WO1999012423A1

WO1999012423A1 - Use of mixtures of polymers and aminonisothiazols as biocides

Info

Publication number: WO1999012423A1
Application number: PCT/EP1998/005619
Authority: WO
Inventors: Jürgen Tropsch; Dieter Zeller
Original assignee: Basf Aktiengesellschaft
Priority date: 1997-09-08
Filing date: 1998-09-05
Publication date: 1999-03-18
Also published as: AU749071B2; JP2001515847A; NZ502662A; PL339260A1; NO20001176L; HUP0004934A2; CA2303189A1; HUP0004934A3; BR9812042A; EP1014793A1; NO20001176D0; AU9741498A

Abstract

The invention relates to the use of mixtures of (A) polymers and aminoisothiazols (B) in addition to the metal complexes and acid additive salts thereof as biocides. Said polymers (A) contain the following constituents integrated by means of polymerisation: (a) 0.1 - 100 mol % vinyl amine units or ethylene imine units, (b) 0-99.9 mol % units of at least one monomer from the group consisting of N vinyl carboxylic acid amides of formula (I), wherein R?1, R2=H or C1-C6¿ alkyl, vinyl formiate, vinyl acetate, vinyl propionate, vinyl alcohol, C1-C6 alkyl vinyl ether, monoethylenically unsaturated C3-C8 carboxylic acids, their esters, nitriles, amides and anhydrides, N vinylurea, N vinylimidazoles and N vinylimidazolines and (c) 0-5 mol % units of monomers with at least two ethylenically unsaturated double-bonds, wherein the sum of (a) and (b) and (c) amounts to 100 mol %, and (B) aminoisothiazols of formula (V) wherein R represents hydrogen or C¿1?-C4 alkyl and X stands for halogen, NO2, CN and SCN.

Description

Use of mixtures of polymers and aminoisothiazoles as a biocide.

description

The invention relates to the use of mixtures of

A) polymers that

(a) 0.1 to 100 mol% of vinylamine or ethyleneimine units,

(b) 0 to 99.9 mol% of units of at least one monomer from the group consisting of N-vinylcarboxamides of the formula I.

R ^l

CH ₂ = CH N (I),

^' CO- R2

Vinyl formate, vinyl acetate, vinyl propionate, vinyl alcohol, Cj _. - to C _ß- alkyl vinyl ether, monoethylenically unsaturated C ₃ - to C ₈ ^_ carboxylic acids, their esters, nitriles, amides and anhydrides, N-vinylurea, N-vinylimidazoles and N-vinylimidazolines and

(c) 0 to 5 mol% of units of monomers with at least two ethylenically unsaturated double bonds,

contain polymerized,

and

B) aminoisothiazoles of the formula V

in the

R is hydrogen or Cχ-C ₄ alkyl and X is halogen, N0 ₂ , CN and SCN, and their metal complexes and acid addition salts, as biocides. From Z. Chem., Volume 27, 1 (1987), specially functionalized polyvinyl alcohols, polyacrylates and polyethyleneimines for immobilizing antimicrobial substances are known. The active ingredients are released in a controlled manner when using such systems. However, according to the information in the publication, the antimicrobial effectiveness is based on the release of the biocidal active ingredients.

From SU-A-1 071 630 it is known that copolymers of diallyldimethylammonium chloride and sodium acrylate have a bactericidal activity. EP-A-0 331 528 discloses copolymers of ethylene and dialkylaminoalkylacrylamides with biocidal activity. Antimicrobial polymers containing vinylphosphonium and vinylsulfonium groups have been described in J. Poly. Be. Part A: Polym. Chem., Vol. 31, 335, 1441, 1467 and 2873 (1993) and Arch. Pharm. (Weinheim) 321, 89 (1988). Biocidally active copolymers of N-vinylpyrrolidone and vinylamines are made of macromol. Chem., Suppl. Volume 9, 25 (1985) known.

