SK285376B6 - Washing or cleaning agent, compound or treated raw material and a method of their preparation - Google Patents

Abstract

Particulate washing or cleaning agent, compound or treated raw material having bulk densities above 600 g/l, prepared from a solid bulk premix containing individual raw materials and/or compounds, which at room temperature and pressure of 10exp(5) Pa are in solid state, and have a melting point or softening point not below 45 °C, with the provision that the content of free water in the premix, based on the premix, is below 2 % by weight and a total water content of 15 % by weight in the premix, based on the premix, and comprise one or more anionic surfactants in a minimum amount of 0.5 % by weight, based on the agent, at least one raw material or one compound which is introduced via the premix and is in solid form at a pressure of 10exp(5) Pa and temperatures below 45 °C , but is in the form of a melt under the processing conditions, where this raw material or compound is chosen from particular defined group of compounds. A process for producing consist in that firstly a solid, bulk premix is produced, where the individual raw materials and/or compounds are in the form of solids at room temperature and pressure of 10exp(5) Pa and have a melting point or softening point not below 45 °C, where the mixing operation takes place at room temperature up to temperatures below the melting or softening points of the described individual raw materials and or compounds, and where this premix is converted to a particle with the use of compaction forces at temperatures of at least 45 °C.

Description

Technical field

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to prepared laundry detergents or compositions or compositions or formulated raw materials for said purpose, which are of significantly better quality for consumers, and to a process for preparing rapidly soluble, compacted particulate laundry detergents or formulations. .

BACKGROUND OF THE INVENTION

Particulate washing or cleaning agents with a bulk density of more than 600 g.dm ³ have long been known in the art. In recent years, as the bulk density has increased, the concentration of active laundry detergents and cleaners has increased so that the consumer has to dispense not only a smaller volume but also a smaller product weight for washing or cleaning. The increase in bulk density and, in particular, the higher concentration of detergents or cleaning active ingredients in the composition at their general sale is accompanied, from a subjective point of view of the consumer, by poor solubility, since the composition used dissolves more slowly. This undesired retardation of solubility is solved, inter alia, by the use of a variety of conventional anionic or nonionic surfactants, in particular by the use of suitable surfactant mixtures which tend to form gel phases when dissolved in water. Gelling can occur at a surfactant content of from 10% (w / w), based on the total weight of the composition, that is to say with the customary surfactant contents in detergents or cleaning compositions. The tendency to form gels has also been reported to increase with increasing compactness of the particle structure of the composition.

EP-B-0 486 592 discloses a granular or extruded detergent or cleaning composition having a bulk density of more than 600 g.dm &^lt; ^-3 &^gt; containing anionic and / or nonionic surfactants in amounts of at least 15% by weight to about 35% ( by weight). The composition is prepared by a process in which a solid free-flowing premix, which comprises a plasticizer and / or lubricant, preferably an aqueous surfactant paste and / or the aqueous polymer solution, at high pressures between 25.10 ⁵ Pa and 200.10 ⁵ Pa (25 and 200 bars) extruded in the form of a thin beam; the bundle is cut off at the exit of the press by means of a slicer and rounded to the required granulate dimensions. The masterbatch consists, at least in part, of solid components, optionally mixed with liquid components, such as nonionic surfactants, liquid at room temperature. As mentioned above, aqueous solution formulations are preferably used as plasticizer and / or glidant. Also suitable are organic liquids with a relatively high boiling point, in this case mixed with water. However, the patent for water-free extrusion does not disclose any data on the preparation conditions. The prepared extrudate can either be used directly as a laundry or cleaning agent, or in admixture with other granules or powdered ingredients can be used to complete the preparation of laundry or cleaning agents. Due to the high compactness of the grains and the relatively high surfactant content, but also due to the consumerly desired bead or bead shapes, which have a significantly smaller surface area compared to the prior art granulates, these difficulties may occur depending on the selected surfactant combinations.

It is known from the international patent application WO-A-93/15 180 that the dissolution rate of such extruded compositions can be increased by adding to the premix short-chain alkyl sulfates, in particular C ₈ - to at most C ₁₆ -alkyl sulfates. However, this measure does not in all cases ensure an increase in the dissolution rate of the finished composition to the required extent.

German patent application DE 195 19 139.0 proposes to solve the discrepancies between the high degree of compaction of individual grains, in particular extrudates, on the one hand, and the simultaneous required rapid and in particular gel-free solubility of finished detergents and cleaning agents on the other ) detergents with a bulk density of more than 600 g.dm ^'3, containing at least 15% (by weight) of anionic and / or nonionic surfactants; said compositions comprising at least two different granular ingredients, at least one of which is extruded and at least one is not extruded, with a surfactant content including soaps in the extruded component of at most 15% (by weight) based on the extruded component in question. Additional proportions of surfactants are incorporated into the detergent or cleaning compositions in the second or more non-extruded components. This method, while solving the problem of gelling highly compacted high surfactant detergents and cleaning agents when used in a water bath, also presents a number of new problems. Stirring processes and associated fluctuations in the repeatability of the set washing or cleaning results can occur in the compositions. In addition, the extruded component of the composition does not only have a high density, but the dried extrudate is at the same time relatively hard. Under conditions of transport, storage and use, a relatively softer granular fraction of detergent or cleaning agent may be subjected to the mechanical effects of a harder extruded fraction, which may result in partial crumbling and abrasion of the softer particles and the formation of dust and very fine fractions.

The prior art methods generally use both solid and liquid temperature components of detergents or cleaners; aqueous solutions and / or dispersions, or as mentioned in EP-B-0 486 592, also as plasticizers and / or glidants, are widely used as granulating auxiliaries. The prior art processes are associated with the risk that gel-like structures may already be formed during the preparation of said detergents and cleaning agents, which contribute to retarding dissolution upon re-dissolution in the aqueous wash liquor. Moreover, these methods of preparation, and in particular those in which water, aqueous solutions or aqueous dispersions are used, have the disadvantage that in most cases they require energy-intensive drying in order to achieve free-flowing and shelf-life; in addition, they often form coarse particle agglomerates which must be crumbled and / or sieved (see also: Size Enlargement by Agglomeration, Pietsch, W., John Wiley & Sons, page 180, 1990). A further disadvantage of said process may be that, particularly under the effect of pressure during extrusion, partial dissolution of the water-soluble fractions can occur, which can lead to particle enlargement as well as crystallization; these phenomena are generally disadvantageous in terms of dissolution rate of the finished composition. One method of preparing heavy granulates with water-containing granulating excipients is a two-stage granulation process, in which a plastic primary agglomerate is first prepared in a conventional mixer / granulator and subsequently in a second stage, in a device such as rounder, rotary coater (Rotocoater) ), a marumerizer and the like, processed together with the liquid binder and / or powder and then dried in a conventional manner. Granulation and simultaneous rounding can be carried out, for example, in fluidized bed granulators which operate with a rotating disc. In this process, starting solid materials are initially introduced into the fluidized bed and then agglomerated with a liquid binder which is introduced into the fluidized bed by tangential nozzles (see also: Size Enlargement by Agglomeration, Pietsch, W., John Wiley & Sons, pages 450 and 451, 1990) ). In principle, the process can also be used as the anhydrous process (melt coating process), but does not take advantage of the possibility of a device for simultaneous batch drying.

In the literature (Size Enlargement by Agglomeration, Pietsch, W., John Wiley & Sons, pages 440 and 441, 1990), only two high pressure granulation processes are known which are carried out entirely without the use of water. These are tabletting in tablet presses and compacting on cylindrical presses, the latter method usually producing scales which are subsequently broken into granular but irregularly shaped products by breaking. On this basis, so-called "Pre-breakers" are used in individual systems, in which the shape of the product can be individually adjusted in the granulation or crushing step itself. Subsequently, the undesirable fine and / or coarse fractions of the granulate thus obtained can be desulphurized and optionally recycled to the production process.

International patent application WO-A-93/02 176 describes a process for the preparation of high bulk density solid detergents or cleaners by combining the raw solid and liquid detergents or cleaners with simultaneous or subsequent shaping, wherein, for example, solids may be used for example anionic surfactants and additives to laundry detergents and as liquid fractions may be used nonionic surfactants, the latter are made in the form of an intimate mixture with a substance which prevents the formation of aggregated particles, such as polyethylene glycol, or polypropylene glycol, or ethoxylated C ₈ - to C ₁₈ - fatty alcohols with 20 to 45 EO. Preferred liquid nonionic surfactants are ethoxylated unbranched or in the 2-position with a methyl group of branched alcohols having 8 to 20 carbon atoms in the carbon chain and an average of 1 to 15 moles of ethylene oxide per mole of alcohol. In addition to the foregoing, water is also described as a substance to prevent agglomeration; however, its use is less advantageous as the composition may have a lack of water due to internal storage drying and therefore its anti-agglomeration effect only partially or does not appear at all in the required direction for an improved dissolution rate. As described in said international patent application, mixtures of non-ionic surfactants with agglomeration suppressors, which can be added in liquid form or as dispersions, can be used in all known granulation methods using separately prepared mixtures and / or raw materials. According to the international patent application WO-A-91/02 047 (or European patent EP-B-0 486 592 respectively), the process can also be used in the extrusion process and this use is advantageous. Accordingly, the use of aqueous solutions, pastes, or aqueous dispersions is recommended, the water not being used as an anti-agglomerating agent and usually dried at the exit of the extrusion. Extrusion without the addition of water was not explicitly stated; the addition of aqueous solutions is found in a portion of the examples as a supplement and separately from the mixture of the nonionic surfactant with the anti-clotting agent; in particular, that specification does not indicate any conditions of the preparation process in which extrusion without water is possible.

The European patent application EP-A-0 337 330 describes a method for increasing the bulk density by spray-drying a dried detergent by means of granulation in a mixer with the addition of non-ionic compounds. Such compounds include ethoxylated and / or propoxylated nonionic surfactants, such as primary or secondary alcohols having 8 to 20 carbon atoms and 2 to 20 moles of alkylene oxide per mole of alcohol, with the addition of 2 to 6 EO nonionic surfactants to the mixer and HLB values of 11 or less. Ethylene glycols and propylene glycols can also be added as nonionic compounds.

DE-A-43 19 666 discloses a process for the preparation of high density laundry or cleaning extrudates, wherein a homogeneous and solid premix containing certain alkoxylated alcohols is compressed and formed into a granulate. This document does not mention extrusion without the addition of water.

In the exemplary part, a masterbatch with, for example, a water content of almost 5 wt. free water.

WO-A-92/02608 discloses a free-flowing granular material comprising bleach activators and a mixture of anionic and nonionic surfactant compounds that form a substantially anhydrous binder phase. The surfactant composition which is preferably used as the binder phase is in the solid state at temperatures from about 35 ° C to about 40 ° C. At the granule formation temperature, the binder phase softens or becomes fluid or plastic without the need for water. The granules are formed without the need to use water as a liquid phase.

European patent application EP-A-0 711 828 discloses a process for preparing tablets in which a coated particulate product is compressed. The coating agent is a water-soluble binder or disintegrant with a melting point between 35 and 90 ° C. As an essential feature of this process, it is stated that the compacting / granulating is carried out at a temperature of at least 28 ° C, which in any case is below the melting point of the binder.

International patent application WO-A-96/10071 discloses a process for the preparation of granules with bulk densities of at least 650 g.drrí ³ and of a surfactant at least 40% (by weight), wherein the granulation process is performed in one step in a high speed mixer at a temperature between at room temperature and 60 ° C. Particles between 0.1 and 500 µm are used as the solid starting material, with at least 15% by weight of the particles being greater than 50 µm, but small, fine particles are useful, since the solid input material has a preferred large surface area. The binder is a mixture of surfactants consisting of anionic surfactants and nonionic surfactants in weight ratios of from 2: 8 to 8: 2; the binder content may be up to 20% (w / w). Non-ionic surfactants include primary C ₁₂ -C ₁₅ alcohols having 3 to 7 EO groups.

