DE1948653A1 - Protein-solubilizing detergent - Google Patents

Abstract

A detergent which dissolves protein contains compds. with -SH. gps. and derivs. convertible into these compds. in alkaline medium and selected from mercaptoalkane sulphonic acids, mercaptoalkyl carboxylic acids, mercaptoalkyl ureas, mercaptoalkyl hydrazines, and mercaptoalcohols with 2-20, pref. 2-6C, or salts thereof which contain gps. capable of salt formation.

Description

"E white-dissolving detergents, washing additives and cleaning agents containing protein It is well known that laundry soiling is relatively difficult to remove, which is why the detergents intended for washing textiles are often protein-dissolving Enzyme clogs.

The invention relates to detergents, auxiliary washing agents and cleaning agents good protein-dissolving properties in which the enzymes partially or completely Protein-dissolving substances are replaced, and which are characterized in that they Compounds containing mercapto groups and which can be converted into these in an alkaline medium Derivatives from the series of mercaptoalkanesulfonic acids, mercaptoalkylcarboxylic acids, Mercaptoalkylureas, mercaptoalkanoylhydrazines and mercapto alcohols with 2 - 20, preferably 2-6 carbon atoms, or their salts, provided they are used for salt formation Have capable groups, contain as protein-dissolving agents.

In addition, other customary constituents can be used in the agents according to the invention of detergents, washing auxiliaries and cleaning agents e.g. anionic, zwitterionic and non-ionic surfactants, neutral to alkaline reacting builders, complexing agents, Foam stabilizers, foam inhibitors, plasticizers, fragrances. and dyes etc. be included.

As constituents of the agents according to the invention come as protein-dissolving Active ingredients e.g. the following compounds containing mercapto groups: ß-mercaptopropane sulfonic acid, γ-mercaptopropane sulfonic acid, # -mercaptobutane sulfonic acid, «-Mercaptopropionic acid, ß-mercaptoethylurea, α-mercaptoacetylhydrazine, α-mercaptoglycerin.

Preferred derivatives which can be converted into compounds containing mercapto groups in an alkaline medium are dithiourethanes of the formula Ia and alkyl thiocarbonates of the formula Ib in which Ra is a lower aliphatic radical with 2-4 carbon atoms, n is an integer from 2-20, X1 and X2 are sulfur and / or oxygen, A is a straight-chain or branched aliphatic radical with 1-6 carbon atoms and Ru is the arboxyl or sulfo group mean or the carboxylic or sulfonic acid salts of these derivatives with metal cations, ammonium or alkylolammonium, into consideration.

The dithiourethanes of the formula Ia can be passed through in a known manner Reaction of 2-hydroxyalkylamines with carbon disulfide and halosulfonic acids or prepare alkane sultones. Particularly preferred dithiourethanes of the formula Ia are the hydroxyalkylammonium salts of N-ß-hydroxyethyl-dithiocarbamic acid-S-propylester-g-sulronic acid.

The preparation of the thiocarbonic acid alkyl esters of the formula Ib is known.

The above-defined intracapto-containing compounds as well as the in an alkaline medium in these transferable derivatives, or the salts of such Compounds are referred to below for short as "mercapto compounds".

The mercapto compounds according to the invention containing the above defined mercapto compounds Detergents, auxiliary washing agents and cleaning agents show a remarkable protein-dissolving effect Effect that results from the reductive cleavage of disulride bridges of the protein can explain the mercapto bonds mentioned. The object of the invention is intended to therefore should not be limited to the mercapto compounds defined above, rather This also includes other compounds containing mercapto groups, provided they cause the cleavage of disulfide bridges in protein.

An improvement in the dirt-releasing properties of the invention Means is achieved if these, in addition to the mercapto compounds mentioned, act as dissolving agents Active ingredients still contain enzymes from the class of proteases3 lipases and amylases. The agents according to the invention, which both the mercapto compounds mentioned as also contain enzymes of the type mentioned, surprisingly show a synergistic effect Increase in the dirt-dissolving effect, especially with proteases. A preferred one Embodiment of the invention therefore relates to detergents, auxiliary washing agents and cleaning agents with a content of the mentioned mercapto compounds and enzymes, in particular protein-dissolving enzymes.

The mercapto compounds mentioned can be used as such or optionally in the form of their water-soluble salts, especially the alkali salts, in detergents. Washing aid and detergents can be incorporated by putting them together with the rest Components mixed in the usual way or mixed into a finished product. at the mercapto compounds used according to the invention are protein-dissolving Substances that are easily accessible and stable under normal storage conditions.

The enzymes to be used are usually a mixture of different ones of enzymatic active ingredients. Depending on their effect, they are used as proteases, carbohydrases, Esterases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, Lassen, called transferases, desmolases or nucleases.

Of particular interest are the au-. Strains of bacteria or fungi such as Bacillus subtilis and Streptomyces gr-lseus obtained enzymatic agents, especially proteases or amylases. Preparations made from Bacillus subtilis have the advantage over others that they have the advantage over alkali, per compounds and anionic substances are relatively stable and at temperatures up to 70 0C are still effective.

Enzyme preparations are usually supplied by the manufacturers as aqueous solutions of the active ingredients or with the addition of dispensing agents as a powder. Sodium sulfate, sodium chloride, alkali ortho-, pyro- or polyphosphates, especially tripolyphosphate. Often you bring the still damp ones Prepare enzymes with calcined salts, which then agglomerate if necessary the existing particles to larger particles the existing crystal water and bind the enzymatic agent.

