EP1004658A2 - Washing agent containing citric acid - Google Patents

Abstract

The stain removal properties of washing agents with a bleach content of less than 10 wt. % are improved by incorporation of citric acid and another organic acid in a mixture of coarse and fine grains. A washing agent with less than 10 wt. % bleaching agent contains citric acid as separate or subsequently added component to promote the removal of bleachable stains. The citric acid has a particle size distribution such that at least 80 wt. % of the particles have a size of 1500-2000 mu m. As well as the coarse grain citric acid, an additional organic acid (I), which is also a separate or subsequently added component, is present. (I) has a particle size distribution such that at least 80 wt.% of the particles have a size of less than 450 mu m. Anionic and/or nonionic detergents and builders are also present. 10-30 wt. % of the total acid particles have a size of 1750-2000 mu m and 10-30 wt. % have a size of less than 150 mu m.

Description

The invention is directed to a detergent with less than 10% by weight of bleach and with citric acid as a separately or subsequently mixed component for support the removal of bleachable stains, the citric acid being a Has particle size distribution in which at least 80% by weight of the particles has a Have size between 1500 and 2000 microns, and with the coarse-grained citric acid additional organic acid, also added separately or subsequently, whereby the additional organic acid has a particle size distribution in which at least 80 wt .-% are less than 350 microns, as well as with anionic and / or nonionic Surfactants and builder substances.

Citric acid has long been known as a detergent ingredient. It serves above all to reduce the pH of the mostly strongly alkaline agents in the aqueous liquor, the added benefit is achieved that both the citric acid and have the neutralization of the citric acid obtained citrate (co) builder properties.

sauren Vorwäsche" in handelsüblichen Haushaltswaschmaschinen bereits bei Temperaturen von 25 °C durch die sich bei diesen Temperaturen bereits lösende Citronensäure eine Enthärtung der Flotte erreicht, so daß bei Temperaturen um 40 °C bei Lösebeginn der alkalischen Komponente, die Flotte bereits derart enthärtet ist, daß die Gefahr der Bildung von Calciumcarbonat und damit der Bildung von Calciumcarbonatrückständen auf den Textilien weitgehend minimiert wird. Es werden hierbei weder das Schüttgewicht noch die Teilchengrößenverteilung der zugesetzten organischen Säuren genannt. Zu den weiteren Bestandteilen der Mittel zählen u.a. Peroxybleichmittel wie Perborate.For example, German patent application DE-A-28 27 571 (Akzo) already describes detergents which contain a granular alkaline, in particular carbonate-containing, slower-dissolving component and 5 to 30% by weight of a separate organic acid, preferably citric acid. It is part of a

acidic prewash "in commercially available household washing machines, softening the liquor already at temperatures of 25 ° C due to the citric acid already dissolving at these temperatures, so that at temperatures around 40 ° C when the alkaline component begins to dissolve, the liquor is already softened such that the risk of the formation of calcium carbonate and thus the formation of calcium carbonate residues on the textiles is largely minimized. Neither the bulk density nor the particle size distribution of the added organic acids are mentioned. Other constituents of the agents include peroxy bleaching agents such as perborates.

The international patent application WO-A-91/17232 (P&G) also describes detergents which, as builders, contain 20 to 30% by weight of zeolite, 5 to 20% by weight of alkali metal carbonate and 1 to 3% by weight of alkali metal silicate and 4 have up to 10 wt .-% citric acid. Other ingredients are, for example, peroxy bleaching agents such as perborate. While the granular agents for forming a bulk density of 500 to 600 g / l are usually spray-dried and also contain the carbonate in the spray-dried portion, the citric acid, which the pH in 1% solution in water at 20 ° C to values between 7 and 9.3 should be added subsequently, since if the citric acid were also sprayed into the spray-dried slurry, the neutralization of the citric acid would already take place in the slurry and not - as desired - in the aqueous washing liquor. The particle size distribution of the separately added citric acid is again irrelevant. Due to the relatively low pH in the aqueous liquor, the colors of colored textiles should be better preserved.

