EP0711336A1

EP0711336A1 - Washing agents with acid components

Info

Publication number: EP0711336A1
Application number: EP94925383A
Authority: EP
Inventors: Georg Meine; Günther VOGT
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1993-07-31
Filing date: 1994-07-23
Publication date: 1996-05-15
Also published as: DE4325787A1; WO1995004125A1

Abstract

In order to improve the dispersing power of conventional washing agents having more than 500 g/l apparent density, a component is admixed thereto. For that purpose, washing agents are used that contain one or more admixed acid components from the group of the inorganic acid salts of polybasic acids and of the organic dicarboxylic acids. A considerable improvement is achieved in comparison with agents that contain citric acid as admixed acid component.

Description

"Detergent with an acidic component"

The invention relates to a powdery to granular detergent with a high bulk density and improved redispersion behavior and a process for its production.

It is well known that powdered to granular detergent with high bulk density, i.e. with bulk weights above 500 g / 1, for example around 600 or 650 to 1000 g / 1, lead to problems when washing them in washing machines. The residues remaining in the washing-in chamber not only have a negative impact on the washing results, but also undesirable foaming, and thus a worsening of washing out of the textiles, can also occur in the washing cycles by washing in the detergent residues. One way to remedy these disadvantages of heavy detergents is to add the detergents directly to the washing drum with the aid of a metering device, so that washing in via the chamber is avoided. Metering aids of this type are, however, foreign bodies in the washing process and are largely rejected by the consumer.

To improve the redispersion behavior of the detergents per se, it has been proposed, for example, to add citric acid subsequently to the other constituents of the detergent. For example, the international patent application WO-A-92/18596 discloses a granular detergent with 5 to 70% by weight of surfactants and 5 to 75% by weight of sodium carbonate subsequently added, with up to 15% by weight also being added. Citric acid can be added as an acidic component. The reaction of the citric acid with the sodium carbonate is said to improve the redispersibility of the detergent and to minimize clumping.

From European patent application EP-A-0 534 525, detergents are known which contain surfactants, builder substances and alkaline components such as sodium carbonate, bicarbonate or sesquicarbonate and to improve the redispersing properties as an acidic component, citric acid. The citric acid is subsequently mixed in as a separate component. However, the improvement in the redispersibility of conventional commercial detergents by the subsequent addition of citric acid as an acidic component has not proven to be sufficient.

It was therefore an object to find other, optionally also acidic components which, when added subsequently to conventional commercial detergents with high bulk densities of above 500 g / l, lead to significantly better redispersibility than the subsequent addition Citric acid.

Accordingly, the invention relates in a first embodiment of the invention to a powdery to granular detergent with bulk densities above 500 g / l, containing surfactants, builder substances, one or more alkaline components and at least one separate acid component, the acid component or the acid components Components are selected from the group of inorganic acidic salts of polybasic acids and organic dicarboxylic acids.

Already amounts of 1% by weight of the acidic component or of the acidic components, based on the finished detergents, lead to significant improvements in the detergent behavior of the detergents in the washing machine. In contrast, no significant improvements can be achieved by quantities above 5% by weight. It is therefore preferred that the content of the agents in an acidic component or in several acidic components, preferably using only acidic granules, is 1 to 5% by weight and in particular 1.5 to 5% by weight . In a preferred embodiment of the invention, the agents contain adipic acid, succinic acid, glutaric acid or mixtures of these as the admixed acid component, the content of these agents in these components being in particular 1.5 to 3% by weight.

In a particularly preferred embodiment of the invention, the separately admixed acidic component is sodium hydrogen sulfate, in particular water-containing sodium hydrogen sulfate, as is commercially available. Amounts of 2 to 4% by weight of water-containing sodium hydrogen sulfate, based on the finished agent, are particularly preferred. The acidic component is or the acidic components are separately admixed to a basic detergent, which can be a spray-dried, granulated, roller-compacted or extruded detergent, to which other customary components such as bleaching agents or bleach activators and enzymes have optionally already been added. It is possible and preferred that the basic detergent is partially or completely exposed to nonionic surfactants and then the acidic component (s) are (are) added.