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), as well as mixtures of individual azole derivatives with ammonium compounds (EP- A 533 016) are known. The preparation of these compounds is sometimes very complex and their effect is not always satisfactory, especially when the application rates are low.

5-Aminoisothiazoles 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) is bactericidal and virucidal activity (L. Kuczynski et. Al., Pol. J. Pharmacol. Pharm. (1984), 36 (5), 485-491), and their suitability as intermediates for pharmaceuticals and crop protection agents are also known.

The present invention has for its object to provide new biocidal agents.

The object is achieved according to the invention with the use of the mixtures defined at the outset as biocides.

The polymers contained as component A) in the mixtures to be used according to the invention are known from the prior art, cf. EP-B-0 071 050 and EP-B-0 216 387. The vinylamine 3

Polymers containing units can be obtained, for example, by polymerizing mixtures which

(a) 0.1 to 100 mol% of open-chain N-vinylcarboxamides of the formula I given above,

(b) 0 to 99.9 mol% of at least one monomer from the group consisting of vinyl formate, vinyl acetate, vinyl propionate, Ci to C ₆ alkyl vinyl ether, monoethylenically unsaturated C ₃ to C ₆ carboxylic acids, their esters, nitriles, amides and anhydrides, N-vinylimidazoles and N-vinylimidazolines and

(c) 0 to 5 mol% of at least one monomer with at least two ethylenically unsaturated double bonds,

polymerized and then the group

C R2

(II)

0

in which R ^{2 has} the meaning given in formula I,

partially or completely split off from the copolymerized monomers of the formula I.

Open-chain N-vinylcarboxamides of the formula I are, for example, N-vinylformamide, N-vinyl -N-methylfor amide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl -N-ethylacetamide, N-vinyl-N-Me- thylpropionamide and N-vinylpropionamide. The open-chain vinyl carboxamides can be used alone or as a mixture in the polymerization. From this group of monomers, preference is given to using N-vinylformamide.

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

The polymers to be used according to the invention contain 0.1 to 100, preferably 10 to 90 mol% of vinyl amine or ethyleneimine units as component (a). Of the polymers containing ethyleneimine units, preference is given to using polyethylene having molecular weights of from 500 to 500,000.

Polymers containing vinylamine units can be modified by copolymerizing the monomers of the formula I with other monomers during the preparation. The monomers in question include vinyl formate, vinyl acetate, vinyl propionate, C_ to Cς alkyl vinyl ethers, monoethylenically unsaturated C ₃ to Cs carboxylic acids, their esters, nitriles, amides and, if available, also the anhydrides, N-vinyl urea, N -Vinyl - imidazole and N-vinylimidazolines. Examples of the monomers of group (b) mentioned are vinyl esters of saturated carboxylic acids having 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, dimethyl-acrylic acid, ethacrylic acid, crotonic acid, vinyl acetic acid, allyl acetic acid, maleic acid, fumaric acid, citraconic acid and itaconic acid and their esters, anhydrides, amides and nitriles. Anhydrides which are preferably used are, for example, maleic anhydride, citraconic anhydride and itaconic anhydride.

Suitable esters, which are derived, for example, from alcohols having 1 to 6 carbon atoms, are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, hexyl acrylate or glycols or polyalkylene glycols, where in each case only one OH group of the glycols or polyglycols with a monoethylenically unsaturated carboxylic acid is esterified, for example hydroxyethyl acrylate, hydroxymethacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate. In addition, acrylic acid monoesters and methacrylic acid monoesters of polyalkylene glycols with a molecular weight of up to 10,000, preferably 1,500 to 9,000, and esters of the carboxylic acids mentioned with amino alcohols, for example dimethylaminoethyl acrylate, dirnethylaminoethyl methacrylate, diethylaminoethylacrylate, diethylaminoethyl methylacrylacrylate, dimethylaminopropylate, dimethylaminopropylate, dimethylaminopropylate, Suitable amides are, for example, acrylamide and methacrylamide. The basic acrylates can be used in the form of the free bases, the salts with mineral acids or carboxylic acids or in quaternized form. Also suitable as comonomers are acrylonitrile, methacrylonitrile, N-vinylimidazole and substituted N-vinylimidazoles such as N-vinyl-2-methylimidazole and N-vinyl-2-ethylimidazole, N-vinylimidazoline and substituted N-vinylimidazolines, for example N-vinyl-2-methylimidazoline. In addition to the monomers mentioned, monomers containing sulfo groups, such as, for example, vinylsulfonic acid, allylsulfonic acid, styrene sulfonic acid and 3-sulfopropyl acrylate, can also be used as other monoethylenically unsaturated monomers.

