DE1767684A1 - Detergents, washing auxiliaries and cleaning agents containing antimicrobial agents - Google Patents

Description

"Detergents, washing auxiliaries and cleaning agents containing antimicrobial agents" It is known to add antimicrobial agents to detergents, in particular if the detergents are used under delicate wash conditions, i.e. at temperatures in the range from 30 ° to 50 ° C, should be used. These temperatures range by far not yet sufficient to eliminate unwanted microorganisms, such as bacteria or fungi, kill. The cleaning effect of the detergent must therefore be ensured by a suitable one antimicrobial agent supplements. But also with detergents that are used at higher temperatures, especially in the region of the cooking temperature, determined an addition of antimicrobial agents may be desirable, in particular, if the laundry to be cleaned is underwear or bed linen from hospitals acts where there is strong organic contamination, such as ointments, blood, titer or Sputum delay the killing of microorganisms, even with detergents that in the household, in trade and in industry for cleaning other than textile materials are determined, the presence of antimicrobial agents is often desired.

The older patent (patent application H 63 380 (D 3390)) describes antimicrobial Agents that act as antimicrobial agents in certain nitroalkyl-N-phenylcarbamates contain. These antimicrobial agents can preferably be used with a complexing agent be combined, which in the Hampshire test according to the calcium carbonate method has a complexing capacity contains more than 230 mg CaCO3 / g $ complexing agent.

The invention relates to washing, auxiliary washing and cleaning agents containing antimicrobial agents. The preparations according to the invention are characterized in that they contain: a) 0.2-30, preferably 1-5% by weight of a nitroalkyl-N-phenylcarbamate of the general formula 1 where the symbols used in this formula and in the formulas II and IIt mean: Y fluorine, chlorine, bromine, a trifluoromethyl or a nitro group, n the numbers 0-2, A the carbamic acid ester grouping of the formula IT, R hydrogen or a methyl radical, X hydrogen or bromine and z hydrogen, a methyl radical, an ethyl radical or the phenylcarbamic acid ester grouping of the formula III, b) at least 5 wt.% And preferably at least 10 wt Hampshire test has a complexing capacity of a maximum of 230 mg caco3 / g, c) if necessary, other common components of washing, auxiliary washing or washing agents. Detergents, -. these quantities referring to the sum of the quantities of component a) and the quantities of the water-soluble constituents of components b) and c) minus any solvents present.

The above, under b) defined alkaline builders need to have no complex-forming ability at all. Used preferably one here the mostly inorganic ones known under the name "washing alkalis" Salts. In special cases, free bases, in particular caustic alkalis, can also be used will. The alkaline structural substances. according to b) a certain ability to form complexes own; mathematically, however, they are only then part of component b) considered if the complexo-forming capacity does not exceed the limit given above.

This should ensure the presence of substances with a higher complex-forming capacity in no way be excluded; on the contrary, the structural substances according to # b) are preferably present together with complexing agents, their complexing capacity in the Hampshire test is above 230 mg CaCO3 / g complex bilaner. The quantity ratio from structural substance to complexing agent can vary within wide limits.

A synergistic effect between antimicrobial agent and Complexing agents (above 230 mg CaCO3 / g) can already be determined when the amount this complexing agent at least), preferably at least 10 wt .-%.

The proportion of the complexing agent in the mixture of complexing agent and structural substance b) can be 10-90, preferably 25-75% by weight.

The quantities given apply here as well, insofar as they relate to the whole Preparation and not refer to parts or partial mixtures devon, under the above Conditions.

The alkaline builders in the sink of the invention include also bleach components, provided that they themselves have an alkaline reaction or those after Release of the active oxygen remaining substances. Alkaline reaction demonstrate. Some bleach components, such as monopersulfate or diacyl peroxides, in particular dibenzoyl peroxide, react acidic themselves or deliver after oxygen depletion acidic reac-? tion products. These non-alkaline reacting substances can are used as bleaching components in the products according to the invention, provided that there is enough alkali. to maintain the desired pH.

If the preparations according to the invention are used as laundry detergents and auxiliary washing agents Are intended for use in textiles, they should be in 1% aqueous solution Have pH values of about 8-12, with mild detergents generally being weaker alkaline (pH values 8 - 9.5) and cooking detergents more strongly alkaline (pH values 9.5 - 12, preferably 10 - 11.5) are set. Also in the household, in commercial Operated and often in industry for cleaning the surfaces of solid materials With the exception of products specific to textiles, such pH values can tesitzon; but you can also produce more strongly alkaline reacting products, e.g. may contain free alkaline salts and are generally only used for special purposes will.

The detergents according to the invention can be used for laundry and bleaching laundry of various fibers of natural or synthetic origin use, such as B. cotton, regenerated cellulose or linen, as well as for the so-called "Easy-care" textiles that are wholly or partially made from highly refined cotton or from synthetic fibers, such as. B. polyamide, polyester, polyacrylonitrile polyurethane, Polyvinyl chloride or polyvinylidene chloride lasers exist. But also washing aids, such as soaking or rinsing agents that contain the antimicrobial to be used according to the invention Can contain active ingredients Advantage can be used. To the However, preparations according to the invention also include hair and body washes and cleaning agents for hands and cleaning agents for instruments or for commercial operations, such as dairies, breweries, etc.

The preparations according to the invention can be used as pieces, tablets, powders, Granules, agglomerates, pastes or solutions are present.

Apart from the preparations, where the pasty consistency essentially on the presence of appropriate amounts of pasty surfactants (Nonionics) is to be returned, the pasty or liquid nature is mostly due to the presence of corresponding amounts of liquid solvents, in which the other components of the preparation are suspended or dissolved. Of the The solvent content of these preparations can be 40-90, preferably 50-85% by weight.

The preferred solvent is water; it can be whole or partially replaced by water-soluble organic solvents, e.g. by monohydric alcohols with 1-4, preferably 2-3, carbon atoms, polyhydric alcohols with 2 - 5 carbon atoms, partial ethers of these polyhydric alcohols with one another or with the monohydric alcohols mentioned. Examples include: ethyl, n or i-propyl alcohol, glyco: glycerine, ethylene glycol monomethyl or monoethyl ether, Glycerir.mono- or diether of methyl or ethyl alcohol etc. Ni In the preparations according to the invention can include water as water of crystallization in salts, in particular bound to inorganic salts (Na2CO3 10 H20, NapPOX. 12 H2O, Na5P3O10. 6 H2O) be.

This water is not to be regarded as a solvent.

The substituted phenyl ethers are used as antimicrobial agents of the above constitution suitable.

