DE102015002877A1 - Granular detergent or cleaner with improved dissolution rate - Google Patents

Abstract

The invention relates to washing or cleaning-active extrudates and granular detergents or cleaners containing them and which show an improved dissolution rate compared to conventional detergent granules. The invention further relates to the preparation of such extrudates, the extrudates produced in this way, and the use of these extrudates in detergent formulations and the use of the detergents described herein in machine washing processes, in particular for textile washing.

Description

The invention relates to washing or cleaning-active extrudates and granular detergents or cleaners containing them and which show an improved dissolution rate compared to conventional detergent granules. The invention further relates to the preparation of such extrudates, the extrudates produced in this way, and the use of these extrudates in detergent formulations and the use of the detergents described herein in machine washing processes, in particular for textile washing.

Particulate detergents or cleaning agents with bulk densities above 600 g / l have been part of the state of the art for quite some time. In recent years, the increase in bulk density was accompanied by a concentration of the washing and cleaning active ingredients, so that the consumer had to dose not only less volume, but also less mass per washing or cleaning process. The known agents are predominantly extrudates, as these are perceived by the consumer to be particularly easy to dose. The preparation of such extrudates is for example in the EP-A-0 665 879 described.

The increase in bulk density and, in particular, once again the higher concentration of agents on washing or cleaning-active substances was generally paid for by a subjectively lower solubility from the point of view of the consumer, which is due to a slower rate of dissolution of the agent compared to traditional powders.

The EP-A-0 931 137 describes processes for the preparation of particulate detergents which, even with a reduced surface area, have improved disintegration in the aqueous liquor dissolution and which contain a special binder which performs both the function of a lubricant and an adhesive function in manufacture the dissolution of the agent in the aqueous liquor, however, disintegrating acts.

Although this improves the dissolution rate of the particles, it is still unsatisfactory. The object of the present invention was therefore to provide particulate detergents or cleaners or raw materials for this, which have a further improved disintegration in the dissolution in the aqueous liquor, in particular in the case of a spherical shape (bead shape). The inventors have surprisingly found that this object can be achieved by reducing the amount of inorganic electrolytes, especially inorganic salts and bases, as well as of citrate in the product compared to commercial reference formulations.

The invention therefore in a first aspect is a washing or cleaning-active particulate extrudate containing anionic and / or nonionic surfactants and builders, characterized in that the extrudate based on the total weight of the extrudate less than less than 1.0 wt .-% , preferably less than 0.5% by weight, more preferably less than 0.2% by weight of trisodium citrate, in particular alkali citrate, more preferably citrate, and less than 5% by weight, preferably less than 3% by weight, even more preferably, less than 2% by weight of inorganic electrolytes, especially inorganic salts.

In a further aspect, the invention relates to a granular detergent or cleaner containing the detergent or cleaning active extrudate described herein and to the use of the extrudates described herein as a component of laundry detergents and cleaners.

Another aspect of the invention is directed to a method of making a wash or cleaning active extrudate described herein by extrusion, wherein a solid premix is extruded under pressure and the strand is cut to the pre-determinable granule dimension after exit from the hole form by a cutter, as well as the so-available extrudate. The granule dimension is determined essentially on the basis of the dimensioning of the opening of the hole shape, the extrusion rate, ie the flow rate at which the extrudate leaves the hole shape and the cutting device. The rate at which the cutter cuts determines the length of the particulate extrudates. The extrudate may also be deformed in a desired manner by the impulse during the cutting process. If an elliptical hole form with an inner pin is used, the extrudate can be reshaped by cutting into a circular ring. The "hole shape" represents the exit of the extruder through which the extruded material is pressed.

The term "particulate extrudate" means that the particle is from an extrusion process.

The "cutter" may represent a single knife that cuts the extrusion line, but also an array of multiple blades that are attached to the exit of the extruder and rotated to cut the extrudate.

Finally, the invention also encompasses the use of a granular detergent or cleaning agent described herein in a machine laundering process using the extrudates and detergents described herein.

In the context of the invention, particulate or granular extrudates or detergents or cleaners are preferably understood as meaning those which have no dust-like constituents and in particular no particle sizes of less than 200 μm. In particular, such particle size distributions are preferred which comprise at least 90% by weight, more preferably at least 95, 96, 97, 98, 99 or 100% by weight of particles having a diameter greater than 400 μm. In a particularly preferred embodiment of the invention, the extrudates consist of 100% by weight of particles having a particle size distribution which comprises at least 70% by weight of particles between 0.8 and 2.0 mm, preferably at least 80% by weight of particles between 1.4 and 1.8 mm. In various embodiments, at least 10 wt .-%, preferably at least 15 wt .-% of the particles have a particle size> 1.8 mm.

When referring to particle sizes herein, the figures always refer to values determined by sieve analysis. For example, particle sizes can be determined by sieving the particles by means of a VE1000 sieve (Retsch GmbH, Haan) for 2 minutes with an interval of 10 seconds and an amplitude of 2 mm and determining the proportion of particles per sieve gravimetrically. For this purpose, 100 g sample are given by means of the top sieve of a sieve set, which is assembled in such a way that the mesh size decreases towards the bottom, and which is provided with a closure bottom. After sieving under the conditions mentioned, the proportion of particles per sieve is determined gravimetrically by transferring and weighing the different fractions, including the particles stuck in the sieve meshes, into weighing dishes.

It has surprisingly been found that the subject matter of the claim results in the particulate extrudate having an altered particle distribution. In particular, the proportion of particles that are> 1.8 mm in size increases. Without wishing to be bound by theory, it is believed that the invention provides unexpected synergism. At the same time, a relatively high bulk density, an on average larger particle diameter and an increased solubility rate are achieved. This is surprising, since usually high bulk densities and large particles lead to poor dissolution rates.

Especially when at least 10% by weight, preferably more than 15% by weight, of the particles of the extrudate have a size of> 1.8 mm, particularly good rates of solubility can be observed. In this respect, preferred embodiments are characterized in that the extrudate contains at least 10 wt .-%, preferably at least 15 wt .-% of particles having a particle size> 1.8 mm.

In certain embodiments, however, the proportion of particles having a particle size of> 1.8 mm should not exceed 20% by weight.

Detergents or cleaning agents are understood to mean compositions of this type which can be used for washing or cleaning, without the need to usually add further ingredients. The detergents described herein may be detergents for textiles or natural fibers. Detergents in the context of the invention also include washing aids which are metered into the actual detergent during manual or automatic textile washing in order to achieve a further effect or to enhance an effect.

All amounts stated in connection with the components of the extrudate or washing and cleaning agent described herein, unless stated otherwise, are based on% by weight, in each case based on the total weight of the extrudate / agent. Further, such amounts referring to at least one ingredient always refer to the total amount of that type of ingredient contained in the extrudate / agent unless explicitly stated otherwise. That is, such quantities, for example in connection with "at least one nonionic surfactant", refer to the total amount of nonionic surfactants contained in the extrudate or detergent or cleaner.

"At least one" as used herein refers to 1 or more, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of ingredients of the compositions described herein, this indication does not refer to the absolute amount of molecules but to the nature of the ingredient. Thus, "at least one nonionic surfactant" means, for example, one or more different nonionic surfactants, ie one or more different types of nonionic surfactants. Together with quantities, the quantities refer to the total amount of the corresponding designated type of ingredient as defined above.

