydride.

Suitable esters, which are derived, for example, from alcohols having from 1 to 6 carbon atoms, are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, hexyl acrylate or glycols or polyalkylene glycols, in each case only one OH group of the glycols or polyglycols being esterified with a monoethylenically unsaturated carboxylic acid, examples being hydroxyethyl acrylate, hydroxy methacrylate [sic], hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate. Also suitable are acrylic monoesters and methacrylic monoesters of polyalkylene glycols with a molecular weight of up to 10,000, preferably from 1500 to 9000, and esters of the aforementioned carboxylic acids with amino alcohols, examples being dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methylacrylate, dimethylaminopropyl acrylate and dimethylaminopropyl methacrylate. Examples of suitable amides are acrylamide and methacrylamide. The basic acrylates can be used in the form of the free bases, of the salts with mineral acids or carboxylic acids, or else in quaternized form. Further suitable comonomers are acrylonitrile, methacrylonitrile, N-vinylimidazole and also substituted N-vinylimidazoles such as N-vinyl-2-methylimidazole and N-vinyl-2-ethylimidazole, N-vinylimidazoline and substituted N-vinylimidazolines, e.g.

N-vinyl-2-methylimidazoline. In addition to the aforementioned monomers it is also possible to use monomers containing sulfo 4 groups such as, for example, vinylsulfonic acid, allylsulfonic 0050/48325 acid, styrenesulfonic acid and 3-sulfopropyl acrylate, as other monoethylenically unsaturated monomers.

The polymers containing vinylamine units preferably contain from 1 to 99 mol% of vinylamine units and from 1 to 99 mol% of units of monomers from the group of open-chain N-vinylcarboxamides, vinyl formate, vinyl acetate, vinyl propionate, C 1 to C 6 alkyl vinyl ethers, N-vinylurea, acrylic acid, methacrylic acid, maleic acid and also the anhydrides, esters, nitriles and amides of the aforementioned carboxylic acids, N-vinylimidazoles, N-vinylimidazolines and/or vinyl alcohol units, the sum of and in mol% always being 100.

The polymers containing vinylamine units can be modified by using during the copolymerization monomer mixtures containing as comonomer up to 5 mol% of a compound having at least two ethylenically unsaturated double bonds in the molecule. In that case crosslinked copolymers are formed containing in copolymerized form up to 5 mol% of units of monomers having at least two ethylenically unsaturated double bonds in the molecule.

If crosslinkers are used during the copolymerization, the amount which is preferably used is from 0.05 to 2 mol%. The use of the monomers brings about an increase in the molecular weight of the copolymers. Examples of suitable compounds of this kind are methylenebisacrylamide, esters of acrylic acid or methacrylic acid with polyhydric alcohols, e.g. glycol dimethacrylate or glycerol trimethacrylate, and polyols, such as pentaerythritol and glucose, which are at least diesterified with acrylic acid or methacrylic acid. Suitable crosslinkers are, moreover, divinylethyleneurea, divinylbenzene, N,N'-divinylurea, divinyldioxane, pentaerythritol triallyl ether and pentaallylsucrose. From this group of compounds it is preferred to use water-soluble monomers, examples being glycol diacrylate or glycol diacrylates or glycol dimethacrylates of polyethylene glycols with a molecular weight of up to 3000.

The copolymers have K values of from 5 to 300, preferably from to 200; The K values are determined in accordance with H.

Fikentscher in 5% aqueous sodium chloride solution at a pH of 7, a temperature of 25 0 C and a polymer concentration of 0.5% by weight.

0050/48325 6 The polymers containing vinylamine units are prepared in accordance with known techniques by polymerizing open-chain N-vinylcarboxamides of the formula I with from 0 to 99.9 mol% of at least one monomer from the group consisting of vinyl formate, vinyl acetate, vinyl propionate,

