EP0986629B1 - Granular detergent - Google Patents

Abstract

The invention relates to the use of organic acids, especially citric acid, added separately or at a later stage, to help remove bleachable stains on textiles if the detergent used is essentially free of bleaching agents. To this end, granular detergents are used which have an apparent density of between 650 g/l and 1100 g/l, contain anionic and/or nonionic tensides as well as builders, and between 1 and 15 weight percent of an organic acid which is added separately or at later stage, said detergents being essentially free of bleaching agents. The advantages of such detergents are especially evident when said detergents are used for machine washing at temperatures of up to 60 DEG C and in particular at temperatures as low as 30 DEG C to 40 DEG C.

Description

The invention relates to the use of organic acids / organic acid anhydrides, in particular citric acid, to support the removal of bleachable soiling on textiles in the essential bleach-free granular detergents. The invention also relates granular detergents with bulk weights above 600 g / l, which can be used separately or subsequently admixed organic acids, especially citric acid, and especially are suitable for cleaning colored textiles, and a manufacturing process granular detergent. Furthermore, the use of funds in mechanical Washing process at temperatures up to a maximum of 60 ° C claimed.

Citric acid has long been known as a detergent ingredient. It was mainly used for Lowering the pH of the mostly strongly alkaline agents in the aqueous liquor, the added benefit was achieved that both the citric acid and that by Neutralize the citric acid obtained citrate (co) builder properties.

The German patent application DE-A-28 27 571 (Akzo) already describes this in general Detergent, which is a granular alkaline, especially carbonate-containing slower solvent component and 5 to 30 wt .-% of a separate organic acid, preferably Citric acid. In the course of an "acid prewash" in commercial household washing machines already at temperatures of 25 ° C by the citric acid that is already dissolving at these temperatures softens the liquor reached so that at temperatures around 40 ° C when the alkaline component begins to dissolve, the liquor is already softened such that the risk of calcium carbonate and This largely minimizes the formation of calcium carbonate residues on the textiles becomes. Neither the bulk density nor the particle size distribution of the added organic acids called. Other components of the funds include et al Peroxy bleaches such as perborates.

Detergents are also used in international patent application WO-A-91/17232 (P&G) described, which as a builder 20 to 30 wt .-% zeolite, 5 to 20 wt .-% alkali metal carbonate and 1 to 3% by weight of alkali metal silicate and 4 to 10% by weight of citric acid. Other ingredients are, for example, peroxy bleaching agents such as perborate. While the granular agents for the formation of a bulk density of 500 to 600 g / l usually be spray-dried and also contain the carbonate in the spray-dried portion the citric acid which values the pH in 1% solution in water at 20 ° C should drop between 7 and 9.3, subsequently mixed in, as the Citric acid in the spray-dried slurry already neutralizes the citric acid in the Slurry and not - as desired - would take place in the aqueous wash liquor. The Particle size distribution of the separately added citric acid plays again not matter. Due to the relatively low pH in the aqueous liquor, the colors should of colored textiles are better preserved.

Granular washing or cleaning agents with a bulk density of 650 to 1100 g / l, which anionic and / or nonionic surfactants as well as builder materials etc. 5 to 30% by weight Contain 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 it is 1 to 15% by weight subsequently as a further component contain added citric acid, at least 80% by weight of this citric acid Must have particles with a particle size of 350 and 1500 microns. Both lesser Particle sizes as well as coarser granules do not lead to the desired effect increased dispersion in aqueous liquor. Other common ingredients are in the Agents contain peroxy bleach.

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 have not only the effect that bleachable soiling from textiles removed, they also often catch - especially in the case of those sensitive to oxidation Qualities of textile dyes - colored textiles, so that over time the intensity the textile colors wear off and the textiles look "washed out". It can also Use of bleaching agents for spot color removals on the textiles so-called pinhole spotting effect. Detergents have therefore been in use for some time Trade that are explicitly used for colored textiles and therefore no or only small amounts, for example less than 10% by weight, based on the total agent Have bleaching agents. With such small amounts, the bleach is only used hygienic purposes; the risk of color removal or staining of the textiles the bleaching agent can then almost be excluded. Nevertheless, it is precisely that Stain removal from colored textiles remains a problem to this day.

It has now been found that the use of separately or subsequently admixed organic Acids / organic acid anhydrides, especially citric acid, to aid in the removal of bleachable soiling on textiles results when the detergent used essentially is free of bleach.

