WO2010060652A1

WO2010060652A1 - Antimicrobial compositions

Info

Publication number: WO2010060652A1
Application number: PCT/EP2009/008582
Authority: WO
Inventors: Uwe Falk
Original assignee: Clariant International Ltd
Priority date: 2008-12-24
Filing date: 2009-12-02
Publication date: 2010-06-03
Also published as: DE102008063093A1

Abstract

The invention relates to a composition: containing a) silver and/or one or more silver compounds with the proviso that the compositions are free of formaldehyde and b) one or more biocidal active substances chosen from the isothiazoline family.

Description

description

Antimicrobial compositions

The present invention relates to formaldehyde-free antimicrobial

Compositions containing silver in the form of metallic silver or as silver compound (s) and at least one further biocidal active substance selected from the class of isothiazolines and their use as preservatives and disinfectants.

Biocides are used in a wide variety of applications to control or prevent the growth of microorganisms, thereby ensuring the preservation of products and materials. They are used in the building materials, textiles, leather, paper, electrical and food industries, but also in cosmetics, and agriculture. Likewise, biocidal active substances are used for preserving in paints and adhesives, water-in-oil emulsions and lubricants or for surface treatment. In order to achieve a broad spectrum of action of the preservatives against such different microorganisms, such as bacteria, fungi and molds, combination products of several biocidal active substances are usually used.

The antimicrobial effect of silver and silver salts has long been known and is used for the antibacterial treatment of medical devices and aids, but also for the production of germ-resistant surfaces and textiles.

The state of the art is to adsorb antimicrobial metals or metal compounds onto a carrier material in order to achieve a slow release of silver or silver ions and to achieve a long-lasting antimicrobial effect.

In EP-AO 116 865 metal compounds are applied to zeolites and incorporated into polymers. EP-AO 190 504 discloses antimicrobial Compositions containing metallic silver adsorbed on hydratable or hydrated oxides.

EP-A-0 251 783 and EP-A-0 734 651 describe silver compounds which are applied to water-insoluble, non-hydrated or hydrolyzable oxides and show good bactericidal and fungicidal activity. According to US-A-6 641 829, US-A-6 461 386, US-A-6454 813 and US-A-6 444 726 these supported silver compounds are suitable for finishing textiles with an antimicrobial active substance, for the preservation of cosmetics or also used for the preservation of water-based polymer emulsions.

The silver-containing compositions mentioned in the prior art do not sufficiently fulfill a spontaneous and at the same time a long-lasting antimicrobial effect in an environment which promotes the growth of microorganisms and lose their effect in an aggressive environment. Another problem is the instability of silver compounds, which leads to a darkening of the products within minutes under the influence of light.

To achieve a broader spectrum of activity, combination products of several biocidal active substances are required.

In WO-A-01/00021 it is described that the biocidal effect of pyrithione or pyrithione complexes can be improved by silver, copper or zinc salts. The script uses AgCl and Ag ₂ O. Information on the stability of the biocidal agent, also in terms of color stability are not found.

In EP-A-1 382 248 it is disclosed that biocidal active substances from the group of the haloalkynyls, for example 3-iodo-2-propynylcarbamate, decompose in the presence of metal ions, for example silver ions. This decomposition reaction can be prevented or reduced by adding amines. However, the presence of amines is undesirable in many applications. In addition, aminic components such as. As triazines with silver to colored complexes and are therefore useless for many applications. Formaldehyde is a convenient preservative for almost all industrial uses. Combined with other preservatives, formaldehyde or formaldehyde-releasing products are widely used in the preservation of industrial products. However, a new regulation in France significantly limits the use of formaldehyde and formaldehyde-releasing substances in preservatives. Many preservatives lose their biocidal effects by eliminating formaldehyde and formaldehyde-releasing compounds. An increase in the use concentration of their other ingredients is due to other restrictions, such as

Labeling obligation from a content of CMIT of 15 ppm for the combination CMIT / MIT also not possible or uneconomical. Therefore, a replacement product for the formaldehyde is found in preservatives, or even a preservative, which alone provides adequate protection of the industrial formulations against microbial attack.

It has not yet been sufficiently successful to provide antimicrobial compositions which both have sufficient spontaneous activity to prevent the growth of microorganisms and, at the same time, are antimicrobially effective over long periods of time by slowly releasing toxicologically and ecotoxicologically acceptable levels of active substance (s) ,

In order to achieve the widest possible spectrum of action of antimicrobial compositions against microorganisms as different as bacteria, fungi, molds, algae and yeast, with a good short-term and long-term effect, combination products of antimicrobial active substances are sought. In addition, antimicrobial compositions are required which, even at very low use concentrations, display their spontaneous and sustained action, are toxicologically and ecotoxicologically harmless and are color-stable over long periods of time. The object of the present invention was therefore to provide antimicrobial compositions which are active against microorganisms from the group of bacteria, molds, algae and yeasts, are stable in a wide temperature range with long storage times, in very low concentrations well in formulations and products can be incorporated, show in the final products no color changes, especially under the influence of light and are toxicologically and ecotoxicologically compatible. The compositions should in particular be formaldehyde-free.

Surprisingly, it has now been found that silver in the form of metallic silver, silver compounds or adsorbed on support materials silver or silver compounds in formaldehyde-free environment synergistically enhances the bactericidal and fungicidal activity of isothiazolines, so that the use concentrations of both active substances can be reduced. The compositions containing silver or one or more

Silver compound (s) on a support and at least one other antimicrobial active substance from the group of isothiazolines are characterized by a high, spontaneous and also long-lasting efficiency against bacteria and fungi.

The invention therefore antimicrobial compositions containing

a) silver and / or one or more silver compounds,

with the proviso that the compositions are free of formaldehyde.

In a preferred embodiment, the antimicrobial compositions further contain

b) one or more biocidal active substance (s) from the group of isothiazolines. Metallic silver is used according to the invention, preferably in the form of nanoparticles with particle sizes <100 nm, more preferably <50 nm or in the form of silver compounds. As silver compounds are silver chloride, silver bromide, silver iodide, silver nitrate, Ag ₃ PO _4, Ag ₂ SO _4, Ag2CO _3, silver citrate, silver stearate, silver acetate, silver lactate, silver salicylate, silver oxide (silver hydroxide), silver chloride, silver citrate and silver nitrate preferably used.