However, those through halogen atoms or nitro groups are preferred substituted phenyl ethers. Particularly favorable results can be achieved in many cases with halogen-substituted phenyl ethers on the phenyl nucleus, their aliphatic Ether component substituted by a hydroxyl group or. by an oxygen atom is interrupted, achieve, because with their help preparations -with particularly- higher Effectiveness, i.e. with particularly low bactericidal or fungicidal concentrations if necessary can be produced if the effectiveness is satisfactory.

Nitroalkyl-N-phenylcarbaniates, used as bactericidal and fungicidal agents are possible, e.g. 2-nitroethyl-N-phenylcarbamate, 2-nitroethyl-N- (3-chlorophenyl) -carbamate, 2-nitroethyl-N- (3,4-dichlorophenyl) -carbamate, 2-nitroethyl-N- (4-nitrophenyl) -carbamate, 1-methyl-2-nitroethyl-N- (3,4-dichlorophenyl) -carbamate, 2-nitropropyl-N-phenyl-carbamate, 2-nitropropyl-N- (3-chlorophenyl) -carbamate, 2-nitrobutyl-N-phenylcarbamate, 1-methyl-2-nitropropyl-N-phenylcarbamate, 1 methyl 2-nitrobutyl-N- (4-nitrophenyl) -carbamate, 2-bromo-2-nitroethyl-N- (3-chlorophenyl) -carbamate, l-methyl-2-bromo-2-nitroethyl-N-phenylcarbamate, 2-bromo-2-nitropropyl-N- (3-chlorophenyl) carbamate, 2-bromo-2-nitrobutyl-N-phenylcarbamate, 2-bromo-2-nitrobutyl-N- (3,4-dichlorophenyl) -carbamate, 1-methyl-2-bromo-2-nitropropyl-N- (4-nitrophenyl) -carbamate, 1-methyl-2-bromo-2-nitrobutyl-N-phenylcarbamate, 2-nitropropanediol- (1,3) -bis-N-phenylcarbamate, 2-nitropropanediol- (1,3) -bis-N- (3,4-dichlorophenyl) -carbamate, 1-methyl-2-nitropropanediol- (1,3) -bis-N- (3-chlorophenyl) -carbamate, 1,3-dimethyl-2-nitropropanediol- (1,3) -bis-N- (4-nitrophenyl ) carbamate, 2-bromo-2-nitropropanediol- (1,3) -bis-N-phenyl-carbamate, 2-bromo-2-nitropropanediol- (1, 3) -bis-N- (3-chlorophenyl) -carbamate, 2-bromo-2-nitropropanediol- (1,3) -bis-N- (3,4-dichlorophenyl) -carbamate, 2-Brol-2-nitro-propanediol; (1,3) -bis-N- (4-nitrophenyl) -carbamate, 1-tert-ethyl-2-bromo-2-nitropropanediol- (1, 3) -bis-N- (3-chlorpher * rl) -carbamate, 1,3-dimethyl-2-bromo-nitropropanediol- (1,3) -bis-N- (3,4-dichlorophenyl) -carbamate, 2-nitro-alkyl-N- (3-trifluoromethylphenyl) -carbamate, Seocom-2-nitro-intyl-N- (3-trifluoromethylphenyl) -carbamate.

To the other usual ones in detergents, auxiliary washing agents and cleaning agents Components according to point c) of the definition of the invention include surfactants any textile softeners, foam stabilizers and / or foam inhibitors, dirt carriers, Enzymes, bleach components, stabilizers for the bleach components and, if so these are per compounds, including activators for these, abrasives, Fragrances, dyes, etc.

The composition of the detergents, auxiliary washing agents and cleaning agents according to the invention is, apart from the antimicrobial agent, which is in amounts of 0.2-30, preferably 1 - 5 wt. Is available, generally in the range of the following recipe: 0 - 90, preferably 5-40 and in particular 12-30% by weight of surfactants, including any textile weather or combinations of surfactants, consisting of 0 - 100, preferably 25-65% by weight of surfactants of the sulfonate and / or sulfate type with preferred 8-18 carbon atoms in the hydrophobic residue, 0-100, preferably 5-40% by weight nonionic Surfactants, 0 - 100, preferably 10 - 50% by weight soap, 0 - 6, preferably 0.5 - 3% by weight foam stabilizer, 0-8, preferably 0.5-5% by weight non-surfactant Foam inhibitor, 5-99, preferably 10-70% by weight of a conventional, alkaline reacting structural substance as defined above, in combination with complexing agents may be present as defined above, the complexing agents preferably at least 3, in particular at least 10% by weight of the total preparation make up 0-50, preferably 2 - 15% by weight of other detergent ingredients, such as bleach components, dirt carriers, optical brighteners, enzymes, fragrances, dyes, water.

If the preparations according to the invention are produced by spray drying were produced, they usually contain no more than 25% by weight and preferably at most 20% by weight of water.

But are the preparations from one: '. aqueous, pasty approach has been converted into a solid state by binding the liquid water, then the water content can be up to 50.

The laundry detergents and auxiliary washing agents according to the invention can furthermore Bleach components he. thanten, which then including any activators present and / or stabilizers for the per compound 10-50, preferably 15-35 wt. - make up% of the total detergent. The bleach component is generally present in an amount because # the bleach content, calculated as active oxygen, 1 - 4, preferably 1> 5 - 3.5% by weight. As far as these bleaches or the substances that form after the release of the active oxygen are alkaline react, they can be seen mathematically as alkaline telling substances.

When it comes to detergents, it is the total of alkaline reacting structural substances and any complexing agents present, preferably 0.5 to 7 times and in particular the 1 to 5 ache of the total surfactant combination present.

The cleaning agents according to the invention can also be mechanically cleaning agents Contain substances, the latter usually in amounts of at least 3C% by weight, Preferably from 50-98 and in particular from 75-95% by weight are present. as Mechanically cleaning materials are preferably fine powders made from mostly water-insoluble ones Substances such as quartz powder, marble powder, ground pumice stone, etc. The rest - (at most 70, preferably 50-2 and in particular 25-5% by weight) consists largely of one water-soluble component of the composition according to the invention. This can indeed the concentration of the antimicrobial active ingredients in relation to the entire product relationship. become moderately low; but since these products, especially those that are used a lot Abrasives, which are moistened with just a little water when used, come despite the low active ingredient content, completely sufficient active ingredient concentrations are achieved.

