DE102015002877B4 - Washing or cleaning active extrudates, their production and use in granular washing or cleaning agents - Google Patents

Abstract

Washing or cleaning-active, particulate extrudate containing anionic and/or nonionic surfactants and builder substances, characterized in that the extrudate contains, based on the total weight of the extrudate, less than 1.0% by weight of trisodium citrate and less than 3% by weight of inorganic electrolytes, in particular inorganic salts.

Description

The invention relates to washing or cleaning-active extrudates and granular washing or cleaning agents which contain them and which show an improved dissolving rate compared to conventional washing agent granules. The invention further relates to the production of such extrudates, the extrudates produced in this way, and the use of these extrudates in washing and cleaning agent formulations and the use of the washing agents described herein in machine washing processes, in particular for textile washing.

Particle-shaped washing or cleaning agents with bulk densities of more than 600 g/l have been state of the art for some time. In recent years, the increase in bulk density has been accompanied by a concentration of the washing and cleaning active ingredients, so that the consumer has 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 as being particularly easy to dose. The production of such extrudates is used, for example, in the EP-A-0 665 879 described.

The increase in bulk density and, in particular, the higher concentration of washing or cleaning active substances in the products was generally achieved at the expense of a subjectively poorer solubility from the consumer's point of view, which is due to a slower dissolving rate of the products compared to traditional powders.

The EP-A-0 931 137 describes processes for producing particulate washing or cleaning agents which, even with a reduced surface area, exhibit improved disintegration when dissolved in the aqueous liquor and which contain a special binder which, during production, performs both the function of a lubricant and an adhesive function, but has a disintegrating effect when the agent dissolves in the aqueous liquor.

From the DE 196 11 013 A1 A particulate extrudate is known which contains anionic surfactants and builder substances. The extrudate contains no citrate and 4.1% by weight of anionic electrolytes.

Although this improves the dissolution rate of the particles, it is still not satisfactory. The object of the present invention was therefore to provide particulate washing or cleaning agents or raw materials therefor which, particularly in the case of a spherical shape (pearl shape), have further improved disintegration when dissolved in the aqueous liquor. The inventors have surprisingly found that this object can be achieved by reducing the amount of inorganic electrolytes, particularly inorganic salts and bases, and citrate in the product compared to commercially available reference formulations.

The invention therefore relates, in a first aspect, to a washing or cleaning-active particulate extrudate containing anionic and/or nonionic surfactants and builder substances, characterized in that the extrudate contains, based on the total weight of the extrudate, less than less than 1.0% by weight of trisodium citrate and less than 3% by weight of inorganic electrolytes, in particular inorganic salts.

In a further aspect, the invention relates to a granular washing or cleaning agent containing the washing or cleaning-active extrudate described herein and to the use of the extrudates described herein as a component of washing and cleaning agents.

Another aspect of the invention is directed to a method for producing a washing or cleaning active extrudate described herein by means of extrusion, wherein a solid premix is pressed under pressure into a strand and the strand is cut to the predeterminable granulate dimension by means of a cutting device after it emerges from the hole mold, as well as the extrudate thus obtainable. The granulate dimension is essentially determined based on the dimensions of the opening of the hole mold, the extrusion rate, i.e. the flow rate at which the extrudate leaves the hole mold, and the cutting device. The rate at which the cutting device cuts determines the length of the particulate extrudates. The extrudate can also be deformed in a desired manner by the impulse during the cutting process. If an elliptical hole mold with an inner pin is used, the extrudate can be formed into a circular ring by the cut. The "hole mold" represents the exit of the extruder through which the extruded material is pressed.

The term “particulate extrudate” means that the particle originates from an extrusion process.

The “cutter” may be a single knife that cuts the extruded strand, but may also be an array of multiple blades that are attached to the exit of the extruder and rotated to cut the extrudate.

Finally, the invention also covers the use of a granular washing or cleaning agent described herein in a machine washing process or process for machine washing textiles using the extrudates and detergents described herein.

For the purposes of the invention, particulate or granular extrudates or washing or cleaning agents are preferably understood to mean those which have no dusty components and in particular no particle sizes below 200 µm. In particular, particle size distributions are preferred which have at least 90% by weight, more preferably at least 95, 96, 97, 98, 99 or 100% by weight of particles with a diameter greater than 400 µm. In a particularly preferred embodiment of the invention, the extrudates consist of 100% by weight of particles with a particle size distribution which has 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% by weight, preferably at least 15% by weight of the particles have a particle size >1.8 mm.

Whenever reference is made to particle sizes herein, the information always refers to values determined by sieve analysis. For example, particle sizes can be determined by sieving the particles using a VE1000 sieve (Retsch GmbH, Haan) for 2 minutes at an interval of 10 seconds and an amplitude of 2 mm and determining the proportion of particles per sieve gravimetrically. To do this, 100 g of sample is placed on the top sieve of a set of sieves which is assembled in such a way that the mesh size decreases towards the bottom and which is provided with a cover base. After sieving under the conditions mentioned, the proportion of particles per sieve is determined gravimetrically by transferring the different fractions, including the particles caught in the sieve mesh, to weighing dishes and weighing them.

It was surprisingly found that the subject matter of the claim results in the particulate extrudate having a changed 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 suspected that the invention provides an unexpected synergism. At the same time, a relatively high bulk density, an averagely larger particle diameter and an increased dissolution rate are achieved. This is surprising since high bulk densities and large particles usually lead to poor dissolution rates.

Particularly 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 solubility rates can be observed. In this respect, preferred embodiments are characterized in that the extrudate contains at least 10% by weight, preferably at least 15% by weight, of particles with a particle size of > 1.8 mm.

In certain embodiments, the proportion of particles with a particle size of > 1.8 mm should not exceed 20% by weight. Detergents or cleaning agents are understood to be compositions that can be used for washing or cleaning without the usual need to add additional ingredients. The detergents described here can be detergents for textiles or natural fibers. The detergents within the scope of the invention also include washing aids that are added to the actual detergent during manual or machine washing of textiles in order to achieve an additional effect or to enhance an effect.