The term "trisodium citrate" means the triple sodium salts of citric acid. The term "alkali citrate" refers to all alkali metal salts of citric acid. Alkali salts are sodium, potassium, rubidium, cesium and francium salts of citric acid. Particularly preferred are the sodium salts of citric acid. These are monosodium citrate, disodium citrate and trisodium citrate. The term "citrate" refers to all salts of citric acid. In particular, alkali and alkaline earth salts of citric acid. Alkaline earth salts are beryllium, magnesium, calcium, strontium, barium and radium salts.

When using hydrates of trisodium citrate, alkali citrates or citrates, the proportion by weight of water in the calculation of the proportion of trisodium citrate, alkali citrate or citrate is not to be included. Only the proportion by weight of trisodium citrate, alkali citrates or citrates has to be considered. Also included within the term citrate are organic salts of citric acid, such as ammonium citrate. Ammonium citrate may be present as mono-, di- and triammonium salt.

Very preferably, the triple salts of citric acid, for. B. triple alkali salts of citric acid, triple alkaline earth salts of citric acid or the threefold organic salts of citric acid.

The inventors have surprisingly found that by reducing the amount of citrate and inorganic salts in solid mixtures for the production of detergent-active, granular extrudates with otherwise identical starting formulations, washing or cleaning-active extrudates can be produced, which has a larger particle size compared to the standard and have a reduced bulk density, resulting in an improved rate of dissolution of the granules.

"Inorganic electrolytes" as used herein refers to compounds that are at least partially ionic in the solid, liquid or dissolved state. Important electrolytes for the purposes of the present invention are inorganic acids, bases and salts, in particular salts and here in particular sulfates, chlorides, carbonates, phosphates, etc., where the cation may be any inorganic cation. In particular embodiments, the inorganic salts include in particular sulfates and carbonates. Other important inorganic electrolytes are inorganic bases, such as sodium or potassium hydroxide (NaOH or KOH). The inorganic electrolytes are preferably water-soluble inorganic electrolytes, in particular salts. "Water-soluble" as used in this context means that the solubility in water at a temperature of 20 ° C is at least 1 g / L, in particular at least 10 g / L. The content of such inorganic electrolytes in the extrudates is less than 5% by weight, preferably less than 3% by weight, more preferably less than 2% by weight, most preferably 1% by weight or less. The term does not cover organic electrolytes, in particular no organic sulfates used as surfactants, carboxylic acids, etc ..

The bulk density of the extrudates is preferably more than 600 g / l, in particular 625-700 g / l. Such extrudates are used in compact detergents or concentrates.

The extrudates according to the invention contain anionic and / or nonionic surfactants and builder substances and, if appropriate, further customary constituents, with the proviso that citrate and inorganic electrolytes are contained only in the maximum amount specified above.

surfactants

Important constituents of the extrudates according to the invention are surfactants, in particular anionic surfactants, which are present in the extrudates or extrudates according to the invention at least in amounts of 0.5% by weight. These include in particular sulfonates and organic sulfates, but also soaps.

As surfactants of the sulfonate type are preferably C9-C13-alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are, for example from C12-C18 monoolefins having terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained.

Also suitable are alkanesulfonates which are obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.

Also suitable are the esters of alpha-sulfo fatty acids (ester sulfonates), z. As the alpha-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids prepared by alpha-sulfonation of methyl esters of fatty acids of plant and / or animal origin with 8 to 20 carbon atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts become. These are preferably the alpha-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, with sulfonation of unsaturated fatty acids, such as oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt. %, can be present. In particular, alpha-sulfofatty acid alkyl esters are preferred which have an alkyl chain with not more than 4 C atoms in the ester group, for example methyl ester, ethyl ester, propyl ester and butyl ester. With particular advantage, the methyl esters of the alpha-sulfo fatty acids (MES), but also their saponified disalts are used.

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 especially the sodium salts of the sulfuric monoesters of C12-C18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C10-C20 oxo alcohols and those monoesters of secondary alcohols this chain length is 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 technology interest, C16-C18 alk (en) ylsulfates are particularly preferred. It may also be of particular advantage and particularly advantageous for automatic detergents, C16-C18-alk (en) ylsulfate in combination with lower melting anionic surfactants and in particular with those anionic surfactants having a lower Krafft point and at relatively low washing temperatures of For example, room temperature (20 ° C) to 40 ° C show a low tendency to crystallize, use. In a preferred embodiment of the invention, the extrudates therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C12-C14 fatty alkyl sulfates or C12-C18 fatty alkyl sulfates with C16-C18 fatty alkyl sulfates and in particular C12-C16 fatty alkyl sulfates with C16-C18 fatty alkyl sulfates , In a further preferred embodiment of the invention, however, non-saturated alkyl sulfates, but also unsaturated alkenyl sulfates having an alkenyl chain length of preferably C16 to C22 are used. Particular preference is given to mixtures of saturated sulfonated fatty alcohols consisting predominantly of C16 and unsaturated sulfonated fatty alcohols consisting predominantly of C18. Weight ratios of alkyl sulfates to alkenyl sulfates of from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.

Also 2,3-alkyl sulfates, which, for example, according to the U.S. Patents 3,234,258 or 5,075,041 can be prepared, are suitable anionic surfactants.

Also, the sulfuric acid monoesters of the straight-chain or branched C7-C21-alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C9-C11-alcohols with on average 3.5 moles of ethylene oxide (EO) or C12-C18-fatty alcohols with 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 .-%.

A preferred use of alkyl (ene) sulfate mixtures in which the proportion of alkyl (ene) residues to 15 to 40 wt .-% to C12 to 5 to 15 wt .-% on C14, to 15 to 25 wt. % to C16, to 30 to 60 wt% to C18, and less than 1 wt% to C10.

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 C8 to C18 fatty alcohol residues or mixtures of these. Especially preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are 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 of N-methyltaurine (Tauride) and / or of 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.

As further anionic surfactants are in particular soaps, preferably in amounts of 0.2 to 5 wt .-%, into consideration. 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 from natural fatty acids, for. 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 anionic surfactants (and 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. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The anionic surfactants are contained in the extrudates according to the invention preferably in amounts of 1 to 40 wt .-% and in particular in amounts of 5 to 35 wt .-%. In preferred embodiments, the extrudates contain at least 25 wt%, more preferably at least 30 wt% anionic surfactants.

In various embodiments, the extrudates contain C9-C13 alkylbenzenesulfonates in amounts of 15-25% by weight, especially 20 to 25% by weight, based on the total weight of the extrudate. In preferred embodiments, the extrudates additionally comprise C12-18 fatty alcohol sulfates (FAS, alkyl sulfates) in amounts of from 5 to 10% by weight and soaps, in particular C16-18 soaps, in amounts of from 0.5 to 2% by weight, in each case on the total weight of the extrudate.

In addition to the anionic surfactants, especially nonionic surfactants are preferred.

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 native origin having 12 to 18 carbon atoms, for. From coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C12-C14 alcohols with 3 EO or 4 EO, C9-C11 alcohols with 7 EO, C13-C15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-C18- Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-C14 alcohol with 3 EO and C12-C18 alcohol with 7 EO. Particularly preferred are C12-18 alcohols 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.

The nonionic surfactants also include the alkyl glycosides of the general formula RO (G) _x and the polyhydroxy fatty acid amides of the formulas (I) and (II).

In the alkyl glycosides of the general formula RO (G) _x R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms, and G is the symbol which represents a Monosaccharide with 5 or 6 C-atoms, preferably for 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. Especially Such alkyl glycosides are suitable which have a degree of softening above 80 ° C and a melting point above 140 ° C.