Freedom from formaldehyde for the present invention means that the composition according to the invention preferably contains less than 10 ppm, in particular less than 5 ppm, especially less than 1 ppm of formaldehyde.

In a preferred embodiment of the invention, the silver or the silver compound is adsorbed on a water-insoluble, inert, non-hydratable or non-hydrated, oxidic carrier, and the silver and / or the silver compound (s), always calculated as elemental silver, are based on the weight of the carrier, in amounts of from 0.1% to 75% by weight.

The preferred carrier is selected from titanium, magnesium, aluminum, silicon, calcium and barium oxide, calcium hydroxyapatite, chalk, natural ground or precipitated calcium carbonates, calcium magnesium carbonates, silicates, layered silicates, zeolites, clays or bentonites. Particularly preferably, the carrier is titanium oxide, which is present in one or more of the crystalline forms anatase, rutile and brookite. In likewise preferred embodiments, mixtures of the abovementioned carriers can be used.

The carrier should have a particle size of less than 25 microns, preferably of <5 microns, more preferably <1 micron. In a further preferred embodiment, the carrier has a particle size <120 nm, more preferably <5 nm, in particular <25 nm. The proportion by weight of silver or of the silver compound, based on the weight of the carrier, is in the range from 0.1% by weight to 75% by weight, preferably from 5% by weight to 50% by weight, particularly preferably 10% by weight. -% to 30 wt .-%, calculated as elemental silver.

The supported silver compounds used in the invention are prepared in the manner described in EP-A-251,783 manner and are also available as commercial products (JMAC LP 10 ^®, ^® JMAC Composite PG, Clariant (Germany) GmbH) available. Supported silver can be prepared from supported silver compounds by reduction of the silver compounds to the metal.

Isothiazolines (which in the following include their derivatives) are understood as meaning compounds according to the formula (I) or (II)

or

Formula (I) Formula (II)

and their derivatives, which may carry at positions 2, 3, 4 and / or 5 substituents. Such substituents may be, for example, linear, branched or cyclic hydrocarbon groups, halogen atoms or carbonyl groups. As the hydrocarbon groups are C ₁ - to C preferably ₂ alkyl groups, phenyl groups and fused aromatic systems.

Further preferred derivatives of isothiazolinone are isothiazolinones of the formula (III)

Formula (III) which substituents may carry as the isothiazolines described above.

Isothiazolines with biocidal activity are, for example, non-halogenated isothiazolines. Suitable non-halogenated isothiazolines are, for example, 2-methyl-3-isothiazoline, 2-methyl-4-isothiazolin-3-one, 2-ethyl-3-isothiazoline, 2-propyl-3-isothiazoline, 2-isopropyl-3-isothiazoline , 2-butyl-3-isothiazoline (where butyl may be n-butyl, iso-butyl or tert-butyl), 2-n-octyl-3-isothiazoline, 2-octyl-4-isothiazolin-3-one or 1 , 2-Benzisothiazolin-3-one or its alkali, alkaline earth or ammonium salt.

Isothiazolines with biocidal activity are, for example, halogenated isothiazolines. Suitable halogenated isothiazolines are, for example, 5-chloro-2-methyl-3-isothiazoline, 5-chloro-2-methyl-4-isothiazolin-3-one or 4,5-dichloro-2- (n-octyl) -4-isothiazoline -3-one.

The preferred isothiazoline is 1,2-benzoisothiazolin-3-one according to the formula (IV) and / or its alkali, alkaline earth or ammonium salt, in particular its sodium or potassium salt.

Formula (IV)

The weight fraction of isothiazoline in the antimicrobial compositions according to the invention is from 0.1% to 99%, preferably from 1% to 50%, particularly preferably from 2% to 20%, the proportion by weight of silver or silver compound (s) is from 0.01% to 50%, preferably 0.1% to 20%, more preferably 0.2% to 2%. The weight ratio in which silver or the silver compound a) and the isothiazoline b) are present in the composition according to the invention is preferably a): b) = 100: 1 to 1: 100, in particular a): b) = 10: 1 to 1 : 10, especially a): b) = 3: 1 to 1: 3. Again, any silver compound is calculated as elemental silver.

The antimicrobial compositions according to the invention can be presented in solid form as a powder or as granules or else in liquid form, preferably as aqueous, dispersion, as emulsion or as suspoemulsion. The compositions are white to beige.

In a preferred embodiment, the antimicrobial compositions according to the invention are in solid form as powders, granules or pellets.

The preparation of the antimicrobial compositions according to the invention in solid form can be achieved by mixing the two components isothiazoline and silver or compound or supported, silver or compound, and optionally fillers and dispersants in conventional, batch or continuous mixing devices, which are usually with rotating mixing devices are carried out, for example, in a plowshare mixer. Depending on the effectiveness of the mixing device, the mixing times for a homogeneous mixture are generally between 30 seconds and 5 minutes.

In addition, the solid antimicrobial compositions of the invention optionally contain fillers and dispersants.

Suitable fillers are titanium, magnesium, aluminum, silicon, calcium and barium oxide, calcium hydroxyapatite, chalk, natural ground or precipitated calcium carbonates, calcium magnesium carbonates, silicates, layered silicates, zeolites, clays or bentonites. Suitable dispersants are the dispersants mentioned below, preference being given to polynaphthalenesulfonates, naphthalenesulfonates, alkylsulfosuccinates, in particular sodium dioctylsulfosuccinates.

In a further preferred embodiment, the antimicrobial compositions according to the invention are present as a dispersion, in particular on an aqueous basis.

The dispersions according to the invention are preferably prepared by dispersing isothiazoline in water, if appropriate with addition of a dispersant, and adding to the dispersion with stirring silver or one or more silver compounds or supported silver and / or a supported silver compound. Optionally, additional dispersant may be added. In a further step, the dispersion may preferably be ground in a bead mill and the desired viscosity adjusted with a thickener. If benzisothiazoline is used in salt form, then it is advantageous to first prepare an aqueous dispersion of silver, compound or supported silver or compound and to add the benzisothiazoline salt thereof.

As dispersing agents, nonionic, anionic and cationic dispersants can be used.

