EP0828818B1 - Granular washing or cleaning agent with high bulk density - Google Patents

Abstract

A granular washing or cleaning agent with a high bulk density containing extruded components and anionic and/or non-ionic tensides in quantities of at least 15 wt.% and having improved solubility is to be prepared. The improved solubility is to be obtained in particular in that gelling is largely prevented when the agent is dissolved in water. This is achieved in that the agent contains at least two different granular components, at least one of which is extruded and at least one is not, where the extruded component(s) is/are present in quantities of 30 to 85 wt.% in relation to the whole of the agent, the tenside (including soap) content of the extruded component(s) is 0 to less than 15 wt.% in relation to the extruded component and there is at least one non-extruded, granular and tenside-containing component in the agent in quantities such that at least 1 wt.% in tensides, in relation to the whole of the agent, is prepared by this component.

Description

The invention relates to a granular washing or cleaning agent high bulk densities and improved dissolving properties.

The increasing increase in the bulk density of commercial detergent granules is mainly due to an increasingly compact grain structure of the Granules reached, whereby the porosity of the granules up to one almost complete removal of the connected pore system decreases. However, as the porosity decreases, it is generally undesirable Delayed detachment linked to deposits of detergent granules can lead to textiles.

This undesirable release delay is also caused by the fact that many surfactants, both anionic and nonionic and especially surfactant mixtures for redissolving in water for training tend from gel phases. Already with a surfactant content of 15% by weight and above, based on the means, it can be when the funds are redissolved undesirable gel-retardant gelling occurs in water.

European patent EP-B-0 486 592 describes granular or extruded materials Detergents or cleaning agents with bulk densities above 600 g / l are known, which anionic and / or nonionic surfactants in amounts of at least Contain 15 wt .-% and up to about 35 wt .-%. You will be following a procedure manufactured in which a solid, free-flowing premix, which a Contains plasticizers and / or lubricants at high pressures between 25 and 200 bar extruded and the strand after exiting the Hole shape by means of a cutting device to the predetermined granule dimension is cut. The extrudates produced can be retrofitted can be mixed with other granules, whereby in an advantageous Embodiment of the proportion of extrudates in the finished washing or detergents is more than 60% by weight.

From international patent application WO-A-93/15180 it is known that the dissolution rate of extruded agents can be improved by using short-chain alkyl sulfates, in particular C ₈ - to C ₁₆ -alkyl sulfates, which are used in a certain way in the premix the premix can be introduced. However, this measure is not sufficient in all cases to increase the dissolving speeds of the entire agent.

It was therefore the task of a granular washing or cleaning agent with high bulk density, which contains extruded parts and improved Has dissolving properties to provide. In particular, should the improved dissolving properties are achieved in that when dissolving gelling of the agent in water can be largely avoided.

The invention accordingly relates to a granular washing or Detergent with a bulk density above 600 g / l, containing one extruded component and anionic and / or nonionic surfactants in Amounts of at least 15 wt .-%, the agent at least two different has granular components, at least one of which extruded and at least one is not extruded, the extruded (n) Component (s) in amounts of 30 to 85 wt .-%, based on the total Means, in which means are contained, the content of the extruded Component (s) of surfactants (including soaps) 0 to less than 15 % By weight, based on the respective extruded component, is and at least one non-extruded granular and surfactant-containing component is contained in the amounts on average that at least by this component 1% by weight, based on the total composition, of surfactants becomes.

In the context of this invention, extruded components also become the granular components counted. In all cases where it is immaterial Whether a component is extruded or not is therefore the designation the granular component selected.

The total amount of surfactants, including soaps, in the detergents preferably 15 to 40% by weight and in particular 18 to 30% by weight.

Surfactants come in the granular components and in particular in the extruded components both anionic and anionic nonionic surfactants.

Preferred 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 a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, and their salts. Sulfated fatty acid glycerol esters are also suitable. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures, as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. The sulfonation products are a complex mixture which contains mono-, di- and triglyceride sulfonates with an α-position and / or internal sulfonic acid grouping. As by-products, sulfonated fatty acid salts, glyceride sulfates, glycerine sulfates, glycerin and soaps are formed. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of the α-sulfonated fatty acid disalts can be up to about 60% by weight, depending on the procedure.