In the polyhydroxy fatty acid amides of the formula (I) R ² -CO-N (R ³ ) - [Z] (I) 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. The polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (II) R ⁴ -CO-N (R ⁵ -OR ⁶ ) - [Z '] (II) in which R ^{4 is} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{5 is} a linear, branched or cyclic alkyl radical or an aryl radical having up to 8 carbon atoms and R ^{6 is} a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having up to 8 carbon atoms, wherein C1-4 are alkyl radicals or phenyl radicals, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least 2 hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives thereof Restes stands. [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 used, for example, according to the teaching of the international patent application WO-A-95/07331 be converted by conversion with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired Polyhydroxyfettsäureamide. Particularly preferred glucamides melt even at 95 to 105 ° C.

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, in particular fatty acid methyl ester, as described for example in the Japanese patent application JP 58/217598 are described or preferably according to the in the international patent application WO 90/13533 be prepared described methods. Particularly preferred are C12-C18 fatty acid methyl esters with an average of 3 to 15 EO, in particular with 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.

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 typically 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 tris-sulfate and ether sulfates according to the earlier German patent application DE-A-195 03 061.3 , End-capped dimeric and trimeric mixed ethers according to the earlier German patent application DE-A-195 13 391.9 They are characterized by their bi- and multi-functionality. 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 95/19953 . WO 95/19954 and WO 95/19955 to be discribed.

In preferred embodiments, anionic and nonionic surfactants are used in the extrudates or solid premixes used to make them, the anionic surfactants preferably being selected from linear alkyl benzene sulfonates (LAS), fatty alcohol sulfates (FAS) and soaps, and the nonionic surfactants are preferably selected from alkoxylated fatty alcohols. Particular preference is given to mixtures of C 9 -C 13 -alkylbenzenesulfonates, in particular in amounts of 15-25% by weight, in particular 20 to 25% by weight, based on the total weight of the extrudate, of C12-18 fatty alcohol sulfates (FAS, alkyl sulfates), in particular in amounts of 5 to 10 wt .-%, soaps, especially C16-18 soaps, preferably in amounts of 0.5 to 2 wt .-%, and ethoxylated C12-18 fatty alcohols, in particular with 7 EO, preferably in amounts of 5 to 10 wt .-%, each based on the total weight of the extrudate.

Builder

The term "builder" includes organic and inorganic builders.

In addition to the surfactants, especially the inorganic and organic builder substances are among the most important ingredients of the extrudates according to the invention.

Zeolite is particularly preferred here. The zeolite employed is preferably finely crystalline, synthetic and contains bound water, and is in particular zeolite A and / or P. However, zeolite X and mixtures of A, X and / or P are also suitable. The zeolite can be spray-dried or else undried , from their production still moist, stabilized suspension are used. In the case where 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 having 2 to 5 ethylene oxide groups, C12-C14 fatty alcohols containing 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have, for example, an average particle size of less than 10 μm (volume distribution, measuring method: counter-counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Suitable substitutes or partial substitutes for 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 is and preferred values for x are 2, 3 or 4. Such crystalline sheet silicates are described, for example, in the European patent application EP-A-0 164 514 described. 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 beta- and delta-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

Further suitable substitutes or partial substitutes for the zeolite are phyllosilicates of natural and synthetic origin. Such sheet silicates are, for example, from the patent applications DE-B-23 34 899 . EP-A-0 026 529 DE-A-35 26 405 known. Its usability is not limited to any particular composition or structural formula. However, smectites, in particular bentonites, are preferred here.

Suitable phyllosilicates which belong to the group of water-swellable smectites are, for example, montmorillonite, hectorite or saponite. In addition, small amounts of iron may be incorporated in the crystal lattice of the layered silicates according to the above formulas. Furthermore, the layer silicates may virtue of their ion-exchanging properties of hydrogen, alkali metal, alkaline earth metal ions, include, in particular Na ⁺ and Ca ^2+. The amount of water of hydration is usually in the range of 8 to 20 wt .-% and is dependent on the swelling state or on the type of processing. Useful phyllosilicates are for example off US Patent No. 3,966,629 . EP-A-0 026 529 and EP-A-0 028 432 known. Preferably phyllosilicates are used, which are largely free of calcium ions and strong coloring iron ions due to an alkali treatment.

Useful organic builders include, but are not limited to, 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. Preferably, they are hydrolysis products having average molecular weights in the Range from 400 to 500,000. A polysaccharide having 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 action of a polysaccharide in comparison to dextrose, which has a DE of 100 is. Useful are both maltodextrins with a DE of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000. A preferred dextrin is disclosed in the British patent application GB 94 19 091 described. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and methods of their preparation are, for example, from the European patent applications EP-A-0 232 202 . EP-A-0 427 349 . EP-A-0 472 042 and EP-A-0 542 496 as well as the international patent applications WO-A-92/18542 . WO-A-93/08251 . WO 94/28030 . WO-A-95/07303 . WO 95/12619 and WO 95/20608 known. A product oxidized at C6 of the saccharide ring may be particularly advantageous.

Furthermore, as organic builders, polymeric polycarboxylates, for example the sodium salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular weight of 800 to 150,000 (based on acid), can be used. 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 molecular weight relative to 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. To improve the water solubility, the polycarboxylates may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as monomer. Corresponding sulfopolymers can therefore also be used as builders.

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

Further preferred copolymers are those described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 be described and as monomers preferably 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 the international patent application WO-A-93/08251 be described or their preparation, for example, in the international patent application WO-A-93/16110 is described. Also suitable are oxidized oligosaccharides according to the earlier German patent application DE-A-196 00 018.1 ,

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particularly preferred are polyaspartic acids or their salts and derivatives of those in the German patent application DE-A-195 40 086.0 is disclosed that they also have a bleach-stabilizing effect in addition to Cobuilder properties.

Further suitable builder substances are polyacetals which are prepared by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as in the European patent application EP-A-0 280 223 described, can be obtained. 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 glucoheptone.

Finally, builder salts are in particular the salts of polyphosphonic acids, preferably the neutrally reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate (HEDP), diethylenetriaminepentamethylenephosphonate or ethylenediamine tetramethylenephosphonate, which are usually used in amounts of from 0.1 to 1.5% by weight .-% be used.

The extrudates described herein preferably contain at least 15% by weight, in particular at least 20% by weight, of builders. Zeolite, in particular zeolite A, (co) polymeric polycarboxylates and phosphonates are preferably used as builder substances. The amounts are typically 15 to 45 wt .-%, preferably 35-40 wt .-%, zeolite, 1 to 10 wt .-%, in particular 3 to 5 wt .-%, (co) polymeric polycarboxylates and 1 to 3% by weight of phosphonates, in particular HEDP.

binder

The extrudates may also contain at least one constituent which serves as a binder in the extrudate or for the preparation of the extrudate and is solid at room temperature, while the compaction under the extrusion conditions is liquid in the form of a melt. The binder, which may also be a binder mixture, may be once melted onto the premix or added dropwise to the premix, but on the other hand, it has also proved to be advantageous to introduce the binder in solid form as a powder in the premix. The melting point or the softening point of the binder is at a pressure of 1 bar at least 45 ° C and (especially for economic reasons) preferably below 200 ° C, in particular below 150 ° C. If the binder is introduced in the form of a melt in the premix, the temperature in the melting vessel is also more than 45 ° C to a maximum of about 200 ° C, wherein the temperature in the melting vessel, the melting temperature or the temperature of the softening point of the binder or the binder mixture can exceed significantly significantly.