C

1 to C 6 alkyl vinyl ethers, monoethylenically unsaturated C 3 to C 8 carboxylic acids, their esters, nitriles, amides and anhydrides, N-vinylimidazoles and N-vinylimidazolines and from 0 to 5 mol% of at least one monomer having at least two ethylenically unsaturated double bonds in the presence or else in the absence of inert solvents or diluents. The -CO-R 2 groups are subsequently eliminated in a polymer-analogous reaction to form vinylamine units. Since the polymerization in the absence of inert solvents or diluents generally results in nonuniform polymers, the polymerization in an inert solvent or diluent is preferred. Examples of suitable such inert diluents are those in which the open-chain N-vinylcarboxamides are soluble. Solvents suitable for the solution polymerization are, for example, inert solvents such as methanol, ethanol, isopropanol, n-propanol, n-butanol, sec-butanol, tetrahydrofuran, dioxane, water and also mixtures of said inert solvents. The polymerization can be conducted continuously or batchwise. It takes place in the presence of polymerization initiators which form free radicals and which are used, for example, in amounts of from 0.01 to 20, preferably from 0.05 to 10% by weight, based on the monomers. The polymerization can be initiated solely, if desired, by the action of high-energy radiation, e.g. electron beams or UV rays.

In order to prepare polymers having a low K value, for example from 5 to 50, preferably from 10 to 30, the polymerization is judiciously conducted in the presence of regulators. Examples of suitable regulators are organic compounds containing sulfur in bonded form. These include, for example, mercapto compounds, such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, butyl mercaptan and dodecyl mercaptan. Further suitable regulators are allyl compounds, such as allyl alcohol, aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formate, propionic acid, hydrazine sulfate and butenols. If the polymerization is conducted in the presence of regulators, the amount thereof 0050/48325 7 required is from 0.05 to 20% by weight, based on the monomers used in the polymerization.

The polymerization of the monomers takes place usually in an inert gas atmosphere with exclusion of atmospheric oxygen. During the polymerization, measures are generally taken to ensure thorough mixing of the reactants. In the case of relatively small batches, in which safe dissipation of the heat of polymerization is ensured, the monomers can be copolymerized batchwise by heating the reaction mixture to the polymerization temperature and then leaving the reaction to proceed. These temperatures are in this case in the range from 40 to 1800C, it being possible to operate under atmospheric pressure, reduced pressure or else increased pressure. Polymers having a high molecular weight are obtained if the polymerization is conducted in water. This can take place, for example, for the preparation of water-soluble polymers in aqueous solution, as a water-in-oil emulsion or in accordance with the technique of inverted suspension polymerization.

In order to prevent saponification of the monomeric N-vinylcarboxamides during the polymerization in aqueous solution, the polymerization is preferably conducted in a pH range from 4 to 9, in particular from 5 to 8. In many cases it is advisable to operate additionally in the presence of buffers as well; for example, to add primary or :secondary sodium phosphate to the aqueous phase.

The elimination of groups of the formula C- -R 2 II

(II),

0 from the monomer units of the formula III in the polymers described above, to form amine and/or ammonium groups, gives the polymers which contain vinylamine units and are to be used in accordance with the invention: 0050/48325 8 CH2CH CH 2 CH I hydrolysis N N

R

1

C--R

2

R

1

H

0 (III) (IV) The substituents R 1 and R 2 in the formulae (II) to (IV) are each as defined for formula I.

The hydrolysis is preferably conducted in the presence of water under the action of acids, bases or enzymes, but can also take place in the absence of acids, bases or enzymes. Depending on the reaction conditions during the hydrolysis, i.e. the amount of acid or base, based on the polymer to be hydrolyzed, and the reaction temperature during the hydrolysis, different degrees of hydrolysis are obtained. The hydrolysis is carried on such that from 0.1 to 100 mol%, preferably from 1 to 99 mol%, of the copolymerized monomer units III are eliminated from the polymer.

Particular preference is given to the use in accordance with the invention of those polymers which contain from 1 to 99 mol% of vinylamine units and from 1 to 99 mol% of units of the formula III, preferably N-vinylformamide units, the sum of the amounts in mol% always being 100.

Examples of acids which are suitable for the hydrolysis are mineral acids, such as hydrogen halide (gaseous or in aqueous solution), sulfuric acid, nitric acid, phosphoric acid (ortho-, meta- or polyphosphoric acid) and organic acids, for example C1 to carboxylic acids, such as formic acid, acetic acid and propionic acid, or the aliphatic or aromatic sulfonic acids, such as methanesulfonic acid, benzenesulfonic acid or toluenesulfonic acid. For the hydrolysis it is preferred to use hydrochloric acid or sulfuric acid. In the case of hydrolysis with acids the pH is from 0 to 5. For each formyl group equivalent in the polymer the amount of acid required is, for example, from 0.05 to equivalents, preferably from 0.4 to 1.2.