The polymers containing vinylamine units preferably contain

(a) 1 to 99 mol% vinylamine units and

(b) 1 to 99 mol% units of monomers from the group of open-chain N-vinylcarboxamides, vinyl formate, vinyl acetate, vinyl propionate, C] _- to Cς alkyl vinyl ether, N-vinyl urea, acrylic acid, methacrylic acid, maleic acid and the anhydrides , Esters, nitriles and amides of the carboxylic acids mentioned, N-vinylimidazoles, N-vinylimidazolines and / or vinyl alcohol units, the sum of (a), (b) and (c) in mol% always being 100 .

The polymers containing vinylamine units can also be modified to the extent that monomer mixtures are used in the copolymerization which, as comonomer (c), contain up to 5 mol of a compound having at least two ethylenically unsaturated double bonds in the molecule. Crosslinked copolymers are then formed which contain up to 5 mol% units of monomers with at least two ethylenically unsaturated double bonds polymerized in the molecule. If crosslinkers are used in the copolymerization, the amount preferably used is 0.05 to 2 mol%. The use of the monomers (c) also increases the molecular weight of the copolymers. Suitable compounds of this type are, for example, methylene-bis -acryl amide, esters of acrylic acid or methacrylic acid with polyhydric alcohols, for example glycol dimethacrylate or glycerol trimethacrylate, and polyols esterified at least twice with acrylic acid or methacrylic acid, such as pentaerythritol and glucose. Suitable crosslinkers are also divinylethyleneurea, divinylbenzene, N, N'-divinylurea, divinyldioxane, pentaerythritol triallyl ether and pentaallylsucrose. From this group of compounds, preference is given to using water-soluble monomers, for example glycol diacrylate or glycol diacrylates or glycol dimethacrylates of polyethylene glycols having a molecular weight of up to 3000. The copolymers have K values of 5 to 300, preferably 10 to 200. The K values are determined according to H. Fikentscher in 5% aqueous saline solution at pH 7, a temperature of 25 ° C. and a polymer concentration of 0.5% .-%. 5

The polymers containing vinylamine units are prepared by known processes by polymerizing open-chain N-vinylcarboxamides of the formula I.

10 (b) 0 to 99.9 mol% of at least one monomer from the group consisting of vinyl formate, vinyl acetate, vinyl propionate, Ci to C _δ alkyl vinyl ether, monoethylenically unsaturated C ₃ to C 8 carboxylic acids, their esters, nitriles, Amides and anhydrides, N-vinylimidazoles and N-vinylimidazolines and

15

(c) 0 to 5 mol% of at least one monomer with at least two ethylenically unsaturated double bonds

in the presence or absence of inert dissolving or

20 diluents prepared. The -CO-R ² groups are then split off in a polymer-analog reaction to form vinylamine units. Since the polymerization in the absence of inert solvents or diluents usually leads to non-uniform polymers, the polymerization is inert

25 solvents or diluents preferred. For example, inert diluents in which the open-chain N-vinylcarboxamides are soluble are suitable. For example, inert solvents such as methanol, ethanol, isopropanol, n-propanol, n-butanol, sec-

30 butanol, tetrahydrofuran, dioxane, water and mixtures of the inert solvents mentioned. The polymerization can be carried out continuously or batchwise. It takes place in the presence of radical-forming polymerization initiators, for example in amounts from 0.01 to 20, preferably 0.05 to

35 10% by weight, based on the monomers, can be used. The polymerization can optionally be carried out solely by exposure to high-energy radiation, e.g. Electron beams or UV rays are initiated.