It has proved to be advantageous if the binder is distributed as homogeneously as possible in the material to be compacted in the process step of compaction. For this purpose, temperatures must be present in the process step of compaction in which the binding agent is at least softened, but preferably completely and not only partially present in molten form. Thus, if a binder with a high melting point or high softening point is selected, a temperature must be set in the process step of the compression, which ensures the melting of the binder. In addition, depending on the desired composition of the end product, temperature-sensitive raw materials can also be processed. Here, the upper temperature limit is given by the decomposition temperature of the sensitive raw material, it being preferred to work significantly below the decomposition temperature of this raw material. On the other hand, the lower limit for the melting point or the softening point is of such great importance, since at melting points or softening points below 45 ° C., as a rule, a final product is obtained which is already at room temperature and slightly elevated temperatures around 30 ° C., So at summer temperatures and under storage or transport conditions tends to stick. It has proven to be particularly advantageous if a few degrees, for example 2 to 20 ° C, above the melting point or above the softening point is used.

The binder or binders must be such that the adhesive properties are retained even at temperatures which are significantly above the melting point or the softening point. On the other hand, it is also essential for the choice of the type and amount of the binder or binder (s) used, that although the binding properties are not lost after re-cooling within the final product, the cohesion of the final product is thus secured, but the final product itself under usual storage and transport conditions not glued.

In the further course of the description of this invention, for the sake of simplicity, only one or the binder will be discussed. However, it should be made clear that it is always possible to use several different binders and mixtures of different binders.

In a preferred embodiment of the invention, a binder is used which is completely present as a melt at temperatures up to a maximum of 130 ° C., preferably up to a maximum of 100 ° C. and in particular up to 90 ° C. The binder must therefore be selected depending on the process and process conditions or the process conditions, in particular the process temperature must - if a particular binder is desired - be adapted to the binder.

Preferred binders which can be used alone or in admixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols. The modified polyalkylene glycols include, in particular, the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols having a molecular weight between 600 and 12000 and in particular between 1000 and 4000. Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which in turn are molecular weights between 600 and 6000, preferably between 1000 and 4000. For a more detailed description of the modified polyalkylene glycol ethers, refer to the disclosure of the international patent application WO-A-93/02176 directed. In the context of this invention, polyethylene glycols include polymers in the production of which ethylene glycol as well as C3-C5 glycols and also glycerol and mixtures thereof are used as starting molecules. Also included are ethoxylated derivatives such as trimethylolpropane containing 5 to 30 EO.

The polyethylene glycols preferably used may have a linear or branched structure, with particular preference being given to linear polyethylene glycols.

Particularly preferred polyethylene glycols include those having molecular weights between 2,000 and 12,000, advantageously about 4,000, wherein polyethylene glycols having molecular weights below 3500 and above 5000, especially combination with polyethylene glycols having a molecular weight of 4000, can be employed and such combinations advantageously greater than 50 Wt .-%, based on the total amount of polyethylene glycols, polyethylene glycols having a molecular weight between 3500 and 5000 have. However, polyethylene glycols which are present in liquid state at room temperature and a pressure of 1 bar can also be used as binders; Here is mainly of polyethylene glycol with a molecular weight of 200, 400 and 600 the speech. However, these per se liquid polyethylene glycols should be used only in a mixture with at least one other binder, this mixture should again meet the requirements to have a melting point or softening point of at least above 45 ° C.

Also suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives of these having molecular weights of up to 30,000. Preference is given here to molecular weight ranges between 3,000 and 30, for example around 10,000. Polyvinylpyrrolidones are preferably not used as sole binders but in combination with others, in particular in combination with polyethylene glycols used.

Suitable further binders have proven to be raw materials which have washing or cleaning-active properties, that is, for example, nonionic surfactants having melting points of at least 45 ° C. or mixtures of nonionic surfactants and other binders. The preferred nonionic surfactants include the alkoxylated fatty or oxo alcohols already described above, in particular C12-C18 alcohols. In this case, degrees of alkoxylation, in particular degrees of ethoxylation averaging 18 to 80 AO, in particular EO per mole of alcohol and mixtures thereof, have proven to be particularly advantageous. Especially fatty alcohols with an average of 18 to 35 EO, in particular with an average of 20 to 25 EO, show advantageous binding properties in the sense of the present invention. Optionally, ethoxylated alcohols having an average of less EO units per mole of alcohol may also be present in binder mixtures, for example tallow fatty alcohol with 14 EO. However, it is preferred to use these relatively low ethoxylated alcohols only in mixture with higher ethoxylated alcohols. Advantageously, the content of the binder in these relatively low ethoxylated alcohols is less than 50% by weight, in particular less than 40% by weight, based on the total amount of binder used. In particular, conventionally used in detergents or cleaning agents nonionic surfactants such as C12-C18 alcohols having an average of 3 to 7 EO, which are liquid at room temperature, are preferably present in the binder mixtures only in the amounts that thereby less than 2 wt. % of these nonionic surfactants, based on the final process product. However, as already described above, it is less preferred to use liquid nonionic surfactants in the binder mixtures at room temperature. In a particularly advantageous embodiment, however, such nonionic surfactants are not part of the binder mixture, since they not only reduce the softening point of the mixture, but also contribute to the stickiness of the final product and also by their tendency to lead to gelling on contact with water, also the Requirement of rapid resolution in the final product is not sufficient to the desired extent. Likewise, it is not preferred that conventional anionic surfactants used in detergents or cleaners or their precursors, the anionic surfactant acids, are present in the binder mixture.

Other nonionic surfactants which are suitable as binders are the non-gelatinous fatty acid methyl ester ethoxylates, in particular those with an average of 10 to 25 EO (for a more detailed description of this substance group, see below). Particularly preferred representatives of this substance group are predominantly C16-C18 fatty acid-based methyl esters, for example hydrogenated beef tallow methyl ester with an average of 12 EO or with an average of 20 EO.

In one embodiment of the invention, the binder used is a mixture which comprises C12-C18 Coconut or tallow based fatty alcohol having an average of 20 EO and polyethylene glycol having a molecular weight of 400 to 4000.

In a further embodiment of the invention, the binder used is a mixture containing predominantly C16-C18 fatty acid-based methyl esters with an average of 10 to 25 EO, in particular hardened beef tallow methyl ester with an average of 12 EO or an average of 20 and a C12-C18 fatty alcohol based on coconut or tallow containing on average 20 EO and / or polyethylene glycol having a molecular weight of 400 to 4000.

As particularly advantageous embodiments of the invention, binders have proven, either alone on polyethylene glycols having a molecular weight around 4000 or on a mixture of C12-C18 fatty alcohol based coconut or tallow with an average of 20 EO and one of the fatty acid methyl ester described above or on a Mixture of C12-C18 fatty alcohol based on coconut or tallow with an average of 20 EO, one of the above-described fatty acid methyl ester ethoxylates and a polyethylene glycol, in particular having a molecular weight of 4000 based.

Although other raw materials such as trimethylolpropylenes (commercial products from BASF) may be present in binder mixtures, in particular in admixture with polyethylene glycols; however, they can not be used as the sole binder because, while having a binding / adhesive function, they have no disintegrating effect.