If the enzymatic active ingredients are in the form of a dry powder, then liquid, paste-like and possibly also solid, nonionic, preferably capillary-active, organic compounds, in particular those described above Nonionics use the enzymes in the powder of wax or washing aids to , tie. A mixture is preferably sprayed for this purpose from the respective product and the enzymatic active ingredient with the above nonionic substances, or the enzyme preparation is dispersed in said non-ionic substance and combines this dispersion with the other components of the product. If these remaining components of the product are solids, can also the dispersion of the enzymatic active ingredients in the nonionic component Spray onto the remaining solid components.

The enzymes or Combinations of enzymes with different effects. are generally used in amounts such that the finished products have protease activities from 50-5,000, preferably 100-2,500 LSWE / g and / or amylase activities of 20-5,000, preferably 50-2,000 SKBE / g and / or lipase activities of 2 - 1,000, preferably 5 - 5.00 IU / g.

These details about the enzyme ac,; ivities result from the activities of those enzyme preparations which on the day of registration for use in the detergent sector appear justifiable from an economic point of view. From the chemical-technical From the standpoint, the enzyme activities of the preparations can be increased as required, so that the activities with proteases and amylases e.g. up to 5 times, with lipases e.g. can be increased up to 10 times the maximum values given above. Therefore, preparations with high activities should also be available in the future economically suitable for use in the detergent sector appear, the enzyme activities can be increased as needed. ever In terms of For the determination of the enzyme activities, reference is made to the following literature : Determination of the activity of proteases according to Löhlein-Volhard A. Künzel: "Gerbereichemisches Taschenbuch ", 6th edition, Dresden and Leipzig 1955; determination of the activity of Amylases J. Wohlgemuth: "Biochemische Zeitschrift", Volume 9, (1908), pages 1 - 9, as well as R.M. Sandstedt, E. Kneen and M.J. Blish: "Cereal Chemistry", Volume 16 (1939), Pages 712-723; Determination of the activity of the lipases = R. Willstätter, E. Waldschmidt - Leitz and Fr.

Memmen: "Hoppe-Seyler's Journal for Physiological Chemistry", Volume 125 (1923) pp. 110-117; R. Boissonas: "Helvetica Chimica Acta", Volume 31 (1948), pages 1571-1576.

The composition of the M according to the invention is generally in the range in the range of the following formulation: 1-50, preferably 2-15% by weight of those defined above Mercapto compounds, 99-50, preferably 98-85% by weight of at least one conventional, component of detergents, washing auxiliaries and cleaning agents with a cleaning effect, and optionally enzymes in such amounts that the agents according to the invention the Have activities specified above.

Preferred soaking or prewashing agents are those according to the invention Washing auxiliaries are considered that contain no bleaching component and their surfactant content is preferably at most 8% by weight.

The composition of such soaking or prewash detergents is easy generally in the range of the following narrow formulation: 0 - 8, preferably 2 - 7 wt .- 'anionic surfactants, especially those of the sulfonate and / or sulfate type with preferably 8-18 carbon atoms, 0-8, preferably 1-7 wt .-% nonionic Surfactants being the amount of anionic and nonionic surfactants together makes up a maximum of 8% by weight of the total soaking or prewash detergent, 20 - 99, preferably 60-95% by weight of builders, with at least some of the builders reacts alkaline, 1 - 50, preferably 2 - 15 wt .-% of the mercapto compounds defined above, 0-20, preferably 1-15% by weight of other common ingredients of soaking and Pre-wash agents, such as, in particular, plasticizers, brighteners, fragrances and dyes, Water, and optionally enzymes, in such amounts that the agent according to the invention has the activities specified above.

Among the agents according to the invention, which are preferably used as mild detergents or heavy-duty detergents Are used, include those with a surfactant combination, the amount of 8 - 40 % By weight.

The composition of a preferably usable as a mild detergent The detergent according to the invention is generally in the range of the following formulation: 8 - 40% by weight surfactant combination consisting of: 20 - 80, preferably 55 - 80% by weight Surfactants of the sulfonate and / or sulfate type with preferably 8-18 carbon atoms in the hydrophobic residue, 0 - 50> preferably 5 - 40 wt. nonionic surfactants, 0-50, preferably 10-50% by weight soap, 0-6, preferably 0.5-3% by weight foam stabilizer -sators, 0-8, preferably 0.5-5% by weight of non-surfactant foam inhibitors, 20-91, preferably 60-90% by weight of builder substances, at least some of which this structural substance reacts alkaline and the amount of alkaline up neutrally reacting builder substances preferably 0.15 to 7 times and in particular 1 to 5 times the total surfactants, 1 - 50, preferably 2 - 15% by weight of the mercapto compounds defined above, 0-30, preferably 3-30% by weight, others Detergent ingredients such as softeners, brighteners, fragrances and dyes, Water, and optionally enzymes, in such amounts that the agent according to the invention has the activities specified above.

Foam-suppressed ones suitable for use in drum washing machines Detergents according to the recipe above contain either a combination of Surfactants of the sulfonate and / or sulfate type and soap in a ratio of 30: 1 up to 1: 5, preferably 20: 1 to 1: 2, and / or a non-surfactant foam inhibitor.

Those according to the invention which can preferably be used as mild detergents Detergents preferably contain a bleach component. Can be used as a heavy-duty detergent However, detergents can contain a bleaching component, the particles of which are in such The condition should be such that the bleaching effect is reflected in the wash liquor unfolded only above 60 ° C, preferably above 75 °. To do this, will the bleaching component which may be present is advantageously used in coated form. Such a bleaching component used in the above detergent formulation as part of the Structural substances are to be considered, including any stabilizers that may be present 2-35, preferably 7-30% by weight of the total. Make up the detergent.

