EP0746601B1 - Granular washing or cleaning agent - Google Patents

Abstract

Described are extruded washing or cleaning agents containing bleach, the washing or cleaning agents having an improved soil-releasing capability by virtue of the fact that they are made up of at least two extrudates. Extrudate I contains 20 to 50 % by wt. of surfactants and no bleach while extrudate II contains 0 to 15 % by wt. of surfactants and 20 to 60 % by wt. of bleach. The surfactants in extrudate II are preferably anionic surfactants such as alkyl or alkenyl sulphates and/or alkylbenzene sulphonates.

Description

The invention relates to a granular detergent or cleaning agent which a high proportion of extruded components and an improved Has dissolving behavior.

From the international patent application W0-A-91/02047 granules for Use in washing or cleaning agents known, which by extrusion be preserved. A homogeneous premix with the addition of a Plasticizer and / or lubricant extruded under pressure (extruded). The extrudates produced in this way can be retrofitted with others Ingredients of detergents or cleaning agents, these ingredients preferably in granular form, especially in extruded form Form can be prepared.

International patent application WO-A-93/02176 discloses that extrudates have an improved dissolving behavior when the liquid used Nonionic surfactants used in intimate mixing with a structure breaker become.

The object of the invention was both to dissolve the extrudate Detergents or cleaning agents in the washing or cleaning liquor as well as the induction behavior of extrudate-containing detergents to improve.

The invention accordingly relates to the first embodiment a granular washing or cleaning agent containing granules, which be produced by extrusion, the agent having at least two partial extrudates contains, of which the partial extrudate I 20 to 50 wt .-%, based on the partial extrudate I, contains surfactants and is free from bleaching agents and the partial extrudate II 0 to 15 wt .-%, based on the partial extrudate II, surfactants and contains 20 to 60% by weight of bleach.

The agents according to the invention can also contain further granular ones, in particular contain extruded components that are added to the mixture of these two partial extrudates are added. In particular, however, are means preferred, which contain a partial extrudate I, which contains surfactants from 25 to 40 wt .-% and a content of builder substances from the Group of zeolites (based on anhydrous active substance) and others Silicates, such as the amorphous silicates and the crystalline layered silicates, from 20 to 60% by weight.

All known anionic, nonionic, amphoteric and zwitterionic surfactants are suitable as surfactants. Suitable anionic surfactants of the sulfonate type are preferably the known C ₉ -C ₁₃ alkylbenzenesulfonates, α-olefinsulfonates and alkanesulfonates. Esters of α-sulfofatty acids or the disalts of α-sulfofatty acids are also suitable. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those used in the production by esterification of a monoglycerol with 1 to 3 mols of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mols of glycerol be preserved.

In particular, however, anionic surfactants of the sulfate type are like the salts the sulfuric acid monoester from primary alcohols natural and synthetic Origin preferred.

As alk (en) yl sulfates, the alkali metal salts and in particular the sodium salts of the sulfuric acid half esters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ₁₀ -C ₂₀ oxo alcohols, and preferred those secondary alcohols of this chain length. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical 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 and in particular C ₁₂ -C ₁₆ -Fatty alkyl sulfates with C ₁₆ -C ₁₈ fatty alkyl sulfates. In a further preferred 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.

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. Due to their high foaming behavior, they are only used in relatively small amounts in detergents.

Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, also known as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols represent. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or use their salts.

Other constituents of the partial extrudates I to be used according to the invention can be soaps, for example in amounts of 0.5 to 5% by weight. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid or behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. In particular, those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C ₁₂ -C ₂₄ fatty acid soaps.

The anionic surfactants and the soaps can be in the form of their alkali salts such as the sodium, potassium or ammonium salts and as soluble organic salts Bases, such as mono-, di- or triethanolamine, are present. Preferably are the anionic surfactants and soaps in the form of their sodium or potassium salts, especially in the form of the sodium salts.

The content of the partial extrudates I in anionic surfactants is preferably 10 to 35 wt .-%, in particular 15 to 30 wt .-% fatty alk (en) yl sulfates and / or alkylbenzenesulfonate.