Granular detergents or cleaning agents with a bulk density of 650 to 1100 g / l, which contain anionic and / or nonionic surfactants and as builder materials including 5 to 30% by weight sodium carbonate and / or bicarbonate and / or sesquicarbonate, according to the Teaching of the European patent EP-B-0 534 525 (Henkel) good dispersing properties in the aqueous liquor, if they contain 1 to 15% by weight of subsequently added citric acid as a further component, said citric acid containing at least 80% by weight of particles of a Particle size of 350 and 1500 microns must have. Both smaller particle sizes and coarser granules do not lead to the desired effect of increased dispersion in an aqueous liquor. Peroxy bleaching agents are contained in the agents as further usual constituents.

As well as for reducing the pH in the aqueous liquor and for water softening organic acids and in particular citric acid are used in detergents, so are usually - as also stated above - bleaching agents and in particular peroxy bleaching agents such as perborate or percarbonate in detergents, usually in amounts of 15% by weight and above used to remove bleachable stains from textiles.

However, bleaching agents not only have the effect of removing bleachable stains from textiles, they also frequently attack colored textiles, in particular in the case of qualities of textile dyes which are sensitive to oxidation, so that the intensity of the textile colors and the textiles diminish over time washed out ". The use of bleaching agents can also lead to spot-like color removal on the textiles, the so-called pinhole spotting effect. Detergents that are explicitly used for colored textiles have therefore been on the market for some time and therefore have little or no amounts With, for example, less than 10% by weight, based on the total agent, of bleaching agents, the bleaching agent is only used for hygienic purposes in such small amounts, the risk of the bleaching agent removing color or staining the textiles can then almost be ruled out Stain removal from colored textiles is still a problem today.

The object of the invention is therefore to create an essentially bleach-free Detergent with improved stain removal properties.

In the case of a detergent of the type mentioned at the outset, this object is achieved according to the invention solved in that 10 to 30 wt .-% of the total acid particles a size between 1750 and 2000 µm and 10 to 30 wt .-% of the total acid particles one size have less than 150 µm.

It has been found that a generic detergent, which additionally by total 10 to 30% by weight of coarse acid particles with a size between 1750 and 2000 microns and a total of 10 to 30 wt .-% of finely divided acid particles with a Size smaller than 150 microns is marked, to improve the distance support of bleachable soiling on textiles.

As an additional organic acid, use is preferably made of those known is that they also have a significant builder effect. In addition to these organic acids belong to all those already in the German patent application DE 28 27 571 are listed. Also those in the international patent application WO-A-94/04650 mentioned polyhydroxydicarboxylic acids can be used. In particular tartaric acid, succinic acid, maleic acid and / or malic acid are preferred. But Acid anhydrides are also organic in the context of the present invention Acids; succinic anhydride and maleic anhydride are particularly preferred here.

Citric acid is also used. Contrary to the teaching of the international Patent application WO-A-94/06450 shows citric acid on a wide variety of soils seen a better bleaching performance than, for example, tartaric acid, though Tartaric acid on targeted soiling also results better in the bleaching area can achieve as citric acid.

All organic acids are used as raw material, ie not in the form of a processed compound, and are therefore present in the agent according to the invention as a separate or subsequently admixed component. Under separately mixed "means that the organic acid is mixed as one of several components with the other components to form the detergent. Depending on the production process, it is also possible that all other components are first prepared and, if appropriate, premixed with one another and possibly further shaping steps of the mixed Components take place and the organic acid only after that The organic acids can be mixed in their commercial form with the other components. For example, a commercial citric acid quality has a particle size distribution in which at least 80% by weight of the particles are between 350 and 1500 μm. But also more finely divided grades with at least 80% by weight smaller than 350 µm or coarser grades with at least 80% by weight larger than 1500 µm are available, especially the coarser goods with particle diameters of at least 80% by weight larger than 1500 µm This coarser product can even be advantageous from an aesthetic point of view if it is admixed to components which also have a coarser grain spectrum, for example granules or extrudates, which may be rounded and are at least 80% by weight. -% of particles with a particle diameter above around 400 µm and especially those that have an average particle diameter of 0.8 to 1.4 mm. The coarser citric acid product consists of at least 80% by weight of particles with a particle size between 1500 and 2000 µm. The more finely divided product of additional organic acid (80% by weight less than 350 µm) essentially serves to powder off the granular components. In addition to the above-mentioned coarse-grained quality with at least 80% by weight of particles with a particle diameter between 1500 and 2000 μm, this fine-particle product with particle diameters of at least 80% by weight less than 350 μm is also used in the invention.

