EP1268917A1

EP1268917A1 - Use of 3-iodine-2-propinyl-carbamates as antimicrobial active agent

Info

Publication number: EP1268917A1
Application number: EP01936157A
Authority: EP
Inventors: Michael Heinzel
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2000-04-04
Filing date: 2001-03-30
Publication date: 2003-01-02
Also published as: WO2001075213A1; DE10016371A1; JP2003535047A; AU2001262148A1

Abstract

The invention relates to the use of 3-iodine-2-propinyl-carbamates as antimicrobial, especially antimycotic, active agents in washing agents, cleaning agents, hand washing agents, hand washing-up liquids, washing-up liquids for dishwashers and agents for finishing textiles, furs or leather.

Description

Use of 3-iodo-2-propynyl-carbamates as an antimicrobial agent

Description:

The present invention relates to the use of 3-iodo-2-propynylcarbamates as antimicrobial, in particular antimycotic, active ingredients in detergents; Cleaning agents; Hand washing; Hand dishwashing detergents; Dishwasher detergents and agents for finishing textiles, furs, furs or leather.

Hygiene in the washing and cleaning process means not only the removal of visible dirt but also the rendering harmless of germs that have contaminated the items to be cleaned, such as laundry, for use. Such germs are viruses and bacteria, but especially fungi. Hygiene, in particular laundry hygiene, is therefore of particular importance in the commercial sector, where textiles from hospitals, hotels, restaurants, etc. are reprocessed that do not circulate within a specific group of users, but are used by ever different users. But also in the household area, the hygiene aspect is becoming increasingly important, especially because more and more textiles that are worn directly on the body, such as underwear, lingerie or stockings, are made of fabrics, the washing temperatures of 40 ° C or above, proteases and bleach-active substances do not tolerate, so that mild detergents must be used whose germicidal effect is only slight. For ecological reasons - not least because of the voluntary commitment of the industry to reduce energy consumption - the washing processes in their hygienic parameters (temperature, washing times and liquor ratio) were continuously minimized. As a result, all of these factors together can lead to the fact that germs which have contaminated the laundry when worn are no longer rendered harmless in the washing process and later lead to hygienic problems when reused. In addition, washing machines and dishwashers, especially those that are not used for a long time, can also lead to hygienic problems and olfactory annoyances due to the strong growth of germs in the hoses, the pump or the dispenser. If laundry remains damp in the washing machine for a longer period of time, it can fungus - this leads to the well-known foxing.

EP-B-0 093 962 describes 2- (3-iodo-2-propynyloxy) ethyl carbamates and their use for the preservation of technical products (e.g. paints, glues, dispersions, cooling lubricants) for the antimicrobial finishing of Joint sealants, for combating mold on walls, ceilings or wooden floors, for antimicrobial finishing of plastics such as B. PVC films and known as preservatives for cosmetics.

3-Iodine-2-propynyl butyl carbamate (IPBC) is known as a preservative from Appendix 6 of the Cosmetics Regulation.

Applicant's DE-A-199 19 770.9, which was still unpublished at the time of filing the present invention, mentions the use of IPBC in nanoscale form as an antimicrobial active ingredient in oral and / or dental care.

Applicant's DE-A-199 19 769.5, which was still unpublished at the time of the application of the present invention, mentions the use of IPBC in nanoscale form as an antimicrobial agent in body deodorants.

The present invention has for its object to provide agents that have an antimicrobial and in particular antimycotic effect and are suitable for overcoming the above-mentioned disadvantages from the prior art.

Surprisingly, it was found that 3-iodo-2-propynylcarbamates, in particular IPBC, also have antimicrobial and, in particular, antimycotic activity as a constituent of detergents and cleaning agents. This finding was particularly surprising because the uses of 2- (3-iodo-2-propynyloxy) ethyl carbamates known from the prior art and of IPBC made it necessary to keep the active ingredient permanently in the product to be preserved or to be antimicrobially treated suggest.

The present invention therefore relates to the use of 3-iodo-2-propynylcarbamates of the formula (I) as an antimicrobial and in particular antimycotic active ingredient in detergents; Cleaning agents; Hand washing; Hand dishwashing detergents and machine dishwashing detergents as well as textile, fur and leather finishing agents.