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 can 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 alcohol 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 E0. 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). The partial extrudates I preferably contain 2 to 15% by weight of alkoxylated C ₈ -C ₁₈ alcohols and in particular 5 to 10% by weight of ethoxylated C ₁₂ -C ₁₈ alcohols.

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 used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as for example in the Japanese patent application JP-A-58/217598 are described or which are preferably according to the in the international patent application W0-A-90/13533 become. These and other surfactants described in JP 06/116599, which prevent gelation can also improve the Dissolving speed can be used. More structure breakers that instead of these surfactants or can also be used are the Description can be found in the international patent application WO-A-93/02176.

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. The content of partial extrudates I in alkyl glycosides is generally about 0 to 5% by weight and preferably 0.5 to 3% by weight.

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 and the alkoxylated fatty acid alkyl esters, in particular not more than half of it.

in der R²CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R³ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. 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.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 finely crystalline, synthetic and bound water-containing zeolite used as builder substance is preferably zeolite NaA in detergent quality. However, zeolite X or zeolite P and mixtures of NaA and NaX are also suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. 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 or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water.

Layer substitutes are suitable substitutes or partial substitutes for the zeolite natural and synthetic origin. Such layered silicates are, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405. Their usability is not one special composition or structural formula limited. Are preferred here, however, smectites, especially bentonites.

Further suitable substitutes or partial substitutes for the zeolite are crystalline, layered sodium silicates of the general formula (II) 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 Number is 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 (II) are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

Amorphous silicates, in particular sodium silicates with an Na ₂ O: SiO ₂ ratio of 1: 2.0 to 1: 3.0, preferably up to 1: 2.5, and / or carbonate-silicate compounds such as are also suitable they are commercially available as substitutes for the zeolite.

In the context of the invention, the term “amorphous” also means “X-ray amorphous” Roger that. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections as they do for crystalline ones Substances are typical, but at most one or more maxima scattered x-rays that are several units wide of the diffraction angle. However, it may very well be too special good builder properties lead when the silicate particles in electron diffraction experiments provide washed-out or even sharp diffraction maxima. This is to be interpreted as meaning that the products are microcrystalline Have ranges of size 10 to a few hundred nm.

The zeolite content of the partial extrudates I (based on anhydrous active substance) and / or on amorphous silicates and / or carbonate-silicate compounds and / or optionally crystalline layered silicates is preferably 25 to 50 wt .-% and in particular 25 to 45 wt .-%, with the Use of zeolite and crystalline layered silicates (II) a weight ratio 4: 1 to 1: 2, advantageously from 3: 1 to 1: 1, in particular is preferred. For mixtures of zeolite and X-ray amorphous silicates or carbonate-silicate compounds are weight ratios of 3: 1 to 1 : 3 and in particular from 2: 1 to 1: 2 are preferred.

In addition, organic builder substances can also be used. Useful organic builder substances are preferred, for example polycarboxylic acids used in the form of their salts, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided such use ecological reasons are not objectionable, as well as mixtures of these. Preferred salts are the sodium salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. Their content in the partial extrudates I can generally 0 to 15 wt .-%.

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. In particular, polymeric polycarboxylates also preferred terpolymers described in the older German patent DE-C-42 21 381 and the older German patent application DE-A-43 00 722 to be discribed. The content of polymeric polycarboxylates and inclusive the terpolymers is preferably 2 to 7% by weight.

Other suitable ingredients of the partial extrudates I are - as already mentioned in part - water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these; In particular, alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used. The sodium carbonate content of the partial extrudates I is preferably up to 20% by weight, advantageously between 2 and 15% by weight. The content of amorphous sodium silicate in the agents is generally up to 10% by weight and preferably between 1 and 5% by weight if the silicate is not used as a builder, because then the content can also significantly exceed 10% by weight .