Particularly preferred surfactant compositions which contain up to 20% (by weight) of water are preferred in the above preparation processes, since the viscosity of the composition increases and the process is easier to control. The surfactant composition may additionally also contain polyethylene glycols.

U.S. Pat. No. 5,108,646 describes the preparation of detergent or agglomerates of laundry adjuvants in which 50 to 75 parts by weight of aluminosilicates or crystalline layered silicates are agglomerated with 20 to 35 parts by weight of a binder. Particularly suitable binders are highly viscous anionic surfactant pastes which may contain between 0 and 90% by weight of water. Polymers such as polyethylene glycols having a molecular weight of between 1000 and 2000, as well as mixtures of said polymers with conventional nonionic surfactants such as C ₉ - C ₁₆ - alcohols with 4 to 8 EO groups, may also be used as long as their melting range does not start below. 35 ° C, possibly below 45 ° C. The agglomeration takes place in a so-called intensive mixer with quite a certain and relatively high energy consumption.

If the energy expended is higher than the specified value, pre-agglomeration to the paste takes place, with the energy expended below the specified value, only a fine powder or only a very light agglomerate is obtained which, moreover, does not have the required grain size spectrum.

The purpose of this patent, on the other hand, is to provide a particulate laundry detergent or cleaning composition, or mixtures or treated raw materials, the particles of which have a relatively small surface, especially if they are bead-shaped, for improved disintegration when dissolved in a water wash. In addition, the method of preparation must be economically favorable, with the possibility of avoiding the costly degree of drying.

SUMMARY OF THE INVENTION

The present invention is based on a particulate detergent or cleaning composition which has been produced by the process of the present invention and whose dissolution properties depend solely on the properties of the individual raw materials and mixtures used. Without wishing to be limited to this theory, the Applicants are of the opinion that the said exceptional dissolution properties are due to a honeycomb-like particle structure (grains) filled with a solid.

In one preferred embodiment of the invention, the granular or extruded detergent composition comprises at least 80% by weight of the composition and / or treated raw materials prepared according to the invention. The granular or extruded composition preferably comprises at least 80% (by weight) of the base granulate or base extrudate prepared according to the invention. The remaining fractions can be prepared by any of the known methods and admixed. It is also advantageous if the remainder, which can be mixtures and / or treated raw materials, are also produced by the process according to the invention. In particular, this will allow the base granulate and the remaining fractions to be made of approximately equal bulk, with approximately the same bulk density, size and particle size distribution.

In another aspect, the invention includes blends and treated raw materials produced according to the invention, for example, granules (extrudates) of excipients, granules (extrudates) of bleach activators or enzyme granules (extrudates). In particular, the treated feedstocks have an exceptionally high dissolution rate in water, especially when the feedstock is used in very fine form or ground.

Particularly preferred are basic granules, blends and treated raw materials having a spherical shape or bead shapes.

Unexpectedly, the products obtained by the process of the invention exhibit very high bulk weights. The bulk density is preferably higher than 700 g.dm ^-3 , especially between 750 to 1000 g.dm ^-3 . If the extrudates are mixed with other ingredients having lower bulk weights, the bulk density of the final product is reduced, but not in the mixing ratio as would normally be expected. It is believed that a composition with approximately spherical particle shapes, and in particular extrudates produced by the process of the present invention, approximates an ideal spherical shape with a smooth "greasy" surface than compositions and extrudates produced in a known manner, in particular using water. In this way, the compositions according to the invention achieve a higher degree of space filling, leading to higher bulk weights, even though a component which has neither a spherical shape nor such a high bulk density is admixed.

The resulting particulate end products can either be used directly as laundry or cleaning agents, or can be subsequently processed and / or treated by conventional methods. Conventional post-treatment methods may include the application of a very fine detergent or detergent component (" powdering "), whereby the bulk density can generally be further increased. Advantageous post-processing may also be by the method of German patent applications DE-A-19 524 287 and DE-A-19 547 457, wherein the dust or at least very fine particles (the so-called fine fraction) of the additive are adhered to the particulate product of the production according to the invention which serves as a grain and produces a composition comprising a so-called fines as an outer shell. Advantageously, this can again be achieved by melt-agglomeration, using the same binder as in the process of the invention. For the agglomeration of melt-containing fines into a base granulate produced according to the invention, reference is expressly made to the published applications of German patents DE-A-19 524 287 and DE-A-19 547 457.

The treatment is generally understood to mean that the fine particulate products produced by the process of the present invention serve as mixtures to which other components, optionally also other mixtures, are admixed. Here, reference is made to the disclosures in the patent applications and patents cited, in particular the European patent EP-B-0 486 592 as well as the applications of the German patents DE-A-19 519 139, DE-A-19 524 287 and DE-A In addition to enzymes, bleach activators and antifoams, in particular, salts such as silicates (crystalline or amorphous), including metasilicates, carbonates, bicarbonates, sulfates, hydrogensulfates, citrates and other polycarboxylates, but also organic acids such as is citric acid (see below). It is very advantageous to add the admixture in granular form and with a particle size distribution which is suitably adjusted to the particle size distribution of the composition produced by the process of the invention.

The following is a detailed description of possible additives to the composition of the invention and the ingredients used in the method of the invention.

Important additives to the composition of the invention and the ingredients used in the process of the invention are surfactants, in particular anionic surfactants, which should be used or may be present in the composition of the invention in an amount of at least 0.5% (w / w). These surfactants include, in particular, sulfonates and sulfates, but also soaps.

Suitable surfactants of the sulfonate type are preferably C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxyalkane sulfonates, as well as disulfonates which can be obtained, for example, from C ₁₂ -C ₁₈ monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide followed by alkaline or acid hydrolysis of the sulfonated product.

Suitable are alkane sulfonates which are prepared from _C12 - _C18 -alkanes, for example by sulfonation or sulfoxidation followed by hydrolysis or neutralization.

Also suitable are esters of α-sulfonated fatty acids (estersulfonates), for example α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which are prepared by α-sulfonation of fatty acid methyl esters of vegetable or animal origin having from 8 to 20 carbon atoms in a fatty acid molecule. The sulfonation product is neutralized to a water-soluble mono salt. They are preferably α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, and sulfonated unsaturated fatty acid products may also be used, but to a limited extent, for example in an amount of no more than about 2 to 3% by weight. Highly preferred are α-sulfonated alkyl esters of fatty acids whose alkyl chain of the ester group contains no more than 4 carbon atoms, such as, for example, the methyl ester, the ethyl ester, the propyl ester and the butyl ester. Especially preferred is the use of the methyl ester of the α-sulfonated fatty acid (MES), but also the saponified di-salt thereof.

Other suitable anionic surfactants are the sulfated glycerol esters of fatty acids, which are mono-, di- and tri-esters, as well as mixtures thereof, obtained by sterilizing monoglycerol with 1 to 3 moles of fatty acid, or by esterifying triglycerides with 0.3 to 2 moles. moles of glycerol.

As alkyl (en) sulfates are the alkali metal salts, especially the sodium salts of sulfuric acid half esters of C ₂ - to _{C] 8} - fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or fatty stearylated alcohol or a C ₁₀ to C ₂₀ -oxoalcohol and the corresponding semi-esters of secondary alcohols having the indicated chain length. Further preferred are alkyl (en) sulfates with the indicated carbon chain lengths which contain a synthetic, petrochemically based, unbranched alkyl moiety having a similar structure to the corresponding compounds based on fatty chemistry raw materials.

From the point of view of the washing technique, _C12 - _C12 are of interest ₈ alkyl, the preferred C ₁₂ -to C ₅ - alkyl, and particularly preferred are the C ₁₄ - to C <- alkyl. Suitable anionic surfactants are also 2,3-alkyl sulfates which are prepared, for example, according to U.S. Pat. No. 3,234,258 or 5,075,041, and are commercially available under the designation DAN (R) from Shell Oil Company.

Also suitable are the sulfuric acid monoesters with ethoxylated with 1 to 6 moles of ethylene oxide, straight or branched C ₇ - to C ₂ r fatty alcohol, such as 2-methyl-branched C ₉ - to C _lr alcohols with an average of 3.5 moles ethylene oxide (EO), or C ₁₂ to C ₁₈ fatty alcohols with 1 to 4 EO. They are used in laundry detergents only in relatively small amounts, for example from 1 to 5% by weight, because they exhibit high foaming power.

Preferred anionic surfactants are also salts of alkylsulfosuccinic acid, which are referred to as sulfosuccinates or sulfoesters of succinic acid and are monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols, and most preferably ethoxylated fatty alcohols. Preferred sulfosuccinates contain radicals C ₈ - to C _ls - fatty alcohol or mixtures thereof. More preferably, the sulfosuccinates contain a fatty alcohol residue that is derived from ethoxylated fatty alcohols, which themselves are nonionic surfactants (see below). Particularly preferred are again sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homogeneous distribution. Alkyl (en) succinic acids, preferably having 8 to 18 carbon atoms in the alkyl (en) chain, or salts thereof, may also be used.

Suitable further anionic surfactants are amino acid derivatives of fatty acids; examples of said amino acids are N-methyltaurine (taurides) and / or N-methylglycine (sarcosides). Highly preferred are the sarcosides and / or sarcosinates and, in particular, the higher sarcosinates and, optionally, unsaturated fatty acids, such as oleyl sarcosinate.

Of the other anionic surfactants, in particular soaps may be used, preferably in amounts of from 0.2 to 5% by weight. Particularly suitable are saturated fatty acid soaps, such as salts of lauryl, myristic, plamitic, stearic, hydrogenated erucic and behenic acids, in particular from natural fatty acids, for example mixed soaps derived from coconut, palm kernel or tallow fatty acids. Along with the aforementioned soaps or as an additive to the soaps, the above-mentioned alkenylsuccinic acid salts can also be used.

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

The compositions according to the invention contain, optionally in the process according to the invention, anionic surfactants preferably used in amounts of from 1 to 30% by weight and in particular in amounts of from 5 to 25% by weight.

In addition to anionic and cationic surfactants, in addition to zwitterionischen surfactants and amphoteric surfactants, nonionic surfactants are particularly preferred.

Suitable anionic surfactants are alkoxylated, preferably ethoxylated, especially primary alcohols, preferably having 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 residue may be unbranched or branched in the 2-position by methoxy group, optionally unbranched and branched, may be present in the mixture in analogy to the oxoalcohols mentioned above. Particular preference is given to alcohol ethoxylates with unbranched residues of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow alcohol or oleyl alcohol and with an average of 2 to 6 EO per mole of alcohol. Preferred ethoxylated alcohols include, for example, C ₁₂ -C _{18 4-} alcohols with 3 EO or 4 EO, C ₉ to Ch alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ to C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of _{C] 2} - to C ₁₄ alcohol with 3 EO and _{C) 2} - to C ₈ alcohols containing 7 EO. The cationxylation steps given are a statistical mean, which can be an integer or a decimal number for each product. Preferred alcohol ethoxylates have a narrow homolog distribution (NRE). In addition to the aforementioned nonionic surfactants, fatty alcohols with more than 12 EO may be used, as mentioned above. Examples of these are alcohols (tallow derived) of 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

Nonionic surfactants also include, in particular, the alkyl glycosides having the general formula RO (G) _X and the polyhydroxy fatty acid amides having the general formulas (I) and (II).

Another group of preferred nonionic surfactants which are used either alone 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 esters, preferably having 1 to 4 atoms carbon in the alkyl chain, especially a fatty acid methyl ester, such as disclosed in Japanese Patent Application JP 58/2 175 598, or may be conveniently prepared by the method described in International Patent Application WO-A-90/13 533. As nonionic surfactants are: preferred C12- to _C18 -fatty acid methyl esters with an average of 3 to 15 EO, more preferably an average of 5 to 12 EO, while ethoxylated fatty acid methyl esters are particularly preferred as the binder as mentioned above. The methyl ester C ₁₂ - to C ₁₈ -fatty acid of 10 to 12 EO may also be used advantageously as a surfactant, and as a binder.

