DE2113732A1 - Anti-microbial washing composns - contg terpenes as bactericides and optical brighteners - Google Patents

Abstract

The composns. contain (A) 0.2-20, pref. 0.5-10, esp 1-5 wt % aliphatic or alicyclic terpenes, (B) 0.02-2, pref. 0.05-1, esp. 0.1-0.75 wt % optical brighteners and (C) 50-99.78, pref. 70-95, esp. 80-90 wt % various usual org. and inorganic components of washing composns. e.g. surfactants, builder salts etc. The composns. are suitable for washing and disinfecting clothes and bed-linen esp. from hospitals. In addition to their bactericidal action, the terpenes are compatible with the optical brighteners.

Description

"Detergents and washing auxiliaries containing antimicrobial agents" Detergents for delicate washing conditions are mostly used at temperatures in the range of 70 ° to 50 0C applied. However, these temperatures are usually far from being sufficient from unwanted microorganisms such. B. bacteria or fungi to kill.

The cleaning effect of this detergent must therefore be ensured by a suitable one antimicrobial agent supplements. Such detergents are already known. But also with detergents that are used at higher temperatures, in particular in the range of the cooking temperature, can be an addition of antimicrobial Active ingredients are undesirable, especially when it comes to the laundry to be cleaned it concerns underclothes or bed linen from hospitals where strong organic soiling, such as B. ointments, blood, pus or sputum delay the killing of the microorganisms.

It has been found that aliphatic and alicyclic terpenes are excellent are suitable as antimicrobial additives to detergents and washing auxiliaries, especially the good compatibility with optical brighteners of the stilbene, Pyrazoline, coumarin, carbostyril and thiophene series can be observed.

The invention thus optionally relates to water and / or water-soluble Detergents and auxiliary washing agents containing organic solvents with a content of antimicrobial agents, which are made up of a combination of the following ingredients marked are: 0.2-20.0, preferably 0.5-10 and especially 1.0-5.0% by weight of an aliphatic or alicyclic terpene, 0.02-2.0, preferably 0.05 - 1.0 and in particular 0.1 - 0.75% by weight of an optical brightener, 50, Q - 99.78, preferably 70-95 and in particular 80-90% by weight of other customary inorganic or organic constituents of laundry detergents and auxiliary washing agents, the amounts given being refer to - the water- and / or solvent-free preparation.

It has proven to be beneficial if at least some of the others common organic constituents consists of surfactants.-Another part of the organic as well as the other usual inorganic components should expediently consist of inorganic or organic salts with and without complexing capacity. Preferred should be at least 3% by weight, based on the weight of the total agent, of alkaline reacting structural substances that have a complexing capacity in the Hampshire test have a maximum of 200 mg CaCO3 / g alkaline reacting structural substance and at least, preferably at least 10% by weight based on the weight of the whole By means of complexing agents whose complexing capacity in the Hampshire test is above of 200 mg CaCO3 / g complexing agent should be present.

The - quantity ratio of alkaline reacting structural substance to Complexing agent 'can vary within wide limits. When the amount of complexing agent at least 3, preferably at least 10% by weight is a synergistic one Restoring the effect between the antimicrobial agent and the complexing agent. Of the Proportion of complexing agent in the mixture of complexing agent and alkaline reacting agent The structural substance can be 10-90, preferably 25-75, by weight.

Here, too, the quantities given relate to the whole Preparation and not parts or partial mixtures thereof, to anhydrous and solvent-free Substances.

Regarding the alkaline-reacting builder substances within the meaning of the invention also include those bleaching components which themselves react alkaline or which are after Release of the active oxygen or chlorine to residual substances with lead to an alkaline reaction. Some bleach components, such as B. Monoperoxisulfate or diacyl peroxides, in particular dibenzoyl peroxide, react acidic or themselves produce acidic reaction processes after the release of oxygen. These are not alkaline Reactive substances can be used as bleaching components in the products according to the invention can be used if there is enough alkali to achieve the desired pH maintain.

If the preparations according to the invention are used as laundry detergents and auxiliary washing agents If they are intended for use in textiles, they should have pH values in 1% aqueous solution from about 7 to 12, wool detergents generally being less alkaline (pH values 7 - 9.5) and cooking detergents more alkaline (pH values 9.5 - 12, preferably 10 - 11.5) are set.

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 care-calibrated textiles that are wholly or partly made of highly refined cotton or made of synthetic fibers, such as. B.

Polyamide, polyester, polyacrylonitrile, polyurethane, polyvinyl chloride or polyvinylidene chloride fibers. But also Washing aids, such as B. Soaking or rinsing agents that are to be used according to the invention Containing antimicrobial agents can be used with advantage.

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 based, the pasty or liquid nature is mostly due to the presence due to corresponding amounts of solvents in which the other components of the preparation are suspended or dissolved. The solvent content of these preparations can be 40-90, preferably 50-85 wt.

A preferred solvent is water; it can be whole or partially replaced by water-soluble organic solvents, e.g. B. by monohydric alcohols with 1 to 4, preferably 2 to 3 carbon atoms, polyhydric alcohols with 2 - 5 carbon atoms, partial ethers of these polyhydric alcohols with one another or with the called monohydric alcohols. Examples include: ethyl, n- or í-propyl alcohol, Glycol, glycerine, ethylene glycol monomethyl or monoethyl ether, glycerine mono or -diether of methyl or ethyl alcohol.

In the preparations according to the invention, water can be used as water of crystallization to salts, especially to inorganic salts (Na2C05 10 H20, Na3P04 4 12 H20, Na5P3010 . 6 H20).

This water is not to be regarded as a solvent.

Antimicrobial active ingredients used according to the invention are, for example the following aliphatic and alicyclic terpenes of the terpene hydrocarbons, terpene alcohol -, terpene aldehyde, mono- or bicyclic terpene ketone series and conversion products monocyclic terpene ketones suitable: limonene, citral, citronellal, geraniol, menthone, Fenchone, camphor, thyrnol.

If the preparations according to the invention are made by spray drying were prepared, they usually contain no more than 20 wt .-% and preferably a maximum of 5 - 8% by weight of water. But if the preparations are made from an aqueous, paste-like form Approach has been converted into a solid state by binding the liquid water, then the water content can be up to 50 ffi.