40 To low K polymers, e.g. from 5 to 50, preferably 10 to 30, the polymerization is advantageously carried out in the presence of regulators. Suitable regulators are, for example, organic compounds containing sulfur in bound form. These include, for example

45 mercapto compounds, such as mercaptoethanol, mercaptopropanol,

Mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, butyl mercaptan and dodecyl mercaptan. Also suitable as controllers 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 carried out in the presence of regulators, 0.05 to 20% by weight, based on the monomers used in the polymerization, are required.

The monomers are usually polymerized in an inert gas atmosphere with the exclusion of atmospheric oxygen. Good mixing of the reactants is generally ensured during the polymerization. In the case of smaller batches in which a reliable removal of the heat of polymerization is ensured, the monomers can be copolymerized discontinuously by heating the reaction mixture to the polymerization temperature and then allowing the reaction to proceed. These temperatures are in the range from 40 to 180 ° C., it being possible to work under normal pressure, reduced or else elevated pressure. Polymers with a high molecular weight are obtained if the polymerization is carried out in water. This can, for example, for the production of water-soluble polymers in aqueous solution, as a water-in-oil emulsion or after Ver ^¬ go done the reverse suspension.

In order to avoid saponification of the monomeric N-vinylcarboxamides during the polymerization in aqueous solution, the polymerization is preferably carried out in a pH range from 4 to 9, in particular from 5 to 8. In many cases it is advisable to work in the presence of buffers, e.g. add primary or secondary sodium phosphate to the aqueous phase.

The polymers described above are obtained by splitting off groups of the formula

C R2

II ^{(II) <}

0

from the monomer units of the formula III to form amine or ammonium groups, the polymers containing vinyl amine units to be used according to the invention: CH ₂ CH CH ₂ CH -

'Hydrolysis'

N _► N

/ \ / \ Rl C R2 Rl H

0 (III) (IV) The substituents R ¹ and R ² in the formulas (II) to (IV) each have the meaning given in formula I.

The hydrolysis is preferably carried out in the presence of water under the action of acids, bases or enzymes, but can also be carried out in the absence of acids, bases or enzymes. Depending on the reaction conditions in the hydrolysis, i.e. the amount of acid or base, based on the polymer to be hydrolyzed, and the reaction temperature during the hydrolysis give different degrees of hydrolysis. The hydrolysis is carried out to such an extent that 0.1 to 100 mol%, preferably 1 to 99 mol%, of the copolymerized monomer units III are eliminated from the polymer. Those polymers which contain 1 to 99 mol% of vinylamine units and 1 to 99 mol% of units of the formula III, preferably N-vinylformamide units, are particularly preferably used according to the invention, the sum in mol% always being 100 .

Acids suitable for the hydrolysis are, for example, 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 C 1 -C ₅ -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. Hydrochloric acid or sulfuric acid is preferably used for the hydrolysis. In the hydrolysis with acids, the pH is 0 to 5. For each formyl group equivalent in the polymer, 0.05 to 1.5 equivalents of acid, preferably 0.4 to 1.2 equivalents, are required.