In the case of hydrolysis with bases it is possible to use metal hydroxides of metals from the first and second main groups of the Periodic Table; suitable examples are lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide. Likewise, however, it is also possible to use ammonia and alkyl derivatives of ammonia, for example alkylamines or arylamines e.g. triethylamine, 0050/48325 i- 9 monoethanolamine, diethanolamine, triethanolamine, morpholine or aniline. In the case of hydrolysis with bases the pH is from 8 to 14. The bases can be used in solid, liquid or else, if desired, in gaseous state and in diluted or undiluted form. Bases preferably used for the hydrolysis are ammonia, sodium hydroxide solution or potassium hydroxide solution. The hydrolysis in the acidic or in the alkaline pH range takes place, for example, at temperatures from 30 to 1700C, preferably from 50 to 1200C. It is over after about 2 to 8 hours, preferably 3 to 5 hours. A procedure which has proven particularly suitable is that in which, for the hydrolysis, the bases or acids are added in aqueous solution. Following the hydrolysis, a neutralization is generally conducted, so that the pH of the hydrolyzed polymer solution is from 2 to 8, preferably from 3 to 7. Neutralization is required when a continuation of the hydrolysis of partly hydrolyzed polymers is to be prevented or delayed. The hydrolysis can also be performed with the aid of enzymes.

In the case of the hydrolysis of copolymers of open-chain N-vinylcarboxamides of the formula I and at least one of the abovementioned suitable comonomers, a further modification of the polymers may occur as a result of the fact that the copolymerized comonomers are likewise hydrolyzed. For example, vinyl alcohol units are formed from copolymerized units of vinyl esters.

Depending on the hydrolysis conditions, the copolymerized vinyl esters can be fully or partly hydrolyzed. In the case of a partial hydrolysis of copolymers containing vinyl acetate units in copolymerized form, the hydrolyzed copolymer lapses [sic] not only unchanged vinyl acetate units but also vinyl alcohol units and also units of the formulae III and IV. From units of monoethylenically unsaturated carboxylic anhydrides, carboxylic acid units are formed in the course of the hydrolysis.

Copolymerized monoethylenically unsaturated carboxylic acids are chemically unaltered during the hydrolysis. In contrast, ester and amide units are saponified to carboxylic acid units.

Copolymerized monoethylenically unsaturated nitriles give rise, for example, to units of amides or carboxylic acids. From copolymerized N-vinylurea it is likewise possible for vinylamine units to be formed. The degree of hydrolysis of the copolymerized monomers can easily be determined analytically.

It is preferred to use polymers containing in copolymerized form vinylamine units and 0050/48325 N-vinylformamide, vinyl formate, vinyl acetate, vinyl propionate, vinyl alcohol and/or N-vinylurea units.

Polymers to be used with preference contain from 0.1 to 100 mol% of vinylamine units or ethyleneimine units and from 0 to 99.9 mol% of N-vinylformamide units.

These polymers are either partly or fully hydrolyzed homopolymers of vinylformamide or are polyethyleneimines.

The partly hydrolyzed homopolymers of N-vinylformamide contain in copolymerized form preferably from 1 to 99 mol% of vinylamine units and from 1 to 99 mol% of N-vinylformamide units and have a K value of from 5 to 300 (determined in accordance with H. Fikentscher in 0.1% strength by weight aqueous sodium chloride solution at 25 0 C and a polymer concentration of 0.5% by weight). Particular preference is given to the use of those hydrolyzed homopolymers of N-vinylformamide which contain in copolymerized form from 10 to 90 mol% of vinylamine units and from 10 to 90 mol% of N-vinylformamide units and have a K value of from 10 to 120 (determined in accordance with H. Fikentscher in 0.1% strength sodium chloride solution at 0 C and a polymer concentration of 0.5% by weight). The sum of and in mol% is always 100.

The compounds B which are suitable for use in accordance with the invention are obtained with a reaction sequence which is known per se from EP-A-640 597 and in which isothiazoles of the general formula VI 0050/48325 11 R R Hal R X CN- SCN- S NH 2 N NH 2 N NH 2 S S S VI Va Vb are converted by means of a halogenating agent into the halogen compound Va, in which Hal is F, Cl, Br or I, which if required is then converted by reaction with thiocyanates or cyanides into the compound Vb, where X' is SCN or CN. The preparation of isothiazoles of the general formula VI is described, for example, in DE-A 17 70 819. The preparation of has been described by A. Adams et. al. in J. Chem. Soc. 1959, p.