The detergents and auxiliaries according to the invention can be inorganic or contain organic bleaching components such as active chlorine or peroxy compounds, which then including any activators and / or stabilizers present in the In the case of peroxy compounds 10-50, preferably 15-35% by weight of the total detergent turn off. The bleach component is generally present in an amount that the bleach content, calculated e.g. B. as active oxygen 1-4, preferably 1.5-3.5% by weight. So much for this bleaching agent or the one resulting from it after its release the active oxygen or active chlorine forming substances have an alkaline reaction, arithmetically, they are to be regarded as alkaline-reacting structural substances.

When it comes to detergents, it is the sum of the alkaline-reacting structural substance and complexing agents preferably 0.5 to 7 times and especially 1 to 5 times the total existing surfactant combination.

The composition of the laundry detergents and auxiliary washing agents according to the invention is comprised by the following basic formulation: 0.22-22, preferably 0.55-11% by weight Antimicrobial substances and optical brighteners,> 5 - 40, preferably 7-30% by weight of a surfactant component containing at least one anionic and / or nonionic surfactant, especially of the sulfonate, sulfate, soap and / or nonionics, and optionally one or more of the following substances: 0-10, preferably 0.5-8 wt. Foam stabilizers, 0-10, preferably 0.5 - 8% by weight non-surfactant foam inhibitors, 10 - 92, preferably 30 - 70% by weight complex-forming and / or non-complex-forming structural substances, with at least some of these structural substances react alkaline to neutral and the amount of the alkaline to neutrally reacting builder substances, preferably 0.5 to Make up 7 times and especially 1 to 5 times the total surfactant combination, 0-40, preferably 10-35 weight, - other common detergent ingredients such as Fabric softeners, bleaching components and optionally activators and stabilizers for these, corrosion inhibitors, dirt carriers, enzymes, fragrances, dyes, the Surfactants contain at least one hydrophobic residue of usually 8 - 26 in the molecule, preferably 10-22 and in particular 12-18 carbon atoms and at least one anionic, nonionic or zwitterionic water-solubilizing group. The preferably saturated hydrophobic radical is mostly aliphatic, possibly also alicyclic, in nature; it can work with the water-solubilizing groups directly or via intermediate links be connected, e.g. via benzene rings, carboxylic acid ester or carbonamide groups, residues of polyhydric alcohols bound in ether or ester form.

As an anionic active washing substance, soaps are made from natural or synthetic fatty acids, possibly also from resin or naphthenic acids, especially useful if these acids have iodine numbers of at most 30 and preferably less than 10 exhibit.

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

The sulfonates include, for example, the alkylbenzene sulfonates with preferably straight-chain C9-15-, in particular C1O14-alkyl radicals, the alkanesulfonates, obtainable from preferably saturated aliphatic C8-18, especially C12-18 hydrocarbons on sulfochlorination or sulfoxidation, which goes under the name "Olefinsulronate" known mixtures of alkene sulfonates, hydroxy alkane sulfonates and disulfonates, the acidic or alkaline hydrolysis of the terminal or central Ca 18- and preferably C12-18 olefins by sulfonation with sulfur trioxide initially formed sulfonation products arise. Among those that can be used according to the invention Sulphonates also include salts, preferably alkali salts, of cc-sulpho fatty acids as well as salts of esters of these acids with monovalent or molar, 1-4 and preferably 1 - 2 carbon atoms containing alcohols.

Further useful sulfonates are salts of fatty acid esters of oxethane sulfonic acid or of dioxypropanesulfonic acid, the salts of the fatty alcohol esters of lower, 1 - Aliphatic or aromatic sulfomono- or dicarboxylic acids containing 8 carbon atoms, the alkyl glyceryl ether sulfonates and the salts of the amide-like condensation products of fatty acids or sulfonic acids with aminoethanesulronic acid.

Fatty alcohol sulfates are to be mentioned as surfactants of the sulfaute type, in particular produced from Kolcosrettalkcholen, tallow fatty alcohols or from oleyl alcohol, furthermore sulfated fatty acid alkylolamides or fatty acid monoglycerides as well as sulfated ones Alkoxylation products of alkylphenols (C8-15-alkyl), fatty alcohols, fatty acid amides or Fe t t acid alkylolamides with 0.5-20, preferably 1-8 and in particular 2 - 4 ethylene and / or propylene glycol residues in the molecule.

Suitable anionic surfactants of the carboxylate type are, for example, the Fatty acid esters or fatty alcohol ethers of hydroxycarboxylic acids and the amide-like ones Condensation products of fatty acids or sulfonic acids with hminocarboxylic acids, e.g. with glycocolla, sarcosine or with protein hydrolysates.

The anionic surfactants are mostly in the form of salts of the alkali metals, in particular sodium, ammonium, lower aliphatic amines or alkylolamines before.

To the nonionic surfactants, here for the sake of simplicity as "Nonionics" referred to, include those by the addition of 4-100, preferably 6-IrO and in particular 8 - 20 moles of ethylene oxide in fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acids or sulfonic acid amides available polyethylene glycol ethers, as well as the still water-soluble Addition products of propylene or butylene oxide to these. The bionionics include also those known under the trade names "Pluronics" or "Tetronics", from inherently water-insoluble oaks Polypropylene glycols or from water-insoluble propoxylated lower, 1 - 8, preferably from 3 to 6 carbon atoms containing aliphatic alcohols or from water-insoluble alcohols propoxylated alkylenediamines obtained by ethoxylation to water solubility Products. Finally, nonionics are also those known as "Ucon-Fluid", some of them. still water-soluble reaction products of the abovementioned aliphatic alcohols to use with propylene oxide.

As nonionics are also from mono- or diethanolamine, from dihydroxypropylamine or other polyhydric alkylamines, e.g. fatty acid or fatty acids derived from the glyamines Sulfonic acid alkylolamides are useful. Furthermore, the oxides of higher tertiary amines with one hydrophobic alkyl radical and two shorter, bis to alkyl and / or alkylol radicals containing 4 carbon atoms each.