In addition, the above-described alkyl glycosides of the general formula RO (G) _x can also be used as further binders, alone or in combination with other binders. In particular, those alkyl glycosides are suitable which have a degree of softening above 80 ° C and a melting point above 140 ° C. Although alkyl glycosides can also be used as sole binders, it is preferred to use mixtures of alkyl glycosides and other binders. Particular mention should be made here of mixtures of polyethylene glycols and alkyl glycosides, advantageously in weight ratios of from 25: 1 to 1: 5, with particular preference from 10: 1 to 2: 1.

Also suitable as a binder, in particular in combination with polyethylene glycols and / or alkyl glycosides, are polyhydroxy fatty acid amides of the formula (I) or (II), as already described above.

The content of binder or binders in the extrudate or the solid premix before extrusion is preferably at least 1 wt .-%, but less than 15 wt .-%, in particular less than 10 wt .-%, with particular preference from 2 to 6 % By weight, in each case based on the extrudate / premix.

Other ingredients

The extrudates may also contain other ingredients customary for detergents and cleaners which do not decompose under the extrusion conditions. These include, but are not limited to, dyes, preservatives and optical brighteners.

As optical brighteners, derivatives of diaminostilbene disulfonic acid or its alkali metal salts may be present. Suitable z. B. salts of 4,4-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2-disulfonic acid or compounds of similar construction, which instead of the morpholino group a Diethanolaminogruppe , a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the type of substituted Diphenylstyryle be present, for. For example, 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 ) -diphenyls. Mixtures of the aforementioned brightener can be used. The amount is usually not more than 1 wt .-% based on the total weight of the extrudate.

manufacturing

In various embodiments, the extrudates are prepared starting from a solid, free-flowing premix, in particular according to the in the EP-A-0 665 879 and EP-A-0 931 137 described method. In this case, a homogeneous, solid and free-flowing premix of the individual components is first prepared, extruded under pressure extruded and cut the strand after exiting the hole shape by means of a cutter to the desired granule dimension.

For the preparation of the premix, the solids are, for example, initially mixed at room temperature to slightly elevated temperatures, which are preferably below the melting temperature or the softening point of the binder, and in particular at temperatures up to 35 ° C in a conventional mixing and / or granulating. These solids also include those which according to the European patent EP-B-0 486 592 can serve as plasticizer and / or lubricant. These include, in particular, as already described above, anionic surfactants such as alkylbenzenesulfonates and / or (fatty) Alkyl sulfates, but also polymers such as polymeric polycarboxylates. The function of a lubricant can also be perceived by the binder or the binders or the binder mixtures.

The binders are preferably mixed in as the last component. Their addition can, as already stated above, be carried out as a solid, ie at a processing temperature which is below its melting point or its softening point, or as a melt. Advantageously, however, the admixture is carried out under conditions such that the most uniform, homogeneous distribution of the binder in the solid mixture is achieved. For very finely divided binders this can be accomplished at temperatures below 40 ° C, for example at temperatures of the binder between 15 and 30 ° C. Advantageously, however, the binder has temperatures at which it is already present in the form of a melt, ie above the softening point, in particular in the form of a complete melt. Preferred temperatures of the melt are at 60 to 150 ° C, with particular preference to the temperature range of 80 to 120 ° C. During the mixing process, which takes place at room temperature to slightly elevated temperature, the melt solidifies almost instantaneously, and the premix is in a solid, free-flowing form.

• – das Vorgemisch im wesentlichen wasserfrei ist, und
• – im Vorgemisch mindestens ein Bestandteil enthalten ist, der 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 Bestandteile des Extrudats ausübt, bei der Wiederauflösung des Extrudats in wässriger Flotte hingegen desintegrierend wirkt.

In various embodiments of the inventive method for producing the extrudates described herein, the method is carried out with simultaneous or subsequent shaping, wherein in the process firstly a premix is prepared, which components which are present at room temperature and a pressure of 1 bar as a solid and a melting point or Softening point not below 45 ° C, and optionally containing up to 10 wt .-% at temperatures below 45 ° C and a pressure of 1 bar liquid nonionic surfactants, and then using compression forces at temperatures of at least 45 ° C in the Premix is converted into a grain and optionally subsequently further processed or processed. In this case, in preferred embodiments, the provisos that

• The premix is substantially anhydrous, and
• In the premix, at least one constituent is present which is in solid form at a pressure of 1 bar and at temperatures below 45 ° C but is present as a melt under the processing conditions, this melt serving as a polyfunctional, water-soluble binder which is used in the process the preparation of the agent performs both the function of a lubricant and an adhesive function for the solid constituents of the extrudate, in contrast, the disintegration of the extrudate in aqueous liquor disintegrating acts.

It is to be understood in the context of this invention by "substantially anhydrous" a state in which the content of liquid, d. H. is not present in the form of water of hydration and / or water of constitution less than 2 wt .-%, preferably less than 1 wt .-% and in particular even less than 0.5 wt .-%, each based on the premix. Accordingly, essentially only in chemically and / or physically bound form or as a constituent of the constituents present as solids at temperatures below 45 ° C. at a pressure of 1 bar, water can be added to the process for the preparation of the substance as a liquid, solution or dispersion Premixes are introduced. Advantageously, the premix has a total water content of not more than 15 wt .-%, which water is thus not in liquid form, but chemically and / or physically bound, that is not in free form, and it is particularly preferred that the Content of water not bound to zeolite and / or silicates in the solid premix not more than 10 wt .-%, preferably less than 7 wt .-% and with particular preference at most 2 to 5 wt .-% is.

The ingredients used in the process according to the invention can - except for the optionally present at temperatures below 45 ° C and a pressure of 1 bar liquid nonionic surfactants - be separately prepared ingredients which powdery or particulate (finely divided to coarse), but in any case at room temperature and a pressure of 1 bar in solid form. As particulate particles, it is possible, for example, to use beads produced by spray-drying or (fluidized bed) granules, etc. The composition of the ingredients per se is immaterial to the invention except for the water content, which must be such that the premix as defined above is essentially anhydrous and preferably contains not more than 10% by weight of water of hydration and / or makeup water , It is likewise possible for solid constituents to be used in the premix which serve as carriers of liquids, for example liquid nonionic surfactants or silicone oil and / or paraffins. These constituents may contain water in the framework indicated above, the constituents preferably being free-flowing and remaining free-flowing or at least recoverable even at relatively high temperatures of at least 45 ° C. In particular, it is preferred that in the premix ingredients with a maximum of 10 wt .-% and with particular preference with a maximum of 7 wt .-% water, based on the premix, are used. Free water, ie water that is not bound in any way to a solid and therefore "in liquid form", is preferably not even in the premix contain, since even very small amounts, for example by 0.2 or 0.5 wt .-%, based on the premix, sufficient to dissolve the inherently water-soluble binder. This would mean that the melting point or softening point would be reduced and the end product would lose both flowability and bulk density.

Like in the EP-A-0 931 137 It has been shown that it is by no means a matter of indifference to which or in which solid constituent the water is bound. Thus, the water which is to be regarded as less critical to builders such as zeolite or silicates, especially when the water is bound to zeolite A, zeolite P and / or zeolite X, is less critical. On the other hand, it is preferred that water, which is bound to other solid constituents than to the builders mentioned, is preferably present in amounts of less than 3 wt .-% in the premix. In one embodiment of the invention it is therefore preferred that the content of bound water in the premix is not more than 10% by weight and / or the content of water not bound to zeolite and / or silicates is less than 7% by weight. and in particular at most 2 to 5 wt .-% is. It is particularly advantageous if the premix contains no water that is not bound to the builders. However, this is technically difficult to realize, since at least always traces of water are introduced by the other components at least.