3061.

The mixtures to be used in accordance with the invention have a strong microbicidal action and can therefore be used to control unwanted microorganisms. The mixtures and the formulations prepared from them are intended by chemical means to destroy or deter harmful organisms or to render them harmless, prevent damage caused by them, or otherwise control them.

The mixtures and formulations thereof to be used in accordance with the invention prevent the microbial infestation of industrial materials, i.e. they can be used for in-can preservation. They are also suitable for the biocidal treatment of products, i.e. they can be used for film preservation.

By industrial materials are meant nonliving materials as obtained in industrial/technical processes. Examples of industrial materials which the use in accordance with the invention of the mixtures or formulations is intended to protect against microbial alteration or destruction are: finishes, drilling oils, dispersions, adhesives, sizes, pigment preparations, paper, textiles, textile auxiliaries, leather, leather auxiliaries, wood, coating compositions, antifouling paints, articles of plastic, cosmetics, laundry detergents, cleaners, cooling lubricants, hydraulic fluids, joint sealing compounds, window putties, thickener solutions and other materials which can be infested or degraded by microorganisms.

It is likewise possible to use the mixtures or formulations in water treatment. By water treatment is meant the addition of the polymers or formulations to process water for the purpose, for example, of controlling slime in the papermaking industry or for 0050/48325 12 controlling harmful organisms in the sugar industry. They prevent or check the growth of microorganisms in cooling circuits, air humidifiers, or in drilling and conveying liquids in the petroleum industry.

The mixtures and formulations thereof can likewise be used in disinfection.

As microorganisms which can cause degradation or alteration of industrial materials, mention may be made, by way of example, of bacteria, viruses, spores, yeasts, fungi, algae and slime organisms. The polymers to be used in accordance with the invention, or formulations thereof, preferably act against bacteria, yeasts and fungi.

As microorganisms mention may be made, for example, of the following genera [sic]: Staphylococcus aureus Escherichia coli Proteus mirabilis Citrobacter freudii Pseudomonas aeruginosa Candida albicans Saccheromyces cerevisiae [sic] Alternaria alternata Aspergillus niger Penicillium funiculosum Depending on their chemical and physical properties, the mixtures to be used in accordance with the invention can be converted into customary formulations and preparations, such as, for example, emulsions, suspensions, dispersions, solutions, powders, pastes or in combination with carrier materials. Added to the formulations and preparations for this purpose are, if desired, surface-active substances anionic surfactants such as alkylsulfonates, ether sulfates; nonionic surfactants such as fatty alcohol ethoxylates, fatty alcohol ester ethoxylates, sorbitan esters, polyalkylene glycols; amphoteric surfactants), complexing agents ethylenediaminetetraacetic acid, nitrilotriacetic acid, methylglycinediacetic acid, solubilizers alcohols such as ethanol, n-propanol, i-propanol, or glycols, e.g. propylene glycol, polypropylene glycol), acids or bases phosphoric acid, sodium hydroxide solution), inorganic salts and/or further additives (such as, for example, corrosion inhibitors, foam suppressants, guiding substances [sic], dyes).

0050/48325 13 Processes for preparing such biocidally active formulations are known to the skilled worker and are described in the relevant literature.

The activity and the spectrum of action of the polymers to be used in accordance with the invention or of the compositions or formulations preparable from them can be increased by adding, if desired, further microbicidally active compounds such as fungicides, bactericides and/or herbicides, insecticides and/or other active compounds for broadening the spectrum of action or for obtaining particular effects. In many cases, synergistic effects are obtained, i.e. the spectrum of action of the mixture exceeds the action of the individual components. Such compounds are known per se to the skilled worker and are described in the literature.

The mixing ratio of the components A and B in the mixtures or formulations to be used in accordance with the invention is not critical per se and can be chosen within a wide range. The mixing ratio (weight ratio) generally lies within the range from 1:1000 to 1000:1, preferably from 1:100 to 100:1 and, with particular preference, in the range from 20:80 to 80:20.