Zwitterionic surfactants contain both acidic groups, such as carboxyl, sulfonic acid, sulfuric acid half ester, phosphonic acid and phosphoric acid partial ester groups, as well as basic groups such as primary, secondary, tertiary and quaternary Ammonium groupings. Zwitterionic compounds with quaternary ammonium groups belong to the betaine type. Carboxyl for sulfate and sulfonate betaines have because of of particular practical interest because of their good compatibility with other surfactants.

The foaming power of the surfactants can be determined by a combination of suitable Increase or decrease the surfactant types, as well as the addition of non-surfactant types organic substances can be changed, Suitable foam stabilizers are especially with surfactants of the sulfonate or sulfate type, capillary-active carboxy or Sulfobetaines as well as the above-mentioned nonionics of the alkylolamide type; also are fatty alcohols or higher terminal diols have been proposed for this purpose.

A reduced foaming power, which is desirable when working in machines is often achieved by combining different types of surfactants, e.g. from Sulphates and / or sulphonates and / or from nonionics on the one hand with soaps on the other. In the case of soaps, the foam absorption increases with the degree of saturation and the C number of the fatty acid residue at; Soaps made from saturated C2024 fatty acids have proven effective as foam suppressors.

The non-surfactant-like foam inhibitors may include

Chlorine-containing N-alkylated aminotriazines, which can be obtained by reaction of 1 mole of cyanuric acid chloride with 2-3 moles of a mono- and / or dialkylamine with 6'- 20, preferably 8-18 carbon atoms in the alkyl radical. Propoxylated ones have a similar effect and / or butoxylated aminotriazines, e.g. 3. Products that can be obtained by investing 5-10 moles of propylene oxide on 1 mole of melamine and further addition of 10-50 moles of butylene oxide of this propylene oxide derivative.

Other non-surfactant foam inhibitors are water-insoluble organic compounds such as paraffins or haloparaffins with melting points below from 1000 C, aliphatic C18 to C40 ketones and aliphatic carboxylic acid esters, the in the acid or alcohol radical, optionally also in each of these two radicals, at least Contains 18 carbon atoms (e.g. triglycerides or fatty acid fatty alcohol esters); let them especially with combinations of surfactants of the sulfate and / or sulfonate type use with soaps to steam the foam.

As particularly low-foaming nonionics, which can be used both alone and also in combination with anionic, zwitterionic and nonionic surfactants can be used and reduce the foaming power of better foaming surfactants, storage products of propylene oxide on the capillary-active ones described above are suitable Polyethylene glycol ether as well as the Pluronic-> Tetronic- and Ucon fluid types.

Weakly acidic, neutral and alkaline substances are suitable as structural substances reacting inorganic or organic salts, in particular inorganic or organic Complexing agents.

According to the invention, weakly acidic, neutral or alkaline Reacting salts are, for example, bicarbonates, carbonates, borates or silicates the alkalis, furthermore mono-, di- or trialkali orthophosphates, di- or tetraalkali pyrophosphates, as complexing agents known metaphosphates, alkali sulfates and 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 salts of sulfodicarboxylic acids and the salts of acetic acid, lactic acid, citric acid and tartaric acid.

Furthermore, the water-soluble salts are of higher molecular weight as structural substances Polycarboxylic acids can be used, in particular polymers of maleic acid, itaconic acid, Mesaconic acid, fumaric acid, aconitic acid, methylenemalonic acid and citraconic acid. Even Copolymers of these acids with one another or with other polymerizable ones Substances such as B. with 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 weak ones are also suitable as complex-forming structural substances acidic metaphosphates as well as the alkaline reacting polyphosphates, especially the tripolyphosphate. They can be wholly or partially organic Complexing agents are replaced.

The organic complexing agents include, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethyl ethylenediamine triacetic acid, polyalkylene-polyamine-N-polycarboxylic acids and other known organic complexing agents, with combinations of different complexing agents also being used. The other known complexing agents also include di- and polyphosphonic acids of the following constitutions: where R is alkyl and R 'is alkylene radicals with 1-8, preferably with 1-4 carbon atoms, X and Y represent hydrogen atoms or alkyl radicals with 1-4 carbon atoms and Z represents the groups -OH, -NH2 or -NXR. The following compounds are particularly suitable for practical use: methylenediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, aminotri-methylene phosphonic acid, methylamino or ethylamino di (methylene phosphonic acid) ) and ethylenediamine tetra (methylenephosphonic acid). All of these complexing agents can be present as free acids, preferably as alkali salts.

The following table provides information about that after the Hampshire test certain complexing capacities of various complexing agents. The implementation of the Hampshire test is described in the examples.

Calcium carbonate complexing agent binding capacity in mg / g complexing agent hydroxymethylphosphonic acid 1 mesoxalic acid monohydrate 6 t-cysteine hydrochloride monohydrate 14 glycolic acid 45 tetrasodium pyrophosphate 125 n-hexylaminedimethylene phosphonic acid 160 sodium tripolyphosphonic acid 160 sodium tripolyphosphonic acid 160 sodium tripolyphosphonic acid 160 sodium tripolyphosphonate 280 dibasic phosphane-1, 1-hexa-diphosphonic acid 280-aliphosphonate-1, 1-hexa-diaphosphonic acid 280, sodium-tripolyphosphate-1, 1-hexa-di-phosphine-1, 1-hexa-phosphine-220-aliphosphonic acid 280 930 a-aminobenzyl sia-diphosphonic acid, aminotrimethylenephosphonic 1460 820 860 Äthylendiamintetramethylenphosphonsäure Aminodimethylenphosphonsäure-N-acetic acid 850 iminodiacetic acid-N-methylenephosphonic Hydroxyäthandiphosphonsäure 540 810 270 citric acid 328 phosphonoacetic diethylenetriaminepentaacetic 275 1,2-cyclohexanediamine tetraacetic acid, ethylene diamine 285 402 578 nitrilotriacetic Technical mixture of various metaphosphates 500 (Graham's salt) Among the preferably inorganic per-compounds used as bleaching agents, sodium perborate tetrahydrate (NaB02. H2O2. 3 H2O) is of particular practical importance. In its place, partially or completely, ie up to NaB02. H202 dehydrated perborates can be used. They are also the NaB02 borates described in DBP 901 287 and USP 2,491,789. H2O2 in which the ratio Na2O: B20) is less than 0.5: 1 and preferably in the range 0.4-0.15: 1, while the ratio H2O2: Na in the range 0.5-4 : 1 falls. All of these perborates can be wholly or partially replaced by other inorganic per compounds, in particular peroxohydrates, for example the peroxohydrates of ortho-, pyro- or polyphosphates, especially tripolyphosphates, and carbonates.