The invention therefore relates to the use of organic acids / organic acid anhydrides, in particular citric acid, as separate or subsequently admixed Component in detergents which contain less than 10% by weight of bleaching agent, based on the total detergent, as a support the removal of bleachable stains.

The invention also relates to a granular detergent with a bulk density from 650 g / l to 1100 g / l, containing anionic and / or nonionic surfactants and builder substances including 1 to 15 wt .-% of a separately or subsequently mixed organic acid, the agent being less than 10% by weight Contains bleach and a particle size distribution of organic acids / organic Has acid anhydrides of at least 80% of the particles larger than 1500 microns.

As organic acids, preference is given to those which are poor in that they also have a significant builder effect. These include organic acids all of which are already listed in German patent application DE 28 27 571. Also the polyhydroxydicarboxylic acids mentioned in the international patent application WO-A-94/04650 can be used. Citric acid is particularly preferred, Tartaric acid, succinic acid, maleic acid and / or malic acid. But also acid anhydrides count in the context of the present invention to the organic acids; here succinic anhydride and maleic anhydride are preferred. Under special Citric acid is preferred. Contrary to the teaching of the international Patent application WO-A-94/06450 has citric acid in a wide variety of ways Soiling seen a better bleaching performance than, for example, tartaric acid, although tartaric acid also produces better results in the bleaching area can achieve as citric acid.

The organic acids / organic acid anhydrides are used as raw material, i.e. not in the form of a processed compound used and are therefore in the agents according to the invention as separate or subsequently admixed component. In this context, "separately admixed" means that the organic acid as one of several components with the other components is mixed to the detergent. Depending on the manufacturing process, it is also possible that all other components are first manufactured and if necessary together premixed and possibly further shaping steps of the mixed components take place and the organic acid only afterwards, ie "subsequently mixed in" becomes. The organic acids can be in their commercial form with the others Components are mixed. For example, has a commercial citric acid quality a particle size distribution in which at least 80% by weight of the particles between 350 and 1500 µm are. But also more finely divided qualities with at least 80% by weight smaller than 350 µm or coarser qualities with at least 80% by weight larger than 1500 µm are available. Above all, the coarser goods with particle diameters of at least 80 % By weight greater than 1500 μm can be used in the agents according to the invention without loss of performance be used. This coarser product can even be advantageous from an aesthetic point of view if it is mixed into components, which also have a coarser grain spectrum have, for example granules or extrudates, which may be rounded can be and at least 80 wt .-% of particles with a particle diameter above 400 µm and especially those that have an average particle diameter have 0.8 to 1.4 mm. A preferred coarser commodity of organic Acids, especially citric acid, consist of at least 80% by weight of particles of one Particle size between 1500 and 2000 µm. Even more finely divided goods (80% by weight less than 350 µm) can be used in principle. But then it is preferably used for powdering of the granular components and should advantageously not be used as a separate component available in the funds. In a preferred embodiment of the invention, however in addition to the above coarse grain quality with at least 80% by weight particles with a particle diameter between 1500 and 2000 µm also this fine-particle product Particle diameters of at least 80 wt .-% less than 350 microns used.

Granular detergents mean particulate detergents which include at least 60 wt .-% consist 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 or are preferred so-called concentrates with bulk weights above 600 g / l. Claimed according to the invention granular detergents with bulk weights between 650 and 1100 g / l, bulk densities above 700 g / l and especially above 750 g / l particularly are preferred.

The organic acids / organic acid anhydrides are used in the agents according to the invention in amounts of 1 to 15 % By weight, but preferably in amounts of less than 10% by weight and in particular in Amounts of 2 to 6 wt .-% used. Are fine-particle qualities with particle diameters of at least 80 wt .-% less than 350 microns used, their share is based on the total composition, preferably not more than 2% by weight and in particular not more than 1% by weight. In the preferred embodiment of the invention, which means includes both coarse (at least 80 wt .-% greater than 1500 microns) and fine particles contain (at least 80 wt .-% less than 350 microns) organic acids, the proportion of the finely divided organic acids in the total amount of organic acids used Acids preferably at most 50% by weight and in particular 5 to 30% by weight.

The agents according to the invention are essentially free of bleaching agents and in particular essentially free of peroxy bleaching agents, in the context of this invention under "im is understood to be essentially free from "0 to 10% by weight. In a preferred embodiment the agents are absolutely free of bleach. However, if in minor quantities, for example in amounts of 2 to 8 wt .-%, based on the total agent, bleach should be used, the usual peroxy bleaching agents such as perborate monohydrate, Perborate tetrahydrate and / or percarbonate are preferred.