The 3-iodo-2-propynylcarbamates which can be used according to the invention correspond to the general formula (I)

R

in which R ¹ and R ^{2 are the} same or different and are hydrogen, linear or branched alkyl radicals having 1 to 6 carbon atoms;

R ³ , R ⁴ , R ⁵ and R ⁶ , which may be the same or different, are hydrogen or

Are alkyl radicals having 1 to 4 carbon atoms;

R is hydrogen, linear or branched alkyl radicals having 1 to 12 carbon atoms. men or a cyclohexyl radical, a phenyl radical, a substituted phenyl radical, a benzyl radical or a p-toluenesulfonyl radical and n is 0 or 1.

A carbamate which can preferably be used according to the invention is IPBC, which corresponds to the formula I, where R ¹ and R ^{2 are} hydrogen, n is 0 and R is butyl- (-C ₄ H ₉ ), in particular n-butyl.

The compounds which can be used according to the invention are prepared by processes known per se from the prior art, in particular as described in EP-B-0 093 962, to which reference is hereby made in full.

The 3-iodo-2-propynylcarbamates are prepared, for example, by equimolar amounts of the alcohols of the general formula (II)

with suitable isocyanates of the general formula (III),

OCN— R (III)

where in the formulas (II) and (III) the symbols R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R and n have the meanings given for the formula (I). Examples of linear or branched alkyl radicals having 1 to 6 carbon atoms, for which R ¹ and R ² are, are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl and their branched isomers. Compounds of the formula (I) in which both substituents R ¹ and R ^{2 are} simultaneously hydrogen or simultaneously methyl are preferably used, so such as those in which one of R ¹ and R ^{2 is} hydrogen while the other is methyl.

Examples of alkyl radicals with 1 to 4 carbon atoms for which R ³ . R ⁴ , R ⁵ and R ⁶ are methyl. Ethyl, propyl, isopropyl, n-butyl, isobutyl. sec-butyl and tert-butyl, with methyl being preferred.

Compounds which can be used with preference are those of the general formula (I) in which at least 4 of the radicals R ¹ to R ⁶ are hydrogen.

Examples of linear and branched alkyl radicals with 1 to 12 carbon atoms. R stands for methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl. Heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the branched isomers of alkyls with 5 to 12 carbon atoms.

Examples of substituted phenyl radicals which R represents are chlorophenyl,

Bromophenyl, fluorophenyl, dichlorophenyl and trichlorophenyl.

Compounds in which R is a lower alkyl radical having 1 to 4 carbon atoms or a phenyl radical or a phenyl radical substituted by chlorine or bromine are preferably usable.

Examples of particularly preferred compounds are those in which R is propyl, butyl or phenyl.

The N-substituted 3-iodo-2-propynylcarbamates of the general formula (I) are obtained by methods known per se (Houben-Weyl, Methods of Org. Chemistry, Vol. 8, pp. 141-144 (1952)) Implementation of equimolar amounts of the alcohols of the general formula (II) with suitable, for. B. synthesized commercially available isocyanates of the general formula (IM). The reaction is carried out at temperatures from about 10 ° C to about 70 ° C. preferably from about 20 ° C to about 30 ° C.

The reactions are generally carried out in an inert solvent. Examples are ethylene chloride. Dimethylformamide. Toluene. Chlorobenzene. Methylene chloride and tetrahydrofuran called.

The reactions can be accelerated with the help of catalysts. As Catalysts such as dibutyltin dilaurate have proven suitable. Other catalysts that can be used are: dibutyltin diacetate and tert. Bases such as triethylamine.

The alcohols of the general formula (II) can be prepared by known processes by iodinating propargyl alcohol or substituted propargyl alcohols (n = 0) or in two reaction stages by reacting propargyl alcohol or substituted propargyl alcohols with ethylene oxide or substituted epoxides and subsequent iodination of the propynyloxy obtained -Alcohols (n = 1) can be produced.

