EP0986629B2 - 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 granular detergents having bulk densities above 600 g / l, which separately or subsequently admixed organic acids, in particular citric acid, and are particularly suitable for cleaning colored textiles, and a method for producing the granular detergent. Furthermore, the use of the agents in machine washing processes at temperatures up to 60 ° C claimed.

Citric acid has long been known as a detergent ingredient. It was used primarily to reduce the pH of the mostly strong alkaline agent in the aqueous liquor, the added benefit was achieved that both the citric acid and obtained by the neutralization of citric acid citrate (Co) have builder properties.

For example, German Patent Application DE-A-28 27 571 (Akzo) generally describes laundry detergents which comprise a granular alkaline, in particular carbonate-containing, slower-dissolving component and from 5 to 30% by weight of a separate organic acid, preferably citric acid. This is achieved as part of an "acid prewash" in commercial household washing machines already at temperatures of 25 ° C by already dissolving at these temperatures citric acid softening of the liquor, so that at temperatures around 40 ° C at the beginning of dissolution of the alkaline component, the liquor already softened so 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 here. Other components of the means include, but are not limited to: Peroxy bleach such as perborates.

International patent application WO-A-91/17232 (P & G) also describes laundry detergents which contain as builder 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 to 10 wt .-% citric acid. Other ingredients include Peroxyblleichmittel such as perborate. While the granular compositions 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 adjusts the pH in 1% solution in water at 20 ° C to between 7 and 9.3 should be lowered, added later, as in Mitversprühung the citric acid in the spray-dried slurry, the neutralization of the citric acid would already be 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 again plays no role. Due to the relatively low pH in the aqueous liquor, the colors of colored textiles should be better preserved.

Granular detergents having a bulk density of 650 to 1100 g / l, which anionic and / or nonionic surfactants and as builder materials u.a. Contain 5 to 30 wt .-% sodium carbonate and / or bicarbonate and / or sesquicarbonate, according to the teaching of European Patent EP-B-0 534 525 (Henkel) good dispersing properties in the aqueous liquor, if they are used as further component contain up to 15 wt .-% subsequently added citric acid, said citric acid must have at least 80 wt .-% of particles having a particle size of 350 and 1500 microns. Both smaller particle sizes and coarser granules do not lead to the desired effect of increased dispersion in aqueous liquor. Other common ingredients include peroxy bleaches in the compositions.

As are used to reduce the pH in the aqueous liquor and water softening organic acids and especially citric acid in detergents, so are usually - as stated above - bleach and especially peroxy bleach such as perborate or percarbonate in detergents usually in amounts of 15 wt .-% and above used to remove bleachable stains from textiles.

Bleaching agents, however, not only have the effect of removing bleachable stains from textiles, they also often attack colored fabrics, especially in the oxidation-sensitive grades of textile dyes, so that over time the intensity of the textile dyes diminishes and the fabrics look "washed out" , The use of bleaching agents can also lead to punctiform color removal on the textiles, the so-called pinhole spotting effect. For some time, therefore, detergents are commercially available which are explicitly used for colored textiles and therefore have no or only small amounts, for example less than 10 wt .-%, based on the total agent, of bleaching agents. With such small amounts, the bleaching agent is for hygienic purposes only; the risk of color removal or staining of the textiles by the bleach are then almost impossible. Nonetheless, stain removal from colored textiles is still a problem.

It has now been found that the use of separately or subsequently admixed organic acids / organic acid anhydrides, in particular of citric acid, in support of the removal of bleachable stains on textiles, when the detergent used is substantially free of bleach.

The invention therefore provides a granular detergent as defined in claim 1.

The invention also provides a process for the preparation of a granular detergent having the features defined in claim 4.

As organic acids it is preferred to use those which are known to also have a significant builder effect. These organic acids include all those which are already listed in the German patent application DE 28 27 571. The polyhydroxydicarboxylic acids mentioned in international patent application WO-A-94/04650 can also be used. Particularly preferred are citric acid, 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, especially succinic anhydride and maleic anhydride are preferred. With particular preference, citric acid is used. In contrast to the teaching of the international patent application WO-A-94/06450, citric acid has a better bleaching performance over a wide variety of stains than, for example, tartaric acid, although tartaric acid can achieve better results on targeted stains in the bleaching area than citric acid.