Unless otherwise stated, all quantities given in connection with the components of the extrudate or washing and cleaning agent described herein refer to % by weight, in each case based on the total weight of the extrudate/agent. Furthermore, such quantities that refer to at least one component always refer to the total amount of this type of component contained in the extrudate/agent, unless explicitly stated otherwise. This means that such quantities, for example in connection with "at least one non-ionic surfactant", refer to the total amount of non-ionic surfactants contained in the extrudate or washing or cleaning agent.

"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 components of the compositions described herein, this statement does not refer to the absolute amount of molecules but to the type of component. "At least one nonionic surfactant" therefore means, for example, one or more different nonionic surfactants, ie one or more different types of nonionic surfactants. Together with amounts, the amounts refer to the total amount of the correspondingly designated type of component, as already defined above.

The term “trisodium citrate” refers to the triple sodium salts of citric acid.

When using hydrates of trisodium citrate, the weight proportion of water is not included in the calculation of the proportion of trisodium citrate. Only the weight proportion of trisodium citrate is to be taken into account.

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

“Inorganic electrolytes”, as used herein, refers to compounds which, in the solid, liquid or dissolved state, exist at least partially as ions. Important electrolytes in the sense 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 can be any inorganic cation. In specific embodiments, the inorganic salts include in particular sulfates and carbonates. Other important inorganic electrolytes are inorganic bases, such as sodium hydroxide 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 3% by weight, more preferably less than 2% by weight, most preferably 1% by weight or less. The term does not include organic electrolytes, in particular no organic sulfates, carboxylic acids, etc. used as surfactants.

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 optionally other conventional components, with the proviso that citrate and inorganic electrolytes are only contained in maximum amounts as stated above.

Surfactants

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

Preferred surfactants of the sulfonate type are C9-C13 alkylbenzenesulfonates, olefinsulfonates, i.e. mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from C12-C18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.

Also suitable are alkanesulfonates obtained from C12-C18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.

Also suitable are the esters of alpha-sulfofatty acids (ester sulfonates), e.g. the alpha-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which are obtained by alpha-sulfonation of the methyl esters of fatty acids of vegetable and/or animal origin with 8 to 20 C atoms in the fatty acid molecule. and subsequent neutralization to form water-soluble mono-salts. These are preferably the alpha-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, although sulfonation products of unsaturated fatty acids, for example oleic acid, can also be present in small amounts, preferably in amounts not exceeding about 2 to 3% by weight. Alpha-sulfofatty acid alkyl esters are particularly preferred, which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters. The methyl esters of alpha-sulfofatty acids (MES), but also their saponified disalts, are used with particular advantage.

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

Preferred alk(en)yl sulfates are the alkali metal and especially the sodium salts of the sulfuric acid half-esters of the C12-C18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C10-C20 oxo alcohols and those half-esters of secondary alcohols of this chain length. Also preferred are alk(en)yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis and which have a degradation behavior similar to that of the corresponding compounds based on oleochemical raw materials. C16-C18 alk(en)yl sulfates are particularly preferred for washing purposes. It can also be particularly advantageous, and particularly advantageous for machine detergents, to use C16-C18 alk(en)yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants that have a lower Krafft point and show a low tendency to crystallize at relatively low washing temperatures of, for example, room temperature (20°C) to 40°C. 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, not saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C16 to C22 are used. Mixtures of saturated, predominantly C16 sulfated fatty alcohols and unsaturated, predominantly C18 sulfated fatty alcohols are particularly preferred. Weight ratios of alkyl sulfates to alkenyl sulfates of 10:1 to 1:2 and in particular of about 5:1 to 1:1 are preferred.

Also 2,3-alkyl sulfates, which, for example, according to the US Patent 3,234,258 or 5,075,041 are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C7-C21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C9-C11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C12-C18 fatty alcohols with 1 to 4 EO, are also suitable. Due to their high foaming behavior, they are only used in relatively small amounts in detergents, for example in amounts of 1 to 5% by weight.

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

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

Other anionic surfactants that can be considered are fatty acid derivatives of amino acids, for example N-methyltaurine (taurides) and/or N-methylglycine (sarcosides). Particularly preferred are sarcosides or sarcosinates, especially sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate.

Other anionic surfactants that can be considered are soaps, preferably in amounts of 0.2 to 5% by weight. 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 soap mixtures derived from natural fatty acids, e.g. coconut, palm kernel or tallow fatty acids. The well-known alkenyl succinic acid salts can also be used together with these soaps or as a substitute for soaps.

The anionic surfactants (and soaps) can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

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

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

In addition to anionic surfactants, nonionic surfactants are particularly preferred.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, especially primary alcohols with 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 is usually the case in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 carbon atoms, e.g. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred. 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. C12-18 alcohols with 7 EO are particularly preferred. The degrees of ethoxylation stated represent statistical averages which can be a whole or a fractional number for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these non-ionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

The non-ionic 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 C atoms, and G is the symbol that stands for a monosaccharide having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4. Alkyl glycosides which have a degree of softening above 80°C and a melting point above 140°C are particularly suitable.

In the polyhydroxy fatty acid amides of formula (I) R ² -CO-N(R ³ )-[Z] (I) R ² CO represents an aliphatic acyl radical having 6 to 22 carbon atoms, R ³ represents hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] represents 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 an aryl radical or an oxyalkyl radical having up to 8 carbon atoms, with C1-4 alkyl radicals or phenyl radicals being preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least 2 hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example, according to the teaching of the international patent application WO-A-95/07331 by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst into the desired polyhydroxy fatty acid amides. Particularly preferred glucamides melt at 95 to 105°C.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and/or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in the Japanese patent application JP58/217598 or which preferably follow the procedure described in the international patent application WO-A-90/13533 described processes. 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.