In addition to the ingredients mentioned, the partial extrudates I can contain other known additives commonly used in detergents, for example Graying inhibitors, salts of polyphosphonic acids, enzymes, enzyme stabilizers, small amounts of neutral filling salts and, if necessary Dyes and fragrances, opacifiers or pearlescent and optical Brightener included. However, the enzymes are advantageous not as components of partial extrudates I or II, but as a component another preferred granular component that also extrudes can be used.

In addition, the agents can also contain components that the oil and Influencing fat 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 of phthalic acid known from the prior art and / or terephthalic acid or its derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates.

Graying inhibitors have the task of detaching from the fiber Keep dirt suspended in the fleet and prevent graying. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, Glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids Starch or the cellulose or salts of acidic sulfuric acid esters Cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Furthermore, soluble ones Use starch preparations and other starch products than those mentioned above, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, cellulose ethers such as carboxymethyl cellulose are preferred. Methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures used. Carboxymethyl cellulose (sodium salt), Methyl cellulose, methyl hydroxyethyl cellulose and their mixtures and polyvinyl pyrrolidone are preferred, for example in amounts of 0.1 to 5 % By weight, based on the partial extrudates I, used.

The salts of polyphosphonic acids are preferably the neutral ones Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and Diethylenetriaminepentakis (methylenephosphonate) in amounts of 0.1 to 1.5 % By weight used.

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.

The partial extrudate II preferably contains 0.1 to 15% by weight and in particular 2 to 12 wt .-%, each based on the partial extrudate II, surfactants such as given above, anionic surfactants and in particular alk (en) yl sulfates and / or alkylbenzenesulfates are preferred. The content of Soaps as above can range from 0 to about 2% by weight.

In particular, the partial extrudates II contain 30 to 55% by weight, advantageously 40 to 50% by weight, of peroxy bleaching agent, with perborate monohydrate, perborate tetrahydrate or percarbonate being particularly preferred. However, other useful peroxy bleaches are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. Furthermore, the partial extrudates II can contain inorganic and organic builder substances as indicated above. It is preferred that these builder substances are present in amounts not exceeding 35% by weight, in particular in amounts of 10 to 30% by weight, based in each case on partial extrudate II.

In a further particularly preferred embodiment of the invention the partial extrudate II is a foam inhibitor based on silicone and / or paraffin. It was surprisingly found that the effectiveness of the foam inhibitor can be raised after storage of the agent if it is not incorporated into partial extrudate I or subsequently mixed in, but is incorporated into the partial extrudate II.

The washing or cleaning agents according to the invention can be the partial extrudates I and II included in a wide weight ratio. It is however, it is particularly preferred that the agents partial extrudate I and partial extrudate II in a weight ratio greater than 1: 1, preferably from 1.2: 1 to 3: 1 and in particular from 1.5: 1 to 2.5: 1.

The partial extrudates can be made by any of the known extrusion or pelleting processes getting produced. In particular, however, it is preferred the partial extrudates according to the teaching of international patent application WO-A-91/02047 or WO-A-93/02176. The partial extrudates can also contain components that increase the solubility of the densified Improve granules. Such components and the introduction of such Components are, for example, in the international patent application W0-A-93/02176 and in the older German patent application P 42 03 031.5 described. The components preferably used include in particular Fatty alcohols with 10 to 80 moles of ethylene oxide per mole of fatty alcohol, for example tallow fatty alcohol with 30 EO and tallow fatty alcohol with 40 EO, as well as polyethylene glycols with a molecular weight between 200 and 2000. It has now been shown in production engineering trials that the lower pressure of at least 25 bar is not an absolutely fixed limit, but dependent on the type of extruder and throughput, for example can also fall below 7000 kg / h. At such high Throughputs obviously play a major role in apparatus technology parameters Role at smaller throughputs, for example between 600 and 2000 kg / h were unpredictable. In a preferred embodiment of the Invention, the anionic surfactants that may be present during manufacture of the solid premix intended for extrusion in the form of a spray-dried, granulated or extruded compounds. Furthermore, a method is preferred in which the surface of the partial extrudates to reduce the stickiness of the granules rich in nonionic surfactants is treated afterwards. Suitable surface modifiers are known from the prior art. In addition to other suitable ones finely divided zeolites, amorphous aluminosilicates, silicas, amorphous Silicates, fatty acids or fatty acid salts, for example calcium stearate, in particular, however, mixtures of zeolite and silica or zeolite and calcium stearate are particularly preferred.