Examples of alcohols of the general formula (II) are:

3-iodo-2-propinol,

2- (3-iodo-2-propynyloxy) -ethanol,

2- (4-iodo-3-butyn-2-yloxy) ethanol, 1- (3-iodo-2-propynyloxy) -2-propanol and

1- (2-hydroxyethoxy) -1-iodoethynyl cyclohexane.

Examples of isocyanates are methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, phenyl isocyanate, 4-chlorophenyl isocyanate, cyclohexyl isocyanate, 4-fluorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, 2,4,5-trichlorophenyl isocyanate and p-toluenesulfonyl isocyanate.

The 3-iodo-2-propynylcarbamates which can be used according to the invention are added to the liquid compositions in which they are to have their action in a manner known to those skilled in the art. For use in solid compositions, the 3-iodo-2-propynylcarbamates which can be used according to the invention can either be added to the liquid or pasty base materials from which the solid compositions are made or applied to the solid compositions, for example by spraying.

The 3-iodo-2-propynylcarbamates which can be used according to the invention are preferably the detergents; Cleaning agents; Hand washing; hand- schirrspülmitteln; Machine dishwashing detergents and agents for finishing textiles, furs, skins or leather in an organic solvent, in particular in an alcoholic solution, particularly preferably in an ethanolic solution.

Likewise preferably, the 3-iodo-2-propynylcarbamates which can be used according to the invention are added to the abovementioned agents in nanoscale form. Nanoscale substances are substances whose particle diameter in the direction of the greatest expansion of the particles is less than 1000 nm (nanometers). In particular, the particle diameter of the 3-iodo-2-propynylcarbamates which can be used according to the invention is approximately 5 to 500 nm, preferably 10 to 150 nm. The term "nanoparticulate" is used synonymously with the term "nanoscale" in the present document. The nanoscale active substances which can be used according to the invention consist of a discrete phase of the active substance, on the surface of which at least one surface-modifying substance is preferably adsorbed. Emulsifiers and / or protective colloids are particularly suitable as surface-modifying substances. The coating of the particles with emulsifiers and / or protective colloids means that there is no subsequent agglomeration of the particles.

Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups:

(1) Adducts of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group;

(2) Cι _{2 /} ι ₈ fatty acid monoesters and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol; (3) glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products; (4) alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogues;

(5) adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil; (6) polyol and especially polyglycerol esters such as e.g. Polyglycerol polyricoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate. Mixtures of compounds from several of these classes of substances are also suitable;

(7) adducts of 2 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil;

(8) Partial esters based on linear, branched, unsaturated or saturated C _6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerin, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), sucrose, alkyl glucosides (e.g. Methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (eg cellulose);

(9) mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;

(10) wool wax alcohols;

(11) polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

(12) mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 1165574 and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol and (13) polyalkylene glycols.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters, and sorbitan mono- and diesters with fatty acids or with castor oil are known, commercially available products. whose average degree of alkoxylation is the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. C _{12 18} fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE-PS 2024051 as refatting agents for cosmetic preparations.

C _{8 /} i ₈ alkyl mono- and oligoglycosides, their preparation and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. With regard to the glycoside residue, both monoglycosides in which a cyclic sugar residue is glycosidically bound to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to about 8 are suitable. The degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.

Typical examples of anionic emulsifiers are soaps, alkyl benzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxymixed ether ether sulfates, mono sulfate ether sulfates, mono -sulfosuccinates, mono- and dialkylsulfosuccinamates, sulfotriglycides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids such as acyl lactylate, acyl tartrates, acyl glutucate fatty acids (acyl glutoglucate fatty acids), (acyl glutoglucate fatty acids) and insylate acylate methacrylate (acyl glutamate fate) Wheat-based products) and alkyl (ether) phosphates. If the anionic ten-side contains polyglycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution.

Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the trimethylammonium glycinate, cocoalkyldimethylammonium glycinate, N-acylamino-propyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyldimethylammonium, and 2-glycinate, Alkyl-3-carboxylmethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, and also the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. The fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine is particularly preferred. Suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a Cβ _/ iβ-alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts , Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyl taurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkyl- laminoacetic acids each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkyl aminopropionate, cocoacylaminoethyl aminopropionate and of C _12/1 ₈ - sarcosine. In addition to the ampholytic emulsifiers, quaternary emulsifiers are also suitable, those of the ester quat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred. Typical examples of anionic emulsifiers are alkyl sulfates, alkyl ether sulfates and monoglyceride (ether) sulfates.