In the hydrolysis with bases, metal hydroxides of metals of the first and second main group of the periodic system can be used, for example lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide are suitable. However, ammonia and alkyl derivatives of ammonia can also be used, for example alkyl- or arylamines, for example triethylamine, monoethanolamine, diethanolamine, tri- ethanolamine, morpholine or aniline. In the case of hydrolysis with bases, the pH is 8 to 14. The bases can be used in solid, liquid or, if appropriate, also in the gaseous state, diluted or undiluted. Ammonia, sodium hydroxide solution or potassium hydroxide solution are preferably used as bases for the hydrolysis. The hydrolysis in the acidic or in the alkaline pH range takes place, for example, at temperatures from 30 to 170, preferably 50 to 120 ° C. It is complete after about 2 to 8, preferably 3 to 5 hours. A method in which the bases or acids are added in aqueous solution for hydrolysis has proven particularly useful. After the hydrolysis, a neutralization is generally carried out, so that the pH of the hydrolyzed polymer solution is 2 to 8, preferably 3 to 7. Neutralization is necessary if the progress of the hydrolysis of partially hydrolyzed polymers is to be avoided or delayed. The hydrolysis can also be carried out with the aid of enzymes.

In the hydrolysis of copolymers of open-chain N-vinyl-carboxamides of the formula I and at least one of the comonomers mentioned above, a further modification of the polymers optionally occurs in that the copolymerized comonomers are also hydrolyzed. For example, vinyl alcohol units are formed from polymerized units of vinyl esters. Depending on the hydrolysis conditions, the polymerized vinyl esters can be completely or partially hydrolyzed. In the case of partial hydrolysis of copolymers containing copolymerized units of vinyl acetate, the hydrolyzed copolymer, in addition to unchanged vinyl acetate units, does not include vinyl alcohol units and units of the formulas III and IV. Units of monoethylenically unsaturated carboxylic acid anhydrides form carboxylic acid units in the hydrolysis. Polymerized monoethylenically unsaturated carboxylic acids are not chemically changed during the hydrolysis. In contrast, ester and amide units saponify

Carboxylic acid units. Units of amides or carboxylic acids, for example, are formed from polymerized monoethylenically unsaturated nitriles. Polymerized N-vinylurea can also be used to form vinylamine units. The degree of hydrolysis of the copolymerized comonomers can easily be determined analytically.

Polymers which are preferably used

(a) vinylamine units and (b) N-vinyl formamide, vinyl formate, vinyl acetate, vinyl propionate, vinyl alcohol and / or N-vinyl urea units

polymerized included. Polymeric seeds to be used preferably

(a) 0.1 to 100 mol% of vinylamine units or ethyleneimine units and

10 (b) 0 to 99.9 mol% of N-vinylformamide units.

These polymers are either partially or completely hydrolyzed homopolymers of vinylformamide or polyethyleneimines.

15

The partially hydrolyzed homopolymers of N-vinylformamide preferably contain

(a) 1 to 99 mol% vinylamine units and

20th

(b) 1 to 99 mol% of N-vinylformamide units

polymerized in and have a K value of 5 to 300 (determined according to H. Fikentscher in 0.1% by weight aqueous sodium chloride solution at 25 25 ° C. and a polymer concentration of 0.5% by weight). Such hydrolyzed homopolymers of N-vinylformamide are particularly preferably used:

(a) 10 to 90 mol% vinylamine units and 30

(b) 10 to 90 mol% of N-vinylformamide units

contain in copolymerized form and have a K value of 10 to 120 (determined according to H. Fikentscher in 0.1% sodium chloride solution at 25 ° C. 35 and a polymer concentration of 0.5% by weight). The sum of (a) and (b) in mol% is always 100.

The compounds B suitable for the use according to the invention are obtained with a reaction sequence known per se from EP-A-640 597, in which isothiazoles of the general formula VI,

45

VI a Vb

by means of a halogenating agent into the halogen compound Va, where Hai stands for F, CI, Br, or J, which is then converted, if necessary, into the compound Vb, where X 'is SCN or CN, by reaction with rhodanides or cyanides . The preparation of isothiazoles of the general formula VI is described, for example, in DE-OS 17 70 819. The production of 3-methyl-5-aminoisothiazole was carried out by A. Adams et. al. in J. Chem. Soc. 1959, p. 3061.