Contain the anionic, zwitterionic or non-ionic surfactants in the molecule at least one hydrophobic radical of mostly 8-26, preferably 10-22 and in particular 10-18 carbon atoms and at least one anionic, nonionic or zwitterionic water-solubilizing group.

The preferably saturated hydrophobic residue is usually more aliphatic, possibly also of an alicyclic nature; he can work with the water-solubilizing groups directly or be connected via intermediate links. As intermediate links come z. B.

Benzene rings, carboxylic acid ester or carbonamide groups, ether or ester-like bonded residues of polyhydric alcohols, such as. B. that of ethylene glycol, of propylene glycol, glycerine or corresponding polyether residues.

The hydrophobic group is preferably an aliphatic hydrocarbon group with about 10-18, preferably 12-18 0 atoms, but depending on the nature of the respective surfactant, deviations from this preferred range of numbers are possible.

The anionic active washing substance is selfen 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 alkylarylsulphonates, in particular the alkylbenzenesulfonates, which are known, inter alia. from preferably straight-chain aliphatic Hydrocarbons with 9-15, in particular 10-14, carbon atoms by chlorinated ones and alkylating benzene or from corresponding terminally or internally strong olefins obtained by alkylating benzene and sulfonating the resulting tert-alkylbenzenes. Also of interest are aliphatic sulfonates, as shown in z. B. from preferably saturated, 8-18 and preferably 12-18 carbon atoms in the molecule containing hydrocarbons by sulfochlorination with ScllweSeldiox.id and Chlorine or sulfoxidation with sulfur dioxide and oxygen and transfer the thereby products obtained in the sulfonates are accessible. As aliphatic sulfonates are also alkene sulfonates, hydroxyalkanesulfonates and disulfonates containing Mixtures useful, which you z. B. from terminal or intermediate C8-18 and preferably C12-18 olefins by sulfonation with sulfur trioxide and acidic or alkaline Hydrolysis of the sulfonation products obtained. In the case of the aliphatic In sulfonates, the sulfonate group is often located on a secondary carbon atom; but you can also sulfonates obtained by reacting terminal olefins with bisulfite use with a terminal sulfonate group.

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 mono- or polyvalent, 1-4 and preferably 1-2 carbon atoms Alcohols.

Further useful sulfonates are salts of fatty acid esters of oxethanesulfonic acid or of dioxypropanesulfonic acid, the salts of the fatty alcohol esters of lower, l - 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 aminoethanesulfonic acid.

Fatty alcohol sulfates are to be mentioned as surfactants of the sulfate type, in particular made from coconut fatty alcohols, tallow fatty alcohols or from oleyl alcohol. Even from terminal or internal C8-18 olefins are useful sulfonation products sulfate type available. This group of surfactants also includes sulfated surfactants Fatty acid alkylamides or fatty acid monoglycerides and sulfated alkoxylation products of alkylphenols (C8-15-alkyl), fatty alcohols, fatty acid amides or fatty acid alkylolamides, those in the molecule 0.5-20, preferably 1-8 and especially 2-4 ethylene and Z or May contain propylene glycol residues.

As to ionic surfactants of the carboxylate type, for. B. 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 aminocarboxylic acids, e.g. B. with glycocolla, sarcosine or with protein hydrolysates.

To the nonionic surfactants, here for the sake of simplicity as "Nonionics" products, whose water solubility is due to the presence of polyether chains, Amine oxide, sulfoxide or phosphine oxide groups, alkylolamide groups and also whole generally owe to an accumulation of hydroxyl groups.

Of particular practical interest are those caused by attachment Alaylene oxide and / or glycide on fatty alcohols, alkylphenols, fatty acids, fatty amines, Fatty acid or sulfonic acid amides, these nonionics 4 - 100, preferably 6 - 110 and especially 8 - 20 ether residues, especially ethylene glycol ether residues may contain per molecule.

In addition, propylene- or butylene glycol ether residues or polyether chains may be present.

The nonionics also include those under the trade name "Pluronics" or "Tetronics known products. They are obtained from water-insoluble Polypropylene glycols or from water-insoluble propoxylated lower ones, 1-8, preferably Aliphatic alcohols containing 7 - 6 carbon atoms or from water-insoluble alcohols propoxylated alkylenediamines. These water-insoluble (i.e., hydrophobic) propylene oxide derivatives are converted into the nonionics mentioned by athoxylating until they are water-soluble. Finally, nonionics are also those known as 11Ucon fluids, some of which are still water-soluble Reaction products of the abovementioned aliphatic alcohols with propylene oxide can be used.

The nonionics include fatty acid or sulfonic acid alkylolamides; which z. B. from mono- or diethanolamine, from dihydroxypropylamine or others Polyhydroxyalkylamines, e.g. B. derive the Glycaminen. You can get through amides from higher primary or secondary alkylamines and polyhydroxycarboxylic acids.

The capillary-active amine oxides include, for. B. those of higher tertiary, a hydrophobic alkyl radical and two shorter, up to 4 carbon atoms each containing alkyl and / or products derived from amines containing alkylol radicals.

Zwitterionic surfactants contain both acidic and basic hydrophilic groups. The acidic groups include carboxyl, sulfonic acid, Sulfuric acid half ester, phosphonic acid and phosphoric acid partial ester groups. As a basic Groups come primary, secondary, tertiary and quaternary ammonium groupings in question. Zwitterionic compounds with quaternary ammonium groups belong to the Type of betaine.

Carboxy, sulphate and sulphonate betaines are well tolerated 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 receives one by implementing the said tertiary Amines with chloroacetic acid, its salts or with chloroacetic acid esters and columns the ester bond.