As a rule, the active ingredients and the emulsifiers are used in a weight ratio of 1: 100 to 100: 1, preferably 1:25 to 25: 1 and in particular 1:10 to 10: 1. Emulsifiers which are capable of forming microemulsions are particularly preferred.

Suitable protective colloids are, for example, gelatin, casein, gum arabic, lysalbic acid, starch, carboxymethyl cellulose or modified carboxymethyl cellulose. cellulose and polymers, such as polyvinyl alcohols, polyvinyl pyrrolidones, polyalkylene glycols and polyacrylates.

The 3-iodo-2-propynylcarbamates which can be used according to the invention can also be used as nanoparticles which are encased by one or more emulsifiers and / or protective colloids.

Corresponding nanoparticles can be produced, for example, by introducing (a) 3-iodo-2-propynyl-carbamates into a liquid phase in which they are not soluble,

(b) the resulting mixture is heated above the melting point of the 3-iodo-2-propynylcarbamate,

(c) adding an effective amount of at least one emulsifier to the resulting oil phase and finally

(d) the emulsion cools below the melting point of the 3-iodo-2-propynyl-carbamate.

Another process for the production of nanoparticles by rapid relaxation of supercritical solutions (Rapid Expansion of Supercritical Solutions RESS) is, for example, from the article by S.Chihlar, M.Türk and K.Schaber in Proceedings World Congress on Particle Technology 3, Brighton , Known in 1998. To prevent the nanoparticles from caking again, it is advisable to dissolve the starting materials in the presence of suitable protective colloids or emulsifiers and / or to dissolve the critical solutions in aqueous and / or alcoholic solutions of the protective colloids or emulsifiers or else in cosmetic oils relax, which in turn can contain dissolved emulsifiers and / or protective colloids.

Evaporation technology offers another suitable method for producing the nanoscale particles. Here, the starting materials are first in a suitable organic solvent (e.g. alkanes, vegetable oils,

Ethers, esters, ketones, acetals and the like) dissolved. Then the Solutions in water or another non-solvent, usually in the presence of a surface-active compound dissolved in them, such that the homogenization of the two immiscible solvents leads to precipitation of the nanoparticles, the organic solvent preferably evaporating. Instead of an aqueous solution, O / W emulsions or O / W microemulsions can also be used. The emulsifiers and protective colloids already explained at the beginning can be used as surface-active compounds. Another possibility for the production of nanoparticles is the so-called GAS process (Gas Anti Solvent Recrystallization). The process uses a highly compressed gas or supercritical fluid (e.g. carbon dioxide) as a non-solvent for the crystallization of solutes. The compressed gas phase is introduced into the primary solution of the starting materials and absorbed there, which increases the volume of the liquid, the solubility decreases and fine particles are separated out.

The PCA method (Precipitation with a Compressed Fluid Anti-Solvent) is similarly suitable. Here the primary solution of the starting materials is introduced into a supercritical fluid, whereby finely divided droplets form in which diffusion processes take place, so that the finest particles are precipitated. In the PGSS process (Particles from Gas Saturated Solutions), the raw materials are melted by injecting gas (e.g. carbon dioxide or propane). Pressure and temperature reach near or supercritical conditions. The gas phase dissolves in the solid and causes a lowering of the melting temperature, the viscosity and the surface tension. When expanding through a nozzle, cooling effects lead to the formation of very fine particles.

The production processes listed for the nanoparticles according to the invention are only to be understood as examples and do not constitute any restriction.

The concentration of the 3-iodo-2-propynylcarbamates which can be used according to the invention in the agents can be varied within a wide range by the person skilled in the art can be varied depending on the conditions in which the agents are used. The amount of dissolved or nanoscale 3-iodo-2-propynyl-carbamates is chosen so that the concentration of 3-iodo-2-propynyl-carbamates is usually in the order of 0.001 to 5, preferably 0.01 to 2 and in particular 0 , 1 to 1 wt .-% based on the preparations.