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

Other surfactants that can be considered are so-called gemini surfactants. These are generally understood to be compounds that have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated from each other by a so-called "spacer". This spacer is usually a carbon chain that should be long enough so that the hydrophilic groups are sufficiently far apart so that they can 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 trimer alcohol trisulfates and ether sulfates according to the older German patent application DE-A-195 03 061 .3. End-capped dimeric and trimeric mixed ethers according to the older German patent application DE-A-195 13 391.9 are particularly characterized by their bi- and multifunctionality. The end-capped surfactants mentioned have good wetting properties and are low-foaming, making them particularly suitable for use in machine washing or cleaning processes.

However, gemini polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides, as described in the international patent applications WO-A-95/19953 , WO-A-95/19954 and WO95-A -/19955.

In preferred embodiments, anionic and nonionic surfactants are used in the extrudates or the solid premixes used to produce them, the anionic surfactants preferably being selected from linear alkylbenzenesulfonates (LAS), fatty alcohol sulfates (FAS) and soaps and the nonionic surfactants preferably being selected from alkoxylated fatty alcohols. Particularly preferred are mixtures of C9-C13 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, C12-18 fatty alcohol sulfates (FAS, alkyl sulfates), in particular in amounts of 5 to 10% by weight, soaps, in particular C16-18 soaps, preferably in amounts of 0.5 to 2% by weight, 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.

Builders

The term “builder substance” includes organic and inorganic builder substances.

In addition to the surfactants, 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 used 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 used as a spray-dried powder or as an undried, stabilized suspension that is still moist from its production. If the zeolite is used as a suspension, this can contain small additions of non-ionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C12-C18 fatty alcohols with 2 to 5 ethylene oxide groups, C12-C14 fatty alcohols with 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; measurement method: Coulter Counter) and preferably contain 18 to 22 wt.%, in particular 20 to 22 wt.% 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 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in the European patent application EP-A-0 164 514 Preferred crystalline layered silicates of the formula given are those in which M is sodium and x is 2 or 3. In particular, both beta- and delta-sodium disilicates Na ₂ Si ₂ O ₅ yH ₂ O are preferred.

Other suitable substitutes or partial substitutes for zeolite are layered silicates of natural and synthetic origin. Such layered silicates are known, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 DE-A-35 26 405. Their use is not limited to a specific composition or structural formula. However, smectites, especially bentonites, are preferred.

Suitable layered silicates, which belong to the group of smectites that swell with water, are for example montmorillonite, hectorite or saponite. In addition, small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas. Furthermore, due to their ion-exchanging properties, the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na ⁺ and Ca ²⁺ . The amount of hydration water is usually in the range of 8 to 20 wt.% and depends on the swelling state or the type of processing. Useful layered silicates are for example made of US-A-3,966,629 , EP-A-0 026 529 and EP-A-0 028 432 Preferably, layered silicates are used, which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.

Useful organic builder substances 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 conventional methods, for example acid- or enzyme-catalyzed methods. Preferably, these are hydrolysis products with average molecular weights in the range from 400 to 500,000. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a common measure of the reducing effect of a polysaccharide in comparison to dextrose, which has a DE of 100. Maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2000 to 30000 are suitable. A preferred dextrin is described in the British patent application GB94 19 091 The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, 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 and international patent applications WO-A-92/18542 , WO-A-93/08251 , WO-A-94/28030 , WO-A-95/07303 , WO-A-95/12619 and WO-A-95/20608 known. A product oxidized at C6 of the saccharide ring can be particularly advantageous.

Furthermore, polymeric polycarboxylates, for example the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid), can be used as organic builder substances. Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. To improve water solubility, the polycarboxylates can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers. Corresponding sulfopolymers can therefore also be used as builders.

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

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

Other suitable builder substances are oxidation products of carboxyl group-containing polyglucosans and/or their water-soluble salts, as described, for example, in the international patent application WO-A-93/08251 or their manufacture, for example, in the international patent application WO-A-93/16110 Also suitable are oxidized oligosaccharides according to the older German patent application DE-A-196 00 018 .1.

Other preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives of those described in the German patent application DE-A-195 40 086 .0 reveals that in addition to cobuilder properties, they also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are obtained by reacting dialdehydes with polyolcarboxylic acids containing 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in the European patent application EP-A-0 280 223 Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and/or glucoheptone.

Finally, the salts of polyphosphonic acids should also be mentioned as builder substances, preferably the neutrally reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate (HEDP), diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate, which are usually used in amounts of 0.1 to 1.5 wt.%.

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

binder

The extrudates can also contain at least one component which serves as a binder in the extrudate or the premix used to produce the extrudate and which is solid at room temperature but is liquid in the form of a melt during compaction under the extrusion conditions. The binder, which can also be a binder mixture, can be sprayed onto the premix in melted form or added dropwise to the premix, but it has also proven advantageous to introduce the binder in solid form as a powder into the premix. The melting point or softening point of the binder is at least 45°C at a pressure of 1 bar and (in particularly for economic reasons) preferably below 200°C, in particular below 150°C. If the binder is introduced into the premix in the form of a melt, the temperature in the melting vessel is also more than 45°C up to a maximum of about 200°C, whereby the temperature in the melting vessel can significantly exceed the melting temperature or the temperature of the softening point of the binder or the binder mixture.

It has proven to be advantageous if the binding agent is distributed as homogeneously as possible in the material to be compacted during the compaction process step. For this to happen, temperatures must be present during the compaction process step at which the binding agent is at least softened, but preferably completely and not just partially in molten form. If a binding agent with a high melting point or high softening point is selected, a temperature must be set during the compaction process step which ensures that the binding agent melts. In addition, depending on the desired composition of the end product, temperature-sensitive raw materials should also be able to be processed. Here, the upper temperature limit is given by the decomposition temperature of the sensitive raw material, whereby it is preferable to work significantly below the decomposition temperature of this raw material. On the other hand, the lower limit for the melting point or softening point is of great importance because melting points or softening points below 45°C generally produce an end product that tends to stick together even at room temperature and slightly higher temperatures around 30°C, i.e. at summer temperatures and under storage or transport conditions. It has proven particularly advantageous to work a few degrees, for example 2 to 20°C, above the melting point or softening point.