The organic acids / organic acid anhydrides are used as raw material, ie not in the form of a processed compound and are therefore present in the inventive compositions as a separate or subsequently admixed component. By "separately admixed" is meant that the organic acid is mixed as one of several components with the other components to the detergent. Depending on the manufacturing process, it is also possible that all other components are first prepared and optionally premixed with each other and possibly further shaping steps of the mixed components are carried out and the organic acid is added afterwards, ie "subsequently added". The organic acids can be mixed in their commercial form with the other components. Finer-particle grades with at least 80% by weight smaller than 350 μm or coarser qualities with at least 80% by weight greater than 1500 μm are available. The coarser product with particle diameters of at least 80 wt .-% greater than 1500 microns is used in the inventive compositions without sacrificing performance. This coarser article may even be aesthetically advantageous when blended into components which also have a coarser grain spectrum, for example granules or extrudates, which may optionally be rounded, and at least 80% by weight of particles having a particle diameter above 400 microns, and in particular those having an average particle diameter of 0.8 to 1.4 mm. A coarser product of organic acids, as defined in claim 4, in particular citric acid, consists of at least 80 wt .-% of particles having a particle size between 1500 and 2000 microns. Even more finely divided product (80 wt .-% less than 350 microns) can be used in principle. However, it then preferably serves for dusting off the granular components and should advantageously not be present as a separate component in the agents. According to claim 1, in addition to the above-mentioned coarse-grained quality with at least 80 wt .-% of particles having a particle diameter greater than 1500 microns and this finely divided product with particle diameters of at least 80 wt .-% less than 350 microns.

Granular detergents are understood to mean particulate detergents which comprise at least 60% by weight of particles having a particle size of more than 350 μm and preferably contain at least one component which has at least 80% by weight a particle size of more than 350 μm. In particular, the granular agents consist of at least 60% by weight, preferably from 70 to 100% by weight, of components which have at least 80% by weight of a particle size of more than 350 μm.

The bulk density of the funds is of less importance, since the effect of the invention is not dependent on the bulk density. However, compact detergents or so-called concentrates having bulk densities above 600 g / l are preferred. Granular detergents having bulk densities between 650 and 1100 g / l are claimed according to the invention, bulk densities above 700 g / l and in particular above 750 g / l being particularly preferred.

The organic acids / organic acid anhydrides are used in the inventive compositions in amounts of from 1 to 15 wt .-%, but preferably in amounts of less than 10 wt .-% and in particular in amounts of 2 to 6 wt .-%. Finely divided qualities with particle diameters of at least 80% by weight of less than 350 μm, based on the total composition, are preferably not more than 2% by weight and in particular not more than 1% by weight. In the detergents according to the invention as defined in claim 1, both coarse (at least 80 wt .-% greater than 1500 microns) and finely divided (at least 80 wt .-% less than 350 microns) contain organic acids, the proportion of finely divided organic acids the total amount The organic acids used preferably at most 50 wt .-% and in particular 5 to 30 wt .-%.

The compositions according to the invention contain less than 10% bleach and are in particular substantially free from peroxy bleach, being understood in the context of this invention to be "substantially free of" from 0 to 10% by weight. In a preferred embodiment, the agents are absolutely free of bleaches. However, if in minor amounts, for example in amounts of 2 to 8 wt .-%, based on the total agent, bleaches should be used, the usual Peroxyblleichmittel such as, perborate tetrahydrate and / or percarbonate are preferred.

The essential ingredients of the compositions of the invention also include anionic and / or nonionic surfactants, wherein it is particularly preferred if the agents contain both anionic and nonionic surfactants.

As anionic surfactants of the sulfonate type are preferably C ₉ -C ₁₃ alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are, for example, from C ₁₂ -C ₁₈ monoolefins with terminal or internal double bond by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. The use of said alkylbenzenesulfonates is particularly preferred.

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

Other suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof, as in the preparation by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained.

Examples of alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example 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) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing-technical interest, C ₁₂ -C ₁₆ -alkyl sulfates and C ₁₂ -C ₁₅ -alkyl sulfates and C ₁₄ -C ₁₅ -alkyl sulfates are particularly preferred. 2,3-Alkyl sulfates, which are prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products of Shell Oil Company under the name DAN (R), are suitable anionic surfactants.