A particularly preferred embodiment of the invention, however, provides that the acidic component (s), in particular water-containing sodium hydrogen sulfate, are first mixed into the basic detergent and then the agent, ie after the addition of the acidic component (s), with nonionic surfactants is partially or fully loaded. It is particularly preferred that the powdery to granular agent is treated with nonionic surfactants in amounts of 0.5 to 3% by weight, based on the agent treated.

The agents according to the invention are preferably in granular form and have a bulk density above 600 g / 1, in particular between 650 and 1000 g / 1. They contain in particular anionic and nonionic surfactants, optionally also cationic, amphoteric or zwitterionic surfactants, inorganic and organic builder substances, bleaching agents, bleach activators, graying inhibitors, inorganic alkaline and / or neutral salts, enzymes, enzyme stabilizers, foam inhibitors, optical brighteners and optical brighteners - and fragrances.

Anionic surfactants used are, for example, those of the known sulfonate and sulfate type.

Preferred surfactants of the sulfonate type are the known C9-C13-alkylbenzenesulfonates, olefin sulfonates and alkanesulfonates. Also suitable are esters of α-sulfofatty acids or the disalts of oc-sulfofatty acids. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters, and mixtures thereof, as used in the preparation by esterification with a monoglycerol with 1 up to 3 moles of fatty acid or in the esterification of triglycerides with 0.3 to 2 moles of glyce in.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, e.g. from coconut fatty alcohol, tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, mixtures of these or the Cιo-C2θ-oxo alcohols, and those of secondary alcohols of this chain length. The sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol of ethylene oxide, are also suitable.

Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain CQ to Cχ8 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, viewed in isolation, are nonionic surfactants (for a description, see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Other suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.5 to 5% by weight. Saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, pal itic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in Form their sodium or potassium salts, especially in the form of the sodium salts before.

The nonionic surfactants used are preferably alkoxylated, advantageously liquid ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably in 2 Position can be methyl-branched, or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 C atoms are preferred, e.g. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Cn alcohol with 7 EO, Ci3-Cιs alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-Ci8- Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2-Ci4 alcohol with 3 EO and Ci2-Ci8 alcohol with 5 EO. The degrees of ethoxylation given represent statistical mean values which can be an integer or a fractional number for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In a preferred embodiment of the invention, the agents are partially or completely exposed to ethoxylated fatty alcohols.

In addition, alkyl glycosides of the general formula R0 (G) _x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C., can also be used as further nonionic surfactants -Atoms means and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of this non- Ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

R3

I.

R2_CO-N- [Z] (I)

in which R ^{2 is} C0 for an aliphatic acyl radical with 6 to 22 carbon atoms, R3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 is up to 10 hydroxyl groups. The polyhydroxy fatty acid ides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkyl in or an alkanol in and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The surfactant content of the agents can vary within a wide range. It is preferred, however, that the agents contain both anionic and nonionic surfactants in amounts of 5 to 40% by weight, with amounts of 10 to 30% by weight being particularly preferred. In particular, alkylbenzenesulfonates and / or alk (en) ylsulfates, for example fatty alkyl sulfates, are used as anionic surfactants, while the ethoxylated fatty alcohols and alkyl glycosides are among the preferred nonionic surfactants. The weight ratio between anionic surfactants and nonionic surfactants can also vary greatly depending on the type of agent. Agents with a weight ratio of anionic surfactant: nonionic surfactant of 20: 1 also belong to the embodiments of the invention, like agents with weight ratios of 1:10 or 1:20.

Phosphate, zeolite and layered silicates are particularly suitable as inorganic builder substances. The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. However, zeolite NaX and mixtures are also suitable. gene from NaA and NaX. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. If the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 8 -fatty alcohols with 2 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water. The zeolite content of the compositions is preferably 20 to 60% by weight, based on the anhydrous active substance.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates NaMSi _x θ2χ + i * yH2θ, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ'-sodium disilicate a2Sι ^' 2θ5 ^« yH2θ are preferred. In addition to a full exchange of zeolite with crystalline layered silicates, mixtures of zeolite and crystalline layered silicates in a weight ratio between 10: 1 and 1: 3 are preferred.