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.

Foam stabilizers are particularly suitable for surfactants from the sulfonate or sulfate-type capillary-active carboxy- or sulfobetaines as well as those mentioned above Alkylolamide type nonionics; in addition, fatty alcohols or are for this purpose higher terminal diols have been proposed.

Products with reduced foaming power are mainly intended for use determined in washing machines and dishwashers, sometimes with limited foam absorption sufficient, while in other cases a stronger foam suppression is desirable can. Products which are in the medium temperature range are of particular practical importance Foam up to about 650c, but when transitioning to higher temperatures (70 - 1000C) develop less and less foam.

A reduced foaming power is often obtained with combinations different types of surfactants, especially in the case of combinations of synthetic anionic ones Surfactants, especially. of (1) sulphates and / or sulphonates or of (a) nonionics on the one hand and of (3) soaps on the other hand. For combinations of: Components (1) and (2) or (1), (2) and (3) the foaming behavior can be determined by the respective used Influence soaps: in the case of soaps preferably made of saturated fatty acids with 12 - With 18 carbon atoms, the foam attenuation is lower, while soaps are less saturated Fatty acid mixtures with 20 - 26, preferably 20-22 carbon atoms, their amount 5 - 10% by weight of the total amount of soap present in the surfactant combination can make a stronger foam absorption, especially in the higher temperature range, achieved.

The foaming capacity of the surfactants can also be achieved by adding additives Reduce known, non-surfactant foam inhibitors. belong to this optionally chlorine-containing N-alkylated aminotriazines, which can be obtained by reacting 1 Moles of cyanuric acid chloride with 2 - 3 moles of a mono- and / or dialkylamine with 6 - 20, preferably contains 8-18 carbon atoms in the alkyl radical. Aminotriazine or Melamine derivatives containing propylene glycol or butylene glycol ether chains, where the molecule may contain 10-100 such glycol residues. One obtains such Compounds, for example, by attaching appropriate amounts of propylene and / or Butylene oxide on aminotriazines, especially on melamine. Preferred are e.g. B. the Reaction products of 1 mole of melamine with at least 20 moles of propylene oxide or at least 10 moles of butylene oxide can be used. Products have proven to be particularly effective which can be obtained by adding 5-10 moles of propylene oxide to 1 mole of melamine and others Additions of 10-50 moles of butylene oxide to this propylene oxide derivative are obtained.

Also other, non-surfactant, water-insoluble organic compounds, such as paraffins or haloparaffins with melting points below 1000C, aliphatic C1d to C40 ketones and aliphatic carboxylic acids, which are in the acid or alcohol radical, possibly also contain at least 18 carbon atoms in each of these two residues (e.g. Triglycerides or fatty acid fatty alcohol esters), especially in combination made of ionic synthetic surfactants and soaps, use as foam inhibitors.

The non-surfactant foam inhibitors are often only at temperatures fully effective, in which they are in the liquid state, so that the foam behavior control the products in a similar manner by choosing suitable foam inhibitors lets like by the choice of soaps made from fatty acids of suitable chain lengths.

If you combine foam stabilizers with temperature-dependent foam inhibitors, so one gets good at lower temperatures, with increasing approach to the Cooking temperature, products that foam less and less.

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, Addition products of Propyleilox-i-d with the capillary-active ones described above are suitable Polyethylene glycol ether and the Pluronic, Tetronic, and 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, the bicarbonates, carbonates or silicates of the Alkalis, furthermore mono-, di- or trialkali orthophosphates, di- or tetraalkali pyrophosphates, as complexing agents known metaphosphates, alkali sulrates 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 Substances such as ethylene, propylene, acrylic acid, methacrylic acid, crotonic acid, ) -Butencarbonsäure,) -Methyl-3-butencarbonsäure as well as with vinyl methyl ether, vinyl acetate, Isobutylene. Acrylamide and styrene are useful.

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 replaced by organic complexing agents will.

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, and combinations of different complexing agents can also be used. The other known complexing agents also include di- and polyphosphonic acids of the following constitutions: wherein 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, amino-tri- (methylenephosphonic acid), methylamino- or ethylamino-di- (methylenephosphonic acid) and ethylenediamine tetra (methylenephosphonic acid). All of these complexing agents can be present as free acids, preferably as alkali salts. The preparations according to the invention can also contain protective carriers that keep the dirt detached from the fibers suspended in the liquor and thus prevent it from turning gray. 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 soluble starch preparations and other starch products than those mentioned above, such as degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.

The components of the laundry detergents and auxiliary agents according to the invention, in particular the structural substances are usually selected so that the preparations react neutral to clearly alkaline, so that the pH value of a 1% solution of the preparation is usually in the range of 7-12. Thereby, mild detergents usually have neutral to slightly alkaline reaction (pH = 7 - 9.5), while soaking, Prewashing and cooking detergents more alkaline (pH value 9.5 - 12, preferably 10 - 11.5) are set.

As wrapping materials for those in the agents according to the invention, if appropriate Contained coated bleaching components come paraffins, waxes, fatty acids, fatty acid mixtures and mixed glycerides, fatty acid alkylolamides and esteramides, etc. into consideration. Like that Coated bleaching agents only release the active oxygen when the temperature of the Wash liquor reaches the melting temperature of the coating. For wrapping the bleaching component c are the solid per compounds present in powder to granular form brought into contact with the shell materials present in the liquid state, so that the per-connections are surrounded by the covering materials, whereupon these transferred to the solid state. The shell materials can be used as a melt or be present as a solution in a suitable organic solvent, the Spraying the solution onto the moving particles of the per compound evaporates and is preferably removed by means of an inert gas stream.