Suitable nonionic surfactants may also be amine oxide type surfactants, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide and fatty acid alkanolamides. The preferred amount of these nonionic surfactants in the composition is not more than the amount of ethoxylated fatty alcohol, more preferably not more than half its content.

Other surfactants are the so-called gemini surfactants. In the following, the term "compound" will mean those compounds having two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated from each other by an intermediate, "spacer". Said intermediate is generally a carbon chain of a length such that the hydrophilic groups are spaced apart enough to act independently of one another. Surfactants of this kind are generally characterized by an extremely low critical micelle concentration and the ability to greatly reduce the surface tension of water. In exceptional cases, in addition to dimemens, the term gem-surfactants also includes trimeric surfactants.

Suitable gemin-surfactants are, for example, sulfated mixed hydroxyethers according to German patent application DE-A-4,321,022, or dimeric alcohol bis- and trimeric alcohol tris-ether sulfates according to German patent application DE-A-19 503 061. Dimeme and trimeme mixed The end-capped ethers according to German patent application DE-A-19 513 391 are characterized in particular by bi- and trifunctional functions. Since the closed end-group surfactants have wetting properties and are low in foaming properties, they are particularly suitable for machine washing and cleaning applications.

However, gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides as described in International Patent Applications WO-A-95/19 953, WO-A-95/19 954 and WO-A-95/19 955 may also be used.

In addition to surfactants, the most important components of detergents and cleaning agents are, in particular, inorganic and organic auxiliaries.

It is preferred to use zeolite A and / or zeolite P as fine crystalline, synthetic and bound water containing zeolite raw materials. As zeolite P, for example, Zeolith MAP ⁴⁰ (a commercial product of the Crosfield form) can be used. The zeolite is available for use as a spray-dried powder, but also as a non-dried, still wet-stabilized suspension. If zeolite is used in the form of a suspension, the suspension may contain a low proportion of nonionic surfactant additive as stabilizers, for example 1 to 3% by weight, based on the zeolite, ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups, C _{12 to} C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have a mean particle size of less than 10 gm (volume distribution; Coulter assay method)

Counter) and is preferably comprised of 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

A suitable substitute or partial substitute for phosphates and zeolite are crystalline layered silicates having the general formula NaMSi _x O _{2xl |} . 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. Preferred values for x are 2, 3, or 4. Layered silicates of the kind described are described, for example, in European patent application EP-A-0 164 514. Preferred layered silicates of the general formula are those in which M is sodium and x is 2 or 3. Even more preferably, either β- or also δ-sodium silicates are Na ₂ Si ₂ O ₅ . yH ₂ O.

Preferred excipients also include amorphous silicates having a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, more preferably from 1: 2 to 1: 2.8, and most preferably from 1: 2 to 1: 2. 6, which are slowly soluble and have secondary scrubbing capabilities. The slower dissolution of the usual amorphous sodium silicates may be due to various influences, such as surface treatment, mixing, pressing / compacting, or stronger drying, in advance. In the present invention, the term "amorphous" also means "rontgenoamorphic". This means that the silicates in X-ray diffraction analyzes do not give any sharp diffraction maxima, as is typical of crystalline substances; however, amorphous substances may have one or more diffraction maxima whose width is multiple degrees of diffraction angle. However, they may have very good properties as excipients if the silicate particles give blurred or even sharp diffraction maxima in electrodiffraction analyzes. This can be explained by the fact that the products exhibit structures in the microcrystalline region of 10 to several hundred nanometers; values up to a maximum of 50 nm are preferred, and even more preferably values up to a maximum of 20 nm. Said so-called X-ray silicates which are more slowly soluble than conventional waterglass products are described, for example, in German patent application DE-A-4 400 024. Compacted / compacted amorphous silicates and dried X-ray silicates are highly preferred.

Of course, commonly known phosphates can also be used as excipients, unless such use is to be avoided for environmental reasons. Sodium salts of orthophosphoric, pyrophosphoric and especially tripolyphosphoric acid are particularly suitable. Their content should not exceed 25% by weight, preferably not more than 20% by weight, based on the total amount of the finished product. In several cases, in particular, tripolyphosphates, in small quantities, up to a maximum of 10% (by weight, based on the finished product) have been shown to show a synergistic improvement in secondary washing ability in combination with other excipients.

Suitable substitutes or partial substitutes for zeolites are layered silicates from natural sources and also synthetic layered silicates. Said layered silicates are known, for example, from the applications of the inventions DE-B-2,334,899, EP-A-0 026 529 and DE-A-3 526 405. Their use is not limited to a certain chemical composition or structural formula. Smectites, especially bentonites, are preferred.

Suitable layered silicates which belong to the group of water-swellable smectites are, for example, montmorillonite, hectorite or saponite. According to the above formulas, small amounts of iron are incorporated in the crystal structure of the layered silicates. Due to the ion exchange properties, the layered silicates may further comprise hydrogen ions, alkali metal ions, earth metal ions, in particular Na ⁺ and Ca ²⁺ ions. The proportion of hydrate water is generally in the range of 8 to 20% (w / w) and is dependent on the source or the processing method. Useful layered silicates are known, for example, from U.S. Pat. Nos. 3,966,629, EP-A-0 026 529 and EP-A-0 028 432. Layer silicates which, after treatment with alkali, are free of calcium ions and are preferred for use. strong coloring iron ions.

Useful organic bases are, for example, in the form of sodium salts of polycarboxylic acids, such as citric, adipic, succinic, glutaric, tartaric, sugar, aminocarboxylic acids, nitrilotriacetic acid (NTA), and mixtures thereof, unless there is an objection to the use of said substances. in terms of ecology. Preferred salts are salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, and mixtures thereof.

The acids themselves may also be used. In addition to their effect as adjuvants in the composition, the acids also have the acid component properties and thus serve to set lower or moderate pH values of the detergent or cleaning composition. Of this group, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of said acids are mentioned. When using acids, it is preferred that they are used in anhydrous form in the premixes of the present invention and are not subsequently admixed.

Other suitable organic excipients are dextrins, for example oligomers or optionally carbohydrate polymers, which can be obtained by hydrolysis of starches. The hydrolysis can be carried out in a conventional manner, for example by acid hydrolysis or by an enzyme-catalyzed process. Preferably, they will be hydrolytic products having average molecular weight values in the range of 400 to 500,000. A polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40 is preferred, in particular from 2 to 30. DE is a conventional rate of polysaccharide reducing effect as compared to dextrose having a DE of 100. Not only maltodextrins with DE between 3 and 20 and dry glucose syrups with DE between 20 and 37 are usable, but also the so-called yellow and white dextrins with higher molecular weights in the region of 2000 to 30 British Patent Application 9,419,091 discloses a preferred dextrin. The oxidized derivatives of the aforementioned dextrins are their conversion products by the action of oxidizing agents capable of oxidizing at least one sugar group of the sugar ring to a carboxyl group. Said oxidized dextrins and processes for their preparation are known, for example, from the applications of the following patents EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international applications WO-A-92 / 18,542, WO-A93 / 08,251, WO-A-94 / 28,030, WO-A-95/07303, WO-A95 / 12,619 and WO-A-95 / 20,608 C ₆ may be a highly preferred carbohydrate ring oxidation product.

Other suitable excipients are oxydisuccinates and other disuccinate derivatives, preferably ethylenediamine disuccinate. Particularly preferred in this context are glycerol disuccinates and glycerol trisuccinates, as described, for example, in U.S. Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP-A-0 150 930 and Japanese Patent Application JP 93/339 896. Suitable dosages of these substances in zeolite and / or silicate formulations are 3-15% (w / w).

Other useful organic auxiliaries are, for example, acetylated hydroxy acids or their salts, which may also be in the form of lactones and which contain at least 4 carbon atoms, at least one hydroxyl group and at most two acid groups. Excipients of this kind are described, for example, in WO-A-95/200 029.

Suitable polymeric polycarboxylates are, for example, sodium salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular weight of from 800 to 150,000 (based on acid). Particularly suitable copolymer polycarboxylates are copolymers of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Particularly preferred are acrylic acid / maleic acid copolymers containing 50-90% acrylic acid and 50-10% (w / w) maleic acid. Their relative molecular weight (based on the free acids) is generally 5000 to 200,000, preferably 10,000 to 120,000, in particular 50,000 to 100,000.

The content of (co) polymeric polycarboxylates in the composition is in the conventional range and preferably is 1-10% (w / w).

Also particularly preferred are biodegradable polymers from more than two different monomer units, for example those containing, according to DE-A-4 300 772, acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or DE-C as monomeric salts -4,221,381 contain acrylic acid and 2-alkylalyl sulfonic acid as well as carbohydrate derivatives as monomeric salts.

Further preferred copolymers are described in German patent applications DE-A-4 303 320 and DE-A-4 417 734 and preferably have acrolein acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Other suitable excipients are the oxidation products of polyglucosanes containing carboxyl groups and / or their water-soluble salts, such as are disclosed in International Patent Application WO-A-93/08 521, or whose preparation is described, for example, in International Patent Application WO- 93/16 110. Also oxidized oligosaccharides according to German patent application DE-A-19 600 018 are also suitable.

Aminodicarboxylic acids, their salts or their precursors are also known as further preferred excipients. Highly preferred are polyaspartic acids or salts or derivatives thereof, which have been disclosed in German Patent Application DE-A-19 400 086 and exhibit a stabilizing whitening effect in addition to the properties of the additive.

Other suitable excipients are polyacetals which can be prepared by converting dialdehydes with polycarboxylic acids having 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European Patent Application EP-A-0 280 223. Preferred polyacetals are prepared from dialdehydes, such as glyoxal, glutaraldehyde, terephthalaldehyde, as well as mixtures thereof, and from polyolecarboxylic acids, such as gluconic acid and / or glucoheptonic acid.

The compositions may further comprise components which suitably affect the washability of oils and greases from fabrics. This effect is particularly noticeable in the case of a plurality of soiled and washed textile articles which have been washed more than once with the detergent composition of the present invention comprising said oil and a grease-dissolving component. Preferred oils and grease-dissolving components include, for example, non-ionic cellulose ethers such as methylcellulose and methylhydroxycellulose with a proportion of methoxy groups of from 15 to 30% by weight and hydroxyl groups of from 1 to 15% by weight, based on the nonionic cellulose ether. As is well known in the art, these components further include polymers of phthalic acid and / or terephthalic acid or their derivatives, in particular polymers of ethylene terephthalate and / or polyethylene glycol terephthalate, or their anionic and / or nonionic modified derivatives. Of these, sulfonated derivatives of polymers of nitric acid and polymers of terephthalic acid are particularly preferred.

Other suitable formulation ingredients are water-soluble inorganic salts, such as bicarbonates, carbonates, amorphous silicates, as well as the aforementioned slowly soluble silicates, or mixtures thereof; Preferred are alkali metal and amorphous silicates, especially sodium silicate with a molar ratio Na ₂ O:: _SiO2 1: 1 to 1: 4.5, preferably 1: 2 to 1: 3.5. The sodium carbonate content of the composition is preferably up to 20% (w / w), more preferably between 5 and 15% (w / w). The sodium silicate content of the composition is generally up to about 10% (w / w), preferably between 2 and 8% (w / w), unless the silicate is used as an excipient.

As described in International Patent Application WO-A-94/01222, alkali metal carbonates can be replaced by sulfur-free amino acids having 2 to 11 carbon atoms and optionally other carboxyl and / or amine groups, or salts thereof. It is possible within the scope of the invention for partial or complete replacement of the alkali metal carbonate with glycine or glycinate.

Other detergent ingredients include graying inhibitors, antifoams, bleaching agents and bleach activators, optical brighteners, enzymes, textile softeners, dyes and fragrances, as well as neutral salts such as sulfates and chlorides in the form of their sodium or potassium salts.