The content of the solid constituents used in the premix at non-aqueous liquids at temperatures below 45 ° C. is preferably also or additionally up to 10% by weight, advantageously up to 6% by weight, again based on the premix. In particular, solid components are used in the premix, which contain conventional at temperatures below 45 ° C and a pressure of 1 bar liquid nonionic surfactants, which were prepared separately by all known methods of preparation - for example, by spray drying, granulation or spraying of Trägerbeads on this Way can be prepared premixes, for example, up to about 10 wt .-%, preferably below, in particular up to 8 wt .-% and for example between 1 and 5 wt .-% of nonionic surfactants, based on the finished composition, allow.

Ingredients which contain water in the abovementioned form and / or serve as carriers for liquids, in particular for nonionic surfactants which are liquid at room temperature, ie contain liquid ingredients which are liquid at room temperature and can be used according to the invention, by no means have a softening point below 45.degree on. Likewise, the individual constituents / raw materials used separately have a melting point of at least 45.degree. The melting point or the softening point of all individual raw materials and constituents used in the premix is preferably above 45 ° C. and advantageously at at least 50 ° C.

In a preferred embodiment of the invention, at least 80% by weight, in particular at least 85% by weight and with particular preference at least 90% by weight of the constituents used in the premix have a substantially higher softening point or melting point than are achieved under the process conditions , In practice, the process temperatures alone, for economic reasons, not above 150 ° C, preferably not above 120 ° C. Thus, at least 80 wt .-% of the ingredients used have a softening point or melting point above 150 ° C. In general, the softening point or the melting point is even far above this temperature. If ingredients are used which decompose under the influence of temperature, for example peroxy bleaches such as perborate or percarbonate, the decomposition temperature of these ingredients is also significantly above 45 ° C at a pressure of 1 and especially at higher pressures present in the extrusion processes. Preferably, however, such ingredients are added only after the extrusion process.

The premix, in addition to the solid components up to 10 wt .-% at temperatures below 45 ° C and a pressure of 1 bar liquid nonionic, surfactants, in particular the usually used in detergents or cleaning agents alkoxylated alcohols, such as fatty alcohols or oxo alcohols a C chain length between 8 and 20 and in particular an average of 3 to 7 ethylene oxide units per mole of alcohol (for more detailed description see above). The addition of the liquid nonionic surfactants can be carried out in the amounts which still ensure that the premix is in free-flowing form. If such liquid nonionic surfactants are introduced into the premix, it is preferred that liquid nonionic surfactants and the disintegrating binder be introduced separately from each other in the process. In a preferred embodiment of the invention, the liquid nonionic surfactants are applied to the powder stream in a continuous production process, in particular by means of nozzles, and are absorbed by the latter.

The assembly of the components with simultaneous or subsequent shaping is carried out by extrusion. The actual extrusion process takes place, for example, at processing temperatures which, at least in the compression step, correspond at least to the temperature of the softening point, if not even the temperature of the melting point. In a preferred embodiment of the invention, the process temperature is significantly above the melting point or above the temperature at which the binder is present as a melt. In particular, however, it is preferred that the process temperature in the compression step is not more than 20 ° C above the melting temperature or the upper limit of the melting range of the binder. Although it is technically quite possible to set even higher temperatures; However, it has been shown that a temperature difference to the melting temperature or to the softening temperature of the binder of 20 ° C in general is quite sufficient and even higher temperatures cause no additional advantages. Therefore, it is particularly preferred, especially for energetic reasons, to work above, but as close as possible to the melting point or at the upper temperature limit of the melting range of the binder. Such a temperature control has the further advantage that even thermally sensitive raw materials, such as peroxy bleach such as perborate and / or percarbonate, but also enzymes, can increasingly be processed without serious losses of active substance. The possibility of precise temperature control of the binder in particular in the decisive step of the compression, ie between the mixing / homogenization of the premix and the shaping, allows a very favorable energy and extremely gentle for the temperature-sensitive components of the premix process management, since the premix for a short time the is exposed to higher temperatures. Preferably, the duration of the action of temperature is between 10 seconds and a maximum of 5 minutes, in particular, it is a maximum of 3 minutes.

In a preferred embodiment of the invention, the method according to the invention is carried out by means of an extrusion, as described, for example, in the European patent EP-B-0 486 592 or the international patent applications WO-A-93/02176 and WO-A-94/09111 to be discribed. In this case, a solid premix is extruded under pressure strand and cut the strand after exiting the hole shape by means of a cutting device to the predeterminable granule dimension. The homogeneous and solid premix contains a plasticizer and / or lubricant which causes the premix to be plastically softened and extrudable under the pressure of specific work. Preferred plasticizers and / or lubricants are surfactants and / or polymers which, however, in the context of the present invention, with the exception of the abovementioned nonionic surfactants, are not introduced into the premix in liquid form and in particular not in aqueous form but in solid form.

To explain the actual extrusion process, reference is hereby expressly made to the abovementioned patents and patent applications. In a preferred embodiment of the invention, the premix is preferably fed continuously to a 2-screw extruder with a co-rotating or counter-rotating screw guide, whose housing and its extruder granulating head can be heated to the predetermined extrusion temperature. Under the shearing action of the extruder screws, the premix under pressure, which is preferably at least 25 bar, at extremely high throughputs depending on the apparatus used but also may be below, compacted, plasticized, extruded in the form of fine strands through the hole die plate in the extruder head and finally Preferably, the extrudate is reduced to approximately spherical to cylindrical granules by means of a rotating bladed knife. The hole diameter of the hole nozzle plate and the strand cut length are matched to the selected granule dimension. In this embodiment, the production of granules of a substantially uniformly predeterminable particle size succeeds, wherein in detail the absolute particle sizes can be adapted to the intended use. In general, particle diameters of at most 0.8 cm are preferred. Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range of 0.5 to 5 mm and in particular in the range of about 0.8 to 2 mm. The length / diameter ratio of the chopped primary granules is in a preferred embodiment in the range of about 1: 1 to about 3: 1.

Furthermore, it is preferable to supply the still plastic primary granules to a further shaping processing step; At the same time, edges present on the raw extrudate are rounded, so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired, small amounts of dry powder, for example, zeolite powder, such as zeolite NaA powder, may be included in this stage. This shaping can be done in commercially available Rondiergeräten. Care should be taken to ensure that only small amounts of fine grain content are produced in this stage. However, a drying, which is described as the preferred embodiment of the above-mentioned prior art documents, is unnecessary in the context of the present invention, since the process according to the invention is essentially anhydrous, ie without the addition of free, unbound water.

In a particularly preferred embodiment, the invention now provides that the temperature control in the transition region of the screw, the pre-distributor and the nozzle plate is designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least achieved, but preferably exceeded. The duration of the action of temperature in the compression region of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.

In a particularly advantageous embodiment of the invention, the binder used has a melting temperature or a melting range up to 75 ° C .; Process temperatures which are at most 10 ° C. and in particular at most 5 ° C. above the melting point or the upper temperature limit of the melting range of the binder have proven to be particularly favorable.

Under these process conditions, the binder also exerts the function of a lubricant in addition to the previously mentioned modes of action and at least prevents or reduces the occurrence of sticking to apparatus walls and compaction tools. This applies not only to processing in the extruder, but equally also to processing, for example, in continuous mixers / granulators or rolls.