The K values of the polymers A were determined in accordance with H. Fikentscher, Cellulose-Chemie, Volume 13, 58 to 64 and 71 to 74 (1932) in 5% strength by weight aqueous sodium chloride solution at 25 0 C and a pH of 7 and a polymer concentration of by weight.

Microbicidal and microbistatic properties are determined experimentally. Highly suitable test methods have been described in detail for the testing of disinfectants by the Deutsche Gesellschaft fur Hygiene und Mikrobiologie (German Society for Hygiene and Microbiology, DGHM).

Tube dilution tests were- carried out in accordance with the "Guidelines for the Testing and Evaluation of Chemical Disinfection Procedures (status 01.01.81, procedures slightly modified)" using casein peptone-soybean flour peptone medium.

Dilution was carried out using water of standardized hardness without further auxiliaries such as surfactants, for example. The adjustment of the pH to 7.2 0.2 was made with 0.1 mol/l NaOH or 0.1 mol/l HC1. The grading of the test concentrations was made in accordance with the concentration stages proposed by the DGHM.

Evaluation was carried out after incubation at 36 0 C for 72 hours.

EDITORIAL NOTE FOR 97414/98 THE FOLLOWING CLAIM PAGES ARE NUMBERED 1-3

Claims (8)

1. The use of mixtures of A) polymers containing in copolymerized form from 0.1 to 100 mol% of vinylamine or ethyleneimine units, from 0 to 99.9 mol% of units of at least one monomer from the group consisting of N-vinylcarboxamides of the formula CH 2 ==CH N where R 1 R 2 H or C 1 to C 6 alkyl, vinyl formate, vinyl acetate, vinyl propionate, vinyl alcohol, C 1 to C 6 alkyl vinyl ethers, monoethylenically unsaturated C 3 to C 8 carboxylic acids, their esters, nitriles, amides and anhydrides, N-vinylurea, N-vinylimidazoles and N-vinylimidazolines, and from 0 to 5 mol% of units of monomers having at least two ethylenically unsaturated double bonds, the and B) sum of and in mol% always being 100, aminoisothiazoles of the formula V R X NS NH 2 s2 where R is hydrogen or C 1 -C 4 alkyl and X is halogen, NO 2 CN and SCN, and their metal complexes and acid addition salts, as biocides. 0050/48325 2

2. The use as claimed in claim 1, wherein use is made as component A) of polymers containing in copolymerized form vinylamine units, N-vinylformamide, vinyl formate, vinyl acetate, vinyl propionate, vinyl alcohol and/or N-vinylurea units.

3. The use as claimed in claim 1 or 2, wherein use is made as component A) of polymers containing in copolymerized form from 0.1 to 100 mol% of vinylamine units or ethyleneimine units and from 0 to 99.9 mol% of N-vinylformamide units, the sum of and in mol% always being 100.

4. The use as claimed in one of claims 1 to 3, wherein use is made as component A of polymers containing in copolymerized form from 1 to 99 mol% of vinylamine units and from 1 to 99 mol% of N-vinylformamide units, the sum of and in mol% always being 100 and the polymers having a K value of from 5 to 300 (determined in accordance with H. Fikentscher in 5% strength by weight aqueous sodium chloride solution at 25 0 C and a polymer concentration of 0.5% by weight). The use as claimed in one of claims 1 to 3, wherein use is made as component A of polymers containing in copolymerized form from 10 to 90 mol% of vinylamine units and from 10 to 90 mol% of N-vinylformamide units, the sum of and in mol% always being 100 and the polymers having a K value of from 10 to 120 (determined in accordance with H. Fikentscher in 5% strength by weight aqueous sodium chloride solution at 25 0 C and a polymer concentration of 0.5% by weight). 0050/48325 3

6. The use as claimed in one of claims 1 to 5, wherein use is made as component B of aminoisothiazoles in which R is C 1 -C 4 alkyl and X is CN and SCN.

7. The use as claimed in one of claims 1 to 5, wherein use is made as component B of aminoisothiazoles in which R is methyl.

8. The use as claimed in one of claims 1 to 5, wherein use is made as component B of aminoisothiazoles in which X is SCN.

9. The use as claimed in one of claims 1 to 5, wherein use is made as component B of 3-methyl-4-thiocyanato-5-aminoiso- thiazole (formula Ic).