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

Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the 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 of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides). Particularly preferred are the sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate.

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

Suitable anionic surfactants also include soaps, which are preferably present in amounts of from 0.5 to 3% by weight, based on the finished compositions. Particularly suitable are 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 of 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, it is also possible to use the known alkenylsuccinic acid salts. The proportion of soaps and alkenylsuccinic acid salts in 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 may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases such as mono-, di- or triethanolamine. Preferably lie the anionic surfactants 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 on average 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 linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, palm kernel, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are 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 of these, 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 means which, for a particular product, may be an integer or a fractional number. 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 include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Another class of preferred nonionic surfactants 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 from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described for example in Japanese Patent Application JP 58/217598 or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533. Particularly preferred are C ₁₂ -C ₁₈ fatty acid methyl esters having an average of 3 to 15 EO, in particular having an average of 5 to 12 EO.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

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.Further suitable surfactants are polyhydroxy fatty acid amides of the formula (I)

in R ² CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{3 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands. The polyhydroxy fatty acid amides are preferably derived from reducing sugars having 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 the R ^{3 is} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{5 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C ₁ -C ₄ -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain having at least two hydroxyl groups is substituted, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group. [Z] is also obtained here preferably 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 into the desired polyhydroxy fatty acid amides, for example according to the teaching of international patent application WO-A-95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is usually a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. 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, 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 dimer alcohol bis- and trimeralcohol trissulfates 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 earlier German patent application P 195 13 391.9 are distinguished in particular by their bi-and multifunctionality. Thus, the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.

However, it is also possible to use gemini polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO95-A- / 19955.

Optionally, other surfactants such as amphoteric surfactants, cationic surfactants and / or zwitterionic surfactants may be included in the inventive compositions. For example, cationic surfactants having scavenging properties can be used to increase the softness of the fabrics after washing or after drying.

The content of anionic and / or nonionic surfactants in the compositions according to the invention is preferably 15 to 40% by weight, in particular 20 to 35% by weight, advantageously at least one nonionic anionic surfactant and at least one nonionic surfactant and optionally soap contained in the funds.

Agents which have a content of nonionic surfactants of at least 2% by weight, preferably of at least 4% by weight, for example of at least 5% by weight, have been found to be particularly effective, the contents of non-ionic surfactants being between 5 and 12 wt .-% are particularly preferred, especially when the agents are used at low temperatures below 50 ° C. Although a content of nonionic surfactants above 12 wt .-% may in principle lead to a further increase in the performance of the funds, however, it has been found in several cases that the granular agents with such high Niotensidgehalten increasingly lose flowability and sticking can tend to clumping. For this reason, amounts of nonionic surfactants above 12 wt .-% 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, in particular if the soap content, based on the total surfactant content, is at most 5% by weight ,

In addition to the surfactants mentioned and in particular in addition to the organic acids, the agents according to the invention normally contain customary further inorganic and / or organic builders in conventional amounts. In this case, for example, 10 to 30 wt .-% of additional builders may be included in the agents.

The inorganic builders include above all zeolites, crystalline phyllosilicates, carbonates, amorphous silicates and, to a lesser extent, phosphates.

The fine crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As the zeolite P, for example, zeolite MAP ^(R) (commercial product of Crosfield) may be contained in the agents. However, zeolite X and mixtures of A, X and / or P are also suitable. The zeolite can be used as spray-dried powder or else as undried, still moist, stabilized suspension of its preparation. 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 wt .-%, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22 wt .-% 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 is up to 20 and preferred values for x are 2, 3 or 4. Such crystalline sheet 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 is 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 having a modulus Na ₂ O: SiO _{2 of} 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 delay-delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification 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 do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which likewise have a dissolution delay compared with the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates. Their content is generally not more than 25 wt .-%, preferably not more than 20 wt .-%, each based on the finished composition. In some cases it has been shown that in particular tripolyphosphates even in smaller amounts, for example up to a maximum of 10% by weight, based on the finished composition, in combination with other builder substances lead to a synergistic improvement in the secondary washing power.