In addition to the fusible shell materials mentioned, they can also be used as non-fusible Shell materials organic, water-insoluble film formers such as ethyl cellulose be used.

Among the preferably inorganic per compounds used as bleaching agents Sodium perborate tetrahydrate (NaB02. H202. 3 H20) is of particular practical importance. In its place, partially or completely, i.e. up to NaBO2. H202 drained Per borate to be used. There are also those in DBP 901 287 and USP 2,491,789 described borates NaB02. H202 usable in which the ratio Na20: B203 is less than 0.5: 1 and preferably in the range 0.4-0.15: 1, while the H202: Na ratio falls in the range of 0.5-4: 1. All this perborate can be wholly or partially by other inorganic per compounds, in particular by peroxohydrates, e.g. the peroxohydrates of the 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 0.25-10% by weight to be incorporated.

As water-insoluble perstabilizers, e.g. 1 - 8, preferably Make up 2 - 7% of the weight of the entire preparation, they are mostly suitable Precipitation of magnesium silicates obtained 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 complexing agents, the amount of which is 0.25 - 5, can preferably make up 0.5 - 2.5% of the weight of the entire preparation.

The brighteners that can be used are mostly, if not exclusively, Derivatives of diaminostilbene sulfonic acid, diarylpyrazolines and aminocoumarins.

Examples of brighteners from the class of the diaminostilbene sulfonic acid derivatives are compounds according to formula 1 In the formula, R1 and R2 can denote halogen atoms, alkoxyl groups, the amino group or residues of aliphatic, aromatic or heterocyclic, primary or secondary amines and residues of aminosulfonic acids, aliphatic residues present in the above groups preferably 1-4 and in particular 2-4C -Atoms, 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. A brighteners derived from diaminostilbene sulphonic acid are mostly used as cotton brighteners. The following products derived from the formula I are commercially available, where R1 represents the radical -NH-C6H5 and R2 can mean the following radicals -NH2, -NH-CH3, -NH-CH2-CH2OH, -NH-CH2-CH2 -O-CH3, -NH-CH2-CH2-CH2-O-CH3, CH3-N-CH2-CH2OH, -N = (CH2-CH2OH) 2, morpholino-, -NH-C6H5, -NH-C6H4-SO3H , -OCH3. With regard to their fiber affinity, some of these brighteners are to be regarded as transition types to the polyamide brighteners, for example the brighteners with R2 = -NH-C6H5.

Belongs to the diaminostilbene sulfonic acid type cotton whitening agents also the compound 4,4'-bis - (- 4-phenyl-vicinaltriazolyl-2 -) - stilbene disulfonic acid-2,2 '.

The polyamide brighteners, some of which have a certain affinity for cotton fibers, include diarylpyrazolines of the formulas II and III: @@ In formula II, R3 and R5 denote hydrogen atoms, optionally substituted by carboxyl, carbonamide or ester groups, alkyl or aryl radicals, R4 and R6 hydrogen or short-chain alkyl radicals, Arl and Ar2 aryl radicals, such as phenyl, diphenyl or naphthyl, which carry further substituents .en can, 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, -SO2-NH2, -S02-CH = CH2 and -COO-CH2-CH2-0-CH3, while the remainder R8 denotes a chlorine atom in all cases. 9-cyano-anthracene is also commercially available as a polyamide brightener.

In addition to the polyamide brighteners, aliphatic or aromatic ones are still suitable substituted aminocoumarins, e.g. 4-methyl-7-dimethylamino- or 4-methyl-7-diethylaminocoumarin. The compounds 1- (3-zimidazolyl-2 ') - 2- (N-hydroxyethyl-benzimidazolyl-2') -ethylene are also used as polyamide brighteners and 1-N-ethyl-3-phenyl-7-diethylamino-carbostyril can be used.

The compounds are used as brighteners for polyester and polyamide fibers 2,5 ~ di- (uenzoxazoll-2 ") -hio.phen and 1,2-di- (5'-methyl-benzoxazolyl-2 ') - ethylene suitable.

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, become solid State, it is recommended to stabilize the brightener organiscne Complexing agents in amounts of at least 0.1, preferably 0.2-1% by weight of the solid Incorporate products.