It is advisable to use the products to stabilize the per compounds Usual water-soluble and / or water-insoluble stabilizers in amounts of 0.25 - to incorporate 10% by weight.

As water-insoluble perstabilizers, e.g. 1 - 8, preferably 2 - 7% of the weight of the entire preparation. -Make it, they are mostly suitable Magnesium silicates obtained by precipitation from aqueous solutions MgO: SiO 2 = 4 : 1 to 1: 4, preferably 2: 1 to 1: 2 and in particular 1: 1.

In their place are other alkaline earth metal, cadmium or tin silicates appropriate composition usable. There are also hydrous oxides of tin suitable as stabilizers.

Water-soluble stabilizers, which together with water-insoluble may be present, are the organic complex formers, the amount of which is 0.25 - 5, can preferably make up 0.5 - 2.5 ffi of the weight of the entire preparation.

Hesticrnte, with in water, serve as activators for per compounds H2 ° 2 supplying per-compounds organic per-acids forming N-acyl, O-acyl compounds as well as carbonic acid resp.

Pyrocarbonic acid esters, their activation value for the per compounds (= Titer) is at least 3, preferably at least 4.5. This activation value is determined in the following way: Solutions containing 0.615 g / i NaBO2 H202 3 3 H20 (4 iol / l) and 2.5 g / l Na4P207 10 H2 ° contain, after heating to 60 ° C with 4 mmol / l Added activator and kept at the specified temperature for 5 minutes with stirring. 100 ml of this liquid are then added to a mixture of 250 g of ice and 15 ml Glacial acetic acid and titrate immediately after adding OS35 g of potassium iodide with 0.1 N sodium thiosulphate solution and strength as an indicator. Nan consumed under the specified test conditions with a 100% activation of the peroxide used 8.0 ml thiosulfate solution, i.e. the titer is 8.0. However, this maximum value is almost never reached; good activators have a titer of at least 4.5. Often one already reaches activations which can be used with activators whose titer is at least 3.0.

Suitable from the types of activators still to be described below especially compounds n-t a melting point of at least 70 ° C, preferably at least 100 ° C. and in particular at least 150 ° C. Furthermore, the squivalent weight should of these compounds (the equivalent weight here is the quotient of the molecular weight and the number of acyl radicals present in the itolecule) at most 170, preferably at most 130 and in particular at most 110.

The activators which can be used according to the invention include a) those from N-diacylated compounds known from German patents 1,162,967 and 1,291-317 and N, N'-tetraacylated amines such as N, N, N ', N'-tetraacetyl methylenediamine or

ethylenediamine, N, N-diacetylaniline and N, N-diacetyl-p-toluidine or 1,3-dlacylated hydantoins, such as the compounds 1,3-diacetyl-5,5-dimethyl-hydantoin and 1,3-dipropionyl hydantoin; b) those from British patent specification 1 003 310 known N-alkyl-N-sulfonyl-carbonamides, for example the compounds N-methyl-N-mesyl-acetamide, N-methyl-N-mesyl-benzamide, N-methyl-N-mesyl-p-nitrobenzamide, and N-methyl-N-mesyl-p-methoxybenzamide; c) those described in Swiss patent specification 407 387 as activators N-acylated cyclic hydrazides, acylated triazoles or urazoles such as that Monoacetyl maleic hydrazide; d) in the German patent application P 17 19 574.3-43 O, N, N-trisubstituted hydroxylamines described e.g.

O-Benzoyl-N, N-succinyl-hydroxylamine, O-acetyl-N, N-succinylhydroxylamine, O-p-methoxybenzoyl-N, N-succinyl-hydroxylamine, O-p-nitrobenzoyl-N, N-succinyl-hydroxylamine and O, N, N-triacetylhydroxylamine; e) those from the German Offenlegungsschrift 1 801 713 known N, N'-diacyl-sulfurylamide, for example N, N'-dimethyl-N, N'-diacetyl-sulfurylamide, and N, N'-diethyl-N, N'-dipropionylsulfurylamide; f) the triacylcyanurates, for example Triacetylcyanurat and Tribenzoylcyanurat of the German Auslegeschrift 1,294,919; g) those from Swiss patent specification 347 930 or the German patent specification 893 049 or the German Offenlegungsschrift 1 444 001 known carboxylic acid anhydrides like æ.B. @ Benzoic anhydride, m-chlorobenzoic anhydride, phthalic anhydride, 4-chlorophthalic anhydride; h) those from the Swiss patent specification 348,682 known sugar esters, for example glucose pentaacetate; i) the 1,3-diacyl-4,5-diacyloxy-imidazolidines the German Offenlegungsschrift 1 801 141, for example the compounds 1, 3-Diformyl-4, 5-diacetoxy-imidazolidine, 1, 3-diacetyl-4, 5-diacetoxy-imidazolidine, 1,3-diacetyl-4,5-dipropionyloxy-imidazolidine; j) those from the German Offenlegungsschrift 1,594,865 compounds known as activators tetraacetylglycoluril and tetrapropionylglycoluril; k) the diacylated 2, 5-diketopiperazines proposed as activators for per compounds such as 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-diketopiperazine; 1,4-dipropionyl-3,6-dimethyl-2,5-diketopiperazine; 1) the carbonic acid esters of the German Offenlegungsschrift 1 444 024, for example the sodium salts of p- (ethoxycarbonyloxy) benzoic acid and p- (propoxycarbonyloxy) benzene sulfonic acid.

Often it is sufficient to only use part of the available active oxygen to activate; activator additives of at least 0.05 mol of activator are sufficient for this per g-atom of active oxygen. The aim is to activate it as far as possible of the active oxygen value, the activator can be added up to 2 mol, preferably Increase up to 1 mole. It is preferred to work with 0.1-1 mol of activator per g atom Active oxygen. However, these amounts can be adjusted according to the activity of each change the activator used.