The size distribution of coarse and fine particle acid particles according to the invention can be through the metered and proportionate admixing of coarse citric acid goods and finely divided achieve additional organic acidity.

Granular detergents mean particulate detergents which consist of at least 60 wt .-% of particles with a particle size above 350 microns and preferably contain at least one component which is at least 80% by weight have a particle size above 350 microns. In particular, there are granular ones Agents of at least 60% by weight, preferably 70 to 100% by weight, of components, which have at least 80 wt .-% a particle size above 350 microns.

The bulk density of the agents is of less importance because the effect according to the invention is not dependent on the bulk weight. However, compact detergents are preferred or so-called concentrates with bulk weights above 600 g / l. According to the invention Washing agents in granulate form with bulk densities between 650 and 1100 g / l, bulk densities above 700 g / l and in particular above 750 g / l are particularly preferred.

The citric acid is in the agent according to the invention in amounts of 1 to 10 wt .-% and the additional organic acid, preferably in amounts of less than 10% by weight, in particular in amounts of 2 to 6% by weight.

The agent according to the invention is essentially free of bleaching agents and, in particular, essentially free of peroxy bleaching agents is understood to be essentially free from 0.1 to 10% by weight. In a preferred embodiment, the agents are absolutely free from bleaching agents. However, if in minor amounts, for example in amounts of 2 to 8% by weight, based on the Whole agents, bleaching agents should be used, the usual peroxy bleaching agents such as perborate monohydrate, perborate tetrahydrate and / or percarbonate are preferred.

The essential ingredients of the agents according to the invention also include anionic ones and / or nonionic surfactants, it being particularly preferred if the agents contain both anionic and nonionic surfactants.

Preferred anionic surfactants of the sulfonate type are C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C ₁₂ -C ₁₈ monoolefins with an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. The use of the alkylbenzenesulfonates mentioned is particularly preferred.

Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), e.g. the α-sulfonated Methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and Triester and their mixtures represent how they are produced by esterification by a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of Triglycerides with 0.3 to 2 moles of glycerin can be obtained.

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are particularly preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN ^(R) , are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol of ethylene oxide (EO) or C ₁₂ -C ₁₈ -Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues 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 anionic surfactants are fatty acid derivatives of amino acids, for example of N-methyl taurine (tauride) and / or of N-methyl glycine (sarcoside). The sarcosides or sarcosinates are particularly preferred, and above all Sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate.

The anionic surfactants are preferably used in relatively high amounts, i.e. in quantities above 15% by weight. Anionic surfactants are advantageously in quantities between 16 and 30% by weight, based on the finished compositions, contained in the compositions.

Suitable anionic surfactants also include soaps, preferably in quantities from 0.5 to 3 wt .-%, based on the finished agent, are included. Are particularly suitable saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. Together with these soaps or as a substitute for soaps you can also use them known alkenyl succinic acid salts are used. The proportion of soaps and alkenyl succinic acid salts the total surfactant system is preferably below 10 % By weight and in particular at a maximum of 5% by weight.

The anionic surfactants including the soaps can be 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 the form of their sodium and / or potassium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously 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 can be linearly or preferably 2-branched methyl or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, palm kernel, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohols with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms 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.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533. C ₁₂ -C ₁₈ fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO, are particularly preferred.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than that Half of it.

in der R²CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R³ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Vorzugsweise leiten sich die Polyhydroxyfettsäureamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

in the R ² CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ³ 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 to 10 hydroxyl groups stands. The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.

in der R³ für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R⁴ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R⁵ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C₁-C₄-Alkyl- oder Phenylreste bevorzugt sind, und [Z] für einen linearen Polyhydroxyalkylrest, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielsweise nach der Lehre der internationalen Patentanmeldung WO-A-95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in which R ^{3 represents} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{5 represents} a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C ₁ -C ₄ -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

So-called gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually identified by a so-called Spacer "is separated from one another. This spacer is generally a carbon chain which should be long enough that the hydrophilic groups have a sufficient spacing for them to be able to act independently of one another. Such surfactants are generally distinguished by an unusually low critical micelle concentration and the Ability to greatly reduce the surface tension of water, but in exceptional cases the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.

Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or dimeral alcohol bis and trimeral alcohol tris sulfates and ether sulfates according to the earlier German patent application P 195 03 061.3. End-capped dimeric and trimeric mixed ethers according to the older one German patent application P 195 13 391.9 are characterized in particular by their bi- and Multifunctionality. So the end-capped surfactants mentioned good network properties and are low-foaming, so that they are particularly suitable for Suitable for use in machine washing or cleaning processes.

Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides can also be used. as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO95-A- / 19955 can be described.

If necessary, other surfactants such as amphoteric surfactants, cationic surfactants and / or zwitterionic surfactants can be contained in the agents according to the invention. For example Cationic surfactants with softening properties can be used to improve the softness of the textiles after the wash cycle or after drying.

The anionic and / or nonionic surfactants in the agents according to the invention is preferably 15 to 40% by weight, in particular 20 to 35% by weight, advantageously at least one non-soap anionic surfactant and at least one Nonionic surfactant and possibly soap are included in the agents.

Agents with a nonionic content have proven to be particularly powerful Surfactants of at least 2% by weight, preferably of at least 4% by weight, for example of at least 5 wt .-%, with contents of the finished agent nonionic surfactants between 5 and 12 wt .-% are particularly preferred, in particular when the agents are used at low temperatures below 50 ° C become. The content of the agents in nonionic surfactants can exceed 12% by weight in principle lead to a further increase in the performance of the funds, but it has in several cases, the granular agents have been found to contain such high levels of nonionic surfactants increasingly lose their flowability and tend to stick to clumping can. For this reason, amounts of nonionic surfactants above 12% by weight are not particularly preferred.

Weight ratios of anionic surfactants: nonionic surfactants of at least 1: 1, preferably of 2.5: 1 to 1.1: 1, have proven to be particularly advantageous, especially when the Soap content, based on the total surfactant content, is a maximum of 5% by weight.

In addition to the surfactants mentioned and in particular in addition to the organic ones Acids in the agents according to the invention normally contain customary inorganic and / or organic builder substances in customary amounts. For example 10 to 30% by weight of additional builder substances can be contained in the compositions.

The inorganic builder substances include above all zeolites, crystalline layered silicates, Carbonates, amorphous silicates and, to a lesser extent, also phosphates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. Zeolite P can contain, for example, zeolite MAP ^(R) (commercial product from Crosfield) in the compositions. However, zeolite X and mixtures of A, X and / or P are also suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 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% by weight, in particular 20 to 22% by weight, of bound water.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, 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 are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

The preferred builder substances also include amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

It goes without saying that the generally known phosphates are also used as builder substances possible if such use is not avoided for ecological reasons should be. The sodium salts of orthophosphates, pyrophosphates, are particularly suitable and especially the tripolyphosphates. Your salary in general is not more than 25 wt .-%, preferably not more than 20 wt .-%, each based on the finished funds. In some cases it has been shown that tripolyphosphates in particular even in smaller amounts, for example up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances to a synergistic Improve secondary washing ability.

Both the monoalkali metal salts and the dialkali metal salts can be used as carbonates carbon dioxide and sesquicarbonates can be included in the product. Preferred alkali metal ions represent sodium and / or potassium ions. The carbonate content or The bicarbonate content of the agent is preferably 5 to 20% by weight, it being in one embodiment may be preferred, the carbonate and / or bicarbonate at least partially to be added separately or subsequently as a further component. Compounds too for example carbonate, silicate and optionally other auxiliaries such as Anion surfactants or other, especially organic builder substances, can present as a separate component in the finished funds. Another component which can be mixed in later is silicate, for example metasilicate and / or crystalline layered disilicate. Overall, it is preferred to use the above subsequently mixed components, but especially carbonate, bicarbonate, metasilicate - as described above for citric acid - in coarse-grained form, it being particularly advantageous if carbonate, bicarbonate and / or metasilicate at least 50% by weight of a particle size above 1 mm and in particular have at least 50% by weight above 1.2 mm. In a preferred embodiment The invention is based on the mixed alkaline reaction in an aqueous liquor or separately admixed components, in particular carbonate, bicarbonate and / or metasilicate and / or crystalline layered disilicate, in amounts of 1 to 15% by weight, advantageously in amounts of 2 to 10% by weight.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and 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 from these. The salts of the polycarboxylic acids can be in addition to the organic ones Acids may be included in the agents; however, their presence in the media is less prefers.