Suitable as dispersants are adducts of 2 to 30 moles of ethylene oxide and / or up to 5 moles of propylene oxide with linear fatty alcohols having 8 to 22 carbon atoms, fatty acids with 12 to 22 carbon atoms and alkylphenols having 8 to 15 carbon atoms in the alkyl group; Ci2-Ci ₈ fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol; Glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their

ethylene oxide adducts; Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil; Polyol and especially polyglycerol esters such as polyglycerol polyricinoleate and polyglycerol poly-12- hydroxystearate. Preferred liquid fatty acid esters are PEG-10 polyglyceryl-2-laurate and polyglyceryl-2-sesquiisostearate.

Also suitable are ethoxylated and nonethoxylated mono-, di- or tri-alkylphosphoric acid esters and alkylarylphosphoric acid esters, for example, isotridecylphosphoric acid esters and their salts, tri-sec-butylphenolphosphoric acid esters and their salts and tristyrylphenylphosphoric acid esters and salts thereof.

Also suitable are mixtures of compounds of two or more of these classes of substances. The addition products of ethylene oxide and / or propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or to castor oil are known, commercially available products. These are mixtures of homologues whose average degree of alkoxylation the ratio of

Amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out corresponds.

Suitable cationic dispersants, for example, di- come (Cio-C ₂₄₎ alkyl dimethyl ammonium chloride or bromide, preferably di (C ₂ -C ₈₎ alkyl dimethyl ammonium chloride or bromide; _(Cio-C24) alkyl-dimethyl-ethylammonium chloride or bromide; (C 10 -C ₂₄ ) alkyltrimethylammonium chloride or bromide, preferably cetyltrimethylammonium chloride or bromide, and (C ₂ -C ₂₂ ) -alkyltrimethylammonium chloride or bromide; (Ι-C _O -C ₂₄₎ alkyl dimethylbenzyl ammonium chloride or bromide, preferably (C ₂ -C ₈₎ alkyl dimethylbenzyl ammonium chloride; N- (Cio-Ci ₈₎ alkyl-pyridinium chloride or bromide, preferably N- (C ₂ -C ₆₎ alkyl-pyridinium chloride or bromide; N- (C ₀ - C ₈₎ alkyl-isoquinolinium chloride, bromide or monoalkylsulfate; N- (C ₂ -C ₁₈₎ alkyl polyoylaminoformylmethyl chloride; N- (C ₁₂ -C ₈₎ -alkyl-N-methyl-morpholinium chloride, bromide or monoalkylsulfate; N- (C ₂ -C ₈₎ -alkyl-N-ethyl morpholinium chloride, bromide or monoalkylsulfate; (C ₆ -C ₈₎ alkyl-pentaoxethyl- ammonium chloride; Diisobutylphenoxyethoxyethyldimethylbenzylammonium chloride; Salts of N, N-diethylamino-ethylstearylamide and -oleylamide with Hydrochloric acid, acetic acid, lactic acid, citric acid, phosphoric acid; N-acylaminoethyl-N, N-diethyl-N-methyl-ammonium chloride, bromide or monoalkyl sulfate and N-acylaminoethyl-N, N-diethyl-N-benzyl-ammonium chloride, bromide or monoalkyl sulfate, wherein acyl is preferably stearyl or oleyl, into consideration.

In particularly preferred embodiments, polynaphthalenesulfonates, naphthalenesulfonates, alkylsulphosuccinates, in particular dioctylsulfosuccinates such as, for example, sodium dioctylsulfosuccinate, are used. In the presence of these dispersants, a further increase in antimicrobial activity is achieved according to the invention.

The antimicrobial compositions according to the invention may contain from 0.1 to 40% by weight, preferably from 1 to 30% by weight, particularly preferably from 3 to 20% by weight, of one or more emulsifiers or dispersants, based on the finished antimicrobial compositions.

The antimicrobial compositions in the form of dispersions of the invention may contain solvents. Suitable solvents from the group of

- Glykole, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, polybutylene glycol

- end-capped glycols, for example monoethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether and tetraethylene glycol diethyl ether, propylene glycol phenyl ether, polyethylene glycol dibutyl ether;

polyethylene glycol diallyl ether; Polyethylenglykolallylmethylether; polyalkylene; Polyalkylenglykolallylmethylether, Alcohols, for example methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, n-pentanol, n-hexanol, 2-methoxyethanol, 2-butoxyethanol, 2- (2-butoxyethoxyl ) ethanol, phenoxyethanol, 2- (2-butoxyethoxyl) ethanol, 3-methoxybutanol, 1-methoxy-2-propanol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, 2-ethylhexanol, 2-propoxyethanol, benzyl alcohol, phenethyl alcohol, 1, 2,6-hexanetriol,

Alkanes, for example, pentane, hexane, heptane,

chlorinated alkanes, for example methylene chloride, ethylene dichloride;

- aromatics, for example benzene, toluene, xylene;

- nitriles, for example acetonitrile;

Amides, for example dimethylformamide, N, N-dimethylacetamide, hexamethylphosphoramide;

Ketones, for example acetone, ethyl methyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, 2-butanone,

Ethers, for example isopropyl ether,

Acetates, for example ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, i-butyl acetate, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate,

ethylene glycol,

Lactates, for example methyl lactate, ethyl lactate,

Phosphates, for example trihexyl (tetradecyl) phosphonium hexafluorophosphate, trihexyl (tetradecyl) phosphonium tetrafluorophosphate,

Amines, for example monoethanolamine, diethanolamine, triethanolamine, Polyols, for example glycerol, trimethylolethane, trimethylolpropane, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol,

and further tetrahydrofuran, 1, 4-dioxane, dimethyl sulfoxide, diethyl carbonate, propylene carbonate, pyridine, picoline, lutidine, collidine, cyclohexanone and / or water.

According to the invention, the biocidal compositions may contain up to 60% by weight, preferably 40 to 20% by weight, particularly preferably 15 to 5% by weight of one or more of the abovementioned solvents.

In a preferred embodiment, the antimicrobial compositions of the invention may contain, in addition to silver in the form of metallic silver, a silver compound or supported silver or compound and at least one isothiazoline, one or more other biocidal active substances.