Other objects of the present invention are detergents; Cleaning supplies; rinse; Hand washing; Hand dishwashing detergents; Machine dishwashing detergents and agents for finishing textiles, furs, furs or leather, which contain a 3-iodo-2-propynyl carbamate of the formula (I) or more 3-iodo-2-propynyl carbamates, in particular those that contain IPBC. Preferred objects of the present invention are detergents; Cleaning supplies; rinse; Hand washing; Hand dishwashing detergents; Machine dishwashing detergents and agents for finishing textiles, furs, skins or leather, to which 3-iodine-2-propynyl-carbamates, in particular IPBC, have been added in nanoparticulate form.

Another object of the present invention is the use of 3-iodo-2-propynylcarbamates of the formula I, in particular of IPBC, as an antimicrobial and in particular antimycotic active ingredient in agents for the antimicrobial finishing of textiles, furs, skins or leather.

Further objects of the present invention are textiles, furs, furs or leather, equipped with an agent according to the invention.

The textiles, furs, skins or leather are finished in a manner known to those skilled in the art, for example by immersing the textiles, furs, skins or leather in a suitably concentrated solution of an agent according to the invention.

The following examples illustrate the invention without, however, restricting it thereto: 1.1. test substances

IPBC (30% in dipropylene glycol), obtained from Milker & Grüning GmbH, Horhausen, was prediluted as follows because of the poor water solubility:

An alcoholic stock solution with 1% active ingredient was prepared by weighing 3.34 g of 30% IPBC in 100 ml of 99% ethanol and in subsequent dilutions in double dist. H ₂ O further diluted to the required test solutions. These were:

2ml stock solution ad 200ml bidest. H ₂ O - »100ppm IPBC (= 0.99% ethanol) 10ml stock solution ad 200ml bidist. H ₂ O - 500ppm IPBC (= 4.95% ethanol) 15ml stock solution ad 200ml bidist. H ₂ O - »750ppm IPBC (= 7.42% ethanol)

An antibacterial and antimycotic formulation was used as the reference preparation, comprising 70% by weight didecyldimethylammonium chloride, 15% by weight ethylene glycol, the rest water. The reference preparation was also diluted with double-distilled water.

1.2. test fungi

Candida albicans, ATCC 10231, (pre-breeding on CaSo agar, 4d / 25 ° C), Aspergillus niger, ATCC 6275, (pre-breeding on malt agar, 8d / 25 ° C), Trichophyton mentagrophytes, ATCC 9533, (pre-breeding on malt agar , 8d / 25 ° C), Cladosporium cladosporioides, DSM 62121, (pre-cultivation on malt agar, 8d / 25 ° C), Epicoccum nigrum, self-isolate, (pre-cultivation on malt agar, 8d / 25 ° C)

The inocula were obtained by washing off the pre-cultivated plates with 0.05% Tween ^® 80 and had the following germ contents:

Candida albicans 1.9 x 10 ⁹ CFU / ml,

Aspergillus niger 1, 0x10 ⁷ CFU / ml, Trichophyton mentagrophytes 3.4x10 ⁷ CFU / ml,

Cladosporium cladosporioides 5.0x10 ⁷ CFU / ml,

Epicoccum nigrum 1, 9x10 ⁵ CFU / ml.

(KBE: colony forming unit)

1.3. Testing the fungistatic effectiveness in the inhibition test

1x1 cm, pre-washed and autoclaved test specimens made from standard cotton fabric according to DIN 53919 (WfK Testgewebe-GmbH, Adlerstrasse 42, Krefeld) were placed in the test sample for 15 minutes. inserted, then removed sterile and dried at room temperature for 14 h. 0.1 ml vaccine suspensions of the above Test mushrooms were inoculated in liquid malt agar in a petri dish and, after the agar had solidified, 0.1 ml was spatulated on the agar surface. The test specimens impregnated with the test solutions were then placed sterile on the agar surface and the dishes were incubated at 25 ° C. for 7 days. The inhibitory effect was then evaluated according to the following scheme:

0 = clear zone of inhibition, indication of the zone of inhibition in mm,

1 = no growth on the test specimen, but also no inhibition zone, 2 = isolated growth on the test specimen,

3 = moderate growth on the test object,

4 = uninhibited growth on the test specimen.