The anionic, possibly present in the products according to the invention, Zwitterionic or nonionic surfactants contain at least in the Molelcül a hydrophobic residue of 8 to 26, preferably 10 to 20 and especially 12 up to 18 carbon atoms and an anionic, nonionic or zwitterionic water-solubilizing agent Group. The preferably saturated hydrophobic radical is mostly aliphatic or alicyclic in nature; he can directly or with the water-solubilizing groups be connected via intermediate links.

Benzene rings, carboxylic acid esters or Carbonamide groups, residues of polyhydric alcohols bonded in ether or ester-like fashion, such as B. that of ethylene glycol, propylene glycol, glycerol or the like Polyether residues in question.

The hydrophobic group is preferably an aliphatic hydrocarbon group with about 10 to 18 carbon atoms, but; e depending on the nature of the respective surfactant Deviations from this preferred C number range are possible.

As anionic washing active substances soaps can be used which are derived from natural or synthetic fatty acids, possibly also resin or naphthenic acids descend. Fatty, resin or naphthenic acids of natural origin are many more or less unsaturated. They are preferably in part or in full processed in the hydrogenated state so that they have iodine numbers of at most 30 and preferably less than 10.

Of the synthetic anionic surfactants, the sulfonates have and sulfates of particular practical importance.

The sulfonates include, for example, the alkyl laryl sulfate, in particular the alkylbenzenesulfonates, which are known inter alia. from preferably straight-chain aliphatic hydrocarbons with 9 to 15, preferably 10 to 14 carbon atoms by chlorinating and alkylating benzene or from corresponding terminal or internal Olefins by alkylating benzene and sulfonating the resulting alkylbenzenes receives. Furthermore, aliphatic sulfonates are of interest, such as are preferred for example from saturated, 8 to 18 and preferably 12 to 18 carbon atoms in the molecule Hydrocarbons by sulphochlorination with sulfur dioxide and chlorine or sulroxydation with sulfur ioxide and oxygen and ADerading the products obtained in this way in which are accessible to sulronates.

Mixtures of alkene sulfonates, Hydroxyallce nsulfonat en and Hydroxyalkansulfonaten useful, which are e.g. from terminal or intermediate C8-C18 and preferably C12-Cl8 olerins by sulfonation with sulfur trioxide and acidic or alkaline hydrolysis of the sulfonation products receives. The sulfonate group is found in the aliphatic sulfonates produced in this way often on a secondary carbon atom; but you can also do it yourself of terminal olefins with sulfite to produce sulfonates with a sulfonate group at the end.

The sulfonates to be used according to the invention also include salts, preferably dialkali salts of α-sulfofatty acids and salts of esters of these Acids with mutually polyvalent containing 1 to 4 and preferably 1 to 2 carbon atoms Alcohols.

Further useful sulfonates are the fatty acid esters of oxethanesulfonic acid and of dioxypropanesulfonic acid, the fatty alcohol esters of lower 1 to 8 carbon atoms containing aliphatic or aromatic sulfomono- and dicarboxylic acids, the Alkyl glyceryl ether sulfonates and the condensation products of fatty acids or Sulphonic acids with aminoethanesulphonic acid.

Fatty alcohol sulfates are to be mentioned as surfactants of the sulfate type, in particular those made from coconut fatty alcohols, tallow fatty alcohols or from oleyl alcohol. Useful sulfonation products can also be obtained from terminal or internal C8 to C18 olefins Manufacture of the Suifattyp. This group of surfactants also includes sulfated surfactants Fatty acid alkylamides, sulfated monoglycerides and sulfation products from ethoxylated and / or proyoxylated fatty alcohols, alkylphenols with 8 to 0 15 carbon atoms in the alkyl radical, fatty acid amides, fatty acid alkylolamides, etc., with an din moles of the ethoxylated and / or propoxylated compounds mentioned 0.5 to 20, preferably 1 to 8, in particular 2 to 4 mol of ethylin and or propylene oxide attached SCIII can.

The detergents according to the invention can also be synthetic capillary-active Contain carboxylates, e.g. the fatty acid esters or fatty alcohol ethers of oxycarboxylic acids as well as the condensation products of fatty acids or sulfonic acids with aminocarboxylic acids, e.g. with Glycocoll, Sarcosine or with protein hydrolysates.

To the nonionic surfactants, here for the sake of simplicity as "Nonionics" referred to include products that have thre water solubility of presence of polyether chains, amsine oxide, sulfoxide or phosphine oxide groups, alkylolassnide groups as well as an accumulation of hydroxyl groups in general.

Of particular practical interest are those caused by the addition of Ethylene oxide and / or glycide on fatty alcohols, alkylphenols, fatty acids, fatty amines, Fatty acid and sulfonic acid amides, these nonionics 4 - 100, preferably 6 - 40 and especially 8 -. -20 atomic residues, especially ethylene glycol ether residues may contain per molecule. - In addition, polyglycol ether residues can be found in these or at the end of which propylene or butylene glycol ether residues may be present.

The nonionics also include those under the trade name "Pluronics", "Tetronics" or "Ucon Fluid" known, water-soluble due to the addition of ethylene oxide made water-insoluble polypropylene glycols and addition products of propylene oxide of alkylenediamines or lower ones containing 1 to 8 and preferably 3 to 6 carbon atoms, aliphatic alcohols.

Other useful nonionics are fatty acid or sulfonic acid alkylolamides, which are e.g. from mono- or dialkylolamine, from dioxypropylamine or other polyoxyalkylamines, e.g. derive the Glycaminen. They can be replaced by amides from higher primary or replace secondary alkylamines and polyhydroxycarboxylic acids.

From the group of amine oxides are those of higher tertiary, one hydrophobic alkyl radical and two shorter, up to 4 carbon atoms each containing alkyl and or amines derived from alkylol radicals are of particular interest.

Zwitterionic surfactants contain at least one acidic or at least a basic hydrophilic group in the molecule.

The acidic groups include carboxyl, sulfonic acid, semi-ferrous acid tea, Phosphonic acid. and phosphoric acid partial ester groups. Come as basic groups primary, secondary, tertiary and quaternary ammonium groups are possible.

Carboxy, sulphate and sulphonate betaines have because of their good tolerance of particular practical interest with other surfactants. Suitable sulfobetaines obtained for example, by reacting tertiary, at least one hydrophobic alkyl radical containing amines with sultones, for example propane or butane sultone. Appropriate Carboxybetaine is obtained by reacting the tertiary amines mentioned with chloroacetic acid, their salts or with chloroacetic acid esters and cleavage of the ester bond.

The foaming power of the surfactants used can be determined by combining them suitable surfactants increase or decrease, but the foaming power can also change with additives other than surfactants.