The mixtures to be used according to the invention have a strong microbicidal action and can therefore be used to control unwanted microorganisms. The mixtures and the formulations prepared therefrom are intended to destroy harmful organisms by chemical means, to deter them, to render them harmless, to prevent them from being damaged or to combat them in some other way.

The mixtures or their formulations to be used according to the invention prevent the microbial attack on technical materials, i.e. they can be used for in-can preservation. They are also used for the biocidal finishing of products, i.e. they can be used for film preservation.

Technical materials are to be understood as non-living materials as they occur in technical / industrial processes. Technical materials that are to be protected from microbial change or destruction by the use of the mixtures or formulations according to the invention are, for example:

Finishes, drilling oils, dispersions, adhesives, glues, pigment to ^¬ preparations, paper, textiles, textile auxiliaries, leather, leather auxiliaries, wood, paints, antifouling paints, plastics - articles, cosmetics, detergents and cleaners, coolants, hydraulic fluids, joint sealing compounds, window putty , Thickener solutions and other materials that can be attacked or decomposed by microorganisms. The mixtures or formulations can also be used in water treatment. Water treatment is understood to mean the addition of the polymers or formulations to process water, for example to combat slime in the paper industry or to control harmful organisms in the sugar industry. They prevent or control the growth of microorganisms in cooling circuits, humidifiers, or in drilling and production fluids in the petroleum industry.

The mixtures and their formulations can also be used in disinfection.

Bacteria, viruses, spores, yeasts, fungi, algae and slime organisms may be mentioned as examples of microorganisms which can cause a degradation or a change in technical materials. The polymers or their preparations to be used according to the invention preferably act against bacteria, yeasts and fungi.

The following genera may be mentioned as microorganisms:

Staphylococcus aureus

Escherichia coli

Proteus mirabilis Citrobacter freudii

Pseudomonas aeruginosa

Candida albicans

Saccheromyces cerevisiae

Alternaria alternata Aspergillus niger

Penicillium funiculosum

Depending on their chemical and physical properties, the mixtures to be used according to 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. For this purpose, surface-active substances (for example, anionic surfactants such as alkyl sulfonates, ether sulfates; nonionic surfactants such as fatty alcohol ethoxylates, fatty alcohol ester ethoxylates, sorbitan esters, polyalkylene glycols; amphoteric surfactants), complexing agents (e.g. ethylene diamine tetraacetic acid, nitrilotriacetic acid acetic acid, methyl nitrate triacetic acid, methylglycosylate acetic acid, methyl nitrate triacetic acid, methyl methacrylate) B. alcohols such as ethanol, n-propanol, i-propanol, or glycols, for example propylene glycol, polypropylene glycol), acids or bases (for example phosphoric acid, sodium hydroxide solution), inorganic salts and / or other additives (for example corrosion additives, foam suppressants, straightening agents, dyes) are added to the formulations and preparations.

Methods for producing such biocidally active formulations are known to the person skilled in the art and are described in the relevant literature.

The effectiveness and the spectrum of activity of the polymers to be used according to the invention or of the agents or formulations which can be prepared therefrom can be increased if further microbicidally active compounds such as fungicides, bactericides and / or herbicides, insecticides and / or other active substances are used to broaden the spectrum of activity or to achieve them special effects are added. In many cases, synergistic effects are obtained, i.e. the spectrum of action of the mixture exceeds the action of the individual components. Such substances are known per se to the person skilled in the art and are described in the literature.

The mixing ratio of components A and B in the mixtures or formulations to be used according to the invention is not critical per se and can be chosen over a wide range. In general, the mixing ratio (weight ratio) is in the range from 1: 1000 to 1000: 1, preferably from 1: 100 to 100: 1 and particularly preferably in the range from 20:80 to 80:20.

The K values of the polymers A were determined in 5% by H. Fikentscher, Cellulose-Chemie, Vol. 13, 58 to 64 and 71 to 74 (1932). -% aqueous saline solution at 25 ° C and pH 7 and a polymer concentration of 0.5 wt. - Determined.