Other suitable organic builder substances, their use in addition to the organic Acids that can certainly bring advantages are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to customary methods, for example acid-catalyzed or enzyme-catalyzed Procedures are carried out. They are preferably hydrolysis products with average molecular weights in the range of 400 to 500,000. Here is a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Are usable using both maltodextrins with a DE between 3 and 20 and dry glucose syrups a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins higher molar masses in the range from 2000 to 30000.

Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and at most contain two acid groups. Such cobuilders are used, for example, in the international Patent application WO-A-95/20029.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight from 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid have been found to be particularly suitable Maleic acid proved to be 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain. Their relative molecular weight, based on free acids, is in general 5000 to 200000, preferably 10000 to 120000 and in particular 50000 to 100000.

The (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution are used, 20 to 55% by weight aqueous solutions being preferred.

Polymers composed of more than two different monomer units are also particularly preferred, for example those which, according to DE-A-43 00 772, are monomers as salts acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.

Further preferred copolymers are those described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Other suitable builder substances are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts, such as those in the international patent application WO-A-93/08251 can be described or their preparation described, for example, in international patent application WO-A-93/16110 becomes. Oxidized oligosaccharides according to the German patent application are also suitable DE 196 00 018.

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Polyaspartic acids are particularly preferred or their salts and derivatives.

Other suitable builder substances are polyacetals, which are obtained by reacting dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups have, for example as in European patent application EP-A-0 280 223 can be obtained. Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

In addition, the agents can also contain components that make the oil and fat washable made of textiles. This effect is particularly evident if a textile is soiled, which has previously been repeatedly with an inventive Detergent containing this oil and fat-dissolving component is washed has been. The preferred oil- and fat-dissolving components include, for example, nonionic Cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with one Proportion of 15 to 30% by weight of methoxyl groups and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and also from polymers of phthalic acid and / or terephthalic acid known in the prior art or of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

In addition to the ingredients mentioned, the agents can usually be found in detergents additives used, for example foam inhibitors, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, graying inhibitors, contain small amounts of neutral filling salts as well as colors and fragrances.

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 C ₁₈ -C ₂₄ 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 various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bisstearylethylenediamides are particularly preferred.

The salts of polyphosphonic acids are preferably the neutral sodium salts for example 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate in amounts of 0.1 to 1.5 wt .-% used.

Enzymes in particular come from the class of hydrolases, such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases wear in the laundry to remove stains, such as protein, fat or starchy stains and graying. Cellulases and other glycosyl hydrolases can be used for color preservation and removal by removing pilling and microfibrils contribute to increasing the softness of the textile. To bleach or inhibit the Color transfer can also be used with oxidoreductases.

Bacterial strains or fungi such as Bacillus subtilis or Bacillus are particularly suitable licheniformis, Streptomyces griseus and Humicola insolens Active ingredients. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic acting enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic acting enzymes or protease, lipase or lipolytically acting enzymes and cellulase, in particular, however, mixtures or mixtures containing protease and / or lipase with lipolytic enzymes of particular interest. Examples of such The well-known cutinases are lipolytic enzymes. Also peroxidases or oxidases have proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which also Cellobiases are called, or mixtures of these are used. Because the different Distinguish cellulase types by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases become.

The enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.

The agents can contain, for example, 0.5 to 1% by weight of sodium formate as enzyme stabilizers. It is also 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. In addition to calcium salts, magnesium salts also serve as stabilizers. 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 (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous.

Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening. Water-soluble colloids of mostly organic nature are suitable for this purpose, 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 cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Soluble starch preparations can also be used and use starch products other than the above, e.g. degraded starch, aldehyde starches etc. Polyvinylpyrrolidone can also be used. However, are preferred Cellulose ethers, such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, Methyl carboxymethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone for example in amounts of 0.1 to 5 wt .-%, based on the agent used.