In a preferred embodiment of the invention, the agents contain in addition to the partial extrudates I and II at least one further solid, which is preferably present as a granular component. In particular it is preferred to subsequently add bleach activators, enzymes and / or perfume to mix. It is also possible and can be dependent be of advantage from the recipe if other individual components of the By means of, for example, carbonate, citrate or citric acid or others Polycarboxylates or polycarboxylic acids, polymeric polycarboxylates, zeolite and / or layered silicates, which can optionally be crystalline, subsequently to be added to the partial extrudates.

Examples of suitable bleach activators are the N-acyl or O-acyl compounds forming with H ₂ O ₂ organic peracids, preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonate, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate . Particularly preferred bleach activators are N, N, N'N'-tetraacetylethylene diamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.

Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. They are particularly well suited from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably become proteases of the subtilisin type and in particular proteases, which are obtained from Bacillus lentus. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, Amylase and lipase or protease, lipase and cellulase, in particular Cellulase-containing and protease-containing mixtures of particular interest. (Per) oxidases are also suitable. The enzymes can on carriers adsorbed and / or embedded in enveloping substances around them protect against premature decomposition. It is also possible to use Proteases with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme, are stabilized.

The bulk density of the preferred granular agents is generally 300 to 1100 g / l, in particular 500 to 1000 g / l. Particularly preferred are agents according to the invention, which total about 10 to 35% by weight, advantageously 12 to 30% by weight of anionic and nonionic surfactants, 20 up to 60% by weight of builder substances, 10 to 25% by weight of peroxy bleach, 2 up to 15 wt .-%, in particular 5 to 10 wt .-% inorganic and alkaline acting salts such as carbonate and amorphous silicates, insofar as they do not belong to the Builder substances are to be expected, as well as foam inhibitors, bleach activators and contain enzymes. It is particularly preferred that the Agents according to the invention at 80 to 95% by weight from the partial extrudates, advantageously consists of the partial extrudates I and II.

Such agents preferably have a bulk density above 650 g / l and in particular at least 700 g / l.

Examples

In a continuously working mixer with a cutter head shredder (Chopper) was equipped, two premixes I and II produced and according to the teaching of international patent application WO-A-91/02047 extruded. The finished partial extrudates I and II, their compositions were dried, but not further worked up.

Partial extrudate I contained 14.5% by weight of C ₁₆ -C ₁₈ alkyl sulfate, 8.5% by weight of C ₁₂ -C ₁₄ alkyl sulfate, 9.5% by weight of C ₁₂ -C ₁₈ fatty alcohol with 3 EO , 5.5% by weight sodium carbonate, 5% by weight Sokalan CP 5 ^(R) (copolymer of acrylic acid; commercial product from BASF, Federal Republic of Germany), 2.5% by weight sodium silicate with a Na ₂ O: SiO ₂ Ratio of 1: 2.0, 38.5 wt .-% zeolite (anhydrous active substance), 4 wt .-% sodium sulfate, 1.65 wt .-% salts from raw materials and the rest water. The bulk density of extrudate I was 773 g / l. Partial extrudate II contained 6.6% by weight of C ₁₆ -C ₁₈ alkyl sulfate, 4% by weight of C ₁₂ -C ₁₄ alkyl sulfate, 5.5% by weight of sodium carbonate, 5% by weight of Sokalan CP 5 ^{( R)} , 1.7 wt .-% silicone oil, 2.2 wt .-% sodium silicate with a modulus of 2.0, 1.2 wt .-% sodium silicate with a modulus of 3.0, 7 wt .-% zeolite (based on anhydrous active substance), 49.5% by weight sodium perborate monohydrate, 9.5% by weight sodium sulfate, 0.8% by weight other salts from raw materials and the rest water. The bulk density of extrudate II was 787 g / l.