When the per compounds are activated by the aforementioned N-acyl and O-acyl compounds become part of the alkali in the washing and bleaching liquors the resulting organic peracids or the resulting organic Carboxylic acids such as acetic acid, propionic acid, benzoic acid consumed and advantageously replaced by adding appropriate amounts of alkalizing agent.

The active chlorine compounds used as bleaching agents can be more inorganic or be organic in nature.

The inorganic active chlorine compounds include alkali hypochlorites, in particular in the form of their mixed salts or addition compounds to orthophosphates or to condensed phosphates such as pyro- and polyphosphates or can be used on alkali silicates.

If the detergents and auxiliary agents contain monopersulphates and chlorides, active chlorine is thus 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 leads, in particular to a CO or SO2 group. These connections include Dichloro and trichlorocyanuric acid or their salts, chlorinated alkylguanides or Alkyl biguanides, chlorinated hydantoins and chlorinated Mc lamines.

The enzyme preparations to be used are usually a mixture of enzymes with different effects,> æ.B. of proteases, carbohydrases, esterases, lipases, Oxidoreductases, catalases, peroxidases, ureases, isomerases, lyases, transferases, Desmolases or nucleases. Those from bacterial strains are of particular interest or enzymes obtained from fungi such as Bacillus subtilis or Streptomyces griseus, in particular Proteases or amylases that oppose alkali, percompounds and anionic surfactants are relatively stable and are still effective at temperatures of up to 70 ° C.

Enzyme preparations are usually supplied by the manufacturers as aqueous solutions the active ingredients or as a powder, granules or as cold atomized products in the Trade brought. They often contain sodium sulfate, sodium chloride, Alkali ortho-, pyro- or polyphosphates, especially tripolyphosphate. Special ones Value is placed on dust-free preparations; they are obtained in a manner known per se by incorporating oily or pasty nonionics or by granulating with the help of melting salts containing water of crystallization in your own water of crystallization.

Enzymes can be incorporated for a certain type of dirt are specific, for example proteases or amylases or lipases; preferred one uses combinations of enzymes with different effects, especially combinations from proteases and amylases, The brighteners that can be used are usually although not exclusively, derivatives of aminostilbene sulfonic acid or diaminos tllbenr? isulfons Rure, diarylpyrazolines, carbostyrils, 1,2-di- (2-benzoxazolyl) - or 1,2-di- (2-benzimidazolyl) -ethylene, benzoxazolyl-thiophene and coumarin.

Examples of brighteners from the class of the diaminostilbene disulfonic acid derivatives are compounds according to formula I: In the formula, R1 and R2 alkoxyl groups can denote the amino group or residues of aliphatic, aromatic or heterocyclic, primary or secondary amines and residues of aminosulfuric acids, aliphatic residues present in the above groups preferably 1 to 4 and in particular 2 to 4 carbon atoms ent, hold, while the heterocyclic ring systems are mostly 5- or 6-membered rings. The radicals of aniline, anthranilic acid or anilinesulfonic acid are preferred as aromatic amines. Lighteners derived from diaminostilbene disulphonic acid are mostly used as cotton lighteners. There are the following, derived from the formula I Pro-. products on the market, where R1 represents the radical -NHC6H5 and R2 can represent the following radicals: -NH2, -NHCH3, -NHCH2CH2OH, NHCH2CH2OCH3, -NHCH2CH2CH2OCH3, - N (CH3) CH2CH2OH, -N (CH2CH2OH) 2, morpholino-, -NHC6H5, -NHC6H4SO3H, -OCH3. With regard to fiber affinity, some of these brighteners are to be regarded as transition types to the polyamide brighteners, for example the brightener with R2 = -NHC6H5. The compound 4,4'-bis- (4-phenyl-1,2,3-triazol-2-yl) -2,2 'stilbene disulfonic acid also belongs to the cotton whitening agents of the Diamlnos tilbendisulron acid type.

The polyamide brighteners include diarylpyrazolines of the formulas II and III: In formula II, R3 and R5 denote hydrogen atoms, optionally alkyl or aryl radicals substituted by carboxyl, carbonamide or ester groups, R4 and R6 denote hydrogen or short-chain alkyl radicals, Arl and Ar2 aryl radicals such as phenyl, diphenyl or naphthyl, the others May carry substituents, such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, carboxylic acid ester, sulfonic acid, sulfonamide and sulfone groups or halogen atoms. Commercially available brighteners of this type are derived from the formula III, where the radical R7 can represent the groups Cl, -SO2NH2, -SO2CH = CH2 and -COOCH2CH2OCH3, while the radical R8 usually denotes a chlorine atom. 9-Cyanoanthracene is also one of the polyamide brighteners. The polyamide brighteners also include aliphatic or aromatic substituted aminocoumarins, for example 4-methyl-7-dimethylamino- or 4-methyl-7-diethylaminocoumarin. The compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) -ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyril can also be used as polyamide brighteners. The compounds 2,5-di- (2-benzoxazolyl) -thiophene and 1,2-di- (- methyl-2-benzoxazolyl) -ethylene are suitable as brighteners for polyester and polyamide fibers.

If the brighteners are used together with other components of the invention Products are present as an aqueous solution or paste and by hot drying in solid State, it is advisable to use organic brighteners to stabilize them Complexing agents in amounts of at least 0.1, preferably 0.2-1% by weight of the solids Incorporate products.

Dirt carriers can also be used in the preparations according to the invention be included, which suspends the dirt detached from the fiber in the liquor hold and thus prevent graying. For this purpose, water-soluble colloids are usually used of an organic nature, such as, for example, the water-soluble salts of polymeric materials 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 strength. Water-soluble polyamides containing acidic groups are also useful suitable for this purpose. Soluble starch preparations and others can also be used use as the above starch products, Viie e.g. B. degraded starch or Aldehyde strengths. Polyvinylpyrrolidone can also be used.