As optical brighteners, the agents can be derivatives of diaminostilbenedisulfonic acid or whose alkali metal salts contain. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds which, instead of the morpholino group, have a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Farther brighteners of the substituted diphenylstyryl type may be present, e.g. 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 be used.

• das Vorgemisch im wesentlichen wasserfrei ist und
• im Vorgemisch mindestens ein Rohstoff oder Compound, der bzw. das bei einem Druck von 1 bar und Temperaturen unterhalb von 45 °C in fester Form vorliegt, unter den Verarbeitungsbedingungen aber als Schmelze vorliegt, wobei diese Schmelze als polyfunktioneller, in Wasser löslicher Binder dient, welche bei der Herstellung der Mittel sowohl die Funktion eines Gleitmittels als auch eine Kleberfunktion für die festen Wasch- oder Reinigungsmittelcompounds- bzw. -rohstoffe ausübt, bei der Wiederauflösung des Mittels in wäßriger Flotte hingegen desintegrierend wirkt und
• im Aufbereitungsschritt zumindest die organischen Säuren als separate Komponente zugemischt werden.

The granular detergents according to the invention can be produced by any known process, such as spray drying, granulation, compacting, pelletizing, extrusion in combination with one or more downstream processing operations which include shaping steps, drying or surface modification with liquid to wax-like or solid substances and mixing operations. wherein the citric acid and the additional organic acid are mixed separately or subsequently, and thus an agent is produced which contains the organic acids in the finished product as a separate component. Granulation and extrusion methods are advantageously used to achieve the high bulk density. An extrusion process is particularly preferred, which is described for example in European patents and international patent applications EP-B-0 486 592, WO-A-94/09111, WO-A-96/38530. In a particularly preferred embodiment of the invention, the granules or extrudates are produced in accordance with the teaching of German patent application P 196 38 599.7, the granulation or extrusion process being modified in such a way that a solid premix is first prepared which contains individual raw materials and / or compounds, which are present as a solid at room temperature and a pressure of 1 bar and have a melting point or softening point not below 45 ° C, and optionally up to 10% by weight at temperatures below 45 ° C and a pressure of 1 bar, contain liquid nonionic surfactants , and converted into a grain using compaction forces at temperatures of at least 45 ° C. and optionally subsequently processed or processed, with the provisos that

• the premix is essentially anhydrous and
• in the premix at least one raw material or compound which is in solid form at a pressure of 1 bar and temperatures below 45 ° C, but is present as a melt under the processing conditions, this melt serving as a polyfunctional, water-soluble binder, which in the manufacture of the agents has both the function of a lubricant and an adhesive function for the solid detergent or cleaning agent compounds or raw materials, but has a disintegrating effect when the agent is redissolved in an aqueous liquor and
• at least the organic acids are mixed in as a separate component in the treatment step.

The agent according to the invention has significant bleachable stains in particular Advantages on other advantages can also be achieved, for example, on enzymatic ones Soiling can be found while the primary wash performance versus greasy and pigment-containing soiling can be classified as the same on average. Surprisingly, the advantages come especially from the bleachable stains even at washing temperatures of 60 ° C and below. Even with hand washing at 30 ° C or up to 40 ° C, the agent according to the invention shows advantages.

Examples

Waschbedingungen für Primärwaschvermögen:
Leitungswasser von 16 °d (äquivalent 160 mg CaO/l), eingesetzte Waschmittelmenge pro Mittel und Maschine 76 g, Waschtemperatur 40 °C oder 60 °C (Buntwaschprogramm, 60minütige Waschzeit), 5fach-Bestimmung.

Auswertung (künstliche Anschmutzungen): Die Messung der Remission %R (460 nm/FL46; Ausblendung des Aufheller-Effekts) erfolgte mit dem Gerät Spectraflash 503.

Auswertung (natürliche Anschmutzungen): Die Messung der Farbabstandswerte dE(w)(AW-Waschwert) (1-Punktmessung) erfolgte mit dem Gerät Minolta CR200/310.