As carbonates, both the monoalkali metal salts and the dialkali metal salts of carbonic acid as well as sesquicarbonates can be contained in the compositions. Preferred alkali metal ions are sodium and / or potassium ions. The carbonate content or the bicarbonate content of the compositions is preferably 5 to 20% by weight, although in one embodiment it may be preferred to separate the carbonate and / or bicarbonate at least partially as a further component or to be added later. Compounds of, for example, carbonate, silicate and optionally other auxiliaries such as, for example, anionic surfactants or other, in particular organic builders, may be present as a separate component in the finished compositions. Another component which can be added later is silicate, for example metasilicate and / or crystalline layered disilicate. Overall, it is preferable to admix the abovementioned subsequently admixed constituents, but in particular carbonate, bicarbonate, metasilicate - as described above for the citric acid - in coarse-grained form, it being particularly advantageous if carbonate, bicarbonate and / or metasilicate to at least 50 wt .-% have a particle size above 1 mm and in particular at least 50 wt .-% above 1.2 mm. In a preferred embodiment of the invention, the alkaline liquor in aqueous liquor, admixed or separately admixed components, in particular carbonate, bicarbonate and / or metasilicate and / or crystalline layered disilicate, in amounts of 1 to 15 wt .-%, advantageously in amounts from 2 to 10% by weight.

Useful organic builders are, for example, usable in the form of their sodium salts 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 environmental reasons, and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. The salts of the polycarboxylic acids may be included in the agents in addition to the organic acids; however, their presence in the agents is less preferred.

Other suitable organic builder substances whose use in addition to the organic acids can certainly provide advantages are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preference is given to hydrolysis products having average molecular weights in the range from 400 to 500,000. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a customary measure of the reducing one Effect of a polysaccharide compared to dextrose, which has a DE of 100. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2000 to 30,000.

Other suitable co-builders 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 present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such co-builders are described, for example, in 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 having a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 5000 to 200,000, preferably from 10,000 to 120,000 and in particular from 50,000 to 100,000.

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

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

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

Further suitable builder substances are oxidation products of carboxyl-containing polyglucosans and / or their water-soluble salts, as described, for example, in International Patent Application WO-A-93/08251 or the preparation of which is described, for example, in International Patent Application WO-A-93/16110. Also suitable are oxidized oligosaccharides according to the German patent application DE 196 00 018.

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as described in European Patent Application EP-A-0 280 223. Preferred polyacetals are obtained 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 compositions may also contain components that positively affect oil and grease washability from fabrics. This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component. The preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose having a methoxyl group content of 15 to 30% by weight and hydroxypropoxyl groups of 1 to 15% by weight, respectively based on the nonionic cellulose ether, and the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

In addition to the ingredients mentioned, the compositions may contain known additives conventionally used in detergents, for example foam inhibitors, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, grayness inhibitors, small amounts of neutral filler salts and dyes and fragrances.

When used in automatic washing processes, it may be advantageous to add conventional foam inhibitors to the compositions. As 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 foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide. With advantages also mixtures of different foam inhibitors are used, eg those from silicones, paraffins or To grow. Preferably, the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bisstearylethylenediamides are preferred.

The salts of polyphosphonic acids used are preferably the neutral-reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriamine penta-methylenephosphonate or ethylenediamine tetramethylenephosphonate in amounts of from 0.1 to 1.5% by weight.

Suitable enzymes are, in particular, those from the class of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains, and graying. Cellulases and other glycosyl hydrolases can contribute to color retention and increase the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer.

Particularly suitable are enzymatic agents obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved 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 are also called cellobiases, or mixtures thereof used. Since the different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of the cellulases can be used to set the desired activities.

The enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation. The proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.

As enzyme stabilizers, the agents may contain, for example, from 0.5 to 1% by weight of sodium formate. 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, it is particularly advantageous to use 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 pyroboric acid (tetraboric acid H ₂ B ₄ O ₇ ).

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. 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 of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful. However, preference is given to cellulose ethers, such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and polyvinylpyrrolidone, for example, in amounts of from 0.1 to 5% by weight, based on the compositions, used.