As is known, those mentioned above are suitable as foam stabilizers Alkylolamide type nonionics; in addition, fatty alcohols or higher are used for this purpose Terminal diols useful.

The foaming power of synthetic anionic or nonionic surfactants can be reduced by adding soaps; with certain combinations of synthetic anionic surfactants, nonionics and soap, the foaming power is reduced even more. The addition products of propylene oxide to those described above are also notable capillary-active polyethylene glycol ether is characterized by a low foaming power, whereby by varying the number of ethylene glycol and propylene glycol residues in the molecule Have products made with a wide variety of cloud points. These nonionics act on nonionics other than at temperatures above their cloud point Foam inhibitors; but they can also be used with other surfactants or mixtures combine different surfactants.

Mixtures of anionic surfactants, especially those of the sulfonate and and / or sulfate types, nonionic surfactants and soaps have great practicalities Gaining importance, with the foam intensity of such combinations through the choice of soaps can vary. Do these soaps contain e.g. 12 to 18 carbon atoms in the fatty acid residue, the surfactant mixtures show a certain foam suppression, the however, it is often not sufficient if the detergent is used at temperatures of 60 to 100 ° C C should be used in drum washing machines. Achieved in such cases a strong foam dampening with synthetic, anionic, zwitterionic and nonionic surfactants by soaps from fatty acid mixtures with 20 to 30, preferably 20 to 26 carbon atoms.

However, the surfactants can also be combined with foam inhibitors known per se which are not surfactants.

These may include N-alkylated aminotriazines containing chlorine, which can be obtained by reacting one mole of cyanuric acid chloride with 2 to 3 ol of a mono- and / or dialkylamine with 6 to 20, preferably 8 to 18 carbon atoms in the alkyl radical receives. Also leave paraffins, halogen paraffins, aliphatic C8 to C20 xetones can be used as foam inhibitors, especially in combination with soaps.

By choosing suitable foam inhibitors it can be achieved that the foam-pressing effect only sets in when a certain temperature is exceeded, so that detergents can be produced in the medium temperature range up to at 65 ° C., for example, still foaming, but on transition to higher temperatures develop less and less foam. You can even use foam stabilizers and temperature dependent ones Combine foam inhibitors with one another.

The temperature-dependent foam inhibitors include those mentioned above N-alkylated aminotriazines, as well as paraffins, haloparaffins, retone, etc.,. whose foam-inhibiting effect is particularly strong above their melting point.

But also the higher ones, of fatty acids with 20 to 30 carbon atoms in the molecule derived ropes, show a similar effect. These soaps can be in different Names are added; Their proportion can be 5 to 100% of the total, in the surfactant component make up the amount of soap present.

On the alkaline-reacting builder substances defined at the outset as well as the complexing agents that act synergistically with the antimicrobial active ingredients preferably include the usual, alkaline components of detergents, Detergents and cleaning agents. The ingredients according to the invention can except these components also contain neutral salts. Below are such salts essentially from the point of view of their chemical nature enumerated without thereby anything about their belonging to the initially defined heavier or stronger complexing agents or to the alkaline structural substances should be testified.

Useful according to the invention, neutral, weakly or more strongly alkaline reacting salts are, for example, the bicarbonates, carbonates or silicates of the Alkalis, mono-, di- or trialkali orthophosphates, die or tetraalkali pyrophosphates, as complexing agents known metaphosphates, alkali sulfates, as well as the alkali salts of organic, non-capillary-active sulfonic acids, carboxylic acids containing 1 - 8 carbon atoms and sulfocarboxylic acids. These include, for example, water-soluble salts of the benzene, Toluene or xylene sulfonic acid, water-soluble salts of sulfoacetic acid, sulfobenzoic acid or the salts of sulfodicarboxylic acids and the salts of acetic acid, lactic acid, Citric acid and tartaric acid.

Next can höncr. molecular polycarboxylic acids or their water-soluble ones Salts are present, in particular salts of polymers of maleic acid, itaconic acid, Mesaconic acid, fumaric acid, aconitic acid, methylenemalonic acid and citraconic acid. Even Salts of copolymers of these acids with one another or with other polymerizable Substances such as ethylene, propylene, acrylic acid, methacrylic acid, crotonic acid, 3-butenecarboxylic acid, 3-methyl-3-butenecarboxylic acid and with vinyl methyl ether, vinyl acetate, Isobutylene, acrylamide and styrene are useful.

The organic complexing agents include, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-oxethyl-ethylenediamine triacetic acid, polyalkylene-polyamine-N-polycarboxylic acids and other known organic complexing agents, and combinations of different complexing agents can also be used. The other known complexing agents also include di- and polyphosphonic acids of the following constitution: wherein R is alkyl and R 'is alkylene radicals having 1 to 8, preferably having 1 to 4 carbon atoms, and X and Y are hydrogen atoms or alkyl radicals having 1 to 4 carbon atoms. According to the invention, carboxymethylene phosphonic acid (HOOC-CH2-PO (OH) 2) can also be used as a complexing agent. All of these complexing agents can be present as free acids, but preferably as alkali salts.

The following table contains information on the complexing capacity of various complexing agents determined by the Hampshire test. The implementation of the Hampshire test is described in the examples. Calcium carbonate Completely educating dual assets in mgZg Kolexoilaner Hydroxymethylphosphonic acid - 1 Mesoxalic acid monohydrate 6 l-cysteine hydrochloride monohydrate 4 Glycolic acid 45 Tetrasodium pyrophosphate 125 n-hexylamine dimethylene phosphonic acid 160 Sodium tripolyphosphate 214 Hexamethylene diamine tetramethylene phosphonic acid 220 l-hydroxyhexane-l, l-diphosphonic acid 280 (c-Aminoethane-oC, diphosphonic acid 930 R -AmiJlobenzyl- GC, diphosphonic acid 1460 Aminotrimethylene phosphonic acid 820 Ethylenediamine tetramethylene phosphonic acid 860 Aminodimethylene phosphonic acid N-acetic acid 850 Iminodiacetic acid-N-methylenephosphonic acid 540 Hydroxyethane diphosphonic acid 8io Phosphonoacetic acid 270 Citric acid 28 Diethylenetriaminepentaacetic acid 275 1,2-Cyclohexanediamine-tetraacetic acid-285 Ethylenediaminetetraacetic acid 402 Nitrilotriacetic acid 578 CoOH COOH OOH U-CH-NH-CH2-CH2-NH-CH-U 250 OH OH Technical mixture of different netaphosphates 500kl (Craham's salt) Of the bleaching components to be used, the compounds which react neutrally to alkaline in aqueous solution, in particular the perborates, are of particular practical interest.