EXAMPLES 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 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 C atoms sulfonate obtained by sulfoxidation, "Fs-ester sulfonate" a from the methyl ester of a hardened tallow fatty acid thereby sulfonating with SO3 obtained sulfonate, "Olefinsulfonat" an as olefin mixtures with 12-18 C-atoms by sulfonating with SO3 and hydrolyzing the sulfonation product-es with lye obtained sulfonate, which consists essentially of alkene sulfonate and -oxialkane sulfonate exists, but also contains small amounts of disulfonates. Any olefinsulfonate} oily Preparation was made using two different types of olefin sulfonate; one was made from a mixture of straight-chain terminal olefins, the other made from a mixture of internal olefins has been produced, "KA sulfate" or "TA-sulfate" the salts of sulfated, 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 Tallow fatty alcohol or from 2 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), the numbers being those attached to 1 mole of alcohol Identify molar amount of ethylene oxide, "KA + 9 ÄO + 12 PO" a by reacting nonionide obtained from 1 mole of "KA + 9 o" with 12 moles of propylene oxide, "perborate" Product containing approx. 8% active oxygen with the approximate composition NaBO2.H2.3 H2O, coated with paraffin with a melting point of 65 - 75 ° C, or a mixture of palmitic acid and stearic acid, "NTA", "EDTA" and "EHDP" are the salts of nitrilotriacetic acid, ethylenediaminetetraacetic acid or the hydroxyethane diphosphonic acid, "CMC" the 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 1018 1218 1222 1222 u 1622 1822 C10 1 - - - - -C12 6 20 18 14 - -C14 5 12 8 6 - -16 28 25 17 13 8 -C18 60 43 32 60 32 9 20 - - 4 3 12 14-C22 - - 21 4 48 77 JZ des Fett-7.5 15 12 76 4 3 acid mixture Mixture of about 45% of a di (alkylamino) monochlorotriazine and about 55% of one Related to N, N ', - N "-trialkylmelamine. The alkyl radicals were located in all of these triazine derivatives as a mixture of homologues with 8-18 carbon atoms. With similar success it was also use the monochlorotr iaz inderivat or the trialkylmelamine, if the products described contain synthetic sulfates or sulfonates together with soap, could use the other non-surfactant-like foam inhibitors mentioned in the description used, such as paraffin oil or paraffin0 in the production of the preparations became the related foam inhibitor in a suitable organic Solvent dissolved or in a molten state by means of a nozzle on the moving powdery preparation sprayed on. # The enzyme substituting one or enzyme-activating effect of the mercapto compounds used according to the invention is determined in a washing test with enzyme-free and enzyme-containing detergents. Of the detergents listed in the following examples, only those are considered to be inventions that contain mercapto compounds. The commercial product is used as an enzyme preparation "Alcalase" used.

Method: To determine the protein washout ability of the tested Detergent is cotton fabric with standardized test soiling in the launderometer washed and the lightening measured photometrically as well as the residual protein content of the Fiber determined by nitrogen determination.

Washing program: 1) Washing test: Material: cloth made of cotton fabric each 2.1 g with + EMPA blood contamination (initial remission 13.5 C; initial white 14 ); Detergent cont. : 5 g / l; Fleet. 1:12 (100 ml liquor); Addition: 10 steel balls (Diameter 8 mm); Temperature: 50 ° C; Time: 30 minutes, of which 9-11 minutes Heating up.

+) EMPA = Federal Materials Testing and Research Institute (St. Gallen, Switzerland).

2) Fin softening test: material and detergent conc. as under l), fleet : 1:25 Addition: none Temperature: room temperature Time: 18 h.

Technical details: The washing tests are carried out at pH 10.

An Elre-pho photometer from the company is used to measure the remission Carl Zeiss with Xerlon lighting (filter F 6 and blocking filter FL 46) used. the Remission values are the mean values of 8 measured, soiled cotton swabs.

The residual protein content of the fiber is determined by determining the nitrogen content according to Kjeldahl with fabric samples from each cloth. Total amount approx. 1 g of fabric. The percentages Residual protein on the fiber should be viewed as relative values and can only be used within of an experimental program can be compared with one another, as the blood contamination is caused by aging a change in the leachability of proteins occurs.

In Examples 1 and 2, the formulations are made by mixing the Get components. The detergents of Example 3 are made by adding the mercapto compound and / or the Alcalase to a spray-dried detergent product and the Agents according to the invention of Examples 4-24 in each case by incorporating the mercapto compound obtained in a product made by hot atomization.

EXAMPLE 1 Testing of the protein-dissolving and enzyme-activating effect of the mercapto compounds used according to the invention in the presence of nonionic surfactants detergent 5% by weight OA + 10% 45% by weight sodium tripolyphosphate est sodium sulfate and optionally mercapto compound and / or alealase Washing tests Soaking tests Recipe with in wt .-%%% residual protein less Alcalase on the residual white against% remission No. Mercaptover% by weight (125,000 remission fiber over recipe 1 LVE) retention in% 1 - - - 51.2 0.81 - 58.9 2 - - 0.5 53.1 0.67 17 60.3 3 ß-mercapto- 5 - 54.4 0.62 23 64.3 ethylurea 4 "5 0.5 56.4 0.49 40 65.5 EXAMPLE 2 Testing of the protein-dissolving and enzyme-activating effect of the mercapto compounds used according to the invention in the presence of anionic surfactants detergent 5% by weight olefin sulfonate 45% by weight sodium tripolyphosphate, remainder sodium sulfate and optionally mercapto compound and / or alcalase Recipe with% by weight washing tests soaking seek Mercapto- Alcalase%% residual protein less residual protein in connection on the fiber white opposite (125000 remission% remission % By weight formulation 1 No LVE) in % 1 - - - 51.2 0.81 - 58.9 2 - - 0.5 53.1 0.67 17 60.3 3 DTUMPS * 5 - 54.6 0.61 25 62.3 4 DTUMPS * 5 0.5 56.5 0.49 40 62.7 *) DTUMPS = dithiourethane of mercaptopropionic acid of the formula II Example 3.

Testing of the protein-dissolving and enzyme-activating effect of the mercapto compounds in the presence of anionic and nonionic surfactants.

Detergent 7.0% by weight ABS 2.5% by weight OA + 10 AO 3.0% by weight soap 1822 40.0% by weight sodium tripolyphosphate, remainder sodium sulfate and optionally mercapto compound and / or alcalase Recipe with% by weight washing tests Mercapto-Alcalase%% less residual protein link (125000 remission residual protein compared to recipe 1 No. wt .-% LVE) on the fiber in% 1 - - - 57.5 0.59 - 2 - - 0.5 58.3 0.43 27 3 ß-mercapto- 5 - 58.5 0.39 34 äthylhar @ fabric 4 "5 0.5 59.1 0.34 42 The products described in Examples 4-24 can preferably be used as follows: Examples 4, 9, 10, 18-22: Soaking or prewash agent; Examples 5-7, 11-14: Heavy duty detergent; Examples 8, 23j 24: colored detergent free of perborate and brightener; Example 15: Auihcllerfrcies, but colored detergent containing perborate; Examples 16 and 17: mild detergent, also intended for use on easy-care textiles.