Acid salts or only slightly basic salts may also be used to lower the pH of the detergent or cleaning compositions. Preferred acidic components are the hydrogen sulphates and / or bicarbonates, or the abovementioned organic polycarboxylic acids, which can simultaneously be used as auxiliaries. It is very advantageous to use citric acid which is either additionally admixed (conventional production method) or dosed in the anhydrous solid state already in the masterbatch.

Among the bleaching agents which release H ₂ O ₂ in an aqueous environment, compounds such as sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxopyrophosphate, peroxocitrate as well as H ₂ O ₂ releasing salts, or peracids such as peroxobenzoates, peroxophthalates, diperoxoazelaic acid, phthalimino acid or diperoxodidecanedioic acid. A preferred content of bleaching agents in the composition is 5 to 25% (w / w) and in particular 10 to 20% (w / w), preferably perborate monohydrate or percarbonate.

Bleach activators which may be used are compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids, preferably having 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances having O- and / or N-acyl groups with the indicated number of carbon atoms and / or optionally substituted benzoyl groups are suitable. Preference is given to several acylated alkyl amines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycourils, in particular teacetyl glycouril (TAGU), N acylimides, especially N-non anoylsuccinimide (NOSI), acylated phenolsulfonates, especially N-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene, , 5-diacetoxy-2,5-dihydrofuran, and from the applications of German patents DE-A-19 616 693 and DE-A-19 616 767 known enol esters such as acetylated sorbitol and mannitol, optionally in European patent application EP-A-0 525 239 described mixtures (SORMAN), acylated saccharide derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, as well as acylated or N-alkylated glucamine and gluconolactone n, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are known from international patent applications WO-A-94/27 970, WO-A-94/28 102, WO-A-94/28 103, WO -A-95/0 626, WO-A-95/14 759 and WO-A-95/17 498. It is also advantageous to use known hydrophilic substituted acyl acetals from German patent application DE-A-19 616 769 and German patent application DE -A-19 616 770 as well as the acyl lactams described in International Patent Application WO-A-95/14 075. Known combinations of conventional bleach activators can also be used from DE-A-4,443,177. Said bleach activators are used in customary amounts, preferably in amounts of from 1 to 10% by weight, in particular from 2 to 8% by weight, based on the total weight of the composition.

When used in automatic washing machines, it may be advantageous to add foam inhibitors - antifoams to the detergents. As foam inhibitors are, for example, soaps of natural or synthetic, containing a high proportion of C _{1 B} - to C ₂₄ - fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, in this case silanated, silicic acid, as well as paraffins, waxes, microcrystalline waxes, and mixtures thereof with silanated silicic acid or bistearylethylenediamide. Mixtures of different foam inhibitors are also preferably used, for example those containing silicones, paraffins or waxes. Particularly preferred are those foam inhibitors which contain silicones and / or paraffins which are bound to a granulated, water-soluble carrier. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

The polyphosphonic acid salts used are preferably neutral reacting sodium salts, for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriamine pentamethylene phosphonate or ethylenediaminetetramethylene phosphonate in amounts of from 0.1 to 1.5% by weight.

Suitable enzymes are, in particular, those of the group of hydrolases, such as proteases, lipases, or lipolytic enzymes, amylases, cellulases or mixtures thereof. Oxyreductases are also suitable.

Particularly suitable are enzymatic active substances obtained from strains of bacteria or fungi such as Bacillus subtillis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens. Preferred are proteases of the subtilisin type, and in particular proteases obtained from the Bacillus lentus strain. Of particular interest here are mixtures of enzymes, for example mixtures of proteases and amylases or proteases and lipases, or lipolytically acting enzymes, or proteases and celluloses, or celluloses and lipases, or lipolytically acting enzymes, or proteases, amylases and lipases, or lipolytically acting enzymes, or proteases, lipases or lipolytically acting enzymes and cellulases, in particular mixtures containing proteases and / or lipases, optionally mixtures with lipolytically acting enzymes. Examples of lipolytic enzymes are known cutinases. Peroxidases or oxidases may also be appropriate in individual cases. Suitable amylases include, in particular, α-amylases, iso-amylases, pullulanases and pectinases. Of the cellulases, cellobiohydrolase, endoglucanase and β-glucosidase, which are also known as cellobiases, or mixtures of the said enzymes, are preferred. Because different cellulase types differ from each other by CMCase and avicelase activity, the desired activity of the composition can be adjusted by targeted mixing of cellulases.

Said enzymes may be used adsorbed on carriers and / or incorporated into the hollow forms of the components of the compositions, thereby protecting them from premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules in the composition may, for example, be about 0.1 to 5% by weight, preferably 0.1 to 2% by weight.

In addition to phosphonates, the composition may contain other enzyme stabilizers. For example, 0.5 to 1% by weight of sodium formate may be used. Proteases that are stabilized with soluble calcium salts at a preferred calcium content of 1.2% based on the enzyme may also be used. In addition to calcium salts, magnesium salts can serve as enzyme stabilizers. Further preferred is the use of boron compounds, for example boric acid, boric oxide, borax and other alkali metal borates such as salts of ortho-trihydrogenboronic acid (H ₃ BO ₃ ), hydrogenboronic acid (HBO ₂ ) and dihydrogentetraboronic acid (H ₂ B ₄ O _7). ).

The role of the graying inhibitors in the wash liquor is to maintain loose dirt in the fiber suspension and thus prevent the dirt from being trapped again.

Suitable for this purpose are water-soluble colloids, in particular of organic origin, for example, water-soluble salts of polymeric carboxylic acids, gelatin, gelatin, salts of ether-carboxylic acids or ether-sulfonic acids of starch or cellulose, or salts of acidic esters of sulfuric acid and cellulose or starch. Also suitable for this purpose are polyamides which are water-soluble and contain acidic groups. Furthermore, soluble starch preparations and other starch products such as starch degraded, starch aldehydes and the like can be used. Polyvinylpyrrolidone is also useful. However, it is preferred to use cellulose ethers such as carboxymethylcellulose (Na-salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methyl carboxymethylcellulose and mixtures thereof, as well as polyvinylpyrrolidone, for example in amounts of 0.1 to 5%. (w / w), always referring to the finished composition.

Detergents and cleaning agents may contain as optical brighteners diaminostilbenedisulfonic acid derivatives or alkali metal salts thereof. Suitable salts are, for example, 4,4'-bis (2-anilmo-4-morpholino-1,3,5-triazinyl-6-amino) -stilbene-2,2'-disulfonic acid salts or similarly constructed compounds which instead of the morpholine group have a diethanolamine group, a methylamine group, an aniline group or a 2-methoxyethylamine group. Substituted diphenylstyryl-type brighteners may also be present, for example, the alkali salt 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 said brighteners may also be used.

The present invention further encompasses a process for preparing particulate detergents or cleaning compositions, or mixtures or treated raw materials, having a bulk density of greater than 600 g / d &^lt; ^{3 &gt};, by combining mixtures of detergents or cleaning ingredients and / or raw materials with simultaneous or sequential shaping. a solid, free-flowing premix, the individual raw materials and / or mixtures of which, at room temperature and at a pressure of 10 ⁵ Pa (1 bar), are used as such and do not have a melting or softening point below 45 ° C which optionally contain up to 10% of nonionic surfactants which are liquid at temperatures below 45 ° C and at a pressure of 10 ⁵ Pa (1 bar), the mixing step being carried out at room temperature to below the melting or softening point of the individual raw materials and / or mixtures and, using compaction forces at temperatures of at least 45 ° C, are converted to granular material, subject to u that

(a) the free water content is less than 2% by weight, expressed on the weight of the masterbatch, and the total water content is not more than 15% by weight, expressed on the weight of the masterbatch, and

b) the premix is used, one or more anionic surfactants in an amount of at least 0.5% by wt., expressed on the weight of the composition, and at least one material or a mixture which is at a pressure of 10 ⁵ Pa (1 bar) and a temperature below 45 ° C in the solid state but under the conditions under which it is processed is in the form of a melt, the melt acting polyfunctionally; it serves as a water-soluble binder, which, however, acts as a glidant in production and also serves as an adhesive for solid laundry or cleaning compositions or raw materials; on the other hand, disintegrating in dissolving said composition in a water wash, and wherein the raw material or mixture is selected from the group consisting of unbranched, branched and modified polyethylene glycols, modified polypropylene glycols, 1,2-polypropylene glycols, low molecular weight polyvinylpyrrolidones and their derivatives with their molecular weight derivatives not more than 30 000, alkoxylated fatty alcohols and oxoalcohols, fatty acid methyl ester ethoxylates, branched and unbranched fatty acid ethoxylates of 2 to 100 EO, mixed hydroxyethers, anhydrous swelling polymers, alkyl glycosides having the general formula RO (G) _X , in which

R is a primary linear or methyl branched (C ₈ to C ₂₂₎ alkyl,

G is a glycose unit having 5 or 6 carbon atoms, x is selected from the numbers 1 to 10, of polyhydroxy fatty acids having the general formula (I), ^R '(O,

I

R ² -CO-N {wherein Zl

R ² CO means (G ₈ to C ₂₂ ) -acyl,

R ³ is hydrogen, (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -hydroxyalkyl, [Z] means straight or branched (C ₃ -C ₁₀ ) -polyhydroxyalkyl of 3 to 10 hydroxyl groups, polyhydroxy fatty amides acids having the general formula (II),

R ⁴ —CO-N— {Z'J in which

R ⁴ denotes unbranched or branched (C ₇ -C ₁₂ ) -alkyl, branched or branched (C ₇ -C ₁₂ ) -alkenyl,

R ⁵ represents a linear or branched (C ₂ to C ₈ -alkyl, cycloalkyl having 2 to 8 carbon atoms, aryl having 2 to 8 carbon atoms,

R ⁶ denotes unbranched or branched (C 1 -C ₈ ) -alkyl, (C 1 -C ₈ ) -oxoalkyl, cycloalkyl of 1 to 8 carbon atoms, aryl of 1 to 8 carbon atoms, [Z '] means an optionally alkoxylated unbranched polyhydroxyalkyl a residue whose alkyl chain is substituted with at least two hydroxyl groups and mixtures thereof.

The water content in the liquid state, i.e. in the state, for example, not in the form of hydrate and / or constitutional water, is less than 2% (w / w), preferably less than 1% (w / w) and in particular less than 0.5% (w / w); the percentages are based on the weight of the masterbatch. In the premix process, water can be essentially introduced only in a chemically and / or physically bound form, optionally as a constituent of raw materials or mixtures, which are solid at temperatures below 45 ° C and at a pressure of 10 ⁵ Pa (1 bar). but not as a liquid, solution or dispersion. Preference is given to a masterbatch having a total water content of not more than 15% by weight, which water is also not chemically and / or physically bound in liquid free form; it is particularly preferred that the content of non-zeolite and / or not in the bound water silicates in the solid premix is not more than 10% by weight, more preferably less than 7% and most preferably not more than 2 to 5% by weight.

For the purposes of the present invention, the expression "particulate laundry or cleaning compositions" is preferably understood to mean compositions which do not have dust fractions, and in particular, which have no particles smaller than 200 gm. Particularly preferred is a particle size distribution in which at least 90% by weight of the particles have a diameter of at least 400 gm. In one very preferred embodiment of the present invention, the prepared laundry or cleaning composition, composition or raw materials comprises at least 70% (w / w), more preferably at least 80% (w / w) and most preferably up to 100% (w / w) of spherical particles with such size distribution. wherein at least 80% by weight of the particles are between 0.8 and 0.2 mm in size.

In the present invention, the term "laundry or cleaning agents" refers to compositions which can be used for washing or cleaning without the need for admixture with other conventional ingredients in use. The composition, on the other hand, comprises at least 2 ingredients commonly used in detergents or cleaners; however, the mixtures are normally only used mixed with other components, preferably mixed together with other mixtures. The treated feedstock within the scope of the present invention is a relatively fine feedstock which is converted into coarser particles by the process of the present invention. More specifically, the treated raw material within the scope of the present invention is a composition that is added as a component of conventional detergents or cleaners.