Preferred further biocidal active substances are

Methylene-bis-morpholine, oxazolidine, 3-iodo-2-propynyl butylcarbamate, 2-bromo-2-nitropropanediol, glutaraldehyde, glutardialdehyde, sodium 2-pyridinethiol-1-oxide, p-hydroxybenzoic acid alkyl ester, tris (hydroxymethyl) nitromethane, dimethylol dimethylhydantoin , 1, 6-dihydroxy-2,5-dioxahexane; 1,2-dibromo-2,4-dicyanobutane; 3- (3,4-dichlorophenyl) -1, 1-dimethylurea (diuron); N-cyclopropyl-N '- (1, 1-dimethylethyl) -6- (methylthio) -1, 3,5-triazine-2,4-diamine;

Methylbenzimidazol-2-ylcarbamate (carbendazim); N- (1, 1-dimethylethyl) -N'-ethyl-6- (methylthio) -i, 3,5-triazine-2,4-diamine (terbutryn); 4-chloro-3,5-dimethylphenol; 2,4-dichloro-3,5-dimethylphenol; 2-benzyl-4-chlorophenol; 2,2'-dihydroxy-5,5 ^l - dichlorodiphenylmethane; p-tertiary-amylphenol; o-phenylphenol; Sodium o-phenylphenol; p-chloro-m-cresol; 2- (thiocyanomethylthio) -benzthiazole;

3,4,4'-trichlorocarbanilide;1-hydroxy-2-pyridinethione-zinc; 1- (4-chlorophenyl) -4,4-dimethyl-3- (1H-1,2,4-triazol-1-ylmethyl) -pentan-3-ol (tebuconazole), 1- [2- (2, 4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl) -1 H-1, 2,4-triazole (propiconazole), 3-iodo-2-propynyl-butylcarbamate, 2-bromo-2-nitropropanediol, formaldehyde; Urea; glyoxal; 2,2'-dithio-bis- (pyridine-N-oxide), 3,4,4-trimethyloxazolidine, 4,4-dimethyloxazolidine, N-hydroxy-methyl-N-methyldithiocarbamate, potassium salt adamantane, N-trichloromethyl-thiophthalimide, 2,4,5,6-tetrachloroisophthalonitrile, 2,4,5-trichlorophenol, dehydroacetic acid, copper naphthenate, copper octoate, tributyltin oxide, zinc naphthenate, copper-8-quinolate.

Furthermore, biocides come from the group of quaternary

Ammonium compounds, preferably alkyldimethylammonium chlorides, such as, for example, cocodimethylammonium chloride,

Dialkyldimethylammoniumchloride, such as

Dicocosdimethylammoniumchlorid, Alkyldimethylbenzyl-ammoniumchloride, such as Ci _2/14 -Dimethylbenzylammoniumchlorid or

Cocosdimethyldichlorobenzylammoniumchlorid.

The antimicrobial compositions according to the invention may additionally

Surfactants, thickeners, antigelling agents, solubilizers, cryoprotectants,

Antifoaming agents, buffers, wetting agents, complexing agents, sequestering agents,

Electrolytes, stabilizers, fragrances and dyes included.

In one embodiment, the antimicrobial

Compositions contain anionic surfactants.

Preferred anionic surfactants are straight-chain and branched alkyl sulfates, sulfonates, carboxylates, phosphates, sulfosuccinates and taurates, alkyl ester sulfonates, arylalkyl sulfonates and alkyl ether sulfates.

Alkyl sulfates are water-soluble salts or acids of the formula ROSO ₃ M, wherein R preferably has one

particularly preferably represents an alkyl or hydroxyalkyl radical having 10 to 20 carbon atoms and particularly preferably represents a Ci ₂ -Ci ₈ alkyl or hydroxyalkyl radical. M is hydrogen or a cation, preferably an alkali metal cation (e.g., sodium, potassium, lithium) or ammonium or substituted ammonium, e.g. As a methyl, dimethyl and Trimethylammoniumkation or a quaternary ammonium cation, such as tetramethylammonium and Dimethylpiperidiniumkation and quaternary ammonium cations, derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof.

The alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) _m SO ₃ M, wherein R preferably represents an unsubstituted C 1 -C ₂₄ -alkyl or hydroxyalkyl radical, particularly preferably a C ₁₂ -C ₂ 0-alkyl or hydroxyalkyl radical and is particularly preferred a Ci2-Ciβ-alkyl or hydroxyalkyl radical. A is an ethoxy or propoxy moiety, m is a number greater than 0, typically between 0.5 and 6, more preferably between 0.5 and 3, and M is a hydrogen atom or a cation, preferably a metal cation (e.g. Sodium, potassium, lithium, calcium, magnesium), ammonium or a substituted ammonium cation. Examples of substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof. Examples which may be mentioned C ₂ -C ₈ alkyl polyethoxylate (1, 0) sulfate, C ₂ -C ₈ alkyl polyethoxylate sulfate (2.25), C ₂ -C ₈ alkyl polyethoxylate (3 , 0) sulfate, Ci ₂ -Ci ₈ alkyl polyethoxylate (4,0) sulfate, wherein the cation is sodium or potassium.

Also suitable are alkyl sulfonates with straight-chain or branched C ₆ -C ₂₂ -alkyl chains, for example primary paraffin sulfonates, secondary paraffin sulfonates, alkylarylsulfonates, for example linear alkylbenzenesulfonates with C ₅ -C ₂₀ -alkyl chains, alkylnaphthalenesulfonates, condensation products of naphthalene sulfonate and formaldehyde, lignosulfonate, alkyl ester sulfonates, ie sulfonated linear esters of

(ie fatty acids), C ₈ -C ₂₄ olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of pyrolysis products of alkaline earth metal citrates.

Further suitable anionic surfactants are selected from alkylglycerol sulphates, fatty acylglycerol sulphates, oleylglycerol sulphates, alkylphenol ether sulphates, Alkyl phosphates, alkyl ether phosphates, isethionates such as acyl isethionates, N-acyl taurides, alkyl succinamates, sulfosuccinates, in particular di-nonyl or di-octyl sulphosuccinate, monoesters of sulfosuccinates (especially saturated and unsaturated Ci ₂ -C ₈ monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C ₂ -C ₈ diesters), acyl sarcosinates, sulfates of

Alkylpolysaccharides such as sulfates of alkyl polyglycosides, branched primary alkyl sulfates and alkyl polyethoxycarboxylates such as those of the formula RO (CH ₂ CH ₂ O) _k CH ₂ COO ^" M ⁺ wherein R is a C ₈ -C ₂₂ alkyl group, k is a number from 0 to 10 and M is a soluble , Salt-forming cation is.