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 ₁₆ -C ₁₈ alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C ₁₆ -C ₁₈ alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize. In a preferred embodiment of the invention, the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C ₁₂ -C ₁₄ fatty alkyl sulfates or C ₁₂ -C ₁₈ fatty alkyl sulfates with C ₁₆ -C ₁₈ fatty alkyl sulfates or C ₁₂ -C ₁₆ Fatty alkyl sulfates with C ₁₆ -C ₁₈ fatty alkyl sulfates. In a further embodiment of the invention, however, not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C ₁₆ to C ₂₂ are used. Mixtures of saturated sulfonated fatty alcohols predominantly consisting of C ₁₆ and unsaturated sulfated fatty alcohols predominantly consisting of C ₁₈ are particularly preferred, for example those derived from solid or liquid HD-Ocenol ^(R) fatty alcohol mixtures (commercial product of the applicant) . Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.

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 ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol 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.

However, preferred anionic surfactants are alkylbenzenesulfonates and / or both straight-chain as well as branched alkyl sulfates.

In addition to the anionic surfactants, soaps also come in, preferably Amounts of 0.1 to 5 wt .-%, based on the total agent, into consideration. For example, saturated fatty acid soaps are suitable, 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.

The anionic surfactants and 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 are preferably located Surfactants in the form of their sodium or potassium salts, especially in the form of Sodium 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, 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 5 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 include tallow fatty alcohol with 14 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 preferred non-ionic surfactants that either as the sole nonionic surfactant or in combination with others nonionic surfactants, especially together with alkoxylated Fatty alcohols and / or alkyl glycosides are used, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably with 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 are described or the preferably according to that in international patent application WO-A-90/13533 described methods are produced.

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 may be suitable. The amount of this nonionic Surfactants are preferably no more than that of the ethoxylated ones Fatty alcohols, especially not more than half of them.

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. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können. 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 known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.

According to the invention, the compositions contain at least 2 different granular ones Components whose only difference can be that one Component is extruded while the other component is after another Process was made. The differ advantageously extruded component (s) and the non-extruded component (s) but also in their composition.

In a preferred embodiment of the invention, the agents contain one or more extruded components, the proportion of extruded component (s) 50 to 80% by weight, based on the total agent, is. It is further preferred that at least one of the existing extruded components or in the event that only one extruded component is present then this extruded component Contains surfactants, the content of each extruded component Surfactants not more than 14% by weight, and preferably 6 to 13% by weight, each based on the extruded component. In another preferred embodiment of the invention, the agents contain surfactants extruded components in quantities such that 0.5 to 10 % By weight, based on the total agent, of surfactants are provided.

The extruded components can be by any of the known methods getting produced. However, a method according to is preferred the teaching of the European patent EP-B-0 486 592 or the teaching of the international Patent application WO-A-94/09111. The size of the preferred almost spherical extrudates is advantageously between 0.8 and 2 mm.

Contains the non-extruded granular and surfactant component Anionic surfactants or anionic and nonionic surfactants preferably in Amounts of 30 to 95 wt .-%, based on the non-extruded granular Component. In particular, it is preferred that the non-extruded granular component contains anionic surfactants, but free of non-ionic Is surfactants. Are advantageously used as anionic surfactants Alkylbenzenesulfonates and / or straight-chain and / or branched Alkyl sulfates used. The non-extruded granular and Surfactant-containing components are preferably in the amounts in the Contain agents that 2.25 to 30 wt .-%, in particular 5 to 25th % By weight, based in each case on the total composition, of surfactants become.

In a further preferred embodiment of the invention extruded components containing surfactants and non-extruded surfactants granular components used, the weight ratio extruded component containing tenside: non-extruded component containing tenside granular component greater than 30: 1 to 2: 1 and in particular 25: 1 to 3: 1, with weight ratios between 10: 1 and 5: 1, for example 8.5: 1 to 6: 1 can be particularly preferred.

The non-extruded granular component or the other non-extruded granular components, especially the surfactant-containing components, can by any of the methods known today, for example by means of Spray drying, superheated steam drying, spray neutralization or granulation have been produced. In particular, they contain anionic surfactants Components preferred by spray neutralization according to the German patent application DE 44 25 968 or by granulation and possibly simultaneous drying in a fluidized bed according to the teaching of international Applications WO-A-93/04162 and WO-A-94/18303 can be obtained. The grain size distribution of the non-extruded surfactant-containing granules should not be fundamentally different from those for reasons of homogeneity Grain size distributions of the other components, so that the grain size spectrum is not widened too much. Especially after the apprenticeship of WO-A-93/04162, granules in the fluidized bed can be almost produce any grain size and grain size distribution. Particularly preferred are therefore non-extruded surfactant-containing granules that are almost are spherical and have a grain size distribution that is also approximately the grain size distribution of another granular component, for example an enzyme granulate, a foam inhibitor granulate, one Bleach activator granules and in particular an extruded granulate corresponds.