In the process according to the invention, the components used, except for nonionic surfactants, which are liquid at temperatures below 45 ° C and a pressure of 10 ⁵ Pa (1 bar), can be separately produced mixtures, but also raw materials which are powder or particulate (fine to thick), but in any case at room temperature under 10 ⁵ Pa (1 bar) in solid form. As particulate components, for example, spray-dried beads or fluidized-bed granules and the like can be used. The composition of the compositions is irrelevant to the present invention except for the water content, which must be such that the premix is substantially anhydrous and preferably contains no more than 10% by weight of hydrate and / or constitutional water.

In one preferred embodiment, the dried mixtures are used in the masterbatch. Said compositions may be prepared, for example, by spray drying, wherein the temperature is controlled such that the material at the outlet of the spray dryer is at or above 100 ° C, for example 110 ° C. It is also possible to use in the premix solid mixtures which serve as liquid carriers, for example liquid non-ionic surfactants or silicone oil and / or paraffins. These compositions may contain water within the stated range, said compositions being free-flowing and remaining free-flowing or transportable, even at higher temperatures, at least 45 ° C. It is, however, very advantageous to use in the masterbatch mixtures having a water content of not more than 7% by weight, expressed on the masterbatch weight. It is preferred that the masterbatch does not contain free water, i.e., water which is not bound in any form in a solid and is therefore "in liquid form" or contains only a very limited amount of free water, for example about 0.2 or 0 5% by weight, expressed on the weight of the masterbatch; the presence of water results in a lowering of the melting point or softening point, and the final product will have less flowability and also bulk density.

It has unexpectedly been found that it is by no means indifferent to which solid feedstock or in which solid mixture the water is bound. For example, water bound to excipients such as zeolite or silicates (for a description of excipients, see below), especially if the water is bound to zeoiite A, Zeoiit P or MAP and / or zeoiit X, its content is considered to be less critical. On the other hand, it is preferred that the water content, which is bound to solids other than said excipients, be less than 3% by weight in the masterbatch. Therefore, in one embodiment of the present invention, it is preferred that the bound water content of the masterbatch is not more than 10% (w / w) and / or the water content bound other than zeolite and / or silicates is less than 7% (w / w). up to 5% by weight. In this case, it is preferred that the premix does not at all contain water which is not bound to the auxiliaries. This is technically very difficult to carry out, since the raw materials and mixtures generally bring at least trace amounts of water with them.

The content of solid mixtures used in the masterbatch that is not liquid at temperatures below 45 ° C is likewise, optionally, in addition, up to 10% (w / w), more preferably up to 6% (w / w), again expressed with respect to the total amount of masterbatch. Preference is given to using solid mixtures containing nonionic surfactants which are usually liquid at temperatures below 45 ° C and at a pressure of 1 bar which can be prepared separately by any of the known methods, for example by spray drying, granulation or coating of nasal beads. In this way, masterbatches can be prepared which contain, for example, up to 10% (w / w), preferably less, in particular at most 8% (w / w), for example between 1 and 5% (w / w) nonionic surfactants.

Compositions which contain water in said form and / or serve as carriers for liquid substances, in particular for nonionic surfactants, which are liquid at room temperature, may also contain liquid components at room temperature and may be used according to the invention, if in any case do not have a softening temperature below 45 ° C. Likewise, the individual raw materials used separately have a melting point of at least 45 ° C. It is preferred that the melting point or the softening point of all of the individual raw materials and mixture used is more than 45 ° C, more preferably at least 50 ° C.

In one preferred embodiment of the present invention, at least 80% (w / w), preferably at least 85% (w / w) and most preferably at least 90% (w / w) of the mixtures used in the masterbatch and the individual raw materials have significantly higher softening or melting points than can achieve in production. For purely economic reasons, in practice the operating temperatures do not exceed 150 ° C, preferably not higher than 120 ° C. Therefore, at least 80% (by weight) of the mixtures used and the individual raw materials have a softening or melting point higher than 150 ° C. The softening or melting point is generally well above these temperatures. In the case of the use of temperature-decomposing components, for example peroxide bleaching agents such as perborate or percarbonate, the decomposition temperature of the component at 1 bar and in particular at the higher pressures expected in the extrusion process according to the invention is equally significant higher than 45 ° C.

In addition to the constituents, the masterbatch may additionally contain up to 10% by weight of nonionic surfactants which are liquid at a temperature below 45 ° C and a pressure of 1 bar, in particular alkoxylated alcohols such as fatty alcohols or carbon-chain oxoalcohols commonly used in detergents. having a length of between 8 and 20 carbon atoms, and in particular having an average of three to seven ethylene oxide units per mole of alcohol (for more details, see below). The addition of liquid nonionic surfactants can be chosen to a height as long as it is ensured that the premix is still free-flowing. If liquid nonionic surfactants are used in the masterbatch, it will be preferred that the liquid nonionic surfactants and the disintegrating binder are used separately in the preparation process. In one preferred embodiment of the invention, in the continuous manufacture, liquid nonionic surfactants are applied, in particular by means of nozzles, to the flow of powdered material which absorbs the liquid component.

However, the masterbatch comprises at least one feedstock or at least one mixture which also serves as a binder; although solid (s) at room temperature; however, they are liquid in the form of melt when compacted under production conditions. Said binder may also be separately melted and sprayed onto the masterbatch or dropwise into the masterbatch; it is preferred to introduce the binder into the masterbatch in solid form as a powder. The melting or softening temperature at a pressure of 1 bar is at least 45 ° C, preferably (especially for economic reasons) below 200 ° C, most preferably at most 150 ° C. If the binder is introduced into the masterbatch in the form of a melt, then the temperature in the melting vessel is similarly higher than 45 ° C, up to a maximum of about 200 ° C, and the temperature in the melting vessel can significantly exceed the melting point or softening point of the binder or binder mixture. .

The type of suitable binder and processing temperature during compaction are interdependent. It will be appreciated that in the compaction processing step the binder will be dispersed as best as possible in the batch, and temperatures at which the binder at least softens must be used in this step, it is preferred that the binder be wholly and not only partially in molten form. Thus, a binder having a high melting point or a softening point is chosen and the temperature in the compaction step must be adjusted so that the binder melts with certainty depending on the desired composition of the final product, and the need to process higher temperature sensitive raw materials. In such cases, the upper temperature limit is given by the decomposition temperature of the sensitive feedstock, and it is preferable to operate at a significantly lower temperature than said decomposition temperature. On the other hand, the lower limit for the melting point or softening point is therefore of such great importance that at melting points or softening temperatures below 45 ° C, a finished product is generally obtained which is already at room temperature or at slightly elevated temperatures of about 30 ° C, also at summer temperatures and in storage or transport conditions, it tends to stick to the ag regatta. It has proven to be very advantageous if temperatures of only a few degrees above the melting point or above the softening point, for example by 2 to 20 ° C, are employed.

Without intending to be limited to the following theory, the present inventors are of the opinion that by uniformly distributing the binder in the masterbatch in the compacting step of the solid mixtures and any other individual raw materials, the binder is wrapped and subsequently bonded together that many individual small particles evenly form end products; The fine particles together hold together by the action of a binder which takes on the role of a preferred thin separating wall (layer) between the glued particles. In an idealized form, it is possible to start from similar shapes of honeycomb construction, these honeycomb cells being filled with solids (mixture or individual raw materials). In contact with water, as well as in contact with cold water, such as at the beginning of an automatic washing machine program, said thin separating walls dissolve or disintegrate almost immediately; this is unexpected if the binder itself is not readily soluble in water at room temperature, for example because of its crystalline structure. Preference will then be given to using binders which, under the conditions of the test procedure below, at a concentration of 8 g of binder in 1000 ml of water at 30 ° C almost completely dissolve within 90 seconds.

The binder or binders must be such that their tack properties are maintained even at temperatures significantly higher than their melting or softening point. On the other hand, it is also important for the choice and amount of binder (s) used that the bonding properties do not deteriorate when the final product is cooled again, and that the cohesiveness of the final product is ensured in such a way that larger units.

Hereinafter, the description per single binder is simplified. It is obvious that several different binders and / or mixtures of different binders can also be used.

In one preferred embodiment of the present invention a binder is used which is present as a melt at temperatures up to at most 130 ° C, preferably up to at most 100 ° C and in particular up to 90 ° C. The binder must be chosen according to the manufacturing process and conditions for the preparation of the detergent or cleaning agent, or the manufacturing process and the preparation conditions, in particular the operating temperature, must be adjusted if the use of a particular binder is required to allow its use.

Preferred binders, alone or in admixture with other binders that may be used, include polyethylene glycols, 1,2-polypropylene glycols, as well as modified polyethylene glycols and polypropylene glycols. Modified polyalkylene glycols include the sulfates and / or disulfates of polyethylene glycols or polypropylene glycols with a molecular weight of between 600 and 12,000, in particular between 1000 and 4000. Another group comprises mono- and / or disuccinates of polyalkyl glycol, which again have relative molecular weights of between 600 and 6000 , more preferably between 1000 and 4000. For a more precise description of the modified polyalkylene glycol ethers, reference is made to the published international patent application WO-A-93/02 176. Within the scope of this invention, polymers are included among the polyethylene glycols for which C _{3 has} also been used as starting molecules up to C ₅ -glycols as well as glycerol and mixtures thereof. In addition, ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO groups are also included.

Preferred polyethylene glycols used may have a linear or branched structure, with unbranched polyethylene glycols being particularly preferred.

Highly preferred polyethylene glycols include those having a molecular weight of between 2000 and 12,000, preferably about 4000, and polyethylene glycols with a molecular weight below 3500 and above 5000 can also be used, especially in combination with polyethylene glycols with a molecular weight of about 4000; Such a combination is preferred that the combination of more than 50% (wt), based on the total amount of polyethylene glycols, of polyethylene glycols to the relative molecular mass between 3500 and 5000. The binder may also be used also polyethylene glycols, which are at room temperature and a pressure of 1.10 ⁵ Pa (1 bar) in the liquid state; in particular polyethylene glycol having a relative molecular weight of 200, 400, and 600. The liquid polyethylene glycols must, of course, only be used in a mixture with at least one other binder, and this mixture must again satisfy the requirement of the invention that the melting or softening temperature of said mixture was more than 45 ° C.

The modified polyethylene glycols also include polyethylene glycols terminally capped at one or more sides, the end groups may preferably be a C-C _{r? R} alkyl chains of either straight or branched. As end groups are particularly preferred alkyl chains between C _R and C ₍₎ -, most preferably between C _r and C ₄ -, which may be optional also of isopropyl and isobutyl, or tertiary butyl group.

Polyethylene glycol derivatives with unilaterally closed end groups may also conform to formula C _X (EO) _V (PO) _Z , wherein C _x may be an alkyl chain of 1 to 20 carbon atoms in length, y may be 50 to 500 and z may be 0 to 0 20. For z = 0, these compounds overlap with those of the preceding paragraphs.

EO - PO - polymers can also serve as a binder (x equals 0).

Also suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights up to a maximum of 30,000. Preferred molecular weight weights are between 3000 and 30,000, for example about 10,000. It is preferred that said polyvinylpyrrolidones are not used alone as a binder but in combination with other binders, especially in combination with polyethylene glycols.