Among the various perborates, there is sodium perborate tetrahydrate (NaB02. H202. 3 H20) of great practical importance. In its place you can also partially or completely, i.e. up to the approximate composition NaBO2. H202 dehydrated perborates can be used. Finally, they also contain active oxygen Borates NaBO2. H2O2 usable in which the ratio Na2O: B2O3 is less than 0> 5: 1 and preferably in the range of 0.4-0.15: 1 and where the Ratio H202: Na is in the range of 0.5-4: 1. These products are in the German patent specification 901 287 and American patent specification 2,491,789 described.

The perborate can be wholly or partly by other inorganic per compounds, in particular by peroxyhydrates, such as, for example, the peroxyhydrates the ortho-, pyro- or polyphosphates and the carbonates.

The detergents, auxiliary washing agents and cleaning agents according to the invention can Usual water-insoluble or water-soluble stabilizers for per compounds Contained in amounts of up to 10, preferably from 0> 5 to 8% by weight.

The various water-insoluble perstabilizers are suitable Magnesium silicates. It is mostly a matter of falling products, which when unifying aqueous solutions of alkali silicates with solutions of magnesium salts arise. The NgO: SiO2 ratio can be in the range from 4: 1 to 1: 4, preferably from 2: 1 to 1: 2. A product with a MgO ratio is often used : SiO2 = 1: 1. These magnesium silicates can be replaced by the corresponding silicates other alkaline earth metals, cadmium or tin. Also hydrous Tin oxides can be used as stabilizers. These stabilizers are mostly in amounts from 1 to 8, preferably from 2 to 7% of the weight of the total preparation present.

The water-insoluble stabilizers can be completely or partially through water soluble to be replaced. The ones listed above are particularly suitable as such Substances with a complexing capacity above 230 mg CaOO3 / g. Provided these should only stabilize the active oxygen and / or the brighteners, without a simultaneous synergistic effect with the antimicrobial active ingredients is used, they can, depending on the strength of the complexes formed, in quantities from 0.1 to <5, preferably from 0.2 to 2.5, by weight of the entire preparation are present.

Active chlorine compounds which can be used according to the invention can be more inorganic or be organic in nature.

The inorganic active chlorine compounds include alkali hypochlorites, especially in the form of their mixed salts or addition compounds to orthophosphates or to condensed phosphates such as, for example, to pyrophosphates and polyphosphates or can be used on alkali silicates. Contain the detergents and additives Monopersulphates and chlorides, active chlorine is formed in aqueous solution.

The organic active chlorine compounds are in particular the N-chlorine compounds in question, in which one or two chlorine atoms are bonded to a nitrogen atom, preferably wherein the third valence of the nitrogen atoms is attached to a negative group stirs, especially a CO or SO2 group. These connections include Dichloro and trichlorocyanuric acid, chlorinated alkylguanides or alkyl biguanides, chlorinated Hydantoins and chlorinated melamines.

The preparations according to the invention can also contain enzymes; these have in combination with the. Disinfectants have the advantage of protein, starch or to dissolve greasy dirt and the microbes that may be trapped in it to expose and bring them into contact with the antimicrobial agents. The enzymes can be of the most varied of nature; it can be proteases, carbohydrases, Esterases, lipases, oxidoreductases, catalases, peroxydases, ureases, isomerases, Act as liases, transferases, desmolases or nucleases. Of particular practicality Proteases, amylases and lipases, especially those from Bacillus subtilis, are of interest and Streptomyces griseus obtained enzymatic active ingredients, especially those proteolytic nature. Other useful enzymes are pepsin, pancreatin, trypsin, Papain and diastase.

The antimicrobial active ingredients to be used according to the invention have the particular advantage over optical brighteners, which above all else can be contained in detergents and auxiliary washing agents to behave indifferently.

In contrast to many known, highly effective antimicrobial substances, the compounds to be used according to the invention are well tolerated by the skin and have little toxicity. Therefore, in the event of inadvertent oral ingestion, as has been observed, for example, with liquid detergents bercits, no damage to health is to be expected., Examples of optical brighteners from the class of diaminostilbene sulfonic acid derivatives are compounds according to the following formula: X and Y: e.g. NH2, NH-CH3, NH-CH2-CH2OH, CH3-N-CH2-CH2OH, N (CH2-CH2OH) 2, morpholino, dimethylmorpholino, NH-C6H5, NH-06H4-SO3H, OCH3, C1 , where X and Y can be the same or different.

Optical brighteners of the diarylpyrazoline type according to the following formula can also be present: In this formula, R denotes a hydrogen atom, an alkyl radical or aryl radical, which can optionally be substituted, Ar and Ar 'aryl radicals, such as phenyl, diphenyl or naphthyl, which can carry further substituents, such as hydroxy, alkoxy, hydroxyalkyl, Amino, alkylamino, acylamino, carboxyl, sulfonic acid and sulfonamide groups or halogen atoms. Water-soluble colloids of mostly organic nature are suitable for this, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acid sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. It is also possible to use starch and other starch products than those mentioned above, such as degraded starch, aldehyde starches, etc. Polyvanylpyrrolidone can also be used.