The binding agent(s) must be of such a type that the adhesive properties are retained even at temperatures that are significantly above the melting point or softening point. On the other hand, it is also important for the choice of the type and amount of binding agent(s) used that the binding properties are not lost within the end product after cooling down again, thus ensuring the cohesion of the end product, but that the end product itself does not stick together under normal storage and transport conditions.

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

In a preferred embodiment of the invention, a binder is used which is already completely melted at temperatures of 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 specific binder is desired - be adapted to the binder.

Preferred binders, which can be used alone or in a mixture with other binders, are polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols. Modified polyalkylene glycols include in particular the sulfates and/or disulfates of polyethylene glycols or polypropylene glycols with a relative molecular mass between 600 and 12,000 and in particular between 1,000 and 4,000. Another group consists of mono- and/or disuccinates of polyalkylene glycols, which in turn have relative molecular masses between 600 and 6,000, preferably between 1,000 and 4,000. For a more detailed description of the modified polyalkylene glycol ethers, please refer to the disclosure of the international patent application WO-A-93/02176 In the context of this invention, polyethylene glycols include polymers in the production of which, in addition to ethylene glycol, C3-C5 glycols and glycerin and mixtures of these are used as starter molecules. Furthermore, ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included.

The polyethylene glycols preferably used can have a linear or branched structure, with linear polyethylene glycols being particularly preferred.

The particularly preferred polyethylene glycols include those with relative molecular weights between 2000 and 12000, advantageously around 4000, whereby polyethylene glycols with relative molecular weights below 3500 and above 5000 can be used, in particular in combination with polyethylene glycols with a relative molecular weight around 4000, and such combinations advantageously contain more than 50% by weight, based on the total amount of polyethylene glycols, of polyethylene glycols with a relative molecular weight between 3500 and 5000. However, polyethylene glycols can also be used as binders. glycols can be used which are in liquid form at room temperature and a pressure of 1 bar; this mainly refers to polyethylene glycol with a relative molecular mass of 200, 400 and 600. However, these liquid polyethylene glycols should only be used in a mixture with at least one other binder, whereby this mixture should again meet the requirements of having a melting point or softening point of at least above 45°C.

Low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular masses of up to 30,000 are also suitable as binders. Relative molecular mass ranges between 3,000 and 30, for example around 10,000, are preferred. Polyvinylpyrrolidones are preferably used not as sole binders, but in combination with others, in particular in combination with polyethylene glycols.

Raw materials which have washing or cleaning properties have proven to be suitable additional binders, for example non-ionic surfactants with melting points of at least 45°C or mixtures of non-ionic surfactants and other binders. The preferred non-ionic surfactants include the alkoxylated fatty or oxo alcohols already described above, in particular C12-C18 alcohols. Alkoxylation levels, in particular ethoxylation levels of an average of 18 to 80 AO, in particular EO per mole of alcohol, and mixtures of these have proven to be particularly advantageous. Fatty alcohols with an average of 18 to 35 EO, in particular with an average of 20 to 25 EO, in particular have advantageous binder properties in the sense of the present invention. If necessary, binder mixtures can also contain ethoxylated alcohols with an average of fewer EO units per mole of alcohol, for example tallow fatty alcohol with 14 EO. However, it is preferred to use these relatively low ethoxylated alcohols only in a mixture with higher ethoxylated alcohols. The content of these relatively low ethoxylated alcohols in the binders is advantageously less than 50% by weight, in particular less than 40% by weight, based on the total amount of binder used. In particular, non-ionic surfactants usually used in washing or cleaning agents, such as C12-C18 alcohols with an average of 3 to 7 EO, which are liquid at room temperature, are preferably only present in the binder mixtures in amounts that provide less than 2% by weight of these non-ionic surfactants, based on the end product of the process. As already described above, however, it is less preferred to use non-ionic surfactants that are liquid at room temperature in the binder mixtures. In a particularly advantageous embodiment, such nonionic surfactants are not part of the binder mixture, since they not only reduce the softening point of the mixture, but can also contribute to the stickiness of the end product and, due to their tendency to lead to gelling on contact with water, do not meet the requirement for rapid dissolution in the end product to the desired extent. It is also not preferred that the usual anionic surfactants used in washing or cleaning agents or their precursors, the anionic surfactant acids, are contained in the binder mixture.

Other non-ionic surfactants that are suitable as binding agents are fatty acid methyl ester ethoxylates, which do not tend to gel, especially those with an average of 10 to 25 EO (see below for a more detailed description of this group of substances). Particularly preferred representatives of this group of substances are methyl esters based predominantly on C16-C18 fatty acids, for example hardened beef tallow methyl ester with an average of 12 EO or with an average of 20 EO.

In one embodiment of the invention, a mixture is used as a binder which comprises C12-C18 fatty alcohol based on coconut or tallow with an average of 20 EO and polyethylene glycol with a relative molecular mass of 400 to 4000.

In a further embodiment of the invention, a mixture is used as a binder which contains predominantly methyl esters based on C16-C18 fatty acids 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 with an average of 20 EO and/or polyethylene glycol with a relative molecular mass of 400 to 4000.

Binders which have proven to be particularly advantageous embodiments of the invention are those which are based either solely on polyethylene glycols with a relative molecular mass of around 4000 or on a mixture of C12-C18 fatty alcohol based on coconut or tallow with an average of 20 EO and one of the fatty acid methyl ester ethoxylates 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 fatty acid methyl ester ethoxylates described above and a polyethylene glycol, in particular with a relative molecular mass of around 4000.

Other raw materials such as trimethylolpropylene (commercial products of BASF) can be included in binder mixtures, especially in mixtures with polyethylene glycols; however, they cannot be used as the sole binder because, although they fulfil a binding/adhesive function, they do not have a disintegrating effect.

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

Also suitable as binders, 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% by weight, but less than 15% by weight, in particular less than 10% by weight, with particular preference from 2 to 6% by weight, in each case based on the extrudate/premix.

Other components

The extrudates may also contain other ingredients commonly found in detergents and cleaning agents that do not decompose under the extrusion conditions. These include, but are not limited to, colorants, preservatives and optical brighteners.