13 i p i e l e The following examples describe 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 terms or abbreviations mean: "ABS" das Salt of a obtained by condensing straight chain olefins with benzene and sulfonating of the resulting alkylbenzene obtained alkylbenzenesulfonic acid with 10-15, preferably 11-13 carbon atoms in the alkyl chain, "alkanesulfonate" one made from paraffins with 12-16 carbon atoms on the sulfonate obtained by sulfoxidation, "Fs-ester sulfonate" a from the methyl ester of a hardened tallow acid by sulfonation with SO3 obtained sulfonate, "olefin sulfonate" from olefin mixtures with 12-18 carbon atoms by sulfonating with SO3 and hydrolyzing the sulfonation product with lye obtained sulfonate, which consists essentially of alkene sulfonate and oxyalkane sulfonate exists, but also contains small amounts of disulfonates. Any containing olefin sulfonate Preparation was made using two different types of olefin sulfonate; that, one was made from a mixture of straight chain terminal olefins, the other, produced from a mixture of internal olefins, "KA sulfate" or "TA sulfate" the salts of sulphated, by reduction of coconut fatty acid or, Tallow fatty acid produced, essentially saturated fatty alcohols, "KA-ÄO-sulfate" or "TA-ÄO-sulfate" or "OA-ÄO-sulfate" the sulfated addition products of 2 moles of ethylene oxide to 1 mole of coconut fatty alcohol or 3 moles of ethylene oxide to 1 mole Sebum alcohol or from? Moles of ethylene oxide to 1 mole of oleyl alcohol, "OA + 5 ÄO", "OA + 10 ÄO "and" KA + 20 ÄO "the addition products of ethylene oxide (ÄO) to technical Oleyl alcohol (OA) or coconut alcohol (KA), with the numbers referring to 1 mole of alicohol The molar amount of ethylene oxide added is marked, "KA + 9 ÄO + 12 PO" a through Reacting 1 mole of "KA + 9 ÄO" with 12 moles of propylene oxide obtained nonionic, "perborate" a product of the approximate composition containing about 10% active oxygen NaBO2.H2O2.3 H20, "NTA", "EDTA" or "HEDP" the salts of nitrilotriacetic acid, the ethylenediaminetetraacetic acid or the hydroxyethane diphosphonic acid, "CNC" das Salt of carboxymethyl cellulose.

The composition of the fatty acid mixtures that make up the various Soaps contained in the products according to the invention are made from can be found in the following table: Composition of the soaps corresponding fatty acid mixtures wt .-% fatty acid component for the soap C number of fatty acid B C D G # C10 2 2 4 1 C12 L9 21 16 6 C14 8 6 10 5 C16 4 16 25 28 C18 22 33 45 60 c20 8 4 - -C22 37 .18 - -JZ of the fatty acid mixture 4 8 6 4 As a foam inhibitor a mixture of about 45 ß of a di- (alkylamino) -monochlorotriazine and approx. 55% of an N-N '-N "-trialkylmelamine is used. In all of these triazine derivatives the alkyl radicals were present as a mixture of homologues with 8-18 carbon atoms. With something similar The monochlorotriazine derivative or the trialkylmelamine could also be used successfully. Unless the products described have synthetic sulfates or sulfonates together with Contained soap, the others mentioned in the description could not be surfactant-like Foam inhibitors are used, such as, for example, paraffin oil or paraffin. In the manufacture of the preparations, the foam inhibitor used was used in a suitable one organic solvent dissolved or in a molten state by means of a nozzle sprayed onto the moving powdery preparation.

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 foam inhibitors. However, foam inhibitors and antimicrobial substances 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 1t +11 in the line "Na2SO4" means that small amounts of sodium sulfate are contaminated by the anionic surfactants may exist. The in the line "Antimicr. Subst." located in large letters identify the substance present in each case; in the line below is their amount specified. In the last line is under 1, Remainder1? no numerical value given; he is calculated as the difference between 100 and the amounts of the other components.

From the point of view of substance, the rest is essentially an essential one Part of water; provided Na2S04 only in small amounts, from the synthetic anionic Amounts derived from surfactants are present (characters 1? +! I in the Wa2S04 line of the table), the remainder also includes the Na SG1 present. They also fall under the rest as well any dyes, fragrances and enzymes present.

The following examples make the subject matter of the present Invention explained in more detail. The following antimicrobial agents were used Terpenes used: 1. Limonene 2. Citral 3. Citronellal 4. Geraniol 5. Menthone 6. Fenchone 7. Camphor 8. Thymol Among the key names given in the examples the following optical brighteners were used: BW I: 4,4t-bis-g2-anilino-4-morpholino-1,3,5-triazinyl-6-amino] -stilbenedisulfonic acid-2,2 ' BW II: 4,4-bis [2-anilino-4-methylamino-1,3,5-triazinyl-6-amino7-stilbene-disulronic acid-2,2 ' BW III: 4,4'-bis [2-anilino-4-methoxyethylamino-1,3,5-triazinyl-6-amino] -stilbene-disulfonic acid-2,2 ' BW IV: 4,4'-bis [2-anilino-4-methoxypropylamino-1,3,5-triazinyl-6-amino] -stilbenedisulfonic acid-2,2 ' PA I: 1-p-sulfonamido-phenyl-3-p-chlorophenylpyrazoline PA II: 4-methyl-7-diethylamino-coumarin PA III: 1-ethyl-3-phenyl-7-dimethylamino-carbostyril PE: 2,5-di- (benzoxazolyl) -thiophene SN: 1-p-carboxyphenyl-3-p-chlorophenyl-pyrazoline The ones in the examples The products described 1 - 12 are preferably used for the following purposes: Example 1: Soaking or heavy duty detergent Examples 2 - 4 All-purpose detergent and 6 - 9 perborate-free and brightener example 5. containing mild detergent example 10. Brighteners and mild detergents containing perborate Examples 11. Mild detergent, Also intended for use with easy-care and 12 textiles.