Suitable nonionic surfactants are preferably fatty alcohol ethoxylates (alkylpolyethylene glycols), Alkylphenolpolyethylenglykole, Alkylmercaptanpolyethylen glycols, fatty amine ethoxylates (Alkylaminopolyethylenglykole), fatty acid (Acylpolyethylenglykole) Polypropylenglykolethoxylate (eg., Pluronics ^®), fatty acid alkylolamides (Fettsäureamidpolyethylenglykole), N-alkyl and

N-alkoxy polyhydroxy fatty acid amides, alkyl polysaccharides, sucrose esters, sorbitol esters and polyglycol ethers.

Suitable amphoteric surfactants are preferably amphoacetates, more preferably monocarboxylates and dicarboxylates such as cocoamphocarboxypropionate, cocoamidocarboxypropionic acid, cocoamphocarboxyglycinate (or else referred to as cocoamphodiacetate) and cocoamphoacetate.

As cationic surfactants, for example, di- come (Cio-C ₂₄₎ alkyl dimethyl ammonium chloride or bromide, preferably di (C ₂ -C ₈₎ alkyl dimethyl ammonium chloride or bromide; _(Cio-C24) alkyl-dimethyl-ethylammonium chloride or bromide; (Cio-C ₂₄₎ alkyl-trimethyl ammonium chloride or bromide, preferably cetyltrimethylammonium chloride or bromide, and (C ₂ o-C22) alkyl-trimethyl ammonium chloride or bromide; (C ₁₀ -C ₂₄₎ alkyl dimethyl benzyl ammonium chloride or bromide, preferably (C ₂ -C ₈₎ alkyl dimethylbenzyl ammonium chloride; N- (Cio-Ci ₈₎ alkyl-pyridinium chloride or bromide, preferably N- (C ₂ -C ₆₎ alkyl-pyridinium chloride or bromide; N- (CIO CiβJ-alkyl-isoquinolinium chloride, bromide or monoalkyl sulfate; N- (C ₁₂ -C ₁₈ ) alkyl polyoylaminoformylmethylpyridinium chloride; N- (C 12 -C ₁₈ ) -alkyl-N-methyl-morpholinium chloride, bromide or monoalkyl sulfate; N- (C ₂ -C ₈₎ -alkyl-N-ethyl morpholinium chloride, bromide or monoalkylsulfate; (C ₆ -C ₈₎ alkyl-pentaoxethyl- ammonium chloride; Diisobutylphenoxyethoxyethyldimethylbenzylammonium chloride; Salts of N, N-diethylamino-ethylstearylamide and -oleylamide with hydrochloric acid, acetic acid, lactic acid, citric acid, phosphoric acid; N-acylaminoethyl-N, N-diethyl-N-methyl-ammonium chloride, bromide or monoalkyl sulfate and N-acylaminoethyl-N, N-diethyl-N-benzyl-ammonium chloride, bromide or monoalkyl sulfate, wherein acyl is preferably stearyl or Oleyl is considered.

The antimicrobial compositions according to the invention may contain from 0.1 to 40% by weight, preferably from 1 to 30% by weight, particularly preferably from 3 to 20% by weight, of one or more surfactants, based on the finished antimicrobial compositions.

Preferred thickeners are carboxymethylcellulose and hydroxyethylcellulose, xanthan gum, guar-guar, agar-agar, alginates and tyloses, also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, hydrogenated castor oil, salts of long-chain fatty acids, for example sodium. Potassium, aluminum, magnesium and titanium stearates or the sodium and / or potassium salts of behenic acid, but also polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone, and polysaccharides used. Also suitable are copolymers based on acryloyldimethyltaurine, as described in EP-A-1 060 142, EP-A-1 028 129, EP-A-1 116 733.

The thickening agents may be used in the antimicrobial compositions of the invention preferably in amounts of from 0.01 to 5% by weight and in particular in amounts of from 0.5 to 2% by weight, based on the finished antimicrobial compositions. Suitable solubilizers are sodium toluene sulphonate, sodium cumulosulphonate, sodium xylene sulphonate, alkanephosphonic acids and alkenyldicarboxylic acids and their anhydrides.

Cold stabilizers which can be used are all customary substances which can be used for this purpose. Examples include urea, glycerol and propylene glycol. Hydrogen peroxide may be any inorganic peroxide that releases hydrogen peroxide in aqueous solution, such as sodium perborate (monohydrate and tetrahydrate) and sodium percarbonate.

Suitable defoamers are fatty acid alkyl ester alkoxylates; Organopolysiloxanes such as polydimethylsiloxanes and mixtures thereof with microfine, optionally signed silica; paraffins; Waxes and microcrystalline waxes and their mixtures with signed silicic acid. Also advantageous are mixtures of various foam inhibitors, for example those of silicone oil, paraffin oil and / or waxes.

Suitable buffers are all customary acids and their salts. Preferably mentioned are phosphate buffer, carbonate buffer, citrate buffer.

Alcohol ethoxylates / propoxylates can be used as wetting agents. Furthermore, the mixtures according to the invention preferably contain neutralizing agents and adjusting agents for adjusting the agents to a viscosity of 100 to 2000 mPas, preferably of about 600 mPas. Preferred setting agents are inorganic salts, particularly preferably ammonium or metal salts, in particular of halides, oxides, carbonates, bicarbonates, phosphates, sulfates and nitrates, in particular sodium chloride. Preferred neutralizing agents are NaOH and KOH.

As the electrolyte, the antimicrobial

Compositions contain inorganic and organic salts. Suitable are alkali metal, alkaline earth metal, metal or ammonium halides, nitrates, phosphates, carbonates, bicarbonates, sulfates, silicates, acetates, oxides, citrates or polyphosphates. For example, CaCl ₂ , MgCl ₂ , LiCl, KCl, NaCl, K ₂ SO ₄ , K ₂ CO ₃ , MgSO ₄ , Mg (NO ₃ ) ₂ , ZnCl ₂ , ZnO, MgO ₁ ZnSO ₄ , CuSO ₄ , Cu are preferably used (NOs) ₂ .