Derivatives of diaminostilbenedisulfonic acid or its alkali metal salts can be included as optical brighteners. Suitable examples are salts of 4,4-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2-disulfonic acid or similarly structured compounds which, instead of the morpholino group, have a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type can also be present, e.g. the alkali salts of 4,4-bis(2-sulfostyryl)-diphenyl, 4,4-bis(4-chloro-3-sulfostyryl)-diphenyl, or 4-(4-chlorostyryl)-4-(2-sulfostyryl)-diphenyl. Mixtures of the aforementioned brighteners can also be used. The amount is usually not more than 1% by weight based on the total weight of the extrudate.

Manufacturing

In various embodiments, the extrudates are produced from a solid, free-flowing premix, in particular according to the EP-A-0 665 879 and EP-A-0 931 137 described process. First, a homogeneous, solid and free-flowing premix is produced from the individual components, pressed into a strand under pressure and, after emerging from the hole mold, the strand is cut to the desired granulate dimension using a cutting device.

To produce the premix, the solids are first mixed together in a conventional mixing and/or granulating device at room temperature to slightly elevated temperatures, which are preferably below the melting point or softening point of the binder, and in particular at temperatures up to 35°C. These solids also include those which, according to the European patent EP-B-0 486 592 can serve as plasticizers and/or lubricants. These include, 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 performed by the binder or binders or binder mixtures.

The binding agents are preferably added as the last component. As already explained above, they can be added as a solid, i.e. at a processing temperature that is below their melting point or softening point, or as a melt. However, the addition is advantageously carried out under conditions that achieve the most even, homogeneous distribution of the binding agent in the solid mixture. In the case of very finely divided binding agents, this can be achieved at temperatures below 40°C, for example at binding agent temperatures between 15 and 30°C. However, the binding agent advantageously has temperatures at which it already in the form of a melt, i.e. above the softening point, in particular in the form of a complete melt. Preferred temperatures of the melt are 60 to 150°C, with particular preference for 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 instantly 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 processes according to the invention for producing the extrudates described herein, the process is carried out with simultaneous or subsequent shaping, wherein in the process a premix is first produced which contains components which are present as a solid at room temperature and a pressure of 1 bar and have a melting point or softening point of not less than 45°C, and optionally up to 10% by weight of non-ionic surfactants which are liquid at temperatures below 45°C and a pressure of 1 bar, and is then converted into a grain using compaction forces at temperatures of at least 45°C in the premix and optionally subsequently further processed or prepared. In preferred embodiments, the following conditions apply:

• - the premix is essentially anhydrous, and
• - the premix contains at least one component which is in solid form at a pressure of 1 bar and temperatures below 45°C, but is in melt form under the processing conditions, this melt serving as a polyfunctional, water-soluble binder which, during the manufacture of the agents, performs both the function of a lubricant and an adhesive function for the solid components of the extrudate, but has a disintegrating effect when the extrudate is redissolved in an aqueous liquor.

In the context of this invention, "essentially water-free" is understood to mean a state in which the content of liquid water, i.e. water not present in the form of water of hydration and/or water of constitution, is less than 2% by weight, preferably less than 1% by weight and in particular even less than 0.5% by weight, in each case based on the premix. Accordingly, water can essentially only be introduced into the process for producing the premix in chemically and/or physically bound form or as a component of the components present as a solid at temperatures below 45°C at a pressure of 1 bar, but not as a liquid, solution or dispersion. Advantageously, the premix has a total water content of not more than 15% by weight, whereby this water is not in liquid form but chemically and/or physically bound, i.e. 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 is not more than 10% by weight, preferably less than 7% by weight and with particular preference a maximum of 2 to 5% by weight.

The ingredients used in the process according to the invention can - with the exception of any non-ionic surfactants that are liquid at temperatures below 45°C and a pressure of 1 bar - be separately produced components that are in powder form or particulate (fine to coarse), but in any case in solid form at room temperature and a pressure of 1 bar. Beads or (fluidized bed) granules, etc. produced by spray drying can be used as particulate particles. The composition of the components per se is not important for the invention with the exception of the water content, which must be such that the premix is essentially anhydrous as defined above and preferably contains no more than 10% by weight of water of hydration and/or water of constitution. It is also possible to use solid components in the premix that serve as carriers of liquids, for example liquid non-ionic surfactants or silicone oil and/or paraffins. These components can contain water within the limits specified above, whereby the components are preferably free-flowing and remain free-flowing or at least transportable even at higher temperatures of at least 45°C. In particular, however, it is preferred that components with a maximum of 10% by weight and, with particular preference, a maximum of 7% by weight of water, based on the premix, are used in the premix. Free water, i.e. water that is not bound to a solid in any form and is therefore in “liquid form”, is preferably not contained at all in the premix, since even very small amounts, for example around 0.2 or 0.5% by weight, based on the premix, are sufficient to dissolve the inherently water-soluble binder. This would result in the melting point or softening point being lowered and the end product would lose both flowability and bulk density.

As in the EP-A-0 931 137 As described above, it has been proven that it is by no means unimportant to which solid component the water is bound. The water that is bound to builder substances such as zeolite or silicates, particularly when the water is bound to zeolite A, zeolite P and/or zeolite X, are to be regarded as less critical. On the other hand, it is preferred that water which is bound to solid components other than the builder substances mentioned is contained in the premix, preferably in amounts of less than 3% by weight. 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 a maximum of 2 to 5% by weight. It is particularly advantageous if the premix contains no water at all that is not bound to the builder substances. However, this is technically difficult to achieve since, as a rule, at least traces of water are always introduced by the other components.

The content of the solid components used in the premix of non-aqueous liquid 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 non-ionic surfactants which are liquid at temperatures below 45°C and a pressure of 1 bar and which have been produced separately using all known production methods - for example by spray drying, granulation or spraying carrier beads. In this way, premixes can be produced which allow, for example, up to about 10% by weight, preferably less, in particular up to a maximum of 8% by weight and, for example, between 1 and 5% by weight of non-ionic surfactants, based on the finished agent.