Enzymes come from the class of proteases, lipases or lipolytic acting enzymes, amylases, cellulases or their mixtures in Question. Bacterial strains or fungi such as are particularly well suited Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens obtained enzymatic active substances. Preferably be Subtilisin-type proteases, and in particular proteases derived from Bacillus lentus are used. There are 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 lipolytically active enzymes or from protease, Amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially Protease- and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. examples for Such lipolytic enzymes are the well-known cutinases. Also Peroxidases or oxidases have proven to be suitable in some cases. The enzymes are preferably adsorbed on carriers and / or embedded in coating substances to prevent them from premature decomposition protect. The proportion of enzymes, enzyme mixtures or enzyme granules can for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight be.

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 and thus form a further granular component of the agents according to the invention. Mixtures of paraffins and bistearylethylenediamides and mixtures of paraffins and silicones on inorganic carriers are particularly preferred. Granules which contain mixtures of paraffins and silicones in a weight ratio of 1: 1 to 3: 1 are particularly preferred.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples of these are N-acyl or O-acyl compounds which form organic peracids with H ₂ O ₂ , preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN). The bleach activators contain bleach activators in the usual range. In particular, the bleach activators are introduced in granular form, that is to say as a further granular component, in the compositions according to the invention in amounts such that the compositions contain 1 to 10% by weight and preferably 3 to 8% by weight, in each case based on the total composition Bleach activator included.

Other ingredients of the agents according to the invention are preferably inorganic and organic builder substances, bleaches, substances, which have a positive effect on oil and fat washability, graying inhibitors, optionally substances which increase solubility and Dissolving speed of the individual granular components and / or the entire Improve agents, fabric softening agents, optical brighteners, Dyes and fragrances as well as alkaline and / or neutral salts in the form of their Sodium and / or potassium salts.

Suitable inorganic builder substance is, for example, fine crystalline, synthetic and bound water-containing zeolite in detergent quality. Zeolite A and / or P and, if appropriate, zeolite X and mixtures of A, X and / or P are particularly 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. Zeolites can be contained both in the extruded components and in the non-extruded granular components.

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 disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171. Crystalline layered sodium silicates can be contained both in the extruded and in the non-extruded granular components. However, they are preferably introduced into the composition in non-extruded granular form.

Amorphous silicates, so-called X-ray amorphous silicates, which do not give sharp X-ray reflections in X-ray diffraction experiments, 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, can have secondary washing power and as builder substances be used. It can even lead to particularly good builder properties if the silicate particles provide 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. Silicates and silicate compounds according to German patent application DE 44 00 024 or silicates and silicate compounds, for example those which are commercially available under the names Nabion 15 ^(R) and Britesil ^(R) (Akzo-PQ), are particularly preferred. Spray-dried sodium carbonate-sodium silicate compounds are also particularly preferred, which may additionally contain surfactants, in particular anionic surfactants such as alkylbenzenesulfonates or alkyl sulfates, including the 2,3-alkyl sulfates. Amorphous silicates and silicate compounds such as the above-mentioned silicate-carbonate compounds can also be contained in the extruded as well as in the non-extruded granular components.

In addition to the alkali carbonates or instead of the alkali carbonates, in particular the sodium carbonates, bicarbonates, in particular sodium bicarbonates, can also be present in the compositions. Sodium silicate with a molar ratio Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5 is primarily used as the amorphous silicate, and preferably from 1: 2 to 1: 3.0 as the amorphous silicate. The content of sodium carbonate and / or sodium bicarbonate in the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight. The sodium silicate content of the compositions is generally up to 30% by weight and preferably between 2 and 25% by weight.

Useful organic builder substances are preferred, for example polycarboxylic acids used in the form of their sodium salts, such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, Aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Suitable polymeric polycarboxylates are, for example, the sodium salts polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain. Their relative molecular mass, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. Ter- and Quadropolymers, for example those which according to DE-A-43 00 772 as Monomeric salts of 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.