Microbicides and microbistatic properties are determined experimentally. Very suitable test methods have been described in detail by the German Society for Hygiene and Microbiology (DGHM) for the testing of disinfectants.

Tube dilution tests were carried out in accordance with the "Guidelines for the Testing and Evaluation of Chemical Disinfection Procedures (Status 01.01.81, procedure slightly modified)" with casein peptone soybean meal peptone medium. The dilution was carried out with water of standardized hardness without further aids such as Surfactants. The pH was adjusted to 7.2 + 0.2 using 0.1 mol / 1 NaOH or 0.1 mol / 1 HC1. The test concentrations were graded according to the concentration levels proposed by the DGHM. The evaluation was carried out after 72 hours of incubation at 36 ° C.

Claims

claims

1. Use of mixtures of

A) polymers that

(a) 0.1 to 100 mol% of vinylamine units or ethyleneimine units,

(b) 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 _{(I) /}

CO R ²

in which R ¹ , R ² = H or C] _- to Cg-alkyl,

Vinyl formate, vinyl acetate, vinyl propionate, vinyl alcohol, Cι ~ to Cδ-alkyl vinyl ether, monoethylenically unsaturated C ₃ - to Cs-carboxylic acids, their esters, nitriles, amides and anhydrides, N-vinyl urea, N-vinyl imidazoles and N-vinyl imidazolines and

(c) 0 to 5 mol% units of monomers with at least two ethylenically unsaturated double bonds

polymerized contain, the sum of (a), (b) and (c) in mol% is always 100, and

B) aminoisothiazoles of the formula V

in the

R represents hydrogen or -CC-alkyl and

X stands for halogen, N0, CN and SCN, as well as their metal complexes and acid addition salts, as biocides.

2. Use according to claim 1, characterized in that one uses as component A) polymers which

(a) vinylamine units,

(b) N-vinyl formamide, vinyl formate, vinyl acetate, vinyl propionate, vinyl alcohol and / or N-vinyl urea units

polymerized included.

3. Use according to claim 1 or 2, characterized in that as component A) polymers are used which

(a) 0.1 to 100 mol% of vinylamine units or ethyleneimine units and

(b) 0 to 99.9 mol% of N-vinylformamide units

polymerized contain, the sum of (a), (b) and

(c) is always 100 in mol%.

4. Use according to any one of claims 1 to 3, characterized labeled in ^¬ characterized in that used as component A polymers, which

(a) 1 to 99 mol% vinylamine units and

(b) 1 to 99 mol% of N-vinylformamide units

polymerized contain, the sum of (a), (b) and

(c) in mol% is always 100 and the polymers have a K value of 5 to 300 (determined according to H. Fikentscher in 5% strength by weight aqueous saline solution at 25 ° C. and a polymer concentration of 0.5% by weight). -%) to have.

5. Use according to one of claims 1 to 3, characterized in that the component A used is a polymer which

(a) 10 to 90 mole percent vinylamine units and

(b) 10 to 90 mol% of N-vinylformamide units

in copolymerized form, the sum of (a), (b) and (c) in mol% always being 100 and the polymers having a K value of 10 to 120 (determined according to H-Fikentscher in 5 wt .-% aqueous saline at 25 ° C and a polymer concentration of 0.5 wt .-%).

6. Use according to one of claims 1 to 5, characterized in that aminoisothiazoles are used as component B, in which R is C] _- C ₄ alkyl and X is CN and SCN.

7. Use according to any one of claims 1 to 5, characterized in that aminoisothiazoles are used as component B, in which R is methyl.

8. Use according to one of claims 1 to 5, characterized in that one uses as component B aminoisothiazoles in which X stands for SCN.

Use according to one of Claims 1 to 5, characterized in that 3-methyl-4-rhodano-5-ami-noisothiazole (formula Ic) is used as component B.