All of the detergents described above can also be used in drum washing machines at temperatures of 90-100 ° C. without causing foaming. Part of the% by weight component in the preparation according to the example Preparation 1 2 3 4 5 ABS - 9.0 11.0 - - Olefin sulfonate 5.0 - - - 11.4 Soap 1018 - - - - 8.8 Soap 1622 - 1.9 - - - OA + 5 AO - - - - 5.1 OA + 109 AO - 7.8 6.0 - - KA + 20 ÄO - - - 11.0 - KA + 9 ÄO + 12 PO @, 0 | - | - | @, 5 Foam inhibitor 0.3-0.5-0.8 Na2SO4 - + + - + Na2O. 3.3 SiO2 - 4.5 4.0 4.3 7.4 Na4P2O7 9.0 - - 11.0 - Na6P3O10 61.0 40.5 15.9-29.0 Perborate - 11.1 20.1 16.0 MgSiO3 - 1.0 1.6 1.0 1.6 NTA - - 17.0 17.0 - EDTA 0.5 - - - - EHDP - - 6.6 12.1 25.0 CMC 1.6 1.4 1.2 1.5 1.3 Antimicrobial. Subst. 1.0 3.0 2.0 6.0 4.0 Quantity 1.8 3.2 1.7 3.8 2.1 BW brightener I 0.3 0.3 0.2 0.2 0.2 BW brightener - - 0.1 - - BW brightener III - - - - 0.1 BW brightener IV - - - 0.1 - PA brightener I 0.1 0.1 0.1 0.1 0.1 PA brightener II - - - - - PA brightener III - - - - - PE brightener - 0.05 0.05 0.05 0.05 rest Part of the% by weight component in the preparation according to the example Preparation 6 7 8 9 10 11 12 A 13 S 8.5 - - | - | - | - Alkanesulfonate - - 7.0 - - - - Fs-ester sulfonate - 0.5 - - - - - Olefin sulfonate - - - 3.0 - - 10.0 KA sulfate 1.6 2.8 1.2 - - 1.5 3.8 TA sulfate 0.5 - - 3.0 - 1.5 - KA-AO-sulfate 2.1 - - - 2.3 - 7.5 TA-ÄO-sulfate - - - - - 7.5 - OA-ÄO-sulfate - - - - 5.5 - - Soap 1018 - - - - - 4.15 - Soap 1222 5.3 9.3 - 9.2 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 16.0 10.0 Na2O. 3.3 SiO2 5.2 4.0 - 4.2 3.5 3.7 - Na5P3O10 27.0 25.1 35.3 19.2 31.0 32.3 47.0 Perborate 24.0 26.0 21.9 27.6 22.0 - - MgSiO3 2.0 - - 3.0 - - - NTA 15.0 5.0 - 8.0 - 11.0 - EDTA 0.22 0.25 0.5 0.4 - - - CMC 1.3 1.9 1.3 1.4 1.5 1.3 0.7 Antimicrobial. Subst, 7.0 5.0 8.0 1.0 | 3.0 | 6.0 | 4.0 Amount | 1.6 | 1.9 | 1.4 | 2.2 | 4.0 | 5.0 | 2.3 BW brightener I 0.35 0.5 0.25 0.20 0.35 0.35 0.35 BW brightener II - - 0.15 - - - - BW brightener III - - - 0.20 - - - BW brightener IV - - - - 0.15 - - PA brightener I 0.08 - - - - - - PA brightener II - 0.1 0.1 0.03 0.12 - - PA brightener III - - - - - 0.15 0.10 PE brightener 0.04 - 0.05 0.05 0.1 - 0.05 rest Example 13 A pre-wash which enables disinfection even at temperatures of up to 60 ° C. has the following composition: 10.0% by weight ABS, alkanesulfonate or olefin sulfonate 5.0 "-% soap 1622 0.35" - foam inhibitor 50.0 - "-% Na4P207 6.5" -% NaOH 0.8 "-% Na2SO4 3.5" -% α-aminoethane-α, α-diphosphonic acid 3.0 "-% EHDP 4.5" - antimicrobial agent 3 0 , 20 "-% BW I 0.20" - BW II 0.05 "-% PA III 0.05" - PE ne st water Examples 14 and 15 if complete disinfection is not possible, it has the following composition: 8.0% by weight ABS, alkanesulphonate or olefin sulphonate 4.0 "- soap 1622 0.3" - foam inhibitor 39.0 "-% Na4P2O7 7.5" - NaOH 0.6 "-% Na2SO4 4.0" -% α-aminobenzyl-α.α-diphosphonic acid 1.6 "- EDTA 5.0" -% antimicrobial agent 6 14 15 0.25% by weight BW I 0.15% by weight -% BW I 0.15 "-% BW III 0.15" -% BW IV 0.1 "-% PA III 0.12" -% PA III 0.03 "-% PE 0.03" -% PE Remainder in each case water Example 16 A rinsing agent for washed laundry which simultaneously dissolves fiber incrustations, in particular lime-containing fiber incrustations, has the following composition: 26.0% by weight perborate 25.0 "-% EHDP 1.6" -% antimicrobial substance 2 8.0 "-% MgSiO3 25.7" -% Na2SO4 4.0 "% Na5P3010 6.0" -% NaOH 0.1 "-% BW II 0.1""PA-I rest water Technical effect, the following experiments were carried out: Lobules made of twill about 1 cm2 in size were dipped in skimmed milk containing Staphylococcus aureus (approx. 109-1010 germs / ml) was infected. After the lobules had soaked up, they were removed from the skimmed milk, dried at 37 ° C. for three hours and then used to test the antimicrobial effect of the various detergents.

For this purpose, 15 lobes were placed in a ground-glass stopper bottle given, the 50 cm³ of the detergent solution to be tested (detergent concentration 5 g / l). The solution was heated to 50-60 ° C. before the lamps were inserted; this temperature was maintained for the entire duration of the experiment. To For 5, 10, 15, 30, 45 and 60 minutes, two lobes were removed from each and twice in a sterilized aqueous solution of 3 ffi of an oxethylated sorbitan monooleate (Tween 80) and 0.3% lecithin rinsed. The Läppohen were now on lecithin bouillon agar, the oxethylated sorbitan monooleate contained, given and with the same nutrient medium layered.

After three days of incubation at 37 ° C., the plates became macroscopic examined for germ growth.