To the. essential ingredients of the agents according to the invention also include anionic 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 can be obtained with 0.3 to 2 mol of glycerol.

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 amounts between 16 and 30 wt .-%, based on the finished agent, included in the agents.

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 linear or preferably methyl-branched in the 2-position 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 half from that.

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-Aryloxysubstituierten 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 be converted, for example according to the teaching of international patent application WO-A-95/07331, 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. Below are in generally understood such compounds, the two hydrophilic groups and two hydrophobic Have groups per molecule. These groups are usually identified by a so-called "Spacer" separated from each other. This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient Have a distance so that they can act independently. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases However, under the term Gemini surfactants, not only dimeric but also also understood trimeric surfactants.

Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or dimer alcohol bis and trimer alcohol trissulfates and ether sulfates according to the earlier German patent application P 195 03 061.3. End group capped dimeric and trimeric mixed ethers according to the older German Patent application P 195 13 391.9 is particularly characterized by its bi- and multifunctionality out. The end group-capped surfactants have good wetting properties and are low-foaming, so that they are particularly 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 funds.

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, have, for example, at least 5% by weight, the contents of the finished product being at 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 have shown that the granular agents are at 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 special prefers.

Weight ratios of anionic surfactants: nonionic surfactants of at least 1: 1, preferably of 2.5: 1 up to 1.1: 1, have proven to be particularly advantageous, especially if 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 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 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 no longer than 25% by weight, preferably not more than 20% by weight, in each case based on the finished product Medium. In some cases it has been shown that tripolyphosphates in particular are already 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 improvement of the Secondary washing power.

Both the monoalkali metal salts and the dialkali metal salts of the Carbon dioxide as well as sesquicarbonates can be included in the funds. Preferred alkali metal ions represent sodium and / or potassium ions. The carbonate content or the bicarbonate content the average is preferably 5 to 20% by weight, in one embodiment may be preferred, the carbonate and / or bicarbonate at least partially as further Mix component separately or subsequently. Also compounds from, for example Carbonate, silicate and optionally other auxiliary substances such as anionic surfactants or other, especially organic builder substances, can be used as separate Component present in the finished funds. Another component, which is retrofitted can be admixed is silicate, for example metasilicate and / or crystalline layered disilicate. Overall, it is preferred to add the additives mentioned subsequently Components, but especially carbonate, bicarbonate, metasilicate - as above described for the citric acid - to mix in coarse-grained form, being particularly it is advantageous if carbonate, bicarbonate and / or metasilicate to at least 50 wt .-% a particle size above 1 mm and in particular at least 50% by weight have above 1.2 mm. In a preferred embodiment of the invention those which have an alkaline reaction in aqueous liquor, are mixed or mixed separately 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 both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher ones 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 are also suitable Patent application 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 described, 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 when a textile is soiled that has already been washed several times with an inventive one Detergent containing this oil and fat-dissolving component has been washed. To the preferred oil- and fat-dissolving components include, for example, non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and from 1 to 15% by weight of hydroxypropoxyl groups, in each case based on the nonionic cellulose ether and those from the prior art known polymers of phthalic acid and / or terephthalic acid 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, particular preference is given to the sulfonated derivatives of phthalic acid and Terephthalic acid polymers.

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 ethylenediaminetetramethylene phosphonate in amounts of 0.1 to 1.5 % By weight 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 these Hydrolases contribute to the removal of stains, such as protein, fat or in the laundry starchy stains and graying. Cellulases and other glycosyl hydrolases can remove color and microfibrils for color preservation and Contribute to increasing the softness of the textile. To bleach or inhibit the Color transfer can also be used with oxidoreductases.

From bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens Agents. 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 lipolytic acting enzymes are the well-known cutinases. 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% by weight.

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 also polyvinyl pyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition.