The compacted material preferably has temperatures not exceeding 60 ° C. directly after leaving the production apparatus, temperatures between 35 and 60 ° C. being particularly preferred. It has been found that exit temperatures of 40 to 55 ° C are particularly advantageous.

It is the essence of a preferred embodiment of the invention that the particle size distribution of the premix is applied substantially wider than that of the end product according to the invention and produced according to the invention. In this case, the premix may contain much larger fine grain fractions, even dust fractions, and possibly also coarse-grained fractions, but it is preferred that a premix having a relatively broad particle size distribution and relatively high levels of fine grit in a final product with relatively narrow particle size distribution and relatively low levels of fine grain is transferred.

The fact that the inventive method is substantially anhydrous - d. H. With the exception of water contents ("impurities") of the solid materials used anhydrous - is not only the risk of gelling the surfactant raw materials already minimized in the manufacturing process to exclude, in addition, an environmentally valuable process is also provided by the absence of a subsequent drying step not only energy is saved but also emissions, as they occur predominantly in conventional types of drying, can be avoided.

Another object of the invention, an extrudate, which was prepared by the process according to the invention. With particular preference extrudates are provided which have spherical shape or bead shape.

Detergents and cleaners

The extrudates obtained can either be used directly as detergents or cleaning agents or aftertreated and / or treated by customary methods beforehand. The use of the extrudates as detergents or cleaning agents or as a constituent of such agents is thus also part of the invention.

The usual post-treatments include, for example, powdering with finely divided ingredients of detergents or cleaners, which generally increases the bulk density. However, a preferred aftertreatment is also the procedure according to the German patent applications DE-A-195 24 287.4 and DE-A-195 47 457.0 in which dust-like or at least finely divided ingredients (the so-called fines) are adhered to the particulate process end products (extrudates) used according to the invention, which serve as a core, and thus agents are produced which have these so-called fine fractions as outer shell. Advantageously, this again takes place by melt agglomeration, wherein the same binders can be used as in the process according to the invention. For the melt agglomeration of the fines on the base granules according to the invention and produced according to the invention is expressly to the disclosure in the German patent applications DE-A-195 24 287.4 and DE-A-195 47 457.0 directed.

By treatment, it is generally understood that the particulate process end-products of the present invention serve as a base formulation to which other ingredients, optionally other preformulated ingredients, are also blended. Here is the description of the cited patent applications and patents, in particular so on the European patent EP-B-0 486 592 as well as the German patent applications P 195 19 139.0 . P 195 24 287.4 and P 19 54 7457.0 directed.

The granular detergents of the invention contain the extrudates described herein as base granules or base extrudates typically in amounts of at least 30% by weight, preferably at least 50% by weight, for example in amounts of from 50 to 80% by weight. In addition to the extrudates, the detergents and cleaners may contain other ingredients that are commonly included in such compositions. Such ingredients will be described in more detail below without this enumeration being exhaustive. The remaining ingredients may have been prepared and admixed by any known method. However, it is preferred that these remaining ingredients were prepared by the methods described herein. In particular, this makes it possible to produce base granules and remaining constituents with approximately the same flowability, bulk density, size and particle size distribution.

Other detergent ingredients include graying inhibitors (soil carriers), foam inhibitors, bleaching agents and bleach activators, optical brighteners, enzymes, fabric softening substances, soil release polymers, dyes and fragrances, as well as neutral salts such as sulfates and chlorides in the form of their sodium or potassium salts. Furthermore, additional additional builders and surfactants may also be added.

The agents may contain, for example, components which positively influence oil and grease washability from textiles (Soil Release Polymers (SRP)). The preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose having a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, as well as 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. The amount of such polymers in the final product is usually 1 to 5 wt .-%, in particular 1.5 to 3 wt .-%.

Other suitable ingredients of the compositions are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures thereof. It is possible, for example, to use alkali metal carbonate and amorphous alkali silicate, above all sodium silicate, with a molar ratio of Na ₂ O: SiO _{2 of} from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5. Preference is given to using carbonate, in particular sodium carbonate, and / or bicarbonate, in particular sodium bicarbonate, typically in amounts of up to 10% by weight.

Organic builders, especially citrate, may also be formulated in the granular detergents and cleaners. The amount of citrate in the final product may be 0.5 to 5 wt .-%, in particular 1-3 wt .-% amount.

Further surfactants which can be added, for example, further alkylbenzenesulfonates, for example in amounts of from 1 to 10% by weight.

To reduce the pH of detergents or cleaners, it is also possible to use acid salts or slightly alkaline salts. Bisulfates and / or bicarbonates or the abovementioned organic polycarboxylic acids, which can also be used simultaneously as builders, are preferred as the acidifying component.

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ provide peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. The content of the bleaching agents is preferably from 5 to 25% by weight and in particular from 15 to 25% by weight, it being advantageous to use perborate monohydrate or percarbonate.

As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably up to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and from the German patent applications DE-A-196 16 693 and DE-A-196 16 767 known enol esters and acetylated sorbitol and mannitol or their in the European patent application EP-A-0 525 239 mixtures described (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are known from international patent applications WO 94/27970 . WO-A-94/281 WO 94/28103 . WO-A-95/00626 . WO 95/14759 and WO 95/17498 are known. The from the German patent application DE-A-196 16 769 known hydrophilic substituted acyl acetals and in the German patent application DE-A-196 16 770 as well as the international patent application WO-A-95/14075 Acyllactame described are also preferably used. Also from the German patent application DE-A-44 43 177 Such bleach activators are in the usual amount range, preferably in amounts of 1 wt .-% to 15 wt .-%, in particular 3 wt .-% to 12 wt .-%, based on the total agent included ,

When used in automatic washing processes, it may be advantageous to add conventional foam inhibitors to the compositions. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C18-C24 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 advantage a mixtures of different foam inhibitors are used, for. As those 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. In particular, mixtures of paraffins and bistearylethylenediamides are preferred.

Suitable enzymes are, in particular, those from the class of the hydrolases, such as the proteases, lipases or lipolytic enzymes, amylases, cellulases or mixtures thereof. Oxireductases are also suitable. 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. These 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 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, alpha-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and beta-glucosidases, which are also called cellobiases, or mixtures thereof used. Since the different cellulase types differ by their CMCase avicelase activities, the desired activities can be adjusted by targeted mixtures of the cellulases.

The enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation. The proportion of the enzymes, enzyme mixtures or enzyme granules in the agents may be for example about 0.1 to 10 wt .-%, preferably 0.1 to about 5 wt .-%.

In addition, the agents may still contain enzyme stabilizers. For example, 0.5 to 1 wt .-% sodium formate can be used. It is also possible to use proteases which are soluble in calcium salts and have a calcium content of preferably about 1.2% by weight, based on the enzyme, are stabilized. 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 or 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, for. 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 means may finally also contain optical brighteners defined as described above.

Any of the detergents and cleaners described herein may be any method known in the art.

washing method

The granular detergents or cleaners described herein are used in particular as detergents in a machine washing process for cleaning textiles. A corresponding use and such methods are therefore also part of the invention.

Washing process, d. H. In particular, processes for cleaning textiles are generally distinguished by the fact that cleaning-active substances are applied to the items to be cleaned in one or more process steps and washed off after the action time, or that the items to be cleaned are otherwise treated with a detergent or a solution of this agent. In such washing processes, in various embodiments of the invention, temperatures of up to 95 ° C or less, 90 ° C or less, 60 ° C or less, 50 ° C or less, 40 ° C or less, 30 ° C or less or 20 ° C ° C or less. These temperature data refer to the temperatures used in the washing steps.