Examples The following examples describe the compositions some preparations according to the invention. The salty ingredients it contains - salt-like surfactants, other organic salts and inorganic salts - lie as sodium salts, unless expressly stated otherwise. The related names or abbreviations mean: "ABS" the salt of a through Condensation of straight-chain olefins with benzene and sulfonation of the resulting Alkylbenzenes obtained Lkylbenzenesulfonsäure with 10-15, preferably 11-13 carbon atoms in the alkyl chain, 11alkanesulfonate "one of paraffins with 12-16 carbon atoms on the Ways of sulfonate obtained by sulfoxidation, "Fs-ester sulfonate" also include MethyleSter of a hardened tallow fatty acid obtained by sulfonicren with SO3 Sulphonate, "Olefinsulphonat" from olefin mixtures with 12-18 carbon atoms by sulphonation sulfonate obtained with SO and hydrolyzing the sulfonation product with lye, the ii essentially consists of alkene sulfonate and oxyalkanesulfonate, but also also contains small amounts of disulfonates. Any preparation containing olefin sulfonate wound made using two different types of olefin sulfonate; the one was made from a mixture of straight chain terminal olefins and the other was made from one Mixture of internal olerins has been produced, "KA-sulfate" or "TA-sulfate" the salts of sulfated, by reduction of coconut fatty acid ba. Sebum fatty acid produced, essentially saturated fatty alcohols, "KA-ÄO-Sulft" or "TA-ÄO-Sulft" or "OA-ÄO-sulfate 'the sulfated addition products of 2 moles of ethylene oxide with 1 mole Coconut fatty alcohol or from 3 moles of ethylene oxide to 1 mole of tallow fatty alcohol or from 2 Mole of ethylene oxide to 1 mole of oleyl alcohol, tOA + 5 ÄO "," OA + 10 ÄO "and" KA + 20 ÄO " the addition products of ethylene oxide (ÄO) with technical oleyl alcohol (OA) or Coconut alcohol (KA), where the numbers represent the molar amount attached to 1 mole of alcohol of ethylene oxide, "KA + 9 ÄO + 12 PO" on by repositioning nonionic obtained from 1 mole of "KA + 9 ÄO" with 12 moles of propylene oxide, "perborate" Product with approx. 10% active oxygen and approximate composition NaB02 . H202. 3 H2O, "NTA", "EDTA" or "EHDP" are the salts of nitrilotriacetic acid, the Ethylenediamine tetraacetic acid or hydroxyethyl diphosphonic acid, "CMC" the salt the carboxymethyl cellulose, "BW-Aufheller 1" or "BW-Aufheller II" are preferred for use with cotton certain commercial products "Purwil min or" Blankophor BBH / SII "," PA-Brightener "is the preferred commercial product for use with polyamides "Purwil P", "PE-Brightener ltw or" PE-Brightener II "are the preferred ones for use in the case of polyesters, certain commercial products "Uvitex SOF" or "Calcofluor white ALF".

The composition of the fatty acid mixtures from which the various soaps contained in the products according to the invention were produced can be found in the following table: Composition of the fatty acid mixtures corresponding to the soaps C number of the wt .-% fatty acid component in the Fatty Acid Soap Soap Soap Soap. 1018 1222 - 1222 and 1622 C10 1 - - - C12 6 18 14 - C14 5 8 6 - 016 28 17 13 8 C18 60 32 60 32 C20 - 4 3 12 C22 - 21 4 48 A mixture of about 45% of a di- (alkylamino) -monochlorotriazine and about 55% of an N-N'-N "-trialkylmelamine was used as a foam inhibitor The monochlorotriazine derivative or the trialkylmelamine can also be used with similar success.

If the products described are synthetic sulfates or sulfonates together with soap, the others mentioned in the description can also non-surfactant-like foam inhibitors are used, such as, for example, paraffin oil or paraffin. When making the preparations, the related foam inhibitor was used dissolved in a suitable organic solvent or in a molten state sprayed onto the moving powdery preparation using a nozzle.

So much for the preparations according to the invention as powdery products were present, the antimicrobial substances were incorporated in the same way as described for the sneeze inhibitors. However, foam inhibitors were used and antimicrobial substances are sprayed on one after the other.

The composition of the preparations according to Examples 1-12 is finished can be seen in the following tables. The "+" sign in the "Na2SO4" line means that small amounts of sodium sulfate are contaminated by the anionic surfactants were present. The in the line "Antimicr. Subst." located large letters identify the substance present in each case; in the line below is their amount specified. In the last line there is no numerical value under "Remainder"; he calculates as the difference from 100 and the amounts of the other components. From the substance From the point of view of this, the remainder consists to a large extent of water; provided Na2SO4 only present in small amounts derived from the synthetic anionic surfactant (sign "+" in the Na2SO4 line of the table), the rest also includes the existing Na2SO4. In addition, the remainder also includes any dyes and fragrances that may be present and enzymes.

The subject matter will become clearer through the following examples Registration explained in more detail.

As underlying the antimicrobial agents according to the invention The following nitroalkyl-N-phenylcarbamates were investigated as active substances, A 2-nitropropyl-N-phenylcarbamate B1-methyl-2-nitropropyl-N-phenylcarbamate, C2-nitrobutyl-N-phenylcarbamate, D-2-bromo-2-nitroethyl-N- (3-chlorophenyl) carbamate E 2-Bromo-2-nitrobutyl-N- (4-nitrophenyl) -carbamate F 2-Bromo-2-nitrobutyl-N-phenylcarbamate G 2-Bromo-2-nitrobutyl-N- (3,4-dichlorophenyl) -carbamate H 2-Bromo-2-nitropropyl-N-phenylcarbamate I 2-Bromo-2-nitrobutyl-N- (p-fluorophenyl) -carbamate K 2-Bromo-2-nitropropanediol - (1,3) -bis -N-phenylcarbamate L 2-bromo-2-nitropropanediol- (1,3) -bis-N- (3-chlorophenyl) -carbamate M 2-Bromo-2-nitropropanediol- <1,3) -bis-N- (3,4-dichlorophenyl) carbamate N 2-Bromo-2-nitropropanediol- (1,3) -bls-N- (4-nitrophenyl ) carbamate the Products described in Examples 1-12 can preferably be used for the following Send purposes: Before example 1:: Soaking or detergent examples 2 - 4. All-purpose detergent and 6 - Example 5: Perborate and lightener-free colored detergent Example 10: Colored detergent free from brighteners but containing perborate Examples 11 and 12: mild detergent, also intended for use on easy-care textiles.