Other suitable binders have proved to be raw materials which themselves exhibit washing or cleaning properties, for example nonionic surfactants having a melting point of at least 45 ° C, or mixtures of nonionic surfactants and other binders. Preferred nonionic surfactants are alkoxylated fatty and oxo alcohols, in particular C ₂ - to C ₁₈ -alcohols. Particular preference is given to those alcohols whose alkoxylation stage, in particular the ethoxylation stage, is on average 18 to 100 AO, in particular EO, per mole of alcohol, and mixtures of these surfactants are particularly preferred. In view of the present invention, the preferred binder properties are in particular fatty alcohols having an average of 18 to 35 EO, in particular an average of 20 to 25 EO. Alternatively, ethoxylated alcohols with an average smaller number of EO units per mole of alcohol, for example, a tallow fatty alcohol of 14 EO, may also be used in the binder mixtures. However, it is preferred that these relatively low ethoxylated alcohols be used only in mixtures with higher alkoxylated alcohols. The preferred proportion of 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. Normally, in washing and cleaning composition to a used nonionic surfactants such as C _I2 - to C | _{The 8-} alcohols with an average of 3 to 7 EO, which are liquid at room temperature, are preferably used in the binder mixtures according to the invention only in amounts which are less than 10% by weight, in particular less than 8% by weight, and most preferably less than 2% by weight of these nonionic surfactants, based on the final product of manufacture. As mentioned above, the addition of nonionic surfactants liquid at room temperature is naturally less preferred. Therefore, in one preferred embodiment, said nonionic surfactants do not form part of the binder mixture, since these nonionic surfactants not only lower the softening point of the mixture, but can also lead to tackiness of the final product; furthermore, their tendency to form gels in contact with water also does not meet the requirement of rapid dissolution of the binder / separating layer of the final product to the desired extent. Likewise, it is not preferred that the binder mixtures contain the customarily used anionic surfactants or their precursors, anionic acid surfactants in detergents or cleaners. Fatty alcohols C ₂ to C ₁₈ , fatty alcohols C 1 ₆ - to C | _{On the other hand, an 8} - or pure _C18- fatty alcohol with more than 50 EO, preferably about 80 EO, is referred to as an excellent binder which can be used either alone or in combination with other binders.

Other nonionic surfactants which are suitable as binders are fatty acid methyl esteroxylates which do not tend to gel, especially those containing 10-25 EO (a detailed description of this class of substances is given below). Particularly preferred representatives of this group of substances are predominantly methyl esters based on fatty acids C ₁₆ - to C _R, e.g., fatty acid methyl ester hardening beef tallow, an average of 12 EO, or with an average of 20 EO.

Another group of substances which are suitable as binders within the scope of the present invention are fatty acids with 2 to 100 EO, whose "fatty acid" residues may be unbranched or branched within the scope of the present invention. Particularly preferred are those ethoxylates having a narrow homologous distribution (NRE) and / or a melting point above 50 ° C. These fatty acid ethoxylates may also be used alone as a binder or in combination with other binders; unethoxylated sodium and potassium soaps are less preferred and are used only in combination with other binders.

Mixed hydroxyethers as described in European patent application EP-A-0 754 667 (BASF), which can be obtained by ring opening of unsaturated fatty acid esters, in particular in combination with polyethylene glycols, the abovementioned fatty acid methyl ester ethoxylates or fatty acid ethoxylates.

Unexpectedly, anhydrous swellable polymers, in particular starch diphosphate / glycerol, polyvinylpyrrolidone / glycerol and modified celluloses / glycerol, for example hydroxypropylcellulose / glycerol, have also proved to be excellent binders. Particularly preferred are 5 to 20% (w / w) solutions of said polymers in glycerol, especially about 10% (w / w) solutions.

In one preferred embodiment of the present invention, a binder mixture consisting of a C ₁₂ -C ₁₈ fatty alcohol derived from coconut fat or tallow, on average 20 EO, and polyethylene glycol having a molecular weight of from 400 to 4000 is used as the binder.

In another preferred embodiment of the invention, the binder is a mixture which comprises in particular the methyl ester, based on the fatty acids C | "- to _{C) 8} - on average 10 to 25 EO groups, especially the methyl ester of hydrogenated beef tallow with an average of 12 EO, and an average with 20 PE, a

C | _2- to _C18 -fatty alcohol derived from coconut fat or tallow with an average of 20 EO and / or polyethylene glycol having a molecular weight of from 400 to 4000.

In very preferred embodiments of the invention, suitable binders have been shown to be based on either polyethylene glycols alone having a relative molecular weight of about 4000 or a mixture of C 1-6. ₂ - to _{C] g} - of fatty alcohol derived from coconut or tallow, an average of 20 EO and the fatty acid methyl ester ethoxylates described above and polyethylene glycol, in particular, to the relative molecular weight of about 4000. Most preferably, the mixture of polyethylene glycol, having the relative molecular weight of about 4000 with the aforesaid fatty acid methyl esteroxylates or a C ₁₆ - C ₁₈ fatty alcohol with 20 EO, in a weight ratio of 1: 1 or more.

The binder mixture may further comprise other raw materials such as trimethylolpropylene etc (Product of BASF, BRD), in particular in a mixture of polyethylene glycols; however, they cannot be used as a binder alone, although they function as a binder / adhesive, but have no effect on the disintegration of the product in water.

Alkyl glycosides having the general formula RO (G) _X , in which R represents a primary unbranched or methyl branched, in particular at the 2-position, a methyl branched aliphatic radical having a radical of 8, can be used as further binders alone or in combination with other binders. and G is a symbol which represents a glycose unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the proportions of monoglycosides and oligoglycosides, is arbitrarily selected from the numbers 1 to 10; a preferred value of x is about 1.2 to 1.4. Particularly suitable are those alkyl glycosides having a softening point above 80 ° C and a melting point above 140 ° C. Highly concentrated mixtures containing at least 70% by weight of alkyl glycosides, preferably at least 80% by weight, of alkyl glycosides are also suitable. When using higher shear stresses, the melt-agglomeration and especially the melt-extrusion with these highly concentrated mixtures can be carried out just at temperatures above the softening point but still below the melting point of the mixtures. Although the alkyl glycosides can be used alone as a binder, it is preferable to use mixtures of alkyl glycosides with other binders. Particularly preferred are mixtures of polyethylene glycols and alkyl glycosides, preferably in weight ratios of 25: 1 to 1: 5, in particular from 10: 1 to 2: 1.

Polyhydroxy fatty acid amides having the general formula (I) wherein 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] denotes unbranched or a branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups is also suitable as a binder, especially in combination with polyethylene glycols and / or alkyl glycosides.

R '

I

R’ —CO-N— {ZJ (I)

The polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular glucose.

Also included in the group of polyhydroxy fatty acid amides are compounds having the general formula (II).

CO-N ~ - {Z]

R ⁴ is straight or branched (C 7 to C 12) -alkyl, straight or branched (C 7 to C 12) -alkenyl, R ⁵ is straight or branched (C 2 to C ₈ ) -alkyl, cycloalkyl of 2 to 8 carbon atoms, aryl of 2 to 8 carbon atoms, R ⁶ denotes unbranched or branched (C 1 -C 8) -alkyl, (C 1 -C ₈ ) -oxoalkyl, cycloalkyl of 1 to 8 carbon atoms, aryl of 1 to 8 carbon atoms, [ Z '] represents an optionally alkoxylated unbranched polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of these radicals. Also in this case, it is preferable to prepare [Z] by reductive amination of sugars such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. Said N-alkoxy- or N-aryloxy-substituted compounds may then be prepared, for example, as described in International Patent Application WO-A-95/07 331 by converting fatty acid methyl esters in the presence of an alkoxide catalyst to the desired polyhydroxy fatty acid amides. A particularly preferred glucamide is melted just at 95-105 ° C. However, here too, as in the case of alkyl glycosides, the normal operating temperatures which are above the softening point but below the melting point are sufficient in the process according to the invention.

The preferred binder or binder content in the masterbatch is at least 2% (w / w), but less than 15% (w / w), especially less than 10% (w / w), and particularly preferably the binder (s) content is from 3 to 6% (w / w). based on the total weight of the masterbatch. The anhydrous swellable polymers are used in particular in amounts below 10% by weight, preferably in amounts of from 4 to 8% by weight, most preferably from 5 to 6% by weight.

In a preferred embodiment of the process according to the invention, the solids for the preparation of solid and free-flowing premixes are first mixed together in a conventional mixing and mixing system at room temperature to slightly elevated temperature, preferably below the melting or softening point of the binder. / or granulating device. The solids mentioned are those which, according to European patent EP-B-0 486 592, can serve as plasticizers and / or glidants. These include, in particular, anionic surfactants such as alkylbenzene sulfonate and / or (fatty alkylsulfate), but also polymers such as polymeric polycarboxylates. A more detailed description of possible anionic surfactants and polymers is given elsewhere in the list of possible excipients. a binder or binders or binder mixtures.

Advantageously, the binders are mixed into the mixtures as the last component. As already mentioned, the binders can be added as solids, i.e. at a working temperature below their melting or softening point, or as a melt. However, it is preferable to admix under such conditions as to ensure a homogeneous distribution of the binder in the solid mixture as uniformly as possible. When using very fine binders, the admixing can be carried out at temperatures below 40 ° C, for example at binder temperatures between 15 and 30 ° C. However, it is preferred that the binder has a temperature at which it is already in the form of a melt, that is, a temperature higher than the softening temperature, more preferably the binder is in the fully molten state. Preferred melt temperatures are in the range of 60 to 150 ° C, more preferably the temperature range is from 80 to 120 ° C. During the mixing process at room temperature to a slightly elevated temperature, but below the softening point or the melting point of the binder, solidification of the melt occurs almost immediately and the masterbatch according to the invention takes a dense and free-flowing form. In any case, the preferred mixing process will take until the melt solidifies and the masterbatch is in a solid and free-flowing form.

The joining of the washing or cleaning compositions and / or raw materials with simultaneous or subsequent shaping can be carried out by conventional methods in which compaction forces are applied, i.e. by methods such as granulation, compression (compacting), for example compacting on rolls or extrusion, or tableting, optionally with by adding conventional disintegrating or pelletizing agents. Pre-mixed mixtures such as spray-dried granules can be used in the masterbatch; the invention is not limited thereto. According to the method of the present invention, no spray-dried granules need be added, since very fine raw materials with dust fractions can also be processed without any difficulty by the method of the present invention without being pre-treated by agglomeration, for example in a spray drier.

The actual granulation, compacting, tabletting, pelletizing or extrusion processes are carried out according to the invention at operating temperatures which, at least in the compaction process, correspond at least to the softening point, if not the melting point of the binder. In one preferred embodiment of the invention, the processing temperature is significantly higher than the melting temperature, optionally above the temperature at which the binder is added as a melt. In the compaction process, a working temperature which is not more than 20 ° C above the melting point or above the upper melting point of the binder is particularly preferred. While it is technically possible to work at even higher temperatures, it has been shown that a temperature difference of 20 ° C from the melting point or the binder softening point is quite sufficient and further increase of the temperature does not bring any further advantages. For this reason, especially for energy reasons, it is advantageous to operate above, but as close as possible to the melting point or the upper temperature limit of the binder melting range. Said temperature regime has the further advantage that substances sensitive to higher temperatures, for example peroxide bleaching agents such as perborates and / or percarbonates, but also enzymes can be processed without significant losses of the active substance. The possibility of precisely controlling the temperature of the binders, especially at the critical compaction stage, i.e. between mixing / homogenizing the masterbatch and the molding, allows a very suitable and gentle guidance of the entire production process so that the masterbatch is only briefly exposed to higher temperatures. Said exposure time is preferably between 10 seconds and at most 5 minutes, more preferably the exposure time is at most 3 minutes.

In a process that is substantially water-free, not only can peroxide bleaches be processed without losing their efficacy, but they can also be treated simultaneously with the bleach activator (for detailed description below) without the need for worry about a decrease in activator activity.

In one preferred embodiment, the process of the invention is carried out by extrusion, as described, for example, in European patent EP-B-0 486 592 or in the international patent application WO-A-93/021 176. In this method, the solid masterbatch is extruded by pressure. of the extruder head, the exiting material column is cut with a slicing device to predetermined granulate dimensions. The homogeneous and solid premix comprises a plasticizer and / or a glidant, which causes the premix to soften under extrusion or the effect of specific work and to be extrudable. Preferred plasticizers and / or glidants are surfactants and / or polymers which, within the scope of the present invention, with the exception of said nonionic surfactants, are used in the premix not in a liquid state and especially not in an aqueous environment but in a solid state.