1.4. Examination of the fungicidal effectiveness in the DGHM germ carrier test

The test was carried out in accordance with the guidelines for the testing and evaluation of chemical disinfection processes of the German Society for Hygiene and Microbiology (DGHM), Gustav Fischer Verlag, 1981: 16 pre-washed and autoclaved test specimens were placed in the above-mentioned vaccine pens of the test fungi and included Leave it to be turned over and over for 15 minutes. The test specimens contaminated in this way were then transferred to empty petri dishes and poured over each with 10 ml of the test solutions. After 60 and 120 minutes of exposure time at 20 ° C, 2 of the test specimens were removed and briefly transferred to 10 ml of inactivator solution according to the DGHM guideline and inoculated therefrom onto CaSo (Candida) or malt agar plates (other test fungi). The incubation was carried out for 7 days at 25 ° C. Then the evaluation was qualitative, ie growth yes (+) or no (-).

2 results

2.1. Fungistatic effectiveness of IPBC

2.1.1. Testing the inhibitory activity of IPBC yielded the following results:

2.2. Fungicidal effectiveness of IPBC

2.2.1. Testing the fungicidal activity of IPBC gave the following results (+ = living culture, - = culture killed):

2.2.3. The comparison test with the reference preparation showed positive growth for all test fungi up to the highest test concentration of 250 ppm. 3. Result:

Compared to the reference preparation, IPBC show a very good fungistatic activity against both dermatophytes and fungi that produce mold stains or are harmful to the material.

Claims

claims:

1. Use of 3-iodo-2-propynylcarbamates of the formula (I),

R ³ , R ⁴ , R ⁵ and R ⁶ , which may be the same or different, denote hydrogen or alkyl radicals having 1 to 4 carbon atoms;

R represents hydrogen, linear or branched alkyl radicals having 1 to 12 carbon atoms or a cyclohexyl radical, a phenyl radical, a substituted phenyl radical, a benzyl radical or a p-toluenesulfonyl radical and n represents 0 or 1, as antimicrobial active substances in detergents; Cleaning agents; rinse aid; Hand washing; Hand dishwashing detergents; Dishwasher detergents and agents for the antimicrobial finishing of textiles, furs, skins or leather.

2. Use according to claim 1, wherein IPBC is used as the 3-iodo-2-propynylcarbamate.

3. Use according to claim 1 or 2, wherein the 3-iodo-2-propynyl carbamates are used in nanoparticulate form.

4. Use according to one of claims 1 to 3, wherein antimicrobial means in particular antimycotic.

5. detergent; containing a 3-iodo-2-propynyl carbamate or several 3-iodo-2-propynyl carbamates, in particular IPBC.

6. cleaning agents; containing a 3-iodo-2-propynyl carbamate or several 3-iodo-2-propynyl carbamates, in particular IPBC.

7. rinse aid; containing a 3-iodo-2-propynyl carbamate or several 3-iodo-2-propynyl carbamates, in particular IPBC.

8. hand wash; containing a 3-iodo-2-propynyl carbamate or several 3-iodo-2-propynyl carbamates, in particular IPBC.

9. dishwashing liquid; containing a 3-iodo-2-propynyl carbamate or several 3-iodo-2-propynyl carbamates, in particular IPBC.

10. Machine dishwashing detergent, containing one 3-iodo-2-propynyl carbamate or several 3-iodine-2-propynyl carbamates, in particular IPBC.

11. Agents for finishing textiles, furs, skins or leather, containing one 3-iodo-2-propynyl carbamate or several 3-iodo-2-propynyl carbamates, in particular IPBC.

12. Composition according to one of claims 5 to 11, characterized in that 3-iodo-2-propynyl-carbamates, in particular IPBC, have been added to them in nanoparticulate form.

13. Textiles, furs, skins or leather, equipped with an agent according to claim 11 or 12.