Other suitable builder systems are oxidation products from carboxyl-containing polyglucosans and / or their water-soluble Salts such as those used in the international patent application WO-A-93/08251 are described or their production, for example, in of international patent application WO-A-93/16110.

Also known are the other preferred builder substances To name polyaspartic acids or their salts and derivatives.

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

The organic builder substances can be used both in the extruded and can also be used in the non-extruded granular components, use in the extruded component being preferred.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used. The bleaching agents can be contained both in the extruded and in the non-extruded components of the agent. It is preferred to introduce perborates into the composition via extruded components, while percarbonates are preferably used in the form of almost spherical, non-extruded granules.

In addition, the agents can also contain components which and grease washability from textiles positively. This effect becomes particularly clear when a textile that is already soiled is soiled previously several times with a detergent according to the invention that this oil and contains fat-dissolving component, is washed. Among the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion on methoxyl groups from 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ether, as well as the polymers known from the prior art Phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. These substances can be extruded as well also be included in the non-extruded granular components, where their content in the non-extruded granular components is preferred is.

Graying inhibitors have the task of removing the fiber To keep dirt suspended in the fleet and thus the rewinding of the To prevent dirt. For this purpose, water-soluble colloids are usually more organic Suitable in nature, for example the water-soluble polymeric salts Carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids the starch or the cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water-soluble, acidic Group-containing polyamides are suitable for this purpose. Farther soluble starch preparations and other than the above Use starch products, e.g. degraded starch, aldehyde starches, etc. Also Polyvinyl pyrrolidone is useful. However, cellulose ethers are preferred, such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their Mixtures and polyvinylpyrrolidone, for example in amounts from 0.1 to 5 % By weight, based on the composition. These substances can also both in the extruded and in the non-extruded granular Components may be included.

The agents can also contain components which increase the dissolution rate of the individual granular components and / or of the entire agent. The components preferably used include, in particular, C ₈ -C ₁₈ alcohols with 10 to 80 moles of ethylene oxide per mole of alcohol, for example tallow fatty alcohol with 30 EO and tallow fatty alcohol with 40 EO, but also fatty alcohols with 14 EO, and polyethylene glycols with a relative molecular weight between 200 and 2000. Other suitable substances are described, for example, in international patent application WO-A-93/02176.

The agents can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid 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 connections that instead the morpholino group is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present be, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

In particular, sulfates, optionally and in particular, can be used as neutral salts Chlorides may also be present in cleaning agents.

The above-mentioned further ingredients of the agents according to the invention can also be contained in the compositions as fine-grained components. Fine-grained components are understood to mean those which have a particle size have less than 0.2 mm. For reasons of homogeneity and around Such fine grain fractions are preferred to avoid separations however only in amounts not above 10% by weight and in particular not above 5% by weight in the compositions.

Some fine grain components can also be used to make existing ones To powder granules, thereby stickiness of the granules, for example to reduce and the bulk densities of the individual granules as well to increase total funds. Suitable such surface modifiers are known from the prior art. In addition to other suitable ones finely divided zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts, for example calcium stearate, but especially Precipitated silicas, mixtures of zeolite and silicas or mixtures from zeolite and calcium stearate preferred.

The bulk density of the granular washing or cleaning agents is above 600 g / l, preferably between 650 and 900 g / l. Because of the high Shares in spherical granules, the phenomenon occurs that the density of the granular agent after scooping with a currently commercially available Ladle from a commercial package, the so-called ladle density, is higher than the initially determined bulk density. Preferably the scooping density of the agents is above 650 g / l, in particular between 680 and 950 g / l. To such high bulk densities of the whole To achieve means, it is necessary that the individual and especially the granular components already have very high bulk densities exhibit. Advantageously, not more than 20% by weight and in particular not more than 15% by weight of the granular components and any existing fine grain contents a bulk density of less than 600 g / l.

Are particularly suitable for producing the agents according to the invention such procedures in which several sub-components, of which at least one is extruded, with non-extruded granular components, for example spray-dried and / or granulated components together can be mixed. It is also possible that spray-dried or granulated components afterwards in the preparation, for example with nonionic surfactants, especially ethoxylated fatty alcohols, be applied according to the usual procedures. It is the same possible and can be advantageous depending on the recipe if further individual components of the agent, for example carbonates, Citrate or citric acid or other polycarboxylates or polycarboxylic acids, polymeric polycarboxylates, zeolite and / or layered silicates, for example layered crystalline disilicates are mixed in, where the proportion of fine-grain fractions on average, that is to say particles with a Particle size below 0.2 mm, not above 15% by weight, in particular not above 5% by weight, based in each case on the total agent should.