In order to elucidate the individual extrusion processes, the Applicants explicitly refer to said patents and patent applications. In one preferred embodiment of the present invention, the masterbatch, preferably in a continuous manner, is fed to a planetary screw extruder or to a twin or twin screw extruder with or without rotating worms, the casing and the grinding head of the screw extruder they can be heated to the desired temperature. Under the effect of shear stresses from the extruder screw, the premix is plasticized and compacted by pressure. It is preferred that achieves pressure of 25.10 ⁵ Pa (25 bar) at extremely high flows of material and depending on the equipment used can be pressure and lower extruded material based on the extrusion head of the extruder in the form of a thin beam - column. Finally, the extrudate is crushed by means of a rotary knife divider, preferably into a spherical to cylindrical shape of granular grains. The diameter of the die head and the length of the material to be separated are adjusted to the required granulate dimensions. In this embodiment, it is possible to maintain the production of granules in such a way that substantially uniform, predetermined grain sizes are achieved, and in individual cases, the absolute grain sizes can be adapted to their intended use. Generally, particle diameters of up to 0.8 cm are preferred. Important embodiments envisage the production of individual granules having grain sizes in the millimeter area, for example in the range of 0.5 mm to 5 mm, more preferably in the range of about 0.8 mm to 3 mm. The ratio of length to diameter of the cut primary granules is, in one important embodiment, in the range of about 1: 1 to about 3: 1. It is further preferred that the plastic primary granulate is still guided for further shaping (shaping); in this case, the edges of the raw extrudate are rounded such that spherical or approximately spherical shapes of the extruded grains can finally be obtained. Optionally, a smaller amount of dry powder, for example zeolite powder, such as zeolite NaA powder, may also be used in this manufacturing step. Said shaping can be carried out using rounding machines available on the market. Care must be taken that only a limited amount of fine-grained fraction is produced in this production step. The drying described in the prior art in preferred embodiments in the above-mentioned publications is saved within the scope of the present invention, since the preparation process according to the present invention proceeds substantially free of water, i.e. without the addition of free, unbound water.

Optionally, extrusion / compression can also be carried out in low-pressure screw extruders, holo-presses or extruders.

In one very preferred embodiment of the present invention, the temperature mode in the transition region of the screw between the pre-divider and the die head with the extruder orifice is set to at least reach the binder melting point or the upper limit of the binder melting point; preferably, the temperature is higher. In this case, the time of effect of the high temperature on the material in the compression zone of the extrusion is preferably below 2 minutes and in particular in the range between 30 seconds and 1 minute.

The short residence times allowed by the use of the water-free preparation process of the present invention further allow the extrusion of the blend containing peroxide bleaching agents, optionally together with bleach activators at higher temperatures without loss of bleaching performance.

In one very preferred embodiment of the present invention, the binder used has a melting point or melting temperature range up to 75 ° C; operating temperatures which are at most 10 ° C and in particular at most only 5 ° C higher than the melting point or the upper temperature limit of the binder melting region have proved to be very suitable operating temperatures.

In these operating conditions, the binder also functions as a glidant in addition to the above-mentioned effects and furthermore prevents or at least limits the build-up of stickers on the walls of the device and on the compaction parts. This is true not only for processing in screw extruders, but also for processing, for example, in continuously operating mixers / granulators or in production on roller presses.

The compacted material preferably has temperatures not exceeding 80 ° C upon exit from the production apparatus, more preferably between 35 and 75 ° C. It is very advantageous to consider the outlet temperatures of the material, especially in the extrusion process from 40 to 70 ° C, for example up to 60 ° C.

As in the extrusion process as well as in other processes, it is advantageous to direct the primary granulate (or compactate) produced to the next shaping manufacturing step, in particular for rounding, so that spherical or nearly spherical (beaded) shapes can be achieved in the final product. grains.

It is an essential feature of a preferred embodiment of the present invention that the particle size distribution of the masterbatch may be substantially wider than said distribution in the final product produced according to the present invention. The masterbatch may comprise a significantly larger proportion of fine-grained material, even dusty or coarse-grained, with the advantage that the masterbatch with a relatively broad particle size distribution and a relatively high proportion of fine grains can be converted into an end product having a relatively narrow particle size distribution. and only small proportions of fine grains.

Since the production method of the present invention essentially does not use water, i.e. with the exception of the water contained ("as impurities") in the solid raw materials used, the risk of gelation of surfactant raw materials is minimized in the manufacturing process and, moreover, it also constitutes environmental considerations a full-fledged process which not only saves energy by eliminating subsequent drying, but also reduces emissions that arise in particular from current drying processes.

In contrast to the compositions produced hitherto, it has been shown that the behavior of the detergents produced according to the invention when reconstituting in a washing bath depends in particular on the ability to dissolve the individual components; the more ingredients are present, the faster they will dissolve, the faster the final product will dissolve; the more slowly soluble the components, the slower the dissolution of the final product. Unwanted interactions during re-dissolution, such as gelling and the like, do not appear to play any role in the production process of the present invention, nor in detergents or cleaning compositions with very high densities, for example greater than 750 to 800 ^{g.dm -1} .

The compositions, compositions and treated raw materials produced by the methods described above exhibit an increased dissolution rate compared to the prior art compositions, compositions and treated raw materials, which, although they may have the same final composition, but were not prepared by the process of the invention .

DETAILED DESCRIPTION OF THE INVENTION

Detergent or cleaning agent M1 and M2

Compositions M1 and M2 were prepared as follows.

In a batch mixer (20 dm ³ ) equipped with a knife crusher (Zerhacker), a solid premix was made from the basic ingredients, including the binder, which in this case was added in solid form. (In one preferred embodiment, the binder was injected into the premix by nozzles in the form of a sprayable melt; however, this did not significantly change the end product properties. The melt solidified shortly after introduction into the solids mixture. The mixture was then homogenized for a further 2 minutes and fed to a 2-screw extruder. The pelletizing head of the extruder was preheated to a temperature between 50 and 65 ° C, preferably to 62 ° C. The addition, in this case at a temperature of less than 45 ° C and a pressure of 100 bar (1 bar) of liquid nonionic surfactant, was carried out with the spray nozzles. The effect of shear forces, caused by screws through an extruder, the master batch plasticized and subsequently at a pressure of between 50.10 ⁵ and 100.10 ⁵ Pa (50 to 100 bar), preferably 78.10 ⁵ Pa (78 bar) extruded (extruded) mouth of the extruder head of the extruder, thin bundles - columns with a diameter of 1.4 mm, which, after exiting the orifice, were cut into granules with approximately round granular shapes (length-to-diameter ratio of about 1, hot-cutting) by cutting with separating knives. The outgoing warm granulate was rounded on a conventional Marumerizer® rounding machine for one minute, in which case it was coated with a fine powder material.

The bulk density of the extrudate produced was 800 ± 50 g.dm &^lt; ³ &^gt;.

A homogeneous premix of 61% (by weight) of granulate 1, spray-dried (composition below), 6% (by weight) of C ₁₂ to C ₁₈ fatty alcohols (composition: 92.00% by weight of the active ingredient, 3.70% by weight of sodium sulfate, 2.8% by weight of other salts of raw materials and non-sulfated fractions, as well as 1.5% by weight of water), 3% by weight of copolymeric sodium salt of acrylic and maleic acid ( in powder form), 20% by weight of sodium perborate monohydrate and 6% by weight of polyethylene glycol as a binder having a molecular weight of about 4000. A C ₁₂ to C 8 -g fatty alcohol with an average of 7 EO was sprayed into the powder stream at 4 % by weight. The masterbatch was subsequently extruded. The extrudate showed a bulk density of 758 g.dm &^lt; ³ &gt; in the following sieve analysis and an 8% L-test as described below.

Sieve analysis M1: on sieve 1.60 mm

1.25 mm

1.00 mm

0.80 mm below sieve 0.80 mm residue 6% (w / w)

76%

8%

4% overflow 6% (w / w)

To determine the undissolved residue, more precisely the L-test, in a 2000 ml beaker, mix 8 g of the test product with stirring (800 rpm, laboratory propeller mixer at a height of 1.5 cm centered above beaker bottom) for 1.5 minutes at 30 ° C. The test was performed with water having a hardness of 160 mg equivalents in dm ³ (16 ° German). The wash bath was then poured through a 80 µm sieve. The beaker was rinsed with a very small amount of cold water and the rinsing water was also passed through said sieve. The determination was performed in duplicate. The sieve with residue was dried in an oven at 40 ± 2 ° C to a steady weight to determine the undissolved detergent residue. The residue was expressed as a percentage (w / w) as the mean of the two individual tests. As a rule, a further test was performed with a deviation of more than 20% from each result, but this was not necessary in these cases.

The tendency to gel when dissolving the composition in a water wash bath was tested with a towel and bowl test; a dark plastic wash bowl (e.g., dark red) was used for this purpose; 5 dm ^{3 of} drinking water (16 ° German, 30 ° C) was poured into the bowl and M1 was added in an amount of 25 g. After 15 seconds, the composition was mixed by hand in the bowl. After another 15 seconds, a blue terry towel was placed in the wash bath and moved like a normal hand wash. After 30 seconds the walls of the bowl were wiped with a towel. After a further 30 seconds, the towel was slipped and visually assessed. The evaluation stated:

mark 1: flawless appearance, no observable residues, mark 2: permissible, sporadic residues which do not impair properties, mark 3: visible residues, at critical evaluation residues begin to degrade the product, from mark 4: clearly distinguishable and degrading residues in increasing numbers and increasing is measured.

The wash solution was then separated by decantation and the residue was treated with 5-10 ml of water and again visually assessed. The evaluation stated:

mark 1: flawless appearance, no noticeable residues mark 2: permissible, individual residues, very finely dispersed, by addition of non-gelling water, mark 3: visible residues, at critical evaluation residues begin to degrade product, from mark 4 above: clearly distinguishable and degrading residues in increasing numbers and increasing rates, agglomerates to clusters, with the addition of water gelling.

The M1 composition had marks 1 to 2 in both the towel test and the bowl test.

For comparison, a detergent composition VI was prepared which contained the same ingredients in the final product but in which the copolymer was added not as a powder but as an approximately 30% aqueous solution. The excess water was then dried by fluidized bed drying. The bulk density of the extrudate was about 770 g. Part ^{3. The} L-test gave a value of 28%. In the towel test, the score for Compound VI was graded 3 to 4, in the bowl test it was also graded 4.

Detergent M2 has proven very suitable for washing colored textile products. For its preparation, they were mixed and extruded as follows: 65.71% (by weight of granulate 2 (composition see below)), spray dried, 11.83% (by weight) of the alkyl sulphate mixture produced in the fluidized bed (composition: 75% by weight) ) _{C] 2} - to C ₁₈ - alkyl sulphate, 17% (by weight) sodium sulfate, 3% (by weight) sodium carbonate, 1% (by weight) of water, the remainder of the salt solution), 2.96% (by weight) of a copolymer of the sodium salt of acrylic acid and maleic acid (in powder form), 6.99% (by weight) of trisodium citrate dihydrate, 3.59% (wt) of polyethylene glycol to the relative molecular weight of 4000 and 8.92% (wt) C _I2 -to C | ₈ - fatty alcohol with an average of 7 EO.

The extrudate with a particle size distribution, characterized by the following screening results, had a bulk density of 811 g.dm &^lt; ^{3 &gt;} and a solubility test (L-test) of 2%. In the bowl test, scores of 1-2 were obtained.

remainder 2% (w / w) 90%

7%

0% overflow 1% (w / w)

Sieve analysis M2:

on sieve 1.60 mm

1.25 mm

1.00 mm

0.80 mm below the sieve 0.80 mm

For comparison, a mixture of V2 having the same composition of the final product was prepared, but the copolymer was not added in powder form but added as an approximately 30% solution. Excess water was then removed by fluidized bed drying. The bulk density of the extrudate was clearly below 800 g.dm &^lt; ³ &^gt;, the results of the L-test gave a value greater than 20%. When the alkyl sulphate mixture was not coextruded but additionally admixed according to German patent application DE-A-19 519 139, the bulk density of the extrudate was 780 g.dm &^lt; ³ &^gt;, the L-test result was 7% and the bowl test was 1-2.