Usable organic builders are, for example, polymeric polycarboxylates such as the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. Terpolymers are also particularly preferred, for example those which, as monomers, salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives (P 4300772.4), or which, as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives (P 42 21 381.9 ) contain.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0280 223. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.

The content of the agents in the organic builder substances mentioned is generally 1 to 10% by weight.

In addition, however, the agents can also use the salts of polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), which are preferably used in the form of their sodium salts, provided such use is ecological Is not objectionable for reasons, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these; In particular, alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na2θ: Siθ2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used. The sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight. The content of sodium silicate in the compositions is generally up to 10% by weight and preferably between 1 and 8% by weight. According to the teaching of the older German patent application P 43 19 578.4, alkali metal carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and, if appropriate, a further carboxyl and / or amino group having amino acids and / or their salts. In the context of this invention, it is preferred that the alkali metal carbonates be partially or completely replaced by glycine or glycinate.

Of the compounds which serve as bleaching agents and supply H2O2 in water, the sodium perborate tetrahydrate and the sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate. In most cases, the bleaching agent component is subsequently mixed into the agents.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the preparations. Examples of this are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose sepentaacetate. The bleach activators contain bleaching agents in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.

In addition, the agents can also contain components which have a positive effect on the ability to wash off fat and fat from textiles. This effect is particularly evident when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl hydroxypropyl cellulose with a proportion of methoxyl group pen of 15 to 30 wt .-% and of hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, and the polymers known from the prior art of phthalic acid and / or terephthalic acid or. of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates.

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci8 ~ C24 fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, e.g. those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred. In a further preferred embodiment of the invention, the compositions comprise, as a further separate component, a foam inhibitor granulate, preferably a silicone defoamer granulate, in particular one based on starch, in amounts of 1 to 5% by weight and in particular in amounts of 2 to 5 % By weight. It has been found that the redispersion behavior of the agents according to the invention can be further improved by adding certain foam inhibitor granules in the amounts indicated.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, in particular each but cellulase-containing mixtures of particular interest. Peroxidases and oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in Hü11 substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

The salts of polyphosphonic acids, in particular l-hydroxyethane-l, l-diphosphonic acid (HEDP), are suitable as stabilizers, in particular for per-compounds and enzymes. In addition or instead of, the agents can contain further enzyme stabilizers. It is possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B4O7), is particularly advantageous.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying. Water-soluble colloids of mostly organic nature are suitable for this, 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 acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, preference is given to cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition , used.

As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example Salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure, instead of morpholino Group carry a diethanola ino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

The detergents according to the invention can be produced by any of the known processes, for example by spray drying, granulation and / or extrusion. The agents can contain a base granulate or 2 or more compounds.

Examples

In the examples given below, the induction behavior was determined in the following way:

Conditions were simulated which correspond to a washing-in device of a household washing machine operated under critical conditions. In each case 100 g of product were introduced into the test device (Zanussi induction channel). After a rest period of 1 minute, 10 liters of tap water were fed in within 80 seconds. The amount of the residue which then remains consists on average of 30% by weight of water and 70% by weight of detergent which has not been flushed in and is stated in grams (g).

Sodium hydrogen sulfate (monohydrate), a dicarboxylic acid mixture (DCS) composed of adipic acid, succinic acid and glutaric acid (Sokalan DCS ( ^R ), commercial product from BASF, Federal Republic of Germany) and, for comparison, commercial citric acid (dihydrate) were used as acidic components.

Example 1:

High-quality color detergents Ml to M3 from the trade and mixtures of these with the acidic components of the type specified below according to the invention were examined for their washing-in behavior (see Table 1). By additionally admixing a silicone defoamer granulate (11% by weight of active substance) based on starch (commercial product from Dow Coring), in contrast to admixing a silicone defoamer granulate on an inorganic basis (sodium carbonate and sodium sulfate), a further improved washing-in behavior was achieved become.