To determine the dissolving behavior, 500 ml were in a 1 liter vessel demineralized water (20 ° C) filled, the propeller with a Speed of 900 U / pm switched on and the conductivity measuring cell immersed. Then 5 g of extrudate I and II were added in each case. The Changes in conductivity were recorded by a clerk; the Measurement was carried out until the conductivity no longer increased was. The time to reach constant conductivity is the dissolving time of the respective extrudate (100%). The time to reach a 90% The resolution was calculated. The dissolution time (90%) of extrudate I was only 2 minutes. The dissolution time (90%) of extrudate II was even only 1 minute and 20 seconds.

An agent M1 was produced, which consists of 65% by weight of extrudate I and consisted of 35 wt .-% of extrudate II. Another agent contained M2 59.8% by weight of extrudate 1, 32.2% by weight of extrudate II and 8% by weight of others Ingredients such as tetraacetylethylene diamine, protease, lipase and / or cellulase and perfume.

For comparison, an agent V1 was produced from a uniform extrudate, that the ingredients of extrudates I and II in the quantitative ratio 65: 35 contained. The solving time at 90% resolution was 2 for M1 Minutes and 29 seconds, for V1 3 minutes and 20 seconds.

Claims (12)

1. A granular detergent containing granules produced by extrusion, characterized in that it contains at least two extrudates, extrudate I containing 20 to 50% by weight, based on extrudate I, of surfactants and being free from bleaching agent and extrudate II containing 0 to 15% by weight, based on extrudate II, of surfactants and 20 to 60% by weight of bleaching agent.
2. A detergent as claimed in claim 1, characterized in that extrudate I contains 25 to 40% by weight of surfactants and 20 to 60% by weight, preferably 25 to 50% by weight, of builders from the group of zeolites (based on water-free active substance), amorphous silicates and crystalline layered silicates.
3. A detergent as claimed in claim 1 or 2, characterized in that extrudate I contains zeolite and crystalline layered silicates (II) NaMSi_xO_2x+1 ·yH₂O, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or 4, in quantities of 25 to 45% by weight, a ratio by weight of 4:1 to 1:2 being preferred.
4. A detergent as claimed in claim 1 or 2, characterized in that extrudate I contains zeolite and X-ray amorphous silicates or carbonate/silicate compounds in a ratio by weight of 3:1 to 1:3 and, more particularly, 2:1 to 1:2.
5. A detergent as claimed in any of claims 1 to 4, characterized in that extrudate II contains 0.1 to 15% by weight and preferably 2 to 12% by weight, based on extrudate II, of surfactants and 30 to 55% by weight and preferably 40 to 50% by weight of peroxy bleaching agent, more especially perborate monohydrate, perborate tetrahydrate or percarbonate.
6. A detergent as claimed in any of claims 1 to 5, characterized in that extrudate II contains inorganic or organic builders in quantities of not more than 35% by weight and preferably in quantities of 10 to 30% by weight, based on extrudate II.
7. A detergent as claimed in any of claims 1 to 6, characterized in that extrudate II contains a silicone- and/or paraffin-based foam inhibitor.
8. A detergent as claimed in any of claims 1 to 7, characterized in that it contains extrudate I and extrudate II in a ratio by weight of greater than 1:1, preferably in a ratio by weight of 1.2:1 to 3:1 and more preferably in a ratio by weight of 1.5:1 to 2.5:1.
9. A detergent as claimed in any of claims 1 to 8, characterized in that at least one extrudate was subsequently treated with a surface modifier preferably selected from fine-particle zeolites, amorphous alumosilicates, silicas, amorphous silicates, fatty acids or fatty acid salts and, more particularly, mixtures of zeolite and silicas or zeolite and calcium stearate.
10. A detergent as claimed in any of claims 1 to 9, characterized in that it contains at least one other solid, preferably a granular component.
11. A detergent as claimed in claim 10, characterized in that another granular component contains enzymes.
12. A detergent as claimed in any of claims 1 to 11, characterized in that 80 to 95% by weight of the detergent consists of extrudates, advantageously of extrudates I and II.