In preferred embodiments, the antimicrobial compositions of the invention contain phosphates, especially sodium hydrogen phosphate and sodium dihydrogen phosphate.

Suitable organic salts are ammonium or metal salts, preferably glycolic, lactic, citric, tartaric, mandelic, salicylic, ascorbic, pyruvic, fumaric, retinoic, sulfonic, benzoic, kojic, fruit, malic, gluconic and galacturonic acid. As electrolyte, the compositions may also contain mixtures of different salts.

The antimicrobial compositions of the invention may contain electrolytes in amounts of 0.01 to 50% by weight, preferably 0.1 to 20% by weight, particularly preferably 0.5 to 10% by weight, based on the antimicrobial compositions.

Suitable sequestering agents are, for example, sodium tripolyphosphate (STPP), ethylenediaminetetraacetic acid (EDTA), their salts, nitrilotriacetic acid (NTA), polyacrylate, phosphonate, for example 1-hydroxyethane-1,1-diphosphonic acid (HEDP), salts of polyphosphoric acids, such as ethylenediamine tetramethylenephosphonic acid (EDTMP). and

Diethylenetriaminepentamethylenephosphonic acid (DTPMP), oxalic acid, salt, citric acid, zeolite, carbonates and polycarbonates.

Suitable complexing agents are phosphonates, aminophosphonates and aminocarboxylates.

The antimicrobial compositions according to the invention are preferably used for the preservation of paints, varnishes, printing inks, cooling lubricants, Metalworking agents, crop protection formulations, construction chemicals and building materials, such as sealants, grout and binder, and adhesives and polymer emulsions used.

The antimicrobial compositions according to the invention can be used directly or in dilution as a disinfectant, in particular in the hygiene and sanitary sector. Even in very low concentrations, they have a disinfectant effect in detergents and cleaners, in particular in detergents, in dishwashing detergents and in cleaners for hard surfaces, and in cosmetic products both in rinse off and in leave on products.

The antimicrobial compositions of the present invention may further be incorporated into surface coating materials, such as, for example, surface treatments. As ceramic materials, plastics, wood, concrete, plaster, paints or paints. Surfaces coated with such coating materials are thereby biocidically finished.

Furthermore, the antimicrobial compositions according to the invention are used in packaging materials, for example films, paper, in order to ensure sterility of the materials.

Another use of the antimicrobial compositions of the present invention is the antimicrobial finishing of textiles, leather, nonwoven materials and sanitary napkins.

The antimicrobial compositions according to the invention are used in amounts such that the treated substrate or the treated final product contains 5-1000 ppm, preferably 10 to 600 ppm, particularly preferably 20 to 80 ppm of biocidal active substances.

Formulations containing the compositions of the invention preferably have a pH of 1 to 13. Formulations containing the compositions according to the invention, wherein the composition contains isothiazoline and a water-soluble, unsupported silver salt, preferably have a pH in the range of 5 to 13, preferably 7 to 12, particularly preferably 8 to 10.

Formulations containing the compositions according to the invention, wherein the composition contains isothiazoline and a supported silver compound, preferably have a pH in the range of 5 to 13, preferably 7 to 12, particularly preferably 8 to 10.

Essential to the invention is the synergistic effect of the combination of silver and / or silver compound and / or supported silver or silver compound and biocides from the group of isothiazolines, as well as the good light stability of the compositions.

Furthermore essential to the invention is the increase in the biocidal effect of the compositions according to the invention in the presence of one or more additives, in particular a dispersant, preferably polynaphthalenesulfonate, naphthalenesulfonate, alkylsulfosuccinate, in particular sodium dioctylsulfosuccinate.

The biocidal effect of the antimicrobial compositions according to the invention remains even under storage conditions in the temperature range of up to +50 ⁰ C and maintained over several months. A discoloration of the products under the action of light, containing the compositions of the invention is omitted.

The spontaneous antimicrobial action of the composition according to the invention containing silver or one or more silver compounds and one or more isothiazolinones is considerably stronger than those of the individual constituents applied in equal concentrations. While at a contact time of about 2 hours with the combination products according to the invention a nearly complete kill of microorganisms is achieved, can both with the Silver compounds as well as with the isothiazolines alone this result can not be achieved.

Another surprising advantage of the invention is the superior color stability of the silver or silver compound compositions and one or more isothiazolinones.

The compositions according to the invention are stable at low and high temperatures and under the influence of light for several months and can be presented in solid form or also in combination with a suitable medium, for example water, liquid hydrocarbons, for example ethanol or isopropanol, preferably as dispersions.

Examples

The following examples serve to illustrate the invention. All percentages are by weight unless otherwise specified.

The following biocide compositions were used:

Composition 1

AgCl on TiO ₂ , 10% dispersion with 10% sodium dioctylsulfosuccinate

Composition 2

AgCl on TiO ₂ , 100% solids

Composition 3 AgCl on TiO ₂ , diluted with TiO ₂ , 100% solids

Composition 4 Benzoisothiazoline, about 75% Composition 5 Benzoisothiazoline, 20% dispersion

Composition 6

Benzoisothiazoline, 33% dispersion

Composition 7 Benzisothiazoline, 9.5% solution

Example 1 Rate of antimicrobial action of Ag salt / BIT

(Kill kinetics measurement according to the Clariant method) of the composition Ag / BIT compared to the individual biocides AgCl, AgNO _ß, Composition 1 and Composition 5

reagents:

0.1 M phosphate buffer a) Na ₂ HPO ₄ 7H ₂ O 53.65 g in 1000 ml water b) NaH ₂ PO ₄ 2 H ₂ O 18.07 g in 500 ml water 900 ml phosphate buffer pH 7.0:

600 ml H ₂ O dist. +117 ml (b) + 183 ml (a)

bacteria

Staphylococcus aureus DSM 799 eq .: NCTC 10788

Pseudomonas aeruginosa DSM 1128 eq .: NCiMB 8026 E-CoIi DSM 682 eq .: NCIMB 8545

Enterobacter aerogenes NCIMB 10102

The bacteria were grown on a Caso agar. Sample 1

Description of the kill kinetics measurement according to the Clariant method

After allowing the bacteria to rest on the agar (Caso agar) for 24 hours, add 10 ml of the 0.1M phosphate buffer and mix for 20 seconds with a vortex mixer; to 1 ml of this solution is added 9 ml of 0.1 M

Buffer solution; This solution is again taken 1 ml and 9 ml 0.1 M

Phosphate buffer added. The solution thus obtained is the inoculum with which the

Test series is performed.