Neben fetthaltigen und pigmenthaltigen Anschmutzungen wurden insbesondere die folgenden künstlichen bleichbaren und enzymatischen Anschmutzungen auf Baumwolle getestet: Rotwein (R), Tee (T), Kakao (K), Waldbeere (W) sowie Milch-Kakao (MK).

Neben fetthaltigen, pigmenthaltigen und enzymatischen Anschmutzungen wurden insbesondere die folgenden natürlichen bleichbaren Anschmutzungen getestet: Rotwein (R), Tee (Messmer, TEE), Instant-Kaffee (Nescafé, IK), Johannisbeersaft (Eden, J) sowie Heidelbeersaft (Eden, H).

The application-related testing of the primary washing ability was carried out under practical conditions in household washing machines (Miele Novotronic W918). For this purpose, the machines were loaded with 3.5 kg of clean laundry and 0.5 kg of test fabric. The test fabrics consisted of cotton and were impregnated with the natural and artificial stains explained in more detail below. The soiling showed an aging of 5 to 6 days.

Washing conditions for primary washing ability:
Tap water of 16 ° d (equivalent to 160 mg CaO / l), amount of detergent used per detergent and machine 76 g, washing temperature 40 ° C or 60 ° C (colored washing program, 60-minute washing time), 5-fold determination.

Evaluation (artificial soiling): The remission% R (460 nm / FL46; suppression of the brightener effect) was measured using the Spectraflash 503 device.

Evaluation (natural soiling): The color difference values dE (w) (AW wash value) (1-point measurement) were measured using the Minolta CR200 / 310 device.

In addition to greasy and pigmented stains, the following artificial bleachable and enzymatic stains on cotton were tested in particular: red wine (R), tea (T), cocoa (K), wild berries (W) and milk cocoa (MK).

In addition to fatty, pigment-containing and enzymatic stains, the following natural bleachable stains were tested in particular: red wine (R), tea (Messmer, TEE), instant coffee (Nescafé, IK), currant juice (Eden, J) and blueberry juice (Eden, H) .

The compositions had the following compositions (in parts by weight), M1 and M2 designating compositions according to the invention and V-V3 designating comparative examples. M1 V V1 M2 V V3 Basic granulate 1 88.0 92.0 88.0 - - Base extrudate 2 - - - 86.0 86.0 86.0 Enzyme granules 2.5 2.5 2.5 2.5 2.5 2.5 Citric acid (coarse) 4.0 - - 4.0 - - Citrate (coarse) - - - - 6.1 - Sodium bisulfate - - 4.0 - - - sodium - - - 5.0 5.0 - Sodium bicarbonate - - - - - 10.0 Foam inhibitor granules 4.0 4.0 4.0 4.0 4.0 4.0 additional organic acid (fine) 2.0 - - 2.0 - -

The basic granulate 1 was produced in accordance with the teaching of the European patent EP-B-0 486 592 produced and essentially had the following composition: 14 wt .-% anionic surfactants (Alkyl benzene sulfonate and fatty alkyl sulfate), additionally 2% by weight of soap, 8% by weight ethoxylated fatty alcohols, 40% by weight zeolite (based on anhydrous active substance), 7 % By weight trisodium citrate dihydrate, 5.5% by weight copolymer of acrylic acid and maleic acid, 8% by weight sodium carbonate, 2% by weight polyvinylpyrrolidone (balance: water and Salts from solutions). The bulk density was 780 to 800 g / l. A basic granulate, which was made by conventional granulation / densification and about the same Composition and the same bulk density gave comparable results.

The basic extrudate 2 was prepared in accordance with the teaching of German patent application P 196 38 599.7 and essentially had the following composition: 23 % By weight of anionic surfactants (alkylbenzene sulfonate and fatty alkyl sulfate), in addition 1% by weight of soap, 8% by weight of ethoxylated fatty alcohols, 27.5% by weight of zeolite (based on anhydrous Active substance), 12 wt .-% trisodium citrate dihydrate, 5.5 wt .-% copolymer of Acrylic acid and maleic acid, 6.5% by weight sodium carbonate and 5% by weight polyethylene glycol with a molecular weight of 4000. The bulk density was about 800 g / l.

The enzyme granules contained protease, amylase and cellulase in a weight ratio of 1: 1: 1.