The mereapto compound used in Examples 4-24 was β-mercaptoethyl urea. Part of the% by weight component in the preparation according to the example Preparation 4 5 6 7 8 9 10 ABS - 9.0 11.0 - - 5.0 - Olefin sulfonate - - - - 11.5 - - Soap 1018 - - - - 9.0 - - Soap 1622 - 2.0 - - - - - OA + 5 AO 1.0 - - - 5.0 - - OA + 10 AO 7.0 8.0 6.0 - - - - KA + 20 AO - - - 12.0 - 2.5 4.5 KA + 9 ÄO - - - 7.5 - - 2.5 + 12 PO Foam inhibitor 0.3 - 0.5 - 0.8 0.3 - Na2SO4 + + + + + 29.0 19.5 Na2O. 3.3 SiO2 - 4.5 4.0 4.5 7.5 3.5 4.0 Na4P2O7 9.0 - - 12.0 - - - Na5P3O10 63.0 45.0 19.0 - 32.0 41.0 53.0 Perborate - 16.0 21.0 16.0 - - - MgSiO3 - 1.0 1.6 1.0 1.6 - - NTA - - 18.0 19.0 - - 0.5 EDTA 0.5 - - - - 1.6 - EHDP - - 6.6 14.0 25.0 - - CMC 1.6 1.5 - 1.5 1.3 - 1.5 Mercapto- 8.5 5.0 8.5 5.0 5.0 10.0 8.0 link Brightener 0.35 0.9 0.9 0.7 - 0.33 0.25 Rest water Part of the% by weight component in the preparation according to the example Preparation 11 12 13 14 15 16 17 ABS 8.5 - - - - - - Alkanesulfonate - - 7.5 - - - - Fs-ester sulfonate - 6.5 - - - - - Olefin sulfonate - - - 8.0 - - 15.0 KA sulfate 1.6 2.8 1.7 - - 1.5 3.2 TA sulfate 0.5 - - 3.0 - 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 Na2O. 3.3 SiO2 5.0 4.0 - 4.2 3.5 3.7 - Na5P3O10 28.0 24.0 38.0 21.0 33.0 35.0 48.0 Perborate 24.0 25.0 23.6 25.0 22.0 - - 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 - 1.2 - 1.5 1.3 1.7 Mercapto- 5.0 10.0 7.5 7.5 8.5 10.0 5.0 link Brightener 0.5 0.44 0.95 1.08 - - - Rest water Most of the% by weight constituent in the preparation according to example Preparation 18 19 20 21 22 23 24 ABS 7.0 - - - - 6.5 - Alkanesulfonate - - - - - - 6.5 Fs-ester sulfonate - 7.5 - - - - - Olefin sulfonate - - - 5.0 - - - KA sulfate - - - - - - 4.5 TA sulfate - - - - - 1.5 - KA-ÄO-sulfate - - - - - - 7.5 TA-ÄO-sulfate - - - - - 4.5 - OA-ÄO-sulfate - - - - 5.5 - - Soap 1218 - - - - - - 2.0 Soap 1822 - - - - - 3.0 - Soap 1222 u - - - - - - - OA + 5 ÄO - 1.5 - - 1.5 - - OA + 10 AO 1.0 - 5.2 2.2 - - - Foam inhibitor - - - - - - 0.8 Na2SO4 38.0 33.0 34.0 22.0 31.0 22.0 17.0 Na2O. 3.3 SiO2 2.0 4.0 3.5 4.2 3.5 3.5 - Na5P3O10 - - 46.0 26.0 43.0 42.0 48.0 Na2CO3 42.0 42.0 - 20.0 - - - Perborate - - - - - - - MgSiO3 - - - - - - - NTA - - - 4.0 - - - EDTA - - 0.25 - - - - CMC - - 1.6 1.8 - - 1.7 Mercapto- 7.5 7.5 5.0 5.0 10.0 10.0 5.0 link Brightener - - 0.21 0.35 - - - Rest water Depending on the intended use of the agents according to the invention, the brighteners used are cotton brighteners, polyamide brighteners, polyester brighteners or combinations thereof.

The products described in Examples 4-24 were also used under Addition of enzymes made. Commercially available products, the by the manufacturer by adding sodium sulfate in amounts of 7-15% by weight to the following Activities had been discontinued: a protease with 125,000 LVU / g enzyme preparation; An amylase with 75,000 SKBE / g enzyme preparation; A lipase with 10,000 IU / g enzyme preparation.

In the following list, in addition to the amount of enzyme, there is also the 1 g of the finished agent-related enzyme activity indicated: I) A detergent after one of Examples 4-24 contains 0.3-1.5% by weight protease (375-1875 LVU / g); II) A detergent according to one of Examples 4 - 24 contains 1.2% by weight of lipase (120% by weight) IE / g); III) A detergent according to one of Examples 4-24 contains 0.4% by weight of prtease (500 LVU / g) 1.0 wt% amylase (750 SKBE / g); IV) A detergent according to one of the examples 4-24 contains 2.0 wt% amylase (1500 SKBE / g); V) A detergent according to one of the Examples 4 - 24 contain 0.2% by weight protease (250 LVU / g) 0.5% by weight amylase (375 SKBE / g) 0.5% by weight lipase (50 IU / g); VI) A detergent according to one of the examples 4-- 24 contains 1.0% by weight protease (1250 LVE / g) 0.3% by weight amylase (225 SKBE / g) 0.4 wt% lipase (40 IU / g).