The agents may contain as optical brighteners derivatives of Diaminostilbendisulfonsäure or their 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 similarly constructed compounds which, instead of the morpholino group, a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene 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). Mixtures of the aforementioned brightener 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 preparation of the granular detergents of the present invention may be carried out by any known method such as spray drying, granulation, compaction, pelleting, extrusion in combination with one or more post-processing operations which include shaping steps, drying or surface modification with liquid to waxy or solid materials, and blending operations. wherein at least the organic acid, in particular the citric acid, but optionally also other components separately or be subsequently mixed and thus an agent is prepared which contains the organic acids in the finished product as a separate component. Advantageously, granulation and extrusion methods are used to achieve the high bulk density. Particularly preferred here is an extrusion process 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 prepared according to the teaching of EP-A-0931137, wherein the granulation or extrusion process is modified such that first a solid premix is prepared which contains individual raw materials and / or compounds be 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 contains up to 10 wt .-% at temperatures below 45 ° C and a pressure of 1 bar liquid nonionic surfactants, and converted using compaction forces at temperatures of at least 45 ° C into a grain and optionally subsequently further processed or processed, with the provisos that

• the premix is substantially 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 under the processing conditions as a melt, this melt serving as a polyfunctional, water-soluble binder, which exerts both the function of a lubricant and an adhesive function for the solid washing or Reinigungsmittelompounds- or raw materials in the preparation of the agent, in contrast, the disintegration of the agent in aqueous liquor disintegrating acts and
• in the treatment step, at least the organic acids are admixed as a separate component.

The compositions according to the invention or the compositions prepared according to the invention have significant advantages, in particular on bleachable stains. However, other advantages can also be found, for example, in enzymatic soiling, while the primary washing performance is to be classified as equal to greasy and pigment-containing stains on average. Surprisingly, the advantages occur especially at the bleachable stains even at washing temperatures of 60 ° C and below. In a further preferred embodiment of the invention, therefore, the use of the compositions according to the invention or the compositions according to the invention in a mechanical washing process at temperatures up to 60 ° C, preferably at temperatures below 60 ° C and in particular in washing programs with temperatures up to 40 ° C claimed , Also in the hand wash at 30 ° C or to 40 ° C, the compositions of the invention show advantages.

Examples

The performance testing of the primary washing capacity was carried out under practical conditions in household washing machines (Miele Novotronic W918). For this purpose, the machines were charged with 3.5 kg of clean filling laundry and 0.5 kg of test fabric. The test fabrics were cotton and impregnated with the natural and artificial soils detailed below. The stains showed an aging of 5 to 6 days.

Washing conditions for primary washing power:

Tap water of 16 ° d (equivalent to 160 mg CaO / l), detergent used per agent and machine 76 g, washing temperature 40 ° C or 60 ° C (color wash program, 60-minute wash), 5-fold determination.

Evaluation (artificial soiling): The measurement of the remission% R (460 nm / FL46, suppression of the brightener effect) was carried out with the Spectraflash 503 device.

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

In addition to greasy and pigmented stains, the following artificial bleachable and enzymatic stains were tested for cotton: red wine (R), tea (T), cocoa (K), forest berry (W) and milk cocoa (MK).

In addition to greasy, pigmented and enzymatic soiling, the following natural bleachable soils 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 V V1 M2 V2 V3 Basic granulate 1 88.0 92.0 88.0 ---- ---- ---- Basic 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 prepared in accordance with the teaching of European patent EP-B-0 486 592 and had essentially the following composition: 14% by weight of anionic surfactants (alkylbenzenesulfonate and fatty alkylsulfate), in addition 2% by weight of soap, 8% by weight. % ethoxylated fatty alcohols, 40 wt .-% zeolite (based on anhydrous active substance), 7 wt .-% trisodium citrate dihydrate, 5.5 wt .-% copolymer of acrylic acid and maleic acid, 8 wt .-% sodium carbonate, 2 wt. -% polyvinylpyrrolidone (balance: water and salts from solutions). The bulk density was 780 to 800 g / l. A base granule prepared by conventional granulation densification and having about the same composition and bulk density gave comparable results.

The base extrudate 2 was prepared according to the teaching of EP-A-0931137 and had essentially the following composition: 23% by weight of anionic surfactants (alkylbenzenesulfonate and fatty alkylsulfate), in addition 1% by weight of soap, 8% by weight of ethoxylated fatty alcohols, 27.5 wt .-% zeolite (based on anhydrous active substance), 12 wt .-% trisodium citrate dihydrate, 5.5 wt .-% copolymer of acrylic acid and maleic acid, 6.5 wt .-% sodium carbonate and 5 wt. -% 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 the weight ratio 1: 1: 1.