As roughly designated qualities of citric acid had 83% by weight of particles with a particle diameter between 1500 and 2000 µm. The additional organic acid (fine) each had 81% by weight of particles with a particle diameter of less than 350 µm the acid particles have a size distribution in which 25% by weight have a size between 1750 and 2000 μm and 15% by weight have a size less than 150 μm.

The foam inhibitor granulate was a paraffin defoamer on soda as a carrier.

The primary washing results are summarized (in part) in Tables 1 to 6. The abbreviation AW always means Initial value of the test soiling ". All the tables show that the agents according to the invention have clear advantages over bleachable soils (in particular at 40 ° C.), and in some cases also with enzymatic soils. The results for fatty soils and pigment-containing soils were on average both 40 ° C as well as at 60 ° C. In the case of cosmetic soiling, clear advantages were again achieved for the agents according to the invention in certain cases (not listed in tables). Primary washing power of M1 (reflectance in%) at 40 ° C Pollution medium AW M1 V1 R 25.5 45.3 42.4 T 24.9 34.3 32.4 K 22.1 63.4 60.9 Primary washability of M1 (reflectance in%) at 60 ° C Pollution medium AW M1 V1 V R 25.9 45.9 42.0 40.7 T 24.8 34.7 32.6 31.2 K 21.8 66.8 64.8 65.2 Primary washability of M1 (color difference values dE (w) (AW)) at 40 ° C Pollution medium AW M1 V1 R 27.3 15.1 14.6 TEA 23.3 6.3 5.7 IK 42.9 23.5 21.5 J 33.3 15.8 13.6 H 28.6 15.3 12.7 Primary washability of M1 (color difference values dE (w) (AW)) at 60 ° C Pollution medium AW M1 V1 V R 27.1 17.8 15.6 14.0 TEA 23.9 7.5 6.5 6.2 IK 42.1 25.9 24.1 24.0 J 34.2 16.1 13.9 15.0 H 38.6 25.3 22.7 23.2 Primary washing power of M2 (reflectance in%) at 40 ° C Pollution medium AW M2 V2 V3 T 29.0 35.2 29.7 30.4 K 20.8 62.5 60.5 60.5 W 21.3 54.5 49.7 48.6 MK 21.5 72.7 70.3 71.5 Primary washing power of M2 (color values dE (w) (AW)) at 40 ° C Pollution medium AW M2 V2 V3 R 26.6 14.3 10.5 10.2 TEA 25.3 5.5 1.9 2.7 IK 43.2 27.9 26.2 25.3 J 31.4 15.6 13.5 12.1 H 30.7 15.7 12.3 11.9

Claims (6)

Detergent with less than 10% by weight of bleach and with citric acid as separately or subsequently mixed component to support the removal of bleachable stains, with citric acid having a particle size distribution in which at least 80% by weight of the particles have a size between 1500 and 2000 µm, and with additional to the coarse-grained citric acid, also separately or subsequently mixed organic acid, the additional organic acid has a particle size distribution in which at least 80 wt .-% are less than 350 microns, as well as with anionic and / or nonionic Surfactants and builder substances, characterized in that 10 to 30 % By weight of the total acid particles a size between 1750 and 2000 microns and 10 up to 30 wt .-% of the total acid particles have a size smaller than 150 microns. Detergent according to claim 1, characterized in that it is in the form of granules and has a bulk density of 650 g / l to 1100 g / l. Detergent according to claim 1 or 2, characterized in that it contains 1 to 10% by weight contains separately or subsequently admixed citric acid. Detergent according to one of the preceding claims, characterized in that it as an additional organic acid tartaric acid, succinic acid, succinic anhydride, Maleic acid, maleic anhydride and / or malic acid contains. Detergent according to one of the preceding claims, characterized in that it the additional organic acid in amounts of less than 10 wt .-% and in particular contains in amounts of 2 to 6 wt .-%. Detergent according to one of the preceding claims, characterized in that it in addition to the organic acids at least one alkaline in aqueous liquor reacting component, in particular carbonate, bicarbonate and / or metasilicate and / or crystalline layered disilicate, in amounts of 1 to 15% by weight, advantageously in amounts of 2 to 10% by weight in a subsequently or separately admixed form Contains form.