Two detergent samples were used for the tests, namely once the detergent according to example 3 and secondly a corresponding detergent without the antimicrobial active ingredient 2. In the case of the active ingredient-free detergent were all germs are killed only after 60 minutes of treatment, in the case of the active ingredient-containing one With detergent, this effect was already achieved after 10 minutes.

Example 18 Antimicrobial Soap 97.9% by weight of one Fine soap flake mixture, consisting of 80 parts by weight of sodium tallow soap and 20 parts by weight of sodium coconut soap with a water content of 20 percent by weight were with 0.3 percent by weight EDTA, 0.5 percent by weight sodium sulfite, 1.2 Weight percent antimicrobial substance and 0.1 weight percent brightener SN mixed, deformed in an extruder and pressed into pieces. The soap bars showed not only the expected good antimicrobial effect, but were also colorfast. After exposure to daylight in conditions similar to daylight, the pieces showed the same color values as immediately after their production. The color values were with the aid of a photometer ("Elrepho" from Carl Zeiss) using standardized Color filter determined.

A detailed 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 1960 "Hampshire NTA Technical Bulletin ", Appendix P. A2. After that, exactly 2 g of powdery Complexing agent dissolved in 50 ml of distilled water, neutralized, with 10 ml of a show sodium carbonate solution added, its pH adjusted to 11-12 and the solution diluted to 100 ml. Then with a calcium acetate solution, the 44.1 g calcium acetate monohydrate per liter, until a significant amount appears and permanent turbidity. 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

Claims (11)

Claims 1; Possibly water and / or water-soluble Detergents and auxiliary washing agents containing organic solvents with a content of antimicrobial agents, characterized in that they consist of: 0.2 -20.0, preferably 0.5 to 10 and in particular 1.0 to 5.0 percent by weight of an aliphatic or alicyclic terpene, 0.02-2.0, preferably 0.05-1.0 and especially 0.1 to 0.75% by weight of an optical brightener, 50.0-99.78, preferably 70.0 to 95.0 and in particular 80; 0 to 99> Q% by weight of other customary inorganic or organic constituents of detergents and auxiliary laundry detergents, whereby the quantities refer to the water and / or solvent-free preparation. 2. Washing and washing aid according to claim 1, characterized in that that as aliphatic or alicyclic terpenes they are terpene hydrocarbons, terpene alcohols, Terpene aldehydes, monocyclic terpene ketones, bicyclic terpene ketones or conversion products contain monocyclic terpene ketones. 3. Washing and washing aid according to claim l and 2, characterized in that that they are limonene, citral, citronellal, geraniol, menthone, fenchone, camphor as terpenes or contain thymol. 4. Washing and washing aid according to claim 1 to 3, characterized in that that they are compounds of the class of derivatives of diamino-stilbene disulfonic acid salts as optical brighteners, the derivatives of diarylpyrazoline, the derivatives of aminocuma. rins, the derivatives of carbostyril and / or the derivatives of thiophene. 5. Washing and washing aid according to claim 1 to 4, characterized in that that the other usual organic ingredients according to claim 1 at least partly consist of surfactants. 6. washing and washing aid according to claim 1 to 5, characterized in that that the other usual organic and inorganic ingredients according to claim l at least from inorganic or organic salts with and without complex-forming capacity exist. 7. detergents and @ washing auxiliaries according to claim 1 to 6, characterized in that that the other usual organic and inorganic components at least 5% by weight, based on the weight of the water- and solvent-free product, from alkaline-reacting structural substances which, in the Hampshire test, have the ability to form complexes have a maximum of 200 mg CaCO3 / g alkaline building substance, and to at least 3, preferably at least 10 wt .-%, based on the weight of the water- and solvent-free product, made from complexing agents, their complexing ability in the Hampshire test is above 200 mg CaCO3 / g complex former - pass. 8. detergent and auxiliary agent according to claim 1 to 7, characterized in that that they contain the following substances as other common constituents: 0 - 5.0 % By weight surfactants, 45-94.78% by weight, preferably alkaline substances and optionally per compounds and optionally their usual Accompanying substances, such as activators, stabilizers, complexing agents for Heavy metals etc. 9. Products to be used preferably as prewash and detergent according to claim 1 to 8, characterized in that their composition is approximately im The range of the following formulation is: 0.22 - 22.0, preferably 0.55 - 11% by weight antimicrobial substances and optical brighteners according to claims 1 - 3, > 5.0-40.0, preferably 7-30% by weight of a surfactant component containing at least an anionic and X or nonionic surfactant, in particular of the sulfonate type, Sulphates, soaps and / or nonionics and optionally one or more of the following Substances: 0-10.0, preferably 0.5-8% by weight foam stabilizers, 0-10.0, preferably 0.5-8% by weight of non-surfactant foam inhibitors, 10.0-92.0, preferably 30-70% by weight of complexing and / or non-complexing structural substances, wherein at least some of these builder substances reacts alkaline and wherein the Amount of the alkaline to neutral reacting builder substances preferably the 0.5- up to 7 times and in particular 1 to 5 times the total surfactant combination, O - 40.0, preferably 10-35% by weight - other common detergent ingredients, such as z. B. Fabric softeners, bleaching components and optionally activators and stabilizers for these, corrosion inhibitors, dirt carriers, enzymes, fragrances, Dyes. 10. Preferred for use in washing machines, especially in drum washing machines Agent to be used according to claim 9, characterized in that the surfactant component 7-30% by weight and at least one of the following two types of surfactants in amounts from 15.0-99.0, preferably 35-90 wt. sulfonates and / or sulfates and / or Soaps with preferably 8-18 carbon atoms in the hydrophobic radical, 10.0-60.0, preferably 10 - 50% by weight of nonionics and optionally one or more of the following substances: 0 - 50.0, preferably 2 - 20 weight soaps (total C20 - C26) 0 - 10.0, preferably 0> 5-8% by weight foam stabilizers, 0-10.0, preferably 0.5-8% by weight non-surfactant Contains foam inhibitors, with the foaming capacity of the Tcnsidompomponent by simultaneous Presence of various surfactants that reduce each other's foaming power and / or anti-foaming soap and / or non-surfactant foam inhibitors is. 11. Agent according to claim preferably present in the form of pieces 1 to 3, characterized in that the other usual organic ingredients consist essentially of surfactants.