All facts, objects and embodiments which are described for the production of washing and cleaning agents are also applicable to the means as such and their use and vice versa.

Examples

Example 1: Detergent Formulation

Table 1 shows crude extrudates E1 and E2 according to the invention in comparison with known non-inventive crude extrudates V1 and V2. Table 2 shows the composition of the detergents formulated therefrom (WE1, WE2, WV1, WV2). Table 1: Raw extrudate composition (all data in% by weight of active substance) component V1 E1 V2 E2 LAS-Na (linear alkyl benzene sulphonate, Na salt) 19.4 23.9 19.2 21.4 Fatty alcohol sulfate 6.6 8.2 6.6 7.4 Fatty alcohol ether 7 EO 6.4 8.0 7.0 7.8 C16 / 18 soap 1.0 0.7 1.0 1.1 HEDP, tetrasodium salt 1.2 1.4 1.2 1.3 polycarboxylate 4.0 4.5 2.9 3.2 PEG4000 2.2 2.2 2.2 2.2 trisodium citrate 4.4 - 4.4 - Zeolite A 36.8 39.3 38.5 42.8 NaCl 0.1 0.1 - - sodium 0.02 0.03 - - sodium sulphate 5.2 0.3 3.3 0.2 DTI 0.4 0.4 0.77 0.86 Other ingredients (water, leftovers) Ad 100 Ad 100 Ad 100 Ad 100 Table 2: Detergent composition (all data in% by weight of active substance) component WV1 HS1 WV2 WE2 Raw extrudate (Table 1) 51.0 (V1) 51.0 (E1) 75.0 (V2) 75.0 (E2) alkylbenzenesulfonate 4.0 4.0 5.0 5.0 SRP 2.0 2.0 2.0 2.0 carboxymethylcellulose 2.5 2.5 2.5 2.5 trisodium citrate 2.0 2.0 4.3 4.3 sodium 21.0 21.0 - - TAED 12.0 12.0 - - defoamers 1.0 1.0 1.2 1.2 citric acid - - 1.8 1.8 bicarbonate - - 1.3 1.3 soda - - 1.2 1.2 enzymes 4.0 4.0 4.0 4.0 Other ingredients (water, leftovers) Ad 100 Ad 100 Ad 100 Ad 100

Example 2: Physical Data

To determine the particle sizes, 100 g of crude extrudate or detergent were sieved by means of a VE1000 sieve from Retsch GmbH for 2 minutes at an interval of 10 seconds and an amplitude of 2 mm. For this purpose, a sieve was assembled in such a way that the mesh size decreases towards the bottom. This set will be provided with a closure bottom and inserted into the test sieve machine. Then the sample was placed on the top sieve. After sieving, the proportion of particles per sieve was determined gravimetrically by transferring and weighing the different fractions, including the particles stuck in the sieve mesh, into weigh trays.

To measure the bulk density, the weight of one liter of the raw extrudates or detergents was determined by using a standard cylinder bulk density tester. The determination of the bulk density is carried out according to DIN ISO 697, Jan. 1984 ,

The dissolution rate was determined by dissolving 7.3 g of the crude extrudates or detergent at 30 ° C. with stirring (800 rpm) in 1 l of deionized water and determining the undissolved fraction gravimetrically after 90 s. For this, a 2 L beaker of 115 mm inside diameter was used using an IKA stirrer (350 mm stirrer shaft, mounted 1.5 +/- 0.5 mm above the bottom of the beaker). After 90 s, undissolved solid was filtered through a sieve with a mesh size of 0.2 mm and dried at 80 ° C for at least 2 h.

Tables 3 and 4 show that it was surprisingly found that for the crude extrudate according to the invention and the resulting detergent despite increasing particle size, the bulk density decreases and the dissolution rate is improved. Table 3: Particle sizes, bulk density and solubility of the raw extrudates from Table 1 V1 E1 V2 E2 Particle size (% by weight) > 2.0 mm 1 3 0 4 > 1.8 mm 2 15 8th 14 > 1.6 mm 80 65 69 59 > 1.4 mm 11 8th 11 8th > 1.25 mm 4 6 6 9 > 1.0 mm 1 2 2 3 > 0.8 mm 1 1 2 2 > 0.4 mm 0 0 0 0 0.4-0 mm 0 0 0 0 Bulk density (g / L) 700 650 740 620 Solubility (residual solids in% by weight) 5.4 1.7 4.9 1.8 Table 4: Particle sizes, bulk density and solubility of the detergents from Table 2 WV1 HS1 WV2 WE2 Particle size (% by weight) > 2.0 mm 1 2 1 4 > 1.8 mm 3 11 7 14 > 1.6 mm 44 37 55 52 > 1.4 mm 9 8th 10 8th > 1.25 mm 14 14 11 10 > 1.0 mm 11 11 7 6 > 0.8 mm 16 14 9 5 > 0.4 mm 1 1 1 0 0.4-0 mm 0 0 0 0 Bulk density (g / L) 730 720 780 680 Solubility (residual solids in% by weight) 9.7 7.2 7.3 5.0

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

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Cited non-patent literature

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Claims (10)

Washing or cleaning-active, particulate extrudate containing anionic and / or nonionic surfactants and builders, characterized in that the extrudate based on the total weight of the extrudate less than 1.0 wt .-%, preferably less than 0.5 wt .-% , more preferably less than 0.2 weight percent trisodium citrate, especially alkali citrate, more preferably citrate, and less than 5 weight percent, preferably less than 3 weight percent, more preferably less than 2 weight percent inorganic electrolytes , in particular inorganic salts. Extrudate according to claim 1, characterized in that the extrudate based on the total weight of the extrudate contains at least 25 wt .-%, in particular at least 30 wt .-% of anionic surfactants. Extrudate according to claim 1 or 2, characterized in that the extrudate contains at least 15 wt .-%, in particular at least 20 wt .-% of builders, in particular zeolite. Extrudate according to one of claims 1 to 3, characterized in that the extrudate further contains at least one binder, in particular in an amount of at least 1 wt .-%, but less than 15 wt .-% based on the extrudate. Extrudate according to one of claims 1 to 4, characterized in that the extrudate (1) consists of at least 90 wt .-% of particles having a particle size> 400 microns; and / or (2) at least 10% by weight, preferably at least 15% by weight, of particles having a particle size> 1.8 mm; and / or (3) at 100% by weight of particles having a particle size distribution comprising at least 70% by weight of particles between 0.8 and 2.0 mm, preferably at least 80% by weight of particles between 1.4 and 1.8 mm, consists. Washing or cleaning-active extrudate according to one of claims 1 to 5, characterized in that the extrudate has a bulk density of more than 600 g / l, in particular 625-700 g / l. Granular washing or cleaning agent containing the washing or cleaning-active extrudate according to one of claims 1 to 6, in particular in an amount of at least 30 wt .-%, preferably of at least 50 wt .-% based on the detergent or cleaning agent. A process for producing a washing or cleaning-active extrudate according to any one of claims 1 to 6 by means of extrusion, characterized in that a solid premix compressed extruded under pressure and the strand is cut after emerging from the hole shape by means of a cutting device to the predeterminable granule dimension. Use of a granular detergent or cleaner according to claim 7 as a detergent in a machine washing process for cleaning textiles. Use of a washing or cleaning-active extrudate according to any one of claims 1 to 6 as a constituent of a detergent.