As optical brighteners, the agents can be derivatives of diaminostilbenedisulfonic acid or their Contain alkali metal salts. 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 similar connections, which instead of the morpholino group is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Can continue Present brighteners of the substituted diphenylstyryl type, 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) - biphenyl. Mixtures of the aforementioned brighteners can also 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 subsequent preparation processes, which include shaping steps, drying or surface modification with liquid to wax-like or solid substances and mixing processes, wherein at least the organic acid, in particular the citric acid, but optionally also other components, are mixed separately or subsequently, and an agent is thus 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 EP-A-0931137, the granulation or extrusion process being modified such 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 production of the agents performs both the function of a lubricant and an adhesive function for the solid detergent or cleaning agent compounds or raw materials, on the other hand 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 agents according to the invention or the agents produced according to the invention have in particular significant advantages in bleachable soiling. Other benefits can but can also be found on enzymatic soiling, for example the primary washing performance compared to greasy and pigmented soiling in the Average is to be classified as the same. Surprisingly, the advantages occur in particular on the bleachable stains even at wash temperatures of 60 ° C and below. In a further preferred embodiment of the invention, therefore the use of the agents according to the invention or those produced according to the invention Agent in a machine washing process at temperatures up to a maximum of 60 ° C, preferably at temperatures below 60 ° C and especially in washing programs Temperatures up to 40 ° C. Also for hand washing at 30 ° C or up to 40 ° C the agents according to the invention show advantages.

Examples

The application-related testing of the primary washing ability was carried out under practical Conditions in household washing machines (Miele Novotronic W918). For this, the Machines loaded with 3.5 kg of clean laundry and 0.5 kg of test fabric. The test fabric were made of cotton and were made with the natural and impregnated artificial soiling. The soiling showed an aging of 5 up 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 Medium 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 measurement of the remission% R (460 nm / FL46; Hiding the brightener effect) was done with the Spectraflash 503 device.

Evaluation (natural soiling): The measurement of the color difference values dE (w) (AW wash value) (1-point measurement) was carried out with the Minolta CR200 / 310 device.

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

In addition to fatty, pigmented and enzymatic soiling, in particular tested the following natural bleachable stains: 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 V V1 M2 V2 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

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 by conventional GranulationNerdichtung had been made and about the same composition and had the same bulk density gave comparable results.

The basic extrudate 2 was made according to the teaching of EP-A-0931137 produced and essentially had the following composition: 23 % By weight of anionic surfactants (alkylbenzenesulfonate and fatty alkylsulfate), additionally 1% by weight of soap, 8 % By weight of ethoxylated fatty alcohols, 27.5% by weight of zeolite (based on anhydrous active substance), 12% by weight trisodium citrate dihydrate, 5.5% by weight copolymer of acrylic acid and of maleic acid, 6.5% by weight of sodium carbonate and 5% by weight of polyethylene glycol with a relative molecular mass 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.

The "coarse" qualities of citric acid and citrate indicated more than 50 % By weight of particles with a particle diameter above 1.5 mm.

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 tables show that the agents according to the invention clearly compared to the comparative agents Advantages of bleachable soiling (especially at 40 ° C), partly also of enzymatic ones Show dirt. On greasy stains and pigmented ones Soiling was the result on average at both 40 ° C and comparable at 60 ° C. Cosmetic stains have been used in certain cases achieved clear advantages for the agents according to the invention (not listed in tables).

Examples M1 and V1 were repeated with organic acids other than citric acid: succinic anhydride, tartaric acid and malic acid. Here, too, there were clear advantages over V1; However, citric acid gave the best results on all stains. Primary washing power of M1 (reflectance in%) at 40 ° C soiling medium AW M1 V1 R 26.3 44.8 42.0 T 26.6 34.9 31.6 K 21.3 62.7 61.2 Primary washability of M1 (reflectance in%) at 60 ° C soiling medium AW M1 V1 V R 26.0 45.5 42.2 41.5 T 25.8 35.5 32.8 30.9 K 21.4 66.0 64.6 65.0 Primary washability of M1 (color difference values dE (w) (AW)) at 40 ° C soiling medium AW M1 V1 R 27.0 16.1 14.3 TEA 23.7 7.3 5.1 IK 42.3 24.6 21.1 J 33.4 17.0 13.5 H 29.1 16.3 12.3 Primary washability of M1 (color difference values dE (w) (AW)) at 60 ° C soiling medium AW M1 V1 V R 27.7 17.6 15.3 14.5 TEA 23.5 7.8 6.5 5.9 IK 41.7 26.7 23.9 24.0 J 33.7 16.4 13.3 15.3 H 39.1 25.6 22.3 23.4 Primary washing power of M2 (reflectance in%) at 40 ° C soiling medium AW M2 V2 V3 T 29.6 37.2 29.4 30.4 K 20.1 61.8 60.3 60.1 W 21.0 54.1 49.5 48.1 MK 21.1 72.9 70.9 71.3 Primary washing power of M2 (color level values dE (w) (AW)) at 40 ° C soiling medium AW M2 V2 V3 R 26.2 14.0 10.7 10.8 TEA 25.0 5.7 1.7 2.9 IK 43.8 27.6 26.0 25.7 J 31.9 15.6 13.9 12.4 H 30.0 16.5 12.0 11.4