Claims (15)

P a t e n t a n s p r ü c h e 1. Protein-dissolving detergents, washing additives and cleaning agents, characterized in that they contain compounds containing mercapto groups as well as derivatives from the series of Mcrc aptoalkane sulfonic acids, mercaptoalkylcarboxylic acids, mercaptoalkylureas, mercaptoalkanoylhydrazines and mercapto alcohols with 2 to 20, preferably 2 to 6 carbon atoms, or their Salts, provided they have groups capable of forming salts, contain. 2. Agent according to claim 1, characterized in that it contains enzymes, namely proteases and / or amylases and / or lipases. 3. Means according to claim t and 2, characterized in that the enzyme contents correspond to the following activities: for proteases 50 - 25,000, preferably 50 - 5,000, and in particular 100 - 2500 LVE / g washing or Washing aid for amylases 20-25000, preferably 20-5000, and in particular 50 - 2000 SKBE / g washing or Washing aids; in the case of lipases 2 - 10,000, preferably 2 - 1,000, and especially 5 - 500 IU / g detergent or Washing aid. 4. Means according to claim 1 - 3, consisting of 1 - 50> preferably 2-15% by weight mercapto compounds according to claim 1, 99-50, preferably 98-85 Weight - at least one common, cleaning component -of washing, washing aid- and cleaning agents, and optionally enzymes in such amounts that the agent having the activities according to claim 3. 5. As a soaking agent or pre-wash agent according to claim usable 1 - 4, characterized in that its composition is within the following Ranges: 0-8, preferably 2-7% by weight of anionic surfactants, in particular those of the sulfonate and / or sulfate type with preferably 8-18 carbon atoms, O - 8, preferably 1 - 7% by weight of nonionic surfactants, the narrowest of the anionic and the nonionic surfactants together at most 8% by weight of the total soaking or Pre-wash agent also makes 20-99, preferably 60-95% by weight of builder substances, whereby at least some of the structural substances react alkaline, 1-50, preferably 2-15% by weight of mercapto compounds according to claim 1, 0-20, preferably 1-15 % By weight of other common ingredients of soaking and prewashing agents, such as Example in particular plasticizers, brighteners, fragrances and dyes, water, and optionally enzymes in such amounts that the agent -the activities according to claim 3 has. 6. Can be used as a mild or heavy duty detergent according to claim 1 - 4, characterized in that it contains 8 - 40% by weight of a surfactant combination, consisting of: 20 - 80 »preferably 55 - 80% by weight of sulfonate and / or surfactants Sulfate type with preferably 8-18 carbon atoms in the hydrophobic radical, 0-50, preferably 5 - 40% by weight nonionic surfactants, 0 - 50, preferably 10 - 50% by weight soap, O-6, preferably 0.5-3% by weight foam stabilizers, O-8, preferably 0> 5 5% by weight of non-surfactant foam inhibitors. 7. As a mild detergent usable agent according to claim 1 - 6, characterized characterized in that its composition lies within the following ranges: 8 - 40% by weight surfactant combination consisting of: 20 - 80, - preferably 55 - 80% by weight Surfactants of the sulfonate and / or sulfate type with preferably 8-18 carbon atoms im hydrophobic reads, 0 - 50, preferably 5 - 40% by weight of nonionic surfactants, 0-50, preferably 10-50% by weight soap, 0-6, preferably 0.5-3% by weight foam stabilizers, O - 8, preferably 0.5 - 5% by weight non-surfactant foam inhibitors, 20 - 91, preferably 60-90% by weight of builders, at least some of these builders reacts alkaline, and the amount of the alkaline to neutral reacting builder substances preferably 0.5 to 7 times, and particularly 1 to 5 times the whole Surfactants makes up 1-50, preferably 2-15% by weight of mercapto compounds according to Claim 1, 0-30> preferably 3-30% by weight of other detergent ingredients such as plasticizers, brighteners, fragrances and dyes, water, and optionally Enzymes in such amounts that the agent has the activities according to claim 3. 8. Agent according to claim 6 which can be used as a full washing agent by a further content of 2-35, - preferably 7-30% by weight of one above 60 ° C, preferably above 750C bleaching component. 9. Composition according to claim 1 to 8, characterized in that the mercapto compound ß-mercaptoethyl urea is used. 10. Means according to claim 1 to 8, characterized in that as Mercapto compound N-ß-hydroxyethyl-dithiocarbamic acid-S-propyl ester-γ-sulfonic acid is used. 11. Means according to claim 1 to 8, characterized in that as Mercapto compound γ-mercaptopropane sulfonic acid is used. 12. Foam-dampened detergent according to claim 1-11, characterized in that «, that there are surfactants of the sulfonate and / or sulfate type and soap in a proportion of 30 : up to 1: 5, preferably 20: 1 to 1: 2 and / or a non-surfactant foam inhibitor contains. 13. Foam-dampened detergent according to claim 1 - 12, characterized in that that the fatty acid residues present in the soaps of the surfactant combination are at least 50% from those with 16-30 carbon atoms and preferably at least 3, in particular more than 5 ß consist of those with at least 20 carbon atoms. 14. Composition according to claim 1-17, characterized in that the non-surfactant igen foam inhibitors as discrete particles with the other components of the Preparations are mixed. 15. Laundry detergents, ash additives present in tester, pourable or cleaning agent according to claim 13, characterized in that the foam inhibitors with solid particles of the preparation or a solid component of the preparation are connected, the foam inhibitors said solid particles whole or partially envelop.