Sample 1: 19 ml of 0.1 M phosphate buffer + 1 ml inoculum

Sample 2: Sample 1 + 80 ppm (Ag + BIT, 1: 1) + 500 ppm

sodium dioctylsulfosuccinate

Sample 3: Sample 1 + 80 ppm (Ag + BIT, 1: 1)

Sample 4: Sample 1 + 80 ppm (Ag + BIT, 1: 2)

Sample 5: Sample 1 + 80 ppm (Ag + BIT, 2: 1)

Sample 6: Sample 1 + 80 ppm Composition 2

Sample 7: Sample 1 + 80 ppm Composition 5

Sample 8: Sample 1 + AgNO ₃ (80 ppm Ag)

Sample 9: Sample 1 + AgCl (80 ppm Ag)

Sample 10: Sample 1 + 80 ppm (Ag + BIT, 10: 1)

Sample 11: Sample 1 + 80 ppm (Ag + BIT, 100: 1)

Sample 12: Sample 1 + 80 ppm (Ag + BIT, 1:10)

Sample 13: Sample 1 + 80 ppm (Ag + BIT, 1: 100)

The concentration data given for the above samples refers to elemental silver and pure (ie non-salted) BIT. For example, in Sample 4, AgNO ₃ and BIT were mixed so that the scale contained 26.7 ppm Ag, calculated as element, and 53.3 ppm BIT, calculated as pure substance.

The bacterial count was in each case at the beginning (0 h), after 0.5 h, 1 h; 2 h; 3 h; 5 hours; 7 h and 24 h according to the TVC method European Pharmacopoeia 2.6.12 determined. Tab.1: Germ numbers as a function of time

z. B. 2.2E + 07 = 2.2-10 ⁷

Benzoisothiazoline (Sample 7) alone does not develop its antimicrobial effect until after many hours, and the efficiency of the silver ions (Samples 8 and 9) is moderate in the first few hours. The combination of the two active substances Ag and BIT leads to a synergistic effect that comes after only 1 to 2 hours of exposure to the microorganisms to fruition. A further significant increase in effectiveness is achieved by adding the dispersant sodium dioctylsulfosuccinate (sample 2).

Example 2: Rate of antimicrobial action of supported silver / BIT

(Kill kinetics measurement according to the Clariant method) of silver BIT mixtures compared to the individual biocides silver and BIT reagents:

600 ml H ₂ O dist. +117 ml (b) + 183 ml (a)

bacteria

Staphylococcus aureus DSM 799 eq. NCTC 10788

Pseudomonas aeruginosa DSM 1128 eq. NCIMB 8026

E-CoIi DSM 682 eq. NCIMB 8545

Enterobacter aerogenes NCIMB 10102

The bacteria are grown on a Caso agar.

Sample 1

After allowing the bacteria to rest on the agar (Caso agar) for 24 hours, add 10 ml of the 0.1M phosphate buffer and mix for 20 seconds with a vortex mixer; to 1 ml of this solution is added 9 ml of the 0.1 M buffer solution; In turn, 1 ml of this solution is removed and 9 ml of 0.1 M phosphate buffer are added. The solution thus obtained is the inoculum with which the test series is carried out.

Sample 1: 19 ml of 0.1 M phosphate buffer +1 ml inoculum) Sample 2: Sample 1 + 40 ppm Composition 1 + 40 ppm

Composition 5

Sample 3: Sample 1 + 60 ppm Composition 1 + 20 ppm

Composition 5 Sample 4: Sample 1 + 20 ppm Composition 1 + 60 ppm

Composition 5 Sample 5: Sample 1 + 80 ppm Composition 1 Sample 6: Sample 1 + 40 ppm Composition 1 Sample 7: Sample 1 + 80 ppm Composition 5

The bacterial count was in each case at the beginning (0 h), after 0.5 h, 1 h; 2 h; 3 h; 5 hours; 7 h and 24 h according to the TVC method European Pharmacopoeia 2.6.12 determined.

Tab.2: Germ numbers as a function of time

Benzoisothiazoline alone develops its antimicrobial effect only after many hours, the efficiency of the silver ions is moderate in the first few hours. The combination of the two active substances silver and BIT leads to a synergistic effect that comes after only 1 to 2 hours of exposure to the microorganisms to fruition.

Tab. 3: Color stability of Ag / BIT in comparison AgCl, AgNO ₃ , JMAC

Table 4 pH dependence of silver BIT

It was submitted to silver nitrate and BIT added in the ratio 1: 2. This mixture initially had a pH of 10. The mixture was split and the samples were adjusted to the pH values indicated below using nitric acid or sodium hydroxide solution.

* After 24 hours more than 90% of the precipitate had settled, but a slight white shimmer in the water phase persisted for 3 to 4 days.

^** The discoloration in the acidic pH range occurred in the first 24 hours, then did not change afterwards.

Formulation Examples:

Example 3:

10.0% Composition 1 45.0% Composition 5

0.4% xanthan gum 44.6% water manufacturing

Prepare composition 5 in water, add with stirring (Ultra Turrax) an aqueous dispersion of composition 1, grind in a bead mill and adjust the viscosity with xanthan gum.

Example 4:

20.0% Composition 1 (0.4% silver compound as active substance) 9.1% Composition 6 (3% active substance) 0.4% xanthan gum 70.5% water

Preparation Composition 6 in water, stirring (Ultra Turrax)

Add composition 1, grind in a bead mill and adjust the viscosity with xanthan gum.