Components which contain water in the form specified above and/or serve as carriers for liquids, in particular for non-ionic surfactants that are liquid at room temperature, i.e. which contain these ingredients that are liquid at room temperature and can be used according to the invention, do not under any circumstances have a softening point below 45°C. Likewise, the individual components/raw materials used separately have a melting point of at least 45°C. Preferably, the melting point or softening point of all individual raw materials and components used in the premix is above 45°C and advantageously 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 components used in the premix have a significantly higher softening point or melting point than is achieved under the process conditions. In practice, the process temperatures will not be above 150°C, preferably not above 120°C, for economic reasons alone. Thus, at least 80% by weight of the components used will have a softening point or melting point above 150°C. As a rule, the softening point or melting point is even well above this temperature. If ingredients are used that decompose under the influence of temperature, for example peroxy bleaches such as perborate or percarbonate, the decomposition temperature of these ingredients at a pressure of 1 and in particular at the higher pressures that exist in the extrusion process, is also significantly above 45°C. However, such ingredients are preferably only added after the extrusion process.

In addition to the solid components, the premix can contain up to 10% by weight of liquid non-ionic surfactants at temperatures below 45°C and a pressure of 1 bar, in particular the alkoxylated alcohols usually used in washing or cleaning agents, such as fatty alcohols or oxo alcohols with a C chain length of between 8 and 20 and in particular an average of 3 to 7 ethylene oxide units per mole of alcohol (see above for a more detailed description). The liquid non-ionic surfactants can be added in amounts that still ensure that the premix is in a free-flowing form. If such liquid non-ionic surfactants are introduced into the premix, it is preferred that liquid non-ionic surfactants and the disintegrating binder are introduced into the process separately from one another. In a preferred embodiment of the invention, the liquid non-ionic 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 joining 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 compaction step, correspond to at least 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 compaction step sealing 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 possible to set even higher temperatures, it has been shown that a temperature difference of 20°C to the melting temperature or softening temperature of the binder is generally sufficient and that even higher temperatures do not bring any additional benefits. It is therefore particularly preferable - particularly for energy reasons - to work above, but as close as possible to the melting point or the upper temperature limit of the melting range of the binder. Such temperature control has the further advantage that even thermally sensitive raw materials, for example peroxy bleaching agents such as perborate and/or percarbonate, but also enzymes, can increasingly be processed without serious losses of active substances. The possibility of precise temperature control of the binder, particularly in the crucial step of compaction, i.e. between the mixing/homogenization of the premix and the shaping, allows a process that is very energy-efficient and extremely gentle on the temperature-sensitive components of the premix, since the premix is only exposed to the higher temperatures for a short time. The duration of the temperature exposure is preferably 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 process 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 international patent applications WO-A-93/02176 and WO-A-94/09111 described. A solid premix is pressed into a strand under pressure and the strand is cut to the predeterminable granulate dimension using a cutting device after it emerges from the hole mold. The homogeneous and solid premix contains a plasticizer and/or lubricant, which causes the premix to soften plastically under pressure or with the introduction of specific work and become extrudable. Preferred plasticizers and/or lubricants are surfactants and/or polymers, which in the context of the present invention, with the exception of the above-mentioned non-ionic surfactants, are not introduced into the premix in liquid and in particular not in aqueous form, but in solid form.

To explain the actual extrusion process, reference is hereby expressly made to the above-mentioned patents and patent applications. In a preferred embodiment of the invention, the premix is preferably fed continuously to a 2-screw extruder with co-rotating or counter-rotating screw guides, the housing and extruder granulation head of which can be heated to the predetermined extrusion temperature. Under the shearing effect of the extruder screws, the premix is compressed under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally the extrudate is reduced in size by means of a rotating cutting knife, preferably to approximately spherical to cylindrical granules. The hole diameter of the perforated die plate and the strand cutting length are matched to the selected granulate dimension. In this embodiment, it is possible to produce granules with a substantially uniform, predeterminable particle size, whereby the absolute particle sizes can be adapted to the intended use. In general, particle diameters of up to 0.8 cm are preferred. Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from about 0.8 to 2 mm. The length/diameter ratio of the cut-off primary granules is in a preferred embodiment in the range from about 1:1 to about 3:1.

It is also preferable to feed the still plastic primary granulate to a further shaping processing step; in this process, edges present on the raw extrudate are rounded off so that spherical to almost spherical extrudate grains can ultimately be obtained. If desired, small amounts of dry powder, for example zeolite powder such as zeolite NaA powder, can also be used in this step. This shaping can be carried out in commercially available rounding devices. Care must be taken to ensure that only small amounts of fine grain are produced in this step. Drying, which is described as a preferred embodiment in the above-mentioned prior art documents, is not necessary in the context of the present invention, since the process according to the invention is essentially water-free, i.e. 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 in such a way that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but preferably exceeded. The duration of the temperature effect is in the compression range of extrusion 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 of up to 75°C; process temperatures which are a maximum of 10°C and in particular a maximum of 5°C above the melting temperature or the upper temperature limit of the melting range of the binder have proven to be particularly favorable.

Under these process conditions, the binding agent, in addition to the effects mentioned above, also acts as a lubricant and prevents or at least reduces the formation of sticking to the walls of the equipment and compaction tools. This applies not only to processing in an extruder, but also to processing in continuously operating mixers/granulators or rollers, for example.

The compacted material preferably has temperatures not exceeding 60°C immediately after leaving the production apparatus, with 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 significantly broader than that of the end product produced according to the invention. The premix can contain significantly larger fine grain fractions, even dust fractions, and possibly also coarser grain fractions, although it is preferred that a premix with a relatively broad particle size distribution and relatively high fractions of fine grain is converted into an end product with a relatively narrow particle size distribution and relatively low fractions of fine grain.

Because the process according to the invention is carried out essentially water-free - i.e. with the exception of water contents ("impurities") of the solid raw materials used - not only is the risk of gelling of the surfactant raw materials already minimized or even eliminated in the manufacturing process, in addition an ecologically valuable process is also provided, since by omitting a subsequent drying step not only is energy saved but also emissions, which predominantly occur with conventional drying methods, can be avoided.