Claims (10)

1. The use of organic acids/organic anhydrides as a separate or subsequently added component in detergents containing less than 10% by weight bleaching agents, based on the detergent as a whole, for supporting the removal of bleachable soils.
2. The use claimed in claim 1, characterized in that citric acid, tartaric acid, succinic acid, succinic anhydride, maleic acid, maleic anhydride and/or malic acid, more particularly citric acid, is used as the organic acid/organic anhydride.
3. The use claimed in claim 1 or 2, characterized in that organic acids/organic anhydrides, more particularly citric acid, with a particle size distribution where at least 80% by weight of the particles are between 1500 and 2000 µm in size are used.
4. The use claimed in claim 3, characterized in that fine-particle organic acids/organic anhydrides where at least 80% by weight of the particles are smaller than 350 µm in size are used in addition to the coarse-particle organic acids/organic anhydrides.
5. A granular detergent with a bulk density of 650 g/l to 1100 g/l containing anionic and/or nonionic surfactants and builders, including 1 to 15% by weight of a separately or subsequently added organic acid/organic anhydride, characterized in that the detergent contains less than 10% by weight bleaching agents, based on the detergent as a whole, and the organic acids/organic anhydrides have a particle size distribution where at least 80% by weight of the particles are larger than 1500 µm, fine-particle organic acids/organic anhydrides where 80% by weight of the particles are smaller than 350 µm optionally being additionally present.
6. A detergent as claimed in claim 5, characterized in that it contains citric acid, tartaric acid, succinic acid, succinic anhydride, maleic acid, maleic anhydride and/or malic acid, more particularly citric acid, as the organic acid/organic anhydride.
7. A detergent as claimed in any of claims 1 to 6, characterized in that, in addition to the organic acid/organic anhydride, it contains at least one component showing an alkaline reaction in aqueous liquor in subsequently or separately added form, the subsequently or separately added components showing an alkaline reaction in aqueous liquor, more particularly carbonate, bicarbonate and/or metasilicate and/or crystalline layered disilicate, being present in quantities of 1 to 15% by weight and advantageously in quantities of 2 to 10% by weight.
8. A process for the production of a granular detergent with a bulk density of 650 g/l to 1100 g/l which contains anionic and/or nonionic surfactants and builders, including 1 to 15% by weight of organic acids/organic anhydrides, and less than 10% by weight bleaching agents, based on the detergent as a whole, characterized in that the detergent is produced by standard methods, such as spray drying, granulation, compacting, pelletizing, extrusion, in combination with one or more following aftertreatment steps comprising shaping/forming, drying or surface modification with liquid or wax-like or solid substances and mixing steps, the organic acid/organic anhydride at least, more especially citric acid, but optionally other components also being separately or subsequently added so that the detergent produced contains the organic acids/organic anhydrides as a separate component in the end product.
9. A process as claimed in claim 8, characterized in that the detergent is produced by a granulation or extrusion process, the granulation or extrusion process being modified in such a way that a solid premix containing individual raw materials and/or compounds which are present as solids at room temperature and under a pressure of 1 bar and which have a melting point or softening point no lower than 45°C and which optionally contain up to 10% by weight of nonionic surfactants liquid at temperatures below 45°C/1 bar pressure is initially produced and is then converted by compaction at temperatures of at least 45°C into granules which are optionally further processed or aftertreated, with the provisos that

   the premix is substantially free from water,

   the premix contains at least one raw material or compound which is present in solid form at temperatures below 45°C/1 bar pressure, but which is present as a melt under the processing conditions, this melt acting as a multifunctional water-soluble binder which acts both as a lubricant and as a binder for the solid detergent compounds or raw materials during the production of the detergents, but has a disintegrating effect when the detergent is redissolved in aqueous liquor and

   in the aftertreatment step, the organic acids/organic anhydrides at least are added as a separate component.
10. The use of the detergent claimed in any of claims 5 to 7 or of a detergent produced by the process claimed in claim 8 or 9 in a machine washing process at temperatures of up to at most 60°C, preferably at temperatures below 60°C and more particularly in washing programs with temperatures of up to 40°C.