The "coarse" grades of citric acid and citrate had more than 50% by weight of particles with a particle diameter above 1.5 mm.

The foam inhibitor granules were a paraffin frother 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 compositions according to the invention have clear advantages over bleachable soilings (in particular at 40 ° C.) compared with the comparison agents, and in some cases also on enzymatic soiling. On greasy soils and pigmented soils, the results were comparable on average at both 40 ° C and 60 ° C. In the case of cosmetic soilings, significant advantages were again achieved in certain cases for the compositions according to the invention (not listed in tables).

Examples M1 and V1 were repeated with citric acid other than organic acids: succinic anhydride, tartaric acid and malic acid. Again, there were clear advantages over V1; However, citric acid gave the best results over all soils. Table 1: Primary washability of M1 (% reflectance) 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) 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 washing capacity 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 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 (remission 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 capacity of M2 (color 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 (6)

1. Granular washing composition having a bulk density of 650 g/l to 1100 g/l, comprising anionic and/or nonionic surfactants and also builder substances including 1 to 15% by weight of a separately or subsequently added organic acid/organic acid anhydride, characterized in that the composition, based on the overall composition, contains less than 10% by weight of bleach and the organic acids/organic acid anhydrides have a particle size distribution of at least 80% by weight of the particles larger than 1500 µm, and finely divided organic acids/organic acid anhydrides with particle sizes of at least 80% by weight smaller than 350 µm are additionally present.
2. Composition according to Claim 1, characterized in that it comprises, as the organic acid/organic acid anhydride, citric acid, tartaric acid, succinic acid, succinic anhydride, maleic acid, maleic anhydride and/or malic acid, especially citric acid.
3. Composition according to one of Claims 1 and 2, characterized in that it comprises, in addition to the organic acid/the organic acid anhydride, at least one constituent which has an alkaline reaction in aqueous liquor in subsequently or separately added form, and the post-mixed or separately added constituents which have an alkaline reaction in aqueous liquor, especially carbonate, bicarbonate and/or metasilicate and/or crystalline sheet disilicate, are present in amounts of 1 to 15% by weight, advantageously in amounts of 2 to 10% by weight.
4. Process for producing a granular washing composition having a bulk density of 650 g/l to 1100 g/l, comprising anionic and/or nonionic surfactants and also builder substances including 1 to 15% by weight of organic acids/organic acid anhydrides having a particle size distribution where at least 80% by weight of the particles have a size between 1500 µm and 2000 µm, and also, based on the overall composition, less than 10% by weight of bleach, characterized in that the composition is produced by customary methods such as spray-drying, granulation, compaction, pelletization, extrusion in combination with one or more subsequent processing operations which include shaping steps, drying or surface modification with liquid to waxy or solid substances and mixing operations, and at least the organic acid/the acid anhydride, especially the citric acid, but if appropriate also further components, are admixed separately or subsequently in order to produce a composition which comprises the organic acids/acid anhydrides as a separate component in the finished product.
5. Process according to Claim 4, characterized in that the composition is produced by a granulation or extrusion process, the granulation or extrusion process being modified such that a solid premixture which comprises individual raw materials and/or compounds which are present in solid form at room temperature and a pressure of 1 bar and have a melting point or softening point which is not below 45°C, and optionally comprises up to 10% by weight of nonionic surfactants liquid at temperatures below 45°C and a pressure of 1 bar, is first produced and converted to a granule using compaction forces at temperatures of at least 45°C and is optionally subsequently processed further or finished, with the provisos that

   o the premixture is essentially anhydrous and

   o at least one raw material or compound which is present in solid form at a pressure of 1 bar and temperatures below 45°C, but which is present as a melt under the processing conditions, this melt serving as a polyfunctional water-soluble binder which, in the production of the compositions, performs both the function of a lubricant and an adhesive function for the solid washing or cleaning composition compounds or raw materials, but has a disintegrating action in the redissolution of the composition in aqueous liquor, is present in the premixture, and

   o in the finishing step, at least the organic acids/acid anhydrides are added as a separate component.
6. Use of a composition according to one of Claims 1 to 3 or of a composition produced according to one of Claims 4 or 5 in a machine washing process at temperatures up to a maximum of 60°C, preferably at temperatures below 60°C and especially in wash programmes with temperatures up to 40°C.