Examples Example 1:

Two detergents were made with the same composition given below: composition in% by weight: (a) C ₉ -C ₁₃ alkylbenzenesulfonate 6.54 (b) Granules of 85% by weight of the sodium salts of coconut fatty alcohol sulfate and tallow fatty alcohol sulfate in a weight ratio of 1: 1, 12% by weight of sodium sulfate, the rest unsulfated components and water; produced by granulation and simultaneous drying in the fluidized bed 14.11 (c) C ₁₂ -C ₁₈ fatty alcohol with 7 EO 2.90 (d) Tallow fatty alcohol with 5 EO 0.47 (e) C ₁₂ -C ₁₈ fatty acid soap 0.80 (f) Caustic soda 0.36 (G) Zeolite A 18.47 (H) sodium 7.75 (i) Sodium silicate (Na ₂ O: SiO ₂ 1: 3.0) 1.45 (j) Copolymer sodium salt of acrylic acid 4.95 (k) Perborate monohydrate 14.02 (l) Tetraacetylethylenediamine granules 8.53 (m) Polyethylene glycol (molecular weight 400) 2.05 (n) Foam inhibitor granules containing silicone and paraffin 3.64 (O) Zeolite-silica mixture (weight ratio 1: 1) 1.50 (p) Sodium sulfate 3.45 (q) Enzyme granules containing protease, lipase and cellulase 1.60 (r) water 6.91 (s) Salts from solutions rest

Agent M1 according to the invention contained one according to the teaching of the European one Patent EP-B-0 486 592 extrudate made from the ingredients (a), (c) to (k), (m), (o) to (r) and (s). Component (o) was used for subsequent powdering of the extruded granules. The granular components (b), (l), (n) and (q) were mixed in afterwards.

The comparative agent V1 contained the same components with the difference that that component (b) was coextruded and only the components (l), (n) and (q) were subsequently mixed.

The surfactant content of both agents was thus 21.9% by weight without soap and 22.7% by weight with soap. In M1 were 9.9 wt .-% without soap and 10.7 % By weight of surfactants, including soap, are introduced via the extrudate and 12 % By weight of surfactants subsequently mixed in via component (b). In V1 however, the entire amount of surfactant was introduced via the extrudate.

The bulk density of agents M1 and V1 were 700 g / l and 710 g / l, respectively. The The induction behavior of both agents via the induction chambers is more commercially available Household washing machines was excellent. The grain spectrum of both agents was such that 99% by weight of all particles were not larger than 1.6 mm and more than 90% by weight of all particles were larger than 0.4 mm. Showed differences in a modified hand wash test in the dissolution behavior of the agents in water .

Note 1:

einwandfrei, keine erkennbaren Rückstände

Note 2:

tolerierbare, vereinzelte, noch nicht störende Rückstände

Note 3:

erkennbare, bei kritischer Beurteilung bereits störende Rückstände

ab Note 4:

deutlich erkennbare und störende Rückstände in steigender Anzahl und Menge

Here, 25 g of the test agent were sprinkled in a wash bowl made of dark plastic (for example dark red) in 5 l of tap water (30 ° C.). After 15 seconds, the agent was distributed in the bowl by hand. After a further 15 seconds, 1 blue terry towel was added to the wash liquor and moved as in a typical hand wash. After 30 seconds the wall of the bowl was wiped with the towel. Finally, after another 30 seconds, the towel was wrung out and visually graded. The meanings were:

Note 1:

flawless, no discernible residues

Grade 2:

tolerable, isolated, not yet disturbing residues

Note 3:

recognizable residues that are already annoying in the event of a critical assessment

from grade 4:

clearly recognizable and annoying residues in increasing number and quantity

Note 1:

einwandfrei, keine erkennbaren Rückstände

Note 2:

tolerierbare, vereinzelte, noch nicht störende Rückstände, sehr fein verteilt, bei Zugabe von Wasser nicht gelierend

Note 3:

erkennbare, bei kritischer Beurteilung bereits störende Rückstände,

ab Note 4:

deutlich erkennbare und störende Rückstände in steigender Anzahl und Menge, Agglomerat- bis Klumpenbildung, bei Zugabe von Wasser gelierend