The invention further relates to an extrudate which was produced by the process according to the invention. Extrudates which have a spherical or pearl shape are particularly preferred.

Detergents and cleaning products

The extrudates obtained can either be used directly as washing or cleaning agents or can be post-treated and/or processed beforehand using conventional methods. The use of the extrudates as washing or cleaning agents or as a component of such agents is therefore also part of the invention.

Common post-treatments include, for example, dusting with finely divided ingredients from washing or cleaning agents, which generally increases the bulk density. However, a preferred post-treatment is the procedure according to the German patent applications DE-A-195 24 287 .4 and DE-A-195 47 457 .0, whereby dust-like or at least finely divided ingredients (the so-called fines) are adhered to the particulate end products (extrudates) produced according to the invention, which serve as the core, and thus agents are formed which have these so-called fines as an outer shell. This is advantageously done again by melt agglomeration, whereby the same binding agents as in the process according to the invention can be used. For the melt agglomeration of the fines on the base granules according to the invention and produced according to the invention, reference is expressly made to the disclosure in the German patent applications DE-A-195 24 287 .4 and DE-A-195 47 457 .0.

Preparation is generally understood to mean that the particulate end products of the process produced according to the invention serve as a base formulation to which other ingredients, possibly also other pre-formulated components, are added. Reference is made here to the descriptions of the cited patent applications and patent specifications, in particular to the European patent EP-B-0 486 592 and the German patent applications P195 19 139.0 , P195 24 287.4 and P19 54 7457.0 referred to.

The granular washing or cleaning agents 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 50 to 80% by weight. In addition to the extrudates, the washing and cleaning agents can contain other components that are usually contained in such agents. Such components are described in more detail below, without this list being exhaustive. The remaining components can be produced and mixed in using any known process. However, it is preferred that these remaining components were also produced using the processes described herein. In particular, this makes it possible to produce base granules and remaining components with approximately the same flowability, bulk density, size and particle size distribution.

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

The agents can, for example, contain components that have a positive effect on the ability to wash oil and grease out of textiles (soil release polymers (SRP)). The preferred oil and grease-dissolving components include, for example, non-ionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, each based on the non-ionic cellulose ether, as well as the polymers of phthalic acid and/or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and/or polyethylene glycol terephthalates or anionically and/or non-ionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid 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 agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these. For example, 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 1:2 to 1:3.5, can be used. Carbonate, especially sodium carbonate, and/or bicarbonate, especially sodium bicarbonate, are preferably used, typically in amounts of up to 10% by weight.

Organic builders, especially citrate, can also be formulated into granular detergents and cleaning agents. The amount of citrate in the end product can be 0.5 to 5% by weight, especially 1-3% by weight.

Other surfactants that can be added include, for example, other alkylbenzenesulfonates, for example in amounts of 1 to 10% by weight.

Acidic salts or slightly alkaline salts can also be used to reduce the pH value of washing or cleaning agents. Bisulfates and/or bicarbonates or the above-mentioned organic polycarboxylic acids, which can also be used as builder substances, are preferred as acidifying components.

Among the compounds used as bleaching agents and which yield H ₂ O ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ yielding peracidic salts or peracids such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 15 to 25% by weight, with perborate monohydrate or percarbonate advantageously being used.

As bleach activators, compounds which under perhydrolysis conditions form aliphatic peroxocarboxylic acids with preferably up to 10 C atoms, in particular 2 to 4 C atoms, and/or given if substituted perbenzoic acid is used. Suitable substances are those which contain O- and/or N-acyl groups of the stated number of carbon atoms and/or optionally substituted benzoyl groups. Preference is given to multiply acylated 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 acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and the compounds from the German patent applications DE-A-196 16 693 and DE-A-196 16 767 known enol esters as well as acetylated sorbitol and mannitol or their European patent application EP-A-0 525 239 described mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, 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 the international patent applications WO-A-94/27970 , WO-A-94/281 WO-A-94/28103 , WO-A-95/00626 , WO-A-95/14759 and WO-A-95/17498 The information from the German patent application DE-A-196 16 769 known hydrophilically substituted acyl acetals and the German patent application DE-A-196 16 770 and the international patent application WO A-95/14075 Acyllactams described in the German patent application DE-A-44 43 177 Known combinations of conventional bleach activators can be used. Such bleach activators are contained in the usual quantity range, preferably in quantities of 1 wt.% to 15 wt.%, in particular 3 wt.% to 12 wt.%, based on the total agent.

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors include, for example, soaps of natural or synthetic origin that have a high proportion of C18-C24 fatty acids. Suitable non-surfactant foam inhibitors include, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica, as well as paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica or bis-stearylethylenediamide. Mixtures of different foam inhibitors are advantageously used, e.g. those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone and/or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or water-dispersible carrier substance. Mixtures of paraffins and bis-stearylethylenediamides are particularly preferred.

Enzymes that can be used are particularly those from the class of hydrolases, such as proteases, lipases or lipolytic enzymes, amylases, cellulases or mixtures thereof. Oxireductases are also suitable. Enzymatic active substances obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or cellulase and lipase or lipolytic enzymes or of protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially mixtures containing protease and/or lipase or mixtures with lipolytic enzymes are of particular interest. Examples of such lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and beta-glucosidases, also known as cellobiases, or mixtures of these are preferably used as cellulases. Since the various cellulase types differ in their CMCase Avicelase activities, the desired activities can be set by using targeted mixtures of cellulases.

The enzymes can be adsorbed on carriers and/or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules in the agents can be, for example, about 0.1 to 10% by weight, preferably 0.1 to about 5% by weight.

The agents can also contain enzyme stabilizers. For example, 0.5 to 1% by weight of sodium formate can be used. It is also possible to use proteases that are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. In addition to calcium salts, magnesium salts also serve as stabilizers. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkalis, is particularly advantageous. 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 ).