All of the detergents described above can also be used in drum washing machines at temperatures of 90-100 ° C without causing foaming S constituent of the Cew .-% constituent in the preparation according to the example Preparation 1 2 3 4 5 ABS - 9.0 11.0 - - Olefin sulfonate 5.0 - - - 11.5 Soap 1018 - - - - 9.0 Soap 1622 - 2.0 - - - OA + 5 ÄO - - - - 5.0 OA + 10 AO - 8.0 6.0 - - KA + 20 ÄO - - - 12.0 - KA + 9 AO 3.0 - - 7.5 - + 12 PO Foam inhibitor 0.3-0.5-0.8 Na2SO4 - + + - + Na2O # 3.3 SiO2 - 4.5 4.0 4.5 6.0 Na42207 9.0 - - 12.0 - Na5P3O10 63.0 45.0 19.0-30.0 Perborate - 16.0 21.0 16.0 - MgSiO3 - 1.0 1.6 1.0 1.6 NTA - - 18.0 19.0 - EDTA 0.5 - - - - EHDP - - 6.6 14.0 28.0 CMC 1.6 1.5 1.3 1.5 1.3 Antimicr. Noun FGABH Amount 6.1 4.7 5.0 3.3 4.1 BW brightener I - 0.5 0.5 - - BW brightener II 0.3 - - 0.7 - PA brightener 0.05 0.2 0.2 - - PE brightener I - 0.2 - - - PE brightener II - - 0.2 - - rest Part of the% by weight component in the preparation according to the example Preparation 6 7 8 9 10 11 12 ABS 8.5 - - - - - - Alkanesulfonate - - 7.5 - - - - Fs-ester sulfonate - 6.5 - - - - - Olefin sulfonate - - - 8.0 - - 15.0 KA sulfate 1.6 2.0 1.7 - - 1.5 3.2 TA sulfate 0.5 - - 3.0 o 1.5 - KA-ÄO-sulfate 2.0 - - - 2.3 - 7.5 TA-ÄO-sulfate - - - - - 7.5 - OA-ÄO-sulfate - - - - 5.5 - - Soap 1018 - - - - - 4.15 - Soap 1222 5.8 9.3 - 10.2 6.5 - - soap 1222 u - - 6.8 - - - - OA + 5 ÄO - 2.5 - - 6.5 - - OA + 10 AO - - 2.7 4.2 - - - Foam inhibitor - - 0.6 - - 0.8 0.9 Na2SO4 + + + + 5.0 18.0 10.0 Na20 # 3.3 SiO2 5.0 4.0-4.2 3.5 3.7 Na5P3010 28.0 24.0 38.0 21.0 33.0 35.0 48.0 Perborate 24.0 25.0 23.6 28.0 22.0 0 - - MgSiO3 - 2.0 - - 3.0 - - - NTA 15.0 5.0 - 8.0 - 10.0 - EDTA 0.22 0.25 0.5 0.4 - - - CMC 1.3 1.9 1.2 1.4 1.5 1.3 1.7 Antimicr. Subst. KDCMELN Amount 2.2, 3.8 8.7 4.3 2.4 4.5 3.6 BW brightener II 0.5 0.4 0.2 0.35 - - - PA brightener - 0.04 0.5 0.03 - - - PE brightener I - - 0.15 - - - - PE brightener II - - 0, 10 0.7 7 - - Remainder 1 09 044 7 134 Example 13 A pourable suspension of undissolved constituents. Liquid detergent in an aqueous solution has the following composition: 10.0% by weight ABS 8.5% by weight coconut fatty acid diethanolamide 6.0% by weight potassium toluenesulfonate 20.0% by weight Na5P3O10 10.0% by weight K5P3010 1.5% by weight CMC 7.6% by weight antimicrobial substance 1 remainder water The antimicrobial effect of this product is improved if the Na5P3O10 content is reduced to 18-15% by weight and instead 2 - 5% by weight are added .-% of gDTA or EHDP incorporated.

Example 14 In the usual manufacture of a toilet soap from a mixture of 60% coconut fatty acid and 40% tallow fatty acid is used in the Screw press together with the fabric and the perfume such amounts of the antimicrobial Substance F means that the finished soap contains 2.5% by weight thereof. The effect of the antimicrobial substance is increased if you also have so much NTA, EDTA - or EHDP incorporated so that their proportion in the soap is 8% by weight.

Example 15 As described in Example 14, two pieces of detergent are produced the following compositions a and b here: b 57-59% by weight of a 1-alkanesulfonate, produced from a mixture of terminal olefins containing 12-18 carbon atoms Bisulfite deposition, 28 29% by weight soap (80% tallow and 20% coconut fatty acid) 3 5 % By weight of antimicrobial active ingredient M 50% by weight of NTA, EDTA or EHDP 7 7% by weight of water Example 16 A bottle washing agent to be used in the beverage industry following composition: 53.0 wt .-% sodium hydroxide techn.

15.0% by weight of tetrapolyphosphate, 10.0% by weight of Na20. 3.3 SiO2 12.0% by weight Aminotri (methylene phosphonate) 10.0% by weight antimicrobial substance K Example 17 A pre-wash detergent which, even at temperatures of up to 600 C, if complete desin-section is not possible, has the following composition: 8.0% by weight ABS, alkanesulfonate or olefin sulfonate 4.0% by weight soap 1622 0.3% by weight Foam inhibitor 36.0% by weight Na4P207 7.5% by weight NaOH 0.8% by weight Na2SO4 24.0 cw.- Antimicrobial Active Ingredient H Remainder Water Example 18 A rinse aid for washed Laundry that simultaneously contains fiber incrustations, especially calcareous fiber incrustations, dissolves, has the following composition: 30.0% by weight perborate 30.0% by weight EHFP 2.6% by weight Antimicrobial substance F 8.0 wt% MgSiO3 29.4 wt% Na2SO4 Treated you laundry items in a conventional manner using the preparations according to the Examples 1 - 13, 17 and 18, then one achieves eirß over the entire duration of the treatment attractive antimicrobial effect. If the products contain bleaching components, is the antimicrobial effect of the active ingredients to be used according to the invention still present before the onset or after the effect of the bleaching component has ended. Are rinsing agents with a content. such antimicrobial substances im If the last rinse is used, the small ones left on the fiber have an effect Amounts of antimicrobial substance even after the washing process is finished and after the bleaching of the washed textiles.

Example 19 A disinfecting abrasive did the following Composition: 95% by weight quartz powder, finely ground 5% by weight of a fine powder the following composition: 20% by weight ABS 35% by weight Na5P3010 10% by weight NTA 15% by weight Na2SO4 15% by weight antimicrobial agent F remainder water One precise description of the analytical method for determining the calcium carbonate binding capacity can be found in the corporate publication of Hampshire-Chemical Corp. dated June 19ÓO "Hampshire NTA Technical Bulletin ", Appendix -S. A2. After that, exactly 2 g powdery Complexing agent dissolved in 50 ml of distilled water, neutralized, with 10 ml of a Added 2 fresh sodium carbonate solution, adjusted its pH to 11-12 and the solution diluted to 100 ml. A calcium acetate solution containing 44> 1 g calcium acetate monohydrate per liter, until a significant amount appears and permanent turbidity titrated. The calcium carbonate binding capacity of the complexing agent is calculated according to the formula: ml calcium acetate solution x 25 mg bound CaCO3 / g = Weight of complexing agent complexing agent

Claims (23)