The wash liquor was decanted off and the residue was also visually graded after treatment with 5 to 10 ml of water (bowl test). Here mean:

Note 1:

flawless, no discernible residues

Grade 2:

tolerable, isolated, not yet disturbing residues, very finely divided, non-gelling when water is added

Note 3:

recognizable residues that are already annoying in the event of a critical assessment,

from grade 4:

clearly recognizable and annoying residues in increasing number and quantity, agglomerate to lump formation, gelling when water is added

From Table 1 it can be seen that agent M1 according to the invention did not gel when water was added; the visual grading of the wrung-out towel was correspondingly good. The comparative detergent V1 gelled under the same test conditions and gave worse values in the visual grading of the towel. visual grading of agents M1 and V1 (tendency to gel) Bowl test towel M1 Grade 1-2 Grade 1-2 V1 Grade 4 Grade 3-4

Example 2:

This example demonstrates the influence of the surfactant content in the extruded component on the gelling when the agent is redissolved in water. In compositions V2 and V3, the surfactant content in the extruded component was increased compared to M1, and the proportion of the surfactant blended was reduced via component (b) (Table 2). The total surfactant content was 21.9% by weight without soap and 22.7% by weight with soap. Table 3 shows the results of the bowl test described in more detail above. medium M1 V2 V3 extruded component: (a) C ₉ -C ₁₃ alkylbenzenesulfonate 6.54 9.10 11.09 (c) C ₁₂ -C ₁₈ fatty alcohol with 7 EO 2.90 3.04 3.05 (d) Tallow fatty alcohol with 5 EO 0.47 0.46 0.46 (e) C ₁₂ -C ₁₈ fatty acid soap 0.80 0.80 0.80 Alkyl sulfate (active substance; (coconut fatty alcohol sulfate and tallow fatty alcohol sulfate in a weight ratio of 1: 1) via granules (b) as indicated above 12.0 9.3 7.3 Tendency to gel the agents M1, V2 and V3 (bowl test) Bowl test M1 Grade 1-2 V2 Note 3 V3 Grade 4

Claims (8)

1. A granular detergent with a bulk density above 600 g/l containing an extruded component and anionic and/or nonionic surfactants in quantities of at least 15% by weight, characterized in that the detergent contains at least two different granular components of which at least one is extruded and at least one is not extruded, the extruded component (s) being present in the detergent in quantities of 30 to 85% by weight, based on the detergent as a whole, the content of surfactants (including soap) in the extruded component(s) being 0 to less than 15% by weight, based on the particular extruded component, and at least one non-extruded granular and surfactant-containing component being present in the detergent in such quantities that this component provides at least 1% by weight of surfactants, based on the detergent as a whole.
2. A detergent as claimed in claim 1, characterized in that the non-extruded granular and surfactant-containing component contains anionic surfactants or anionic and nonionic surfactants in quantities of 30 to 95% by weight, based on the non-extruded granular component.
3. A detergent as claimed in claim 2, characterized in that the non-extruded granular component contains alkyl benzenesulfonates and/or linear and/or branched alkyl sulfates as anionic surfactants, but is preferably free from nonionic surfactants.
4. A detergent as claimed in any of claims 1 to 3, characterized in that non-extruded granular and surfactant-containing components are present in the detergent in such quantities that they provide 2.25 to 30% by weight and preferably 5 to 25% by weight - based on the detergent as a whole - of surfactants.
5. A detergent as claimed in any of claims 1 to 4, characterized in that the detergent contains one or more extruded components, at least one extruded component containing surfactants and the surfactant content of each extruded component being no more than 14% by weight and preferably between 6 and 13% by weight, based on the particular extruded component.
6. A detergent as claimed in any of claims 1 to 5, characterized in that the detergent contains surfactant-containing extruded components in such quantities that they provide 0.5 to 10% by weight - based on the detergent as a whole - of surfactants.
7. A detergent as claimed in any of claims 1 to 5, characterized in that the extruded components, preferably surfactant-containing extruded components, make up 50 to 80% by weight, based on the detergent as a whole.
8. A detergent as claimed in any of claims 1 to 7, characterized in that the ratio by weight of surfactant-containing extruded component to non-extruded surfactant-containing granular component is greater than 30:1 to 2:1, preferably 25:1 to 3:1 and, more particularly, 10:1 to 5:1.