By treating extrudate M2 by adding 3 parts by weight of enzyme granulate, 4 parts by weight of granulated defoamer, 2.5 parts by weight of polymers (Repelotex®, manufactured by Rhône-Paulenc) and 0.5 parts by weight of silicic acid per 90 parts by weight of extrudate M2. (for additional treatment of particle surfaces) composition A2 was prepared having a bulk density of 820 g.dm &^lt; ^{-3 &gt;} (increased bulk density!) and a value of 7% in the L-test and with unchanged scores from the bowl test. On the other hand, in the same treatment of 90 parts by weight of the comparative extrudate with the admixed alkylsulfan mixture, the L-test value increased to 12% while the bulk density fell to 735 g.dm &^lt; ³ &^gt;.

The composition of the invention was also prepared by supplying 3-5% by weight of a nonionic surfactant to a spray dried mixture; the mixture was subsequently treated with a nonionic surfactant.

For example, the composition of the invention was also prepared using a blend of polyethylene glycol having a molecular weight of 4000 and cetyl stearyl alcohol with an average of 20 EO in a weight ratio of 1: 2 to 5: 1.

The products of the invention were also prepared by the premix powder employed as the alkyl benzene sodium salt C ₉ - to C ₁₃ -alkylbenzénsulfónovej acid, comprising 85% (by weight) of alkyl benzene sulfonate, 4.5% (wt) of sodium carbonate, 3, 5% (w / w) sodium sulfate, 2% (w / w) sodium chloride and 4% (w / w) water and the unsulfated fraction. Depending on the individual recipes, the extrudates showed L-test result values of less than 15% or less than 10%. As comparative tests to the latter mixtures, tests were performed in which a concentrated aqueous alkylbenzenesulfonate paste was used instead of an alkylbenzene sulfonate powder and the water was then removed by drying; all these products showed values above 20% in the L-tests.

Composition of spray-dried granules

Granulate 1, spray-dried (data expressed in% by weight):

26.30% C ₉ - to C ₃ - alkylbenzésulfonátu,

1.10% tallow fatty alcohol with an average of 5 EO,

1.40% of C ₁₂ - to C ₁₈ fatty acid sodium soap,

9.40% sodium carbonate,

4.00% sodium salt of copolymers of acrylic acid and maleic acid,

39.50% zeolite A; (related to the anhydrous active substance),

2.80% amorphous sodium disilicate,

13.60% water, residual salt from solutions.

Granulate 2, spray-dried (data expressed in% by weight):

12,07% C ₉ - to C ₁₃ -alkylbenzenesulphonate

3.00% of C ₁₂ - to C ₁₈ fatty acid sodium soap,

0.03% sodium hydroxide,

4.15% sodium carbonate,

0,80% phosphonate,

0,80% polyvinylpyrrolidone,

57.75% zeolite A, based on the anhydrous active ingredient,

4.15 sodium salts of copolymers of acrylic acid and maleic acid,

16.65% water, the rest: salts from solutions.

Other compositions M3-M10 of the present invention exhibited the following compositions and were prepared as described above.

Table 1 Composition of M3 to M6 (% by weight)

composition M3 M4 M5 M6 Granulate 1, spray dried 57 60 64 55 Sodium perborate monohydrate 20 23 - 25 Polyethylene glycol (4000) 5 - - - Polyethylene glycol (2000), unilaterally sealed with methyl end groups - - - 7 Fatty acid methyl ester _{6] 8} + 12EO - - 6 - C _2/18 fatty alcohol + 7 EO 6 6 7 7 C | _{2 µg-} alkyl sulphate (92% active ingredient, 3.70% sodium sulfate, 2.80% other raw material salts and unsulphated content, 1.5% water) 7 5 8 6 Polyglycoside of fatty alcohols C ₁₂ / _M (78% active substance, 18% water glass with module 2,4, 5% water) 5 - - - C5 ethoxylate _8- fatty alcohols + 80EO - 6 - - Trisodium citrate dihydrate - - 15 -

Table 2 Composition of M7 to M10 (% by weight)

composition M7 M8 M9 M10 Granulate 1, spray dried 72 51 54.5 52 Sodium perborate monohydrate - 20 20 20 Polyethylene glycol (4000) 6 - 5 - Polyethylene glycol (2000), unilaterally sealed with methyl end groups - 6 - 7 C | ₂ , | _8- fatty alcohol + 7 EO 7 8 7 - _Ci2 / i4 fatty alcohol + 5 EO * - - 7 C12 / 18-alkyl sulphate (92% active ingredient, 3.70% sodium sulphate, 2.80% other raw material salts and unsulphated content, 1.5% water) 15 5 10 Polyglycoside of C12 / 14 fatty alcohols (78% active substance, 18% water- - - - 4

composition M7 M8 M9 M10 glass with module 2,4, 5% water) Trisodium citrate dihydrate 15 - - - Tetraacetylethylenediamine (95%) TAED, 2% carboxymethylcellulose, 2.75% salt, 0.25% water) - - 8.5 -

Bowl test results for mixtures M3 to M10:

M3 1 to 2 M4 1 to 2 M5 1 M6 1 to 2 M7 1 M8 1 M9 1 to 2 M10 1 to 2.

PATENT CLAIMS

Claims (23)

PATENT CLAIMS 1. Detergent or cleaning compositions, mixtures or treated raw materials having a bulk density above 600 g.dm- ³ , in particulate form, prepared from a solid, free-flowing premix containing individual raw materials and / or mixtures at room temperature and pressure 10 ⁵ Pa in the solid state and have a melting point or softening point of not less than 45 ° C, which may also contain up to 10% by weight of non-ionic surfactants which are liquid at temperatures below 45 ° C and a pressure of 10 ⁵ Pa provided that the free water content of the masterbatch is less than 2% by weight, expressed on the weight of the masterbatch, and the total water content is not more than 15% by weight, expressed on the weight of the masterbatch, characterized in that they contain one or more anionic surfactants in an amount of at least 0.5% by wt., expressed on the weight of the composition, of at least one raw material or one mixture that is supplied to the premix and at 10 ⁵ Pa and a temperature below 45 ° C in solid form but under processing conditions it is in the melt state, the melt serving as a polyfunctional, water-soluble binder which performs the function of a glidant in the manufacture of said composition and performs a sticky function for the ingredients of the solid detergent or cleaning composition. when disintegrating the composition in a water wash, disintegrating, and wherein the raw material or mixture is selected from the group consisting of unbranched, branched and modified polyethylene glycols, modified polypropylene glycols, 1,2-polypropylene glycols, low molecular weight polyvinylpyrrolidones and their derivatives having a molecular weight up to 30,000 , alkoxylated fatty alcohols and oxoalcohols, fatty acid methyl ester ethoxylates, branched and unbranched fatty acid ethoxylates with 2 to 100 ethylene oxide units, mixed hydroxyethers, anhydrous swelling polymers, alkylglycosy which have the general formula RO (G) _X , in which R is a primary unbranched or methyl branched (C1 _{- C22} ) -alkyl, G is a glycose unit having 5 or 6 carbon atoms, x is selected from the numbers 1 to 10 of polyhydroxy fatty acids having the general formula (I), R ¹ '-CO-N - [Z]' wherein R ² CO is (C _g to C ₂₂₎ acyl, R ³ is hydrogen, (C, to C ₄₎ alkyl, (Cl to _C4) -hydroxyalkyl, [Z] is nerozvetvcný or branched (C ₃ to _{C) ())} -polyhydroxyalkyl having 3 to 10 hydroxyl groups, polyhydroxy fatty acid amides having the general formula (II), R ⁴ —CO-N— [Z'J] wherein R ⁴ is straight or branched (C 7 to C 12) -alkyl, straight or branched (C 7 to C 12 -alkenyl), R ⁵ is straight or branched (C 2 to C ₈ ) -alkyl, cycloalkyl of 2 to 8 carbon atoms, aryl of 2 up to 8 carbon atoms, R ⁶ denotes unbranched or branched (C 1 -C ₈ ) -alkyl, (C 1 -C ₈ -oxoalkyl, cycloalkyl of 1 to 8 carbon atoms, aryl of 1 to 8 carbon atoms, [Z '] means an optionally alkoxylated unbranched polyhydroxyalkyl radical wherein the alkyl chain is substituted with at least two hydroxyl groups [Z'j is an optionally alkoxylated unbranched polyhydroxyalkyl moiety, the alkyl chain of which is substituted with at least two hydroxyl groups and mixtures thereof, and wherein the laundry or cleaning agents have a cloth-like structure wherein the combs are filled with solid. Washing or cleaning compositions according to claim 1, characterized in that the grains are coated on the surface with a powdered or at least finely divided component, a so-called fine fraction, which adheres to the surface during agglomeration with melt. Washing or cleaning compositions according to claim 1 or 2, in the form of tablets, characterized in that they contain one or more disintegrating agents in the washing bath. Method for preparing detergents or cleaning compositions, compositions or raw materials according to any one of claims 1 to 3 by combining compositions of detergents or cleaning ingredients and / or raw materials with simultaneous or subsequent shaping, characterized in that a solid, free-flowing premix is prepared first, the individual raw materials and / or composition that is at room temperature and a pressure of 10 ⁵ Pa applied in the solid state and have a melting point or softening point below 45 DEG C., which optionally contain up to 10% of nonionic surfactants, which at temperatures of below 45 ° C and a pressure of 10 ⁵ Pa liquid, wherein the mixing step is carried out at room temperature to below the melting point or softening point of the individual raw materials and / or mixtures, and is converted to granular using compaction forces at temperatures of at least 45 ° C material, subject to that (a) the free water content is less than 2% by weight, expressed on the weight of the masterbatch, and the total water content is not more than 15% by weight, expressed on the weight of the masterbatch, and b) the premix is used, one or more anionic surfactants in an amount of at least 0.5% by wt., expressed on the weight of the composition, and at least one material or a mixture which is at a pressure of 10 ⁵ Pa and a temperature below 45 DEG C. in the solid state but under the conditions in which it is processed it is in the form of a melt, the melt acting polyfunctionally; it serves as a water-soluble binder, which, however, acts as a glidant in production and also serves as an adhesive for solid laundry or cleaning compositions or raw materials; on the other hand, disintegrating in dissolving said composition in a water wash, and wherein the raw material or mixture is selected from the group consisting of unbranched, branched and modified polyethylene glycols, modified polypropylene glycols, 1,2-polypropylene glycols, low molecular weight polyvinylpyrrolidones and their molecular weight derivatives not more than 30 000, alkoxylated fatty alcohols and oxoalcohols, fatty acid methyl ester ethoxylates, branched and unbranched fatty acid ethoxylates with 2 to 100 ethylene oxide units, mixed hydroxy ethers, anhydrous swelling polymers, alkyl glycosides having the general formula _X (G) R is a primary linear or methyl branched (C ₈ to C ₂₂₎ alkyl, G is a glycose unit having 5 or 6 carbon atoms, x is selected from the numbers 1 to 10 of polyhydroxy fatty acids having the general formula (I), R 'i (' b R'-CO-N- [Z; in which R ² CO means (C ₈ to C ₂₂ ) -acyl, R ³ represents hydrogen, (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -hydroxyalkyl, [Z] means unbranched or branched (C ₃ -C 10) -polyhydroxyalkyl of 3 to 10 hydroxyl groups, polyhydroxy fatty acid amides having the general formula (II), r'-or · ¹ (ID, R * —CO-N— <Z1 in which R ⁴ represents a linear or branched (C7-C] 2) alkyl, straight or branched (C7-C, 2) alkenyl, R ⁵ represents a linear or branched (C2 to _Cg) -alkyl, cycloalkyl having 2 to 8 carbon atoms, aryl of 2 to 8 carbon atoms, R ⁶ represents a linear or branched (C] to _Cg) -alkyl, (Cl-C _g) -oxoalkyl, cycloalkyl of 1-8 carbon atoms, aryl having 1 to 8 carbon atoms, [Z