Patent claims 1) Detergents, washing auxiliaries and cleaning agents with a content of antimicrobial active ingredients, characterized in that they contain: a) 0.2-30, preferably 1-5% by weight of a nitroalkyl-N- phenylcarbamates of the general formula I. where the symbols used in this formula and in the forms in TI and III mean: Y fluorine, chlorine, bromine, a trifluoromethyl or a nitro group, n the numbers C-2, A the carbamic acid ester grouping of the formula II, R hydrogen or a methyl radical, X is hydrogen or bromine and Z is hydrogen, a methyl radical, an ethyl radical or the phenylcarbamic acid ester grouping of the formula III, b) at least 5% by weight and preferably at least 10% by weight of an alkaline-reacting structural substance which is customary in such preparations and which in Hampshire test has a complexing capacity of a maximum of 230 mg CaCOgg, c) possibly other common constituents of detergents, washing aids or. Cleaning agents, these quantities referring to the sum of the quantities of component a) and the quantities of the water-soluble constituents of components b) and c) minus any solvents present. 2) washing, auxiliary and cleaning agent according to claim 1, characterized in that the alkaline reacting sub-definition in claim lb) punched according to # in amounts of at least 10 wt. is available. 3) detergents, auxiliary washing agents and cleaning agents according to claim 1 and 2, characterized in that the alkaline reacting substance according to # together with Complexing agents are present, their complexing ability in the Hampshire test above of 230 mg CaCO3 / g complexing agent. 4) washing, auxiliary washing and cleaning agent according to claim 1 - 3, characterized in that the complexing agent according to claim 3 in amounts of at least 3, preferably of at least 10 wt .-% is available. 5) washing, auxiliary and cleaning agent according to claim 1 - 4, characterized in that the complexing agent according to claim 3 is present in such amounts that its proportion is 10 - 90 S and preferably 25 - 75 wt .-% of the mixture of complexing agents and alkaline substance as defined in claim 1b). 6) Washing, washing auxiliary s-ur. d cleaning agent according to claim 1 - 5, characterized in that it contains 0.2-30, preferably 1-5% by weight of an antimicrobial Active ingredient according to claim 1, wherein the composition in the üorigen im The range of the following formulation is: 0 - 90, preferably 5 - 40 and especially 12-30% by weight of surfactants, including any fabric softeners or combinations of surfactants, consisting of: o - 100, preferably 25 - 65% by weight of surfactants from sulfonate and / or sulfate type with preferably 8-18 carbon atoms in the hydrophobic radical, 0-100, preferably 5 - 40% by weight nonionic surfactants, o - 100, preferably 10 - 50 % By weight soap, 0-6, preferably 0.5-3% by weight foam stabilizers, 0-8, preferably 0.5-5% by weight non-surfactant foam inhibitor, 5-99, preferably 10-70 % By weight of an alkaline-reacting builder substance customary per se according to claim 1 b), which in combination with complexing agents (complexing ability above 230 mg CaCO3 / g) can be present. Whereby these complexing agents are preferred in Kengen van at least 3 and in particular at least 10% by weight are present. 0 - 50, preferably 2 - 15% by weight of other detergent ingredients, such as B. bleach components, optical brighteners, dirt carriers, enzymes, fragrances, Dyes and water. 7) detergents, auxiliary washing agents and cleaning agents according to claim. 1 - 6, characterized by a content of bleaching components including any activators and / or stabilizers 10-50 that may be present, preferably 15-35% by weight. 8) detergent pieces according to claims 1 - 7, characterized in that that they have a surfactant content above 60 wt .-%, in particular in the range of 75 - Have 90 wt .-%. 9) Paste-like or liquid detergents, auxiliary washing agents and cleaning agents according to claim 1 - 7, characterized in that it is 40 - 90, preferably 50 - Contains 85% by weight of liquid solvents. 'O) Antimicrobial agents and a preferably' water-insoluble, Preparations containing mechanically cleaning components, consisting of 30 - 99, preferably 50-98 and in particular 75-95% by weight of the mentioned, mechanically cleaning component, 70 - 1> preferably 50 - 2 and especially 25-5% by weight of a substantially water-soluble component according to claims 1 - 7. 11) detergents, auxiliary washing agents and cleaning agents according to claims 1 - 10, characterized in that it uses the compound 2-nitropropyl-N-phenylcarbamate as the antimicrobial substance contain. 12) detergents, auxiliary washing agents and cleaning agents according to claim 1 - 10> characterized in that it uses the compound 1-methyl-2-nitropropyl-N-phenylcarbamate as the antimicrobial substance contain. 13) detergents, auxiliary washing agents and cleaning agents according to claims 1 - 10, characterized in that it uses the compound 2-nitrobutyl-N-phenylcarbamate as the antimicrobial substance un-. keep. 14) detergents, auxiliary washing agents and cleaning agents according to claims 1 - 10, characterized in that # they use the compound 2-bromo-2-nitroethyl-N- (3-chlorophenyl) carbamate as an antimicrobial substance contain. 15) detergents, auxiliary washing agents and cleaning agents according to claims 1 - 10, characterized in that # they use the compound 2-bromo-2-nitrobutyl-N- (4-nitrophenyl) carbamate as the antimicrobial substance contain. 16) detergents, auxiliary washing agents and cleaning agents according to claims 1 - 10, characterized in that it uses the compound 2-bromo-2-nitrobutyl-N-phenylcarbamate as the antimicrobial substance contain. 17) detergents, auxiliary washing agents and cleaning agents according to claims 1 - 10, characterized in that it uses the compound 2-bromo-2-nitrobutyl-N- (3,4-dichlorophenyl) carbamate as the antimicrobial substance contain. 18) detergents, auxiliary washing agents and cleaning agents according to claims 1 - 10, characterized in that it uses the compound 2-bromo-2-nitropropyl-N-phenylcarbamate as the antimicrobial substance contain. 19) washing-> washing aid and cleaning agent according to claim 1 - 10, characterized in that it is 2-bromo-2-nitrobutyl-N- (p-fluorophenyl) carbamate as the antimicrobial substance contain. 20) detergents, auxiliary washing agents and cleaning agents according to claims 1 - 10, characterized in that it uses the compound 2-bromo-2-nitropropanediol- (1,3) -bis-N-phenylcarbamate as the antimicrobial substance contain. 21) detergents, auxiliary washing agents and cleaning agents according to claims 1 - 10, characterized in that it uses the compound 2-bromo-2-nitropropanediol- (1,3) -bis-N- (3-chlorophenyl) carbamate as the antimicrobial substance contain. 22) detergents, auxiliary washing agents and cleaning agents according to claims 1 - 10, characterized in that it uses the compound 2-bromo-2-nitropropanediol- (1,3) -bis-N- (3,4-dichlorophenyl) carbamate as the antimicrobial substance contain. 23) detergents, auxiliary washing agents and cleaning agents according to claim 1 - 10> characterized in that it uses the compound 2-bromo-2-nitropropanediol- (1,3) -bis-N- (4-nitrophenyl) -carbamate as the antimicrobial substance contain.