Example 5:

30.0% Composition 1 (0.6% silver compound as active substance) 10.5% Composition 7 (1% active ingredient) 0.4% xanthan gum 59.1% water

manufacturing

Prepare Composition 7, disperse Composition 1 in water with stirring to the solution of Composition 7 (Ultra Turrax) and adjust the viscosity with xanthan gum. Example 6:

1, 0% Composition 2 15.0% Composition 5 1, 5% dioctylsulfosuccinate

0.4% xanthan gum 82.1% water

Preparation of dioctylsulfosuccinate in water, with stirring (Ultra Turrax)

Add composition 5 and composition 1, grind in a bead mill and adjust the viscosity with xanthan gum.

Example 7:

3.0% Composition 2 2.7% Composition 4 2.0% dioctylsulfosuccinate 0.4% xanthan gum 91, 1% water

manufacturing

Present dioctylsulfosuccinate in water and, using an Ultra Turrax, first disperse Composition 4, then Composition 2, grind in the bead mill and adjust the viscosity with xanthan gum.

Example 8:

10.0% Composition 3 15.0% Composition 4 1, 5% Polynaphthalenesulfonate 0.4% xanthan gum 82.1% water

Prepare polynaphthalenesulfonate in water and, using an Ultra Turrax, first disperse Composition 4, then Composition 3, mill in a bead mill and adjust the viscosity with Xanthan gum.

Example 9:

10.0% Composition 1 15.0% Composition 5

1, 0% polynaphthalenesulfonate 1, 5% dioctylsulfosuccinate

0.4% xanthan gum 72.1% water

Prepare polynaphthalenesulfonate and dioctylsulfosuccinate in water and, using an Ultra Turrax, first disperse Composition 5, then disperse Composition 1, mill in the bead mill and adjust the viscosity with xanthan gum.

Example 10:

10.0% Composition 3 4.0% Composition 4 0.5% Polynaphthalenesulfonate 85.5% Titanium Dioxide Example 11:

10.0% Composition 3

4.0% Composition 40.5% polynaphthalenesulfonate 1, 0% sodium dihydrogen phosphate

84.5% titanium dioxide

Example 12:

20.0% Composition 1

9.1% Composition 6

2.0% disodium hydrogen phosphate / sodium dihydrogen phosphate 3: 1 0.4% xanthan gum 68.5% water

Claims

claims

Compositions comprising a) silver and / or one or more silver compounds, with the proviso that the compositions are free of formaldehyde.

A composition according to claim 1, wherein a silver compound selected from silver chloride, silver bromide, silver iodide, silver nitrate, Ag ₃ PO ₄ , Ag ₂ SO ₄ , Ag ₂ CO ₃ , silver citrate, silver stearate, silver acetate, silver lactate, silver salicylate, silver oxide (silver hydroxide) is.

3. A composition according to claim 1 and / or 2, wherein the silver or silver compound is adsorbed on a water-insoluble, inert, non-hydratable or non-hydrated, oxidic support, and the silver and / or the silver compound (s), always calculated as elemental silver , based on the weight of the carrier, in amounts of 0.1 wt .-% to 75 wt .-% present.

4. The composition of claim 3, wherein the carrier is titanium, magnesium, aluminum, silicon, calcium, barium oxide, calcium hydroxyapatite, chalk, natural ground or precipitated calcium carbonates, calcium

Magnesium carbonates, silicates, phyllosilicates, zeolites, clays, bentonites or titanium oxide is selected.

5. Composition according to one or more of claims 1 to 4, wherein b) one or more biocidal active substance (s) from the group of isothiazolines is contained.

6. A composition according to claim 5, wherein the isothiazolines correspond to one of the formulas I to IM

Formula (I) Formula (II)

Formula (III)

or derivatives thereof bearing a substituent selected from at least one of said positions 2, 3, 4 or 5, selected from C _r to C ^ alkyl groups, phenyl groups, fused aromatic systems, halogen atoms or carbonyl groups.

7. A composition according to claim 5 and / or 6, wherein the isothiazoline of 2-methyl-3-isothiazoline, 2-methyl-4-isothiazolin-3-one, 2-ethyl-3-isothiazoline, 2-propyl-3-isothiazoline , 2-isopropyl-3-isothiazoline, 2-butyl-3-isothiazoline (where butyl may be n-butyl, iso-butyl or tert-butyl), 2-n-octyl-3-isothiazoline, 2-octyl-4 -isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 1,2-benzisothiazolin-3-one, salt, 5-chloro-2-methyl-3-isothiazoline, 5-chloro-2-methyl-4 1-isothiazolin-3-one or 4,5-dichloro-2- (n-octyl) -4-isothiazolin-3-one.

8. The composition according to one or more of claims 5 to 7, wherein the weight fraction of isothiazoline 0.1% to 90%, preferably 1% to 50%, particularly preferably 2% to 20%.

9. Composition according to one or more of claims 1 to 8, wherein the weight proportion of silver or silver compound / s, calculated as elemental silver, 0.01% to 50%, preferably 0.1% to 20%, particularly preferably 0, 2% to 2%.

10. The composition according to one or more of claims 5 to 9, containing 0.1 wt .-% to 90 wt .-% of at least one isothiazoline and 0.01 wt .-% to 50 wt .-% silver or at least one silver compound , calculated as elemental silver.

Composition according to one or more of claims 5 to 10, wherein the weight ratio of component a), calculated as elemental silver, to component b) is in the range from 1: 100 to 100: 1.

12. The composition according to one or more of claims 5 to 11, comprising silver nitrate and benzisothiazoline or a salt of benzisothiazoline in a weight ratio of 1: 1 to 1: 3, wherein silver nitrate is calculated as elemental silver.

13. The composition according to one or more of claims 3 to 12, wherein the carrier has a particle size of less than 25 microns.

14. A composition according to one or more of claims 3 to 13, wherein the weight proportion of silver or the silver compound, calculated as elemental silver, based on the weight of the carrier, in the range of 1 wt .-% to 50 wt .-%, preferably 10 wt .-% to 30 wt .-% is.

15. The composition according to one or more of claims 1 to 14, wherein 0.1 to 40 wt .-% Polynaphthalinsulfonate, naphthalenesulfonates or

Alkyl sulphosuccinates are included.

Use of a composition according to one or more of claims 1 to 15 for the antimicrobial finishing of substrates, wherein the finished substrate contains an amount of 5 to 1000 ppm of the composition.