Example 2:

High-quality universal detergents M4 and M5 from the trade and mixtures of these with the acidic components according to the invention of the type specified below were examined for their washing-in behavior (see Table 2). The results show that the use of Sodium hydrogen sulfate and dicarboxylic acid mixture achieved a much greater improvement in the induction behavior than by citric acid.

Table 1: Color detergent Ml to M3

Residues in g for Ml M2 M3

100 g M 28.6 33.2 18.7

99 g M + 1 g sodium bisulfate 18.6 21.4 _-._

98 g M + 2 g sodium hydrogen sulfate 8.5 9.2 -

97.5 g M + 2.5 g sodium bisulfate 4.4-2.5

97 g M + 3 g sodium hydrogen sulfate 1.8 3.2

95 g M + 5 g sodium hydrogen sulfate 0.4 0.4

95 g M +

2.5 g sodium bisulfate +

2.5 g Ci2-Ci8 fatty alcohol with 5 E0 0.1 - 0.2 (sprayed on afterwards)

99.5 g M + 0.5 g DCS 28.5

99 g M + 1 g DCS 24.2

98.5 g M + 1.5 g DCS 18.3 Table 2: Universal detergents M4 and M5

Residues in g for M4 M5

100 g M 33.5 49.1

97.5 g M + 2.5 g sodium bisulfate 15.9 14.4

97.5 g M + 2.5 g DCS 18.2 33.9

97.5 g M + 2.5 g citric acid 28.3 36.0

Claims

claims

1. Powdery to granular detergent with bulk densities above 500 g / 1, containing surfactants, builder substances, one or more alkaline components and at least one separate acidic component, characterized in that the acidic component or the acidic components are selected from the Group of inorganic acidic salts of polybasic acids and organic dicarboxylic acids.

2. Agent according to claim 1, characterized in that the content of the acidic component (s) in the agent is 1 to 5 wt .-%, preferably 1.5 to 5 wt .-%.

3. Composition according to claim 1 or 2, characterized in that the separately admixed acidic component is sodium bisulfate, the Ge content of the agent in water-containing sodium bisulfate being in particular 2 to 4% by weight.

4. Composition according to claim 1 or 2, characterized in that the separately admixed acidic component is adipic acid, succinic acid, glutaric acid or mixtures thereof, the content of these dicarboxylic acids in particular being 1.5 to 3% by weight.

5. Agent according to one of claims 1 to 4, characterized in that it is a granular agent with a bulk density above 600 g / 1, preferably between 650 and 1000 g / 1, the granules partially or completely sprayed with nonionic surfactants are.

6. Composition according to one of claims 1 to 5, characterized in that it as a further separate component, a foam inhibitor granules, preferably a silicone defoamer granules, in particular based on starch, in amounts of 1 to 5 wt .-%, contains in particular in amounts of 2 to 5 wt .-%.

7. A process for producing a powdery to granular detergent according to any one of claims 1 to 6, characterized in that inorganic acid salts of polybasic acids and / or organic dicarboxylic acids are mixed separately as an acid component or as acid components to form a basic detergent.

8. The method according to claim 7, characterized in that a spray-dried, granulated, walzenko paktierter or extruded detergent is used as the Basiswasch¬, which may have already been mixed with other components.

9. The method according to claim 7 or 8, characterized in that the base detergent is charged with nonionic surfactants before the addition of the acidic component (s).

10. The method according to any one of claims 7 or 8, characterized in that the agent after the addition of the acidic component (s) with Niotensi¬ is partially or completely acted upon.

11. The method according to claim 10, characterized in that the agent with nonionic surfactants in amounts of 0.5 to 3 wt .-%, based on the treated agent, is applied.

12. The method according to any one of claims 7 to 11, characterized in that a foam inhibitor granules, preferably a silicone defoamer granules, in particular based on starch, in amounts of 1 to 5 wt .-%, in particular as a separate component Amounts of 2 to 5 wt .-%, based on the finished agent, is added.