The purpose of greying inhibitors is to keep the dirt detached from the fiber suspended in the liquor and thus prevent the dirt from reappearing. Water-soluble colloids, usually of an organic nature, are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, preference is given to using cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, as well as polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the compositions.

Finally, the agents may also contain optical brighteners, which are defined as described above.

Any process known from the prior art is suitable for producing the washing and cleaning agents described herein.

Washing process

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

Washing processes, i.e. in particular processes for cleaning textiles, are generally characterized by the fact that in one or more process steps, cleaning-active substances are applied to the items to be cleaned and washed off after the exposure time, or that the items to be cleaned are treated in some other way with a detergent or a solution of this detergent. In such washing processes, 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 or less are used in various embodiments of the invention. These temperature specifications refer to the temperatures used in the washing steps.

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

Examples

Example 1: Detergent formulations

Table 1 shows raw extrudates E1 and E2 according to the invention in comparison with known raw extrudates V1 and V2 not according to the invention. Table 2 shows the composition of the detergents formulated therefrom (WE1, WE2, WV1, WV2). Table 1: Raw extrudate composition (all data in wt.% active substance) ingredient V1 E1 V2 E2 LAS-Na (linear alkyl benzene sulfonate, 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 carbonate 0.02 0.03 - - Sodium sulfate 5.2 0.3 3.3 0.2 DTI 0.4 0.4 0.77 0.86 Other components (water, residues) Ad 100 Ad 100 Ad 100 Ad 100 Table 2: Detergent composition (all data in wt.% active substance) ingredient WV1 WE1 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 percarbonate 21.0 21.0 - - TAE 12.0 12.0 - - Defoamers 1.0 1.0 1.2 1.2 citric acid - - 1.8 1.8 Bicarbonat - - 1.3 1.3 soda - - 1.2 1.2 Enzymes 4.0 4.0 4.0 4.0 Other components (water, residues) Ad 100 Ad 100 Ad 100 Ad 100

Example 2: Physical data

To determine the particle size, 100 g of raw extrudate or detergent were sieved using 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 set of sieves was assembled in such a way that the mesh size decreases towards the bottom. This set is provided with a cover plate and inserted into the test sieving machine. The sample was then placed on the top sieve. After sieving, the proportion of particles per sieve was determined gravimetrically by transferring the different fractions, including the particles caught in the sieve mesh, to weighing dishes and weighing them.

To measure the bulk density, the weight of one liter of the raw extrudates or detergent was determined using a bulk density tester with a standardized cylinder. The determination of the bulk density is carried out according to DIN ISO 697, January 1984 .

The dissolution rate was determined by dissolving 7.3 g of the raw extrudates or detergent in 1 L of deionized water at 30°C while stirring (800 rpm) and determining the undissolved portion gravimetrically after 90 s. For this purpose, a 2 L beaker with an inner diameter of 115 mm 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 solids were filtered off 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 raw extrudate according to the invention and the resulting detergent, the bulk density decreases and the dissolution rate is improved despite increasing particle size. Table 3: Particle sizes, bulk density and solubility of the raw extrudates from Table 1 V1 E1 V2 E2 Particle size (percent by weight) >2.0mm 1 3 0 4 >1.8mm 2 15 8 14 >1.6mm 80 65 69 59 >1.4mm 11 8 11 8 >1.25mm 4 6 6 9 >1.0mm 1 2 2 3 >0.8mm 1 1 2 2 >0.4mm 0 0 0 0 0.4-0mm 0 0 0 0 Bulk density (g/L) 700 650 740 620 Solubility (residual solids in wt.%) 5.4 1.7 4.9 1.8 Table 4: Particle sizes, bulk density and solubility of the detergents from Table 2 WV1 WE1 WV2 WE2 Particle size (percent by weight) >2.0mm 1 2 1 4 >1.8mm 3 11 7 14 >1.6mm 44 37 55 52 >1.4mm 9 8 10 8 >1.25mm 14 14 11 10 >1.0mm 11 11 7 6 >0.8mm 16 14 9 5 >0.4mm 1 1 1 0 0.4-0mm 0 0 0 0 Bulk density (g/L) 730 720 780 680 Solubility (residual solids in wt.%) 9.7 7.2 7.3 5.0

Claims (10)

Washing or cleaning-active, particulate extrudate containing anionic and/or nonionic surfactants and builder substances, characterized in that the extrudate contains, based on the total weight of the extrudate, less than 1.0% by weight of trisodium citrate and less than 3% by weight of inorganic electrolytes, in particular inorganic salts. Extrudate after Claim 1 , characterized in that the extrudate contains at least 25 wt.% anionic surfactants based on the total weight of the extrudate. Extrudate after Claim 1 or 2 , characterized in that the extrudate contains at least 15 wt.% of builder substances, in particular zeolite. Extrudate according to one of the Claims 1 until 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 the Claims 1 until 4 , characterized in that the extrudate (1) consists of at least 90% by weight of particles with a particle size > 400 µm; and/or (2) contains at least 10% by weight of particles with a particle size > 1.8 mm; and/or (3) consists of 100% by weight of particles with a particle size distribution which has at least 70% by weight of particles between 0.8 and 2.0 mm. Washing or cleaning active extrudate according to one of the Claims 1 until 5 , characterized in that the extrudate has a bulk density of more than 600 g/l. Granular washing or cleaning agent containing the washing or cleaning active extrudate according to one of the Claims 1 until 6 , in particular in an amount of at least 30 wt.% based on the washing or cleaning agent. Process for producing a washing or cleaning active extrudate containing anionic and/or non-ionic surfactants and builder substances by means of extrusion, wherein a solid premix is pressed under pressure into a strand and the strand is cut to the predeterminable granulate dimension by means of a cutting device after emerging from the hole mold, characterized in that the extrudate contains less than 1.0% by weight of trisodium citrate and less than 3% by weight of inorganic electrolytes based on the total weight of the extrudate. Use of a granular washing or cleaning agent after Claim 7 as a detergent in a machine washing process for cleaning textiles. Use of a washing or cleaning active extrudate according to one of the Claims 1 until 6 as a component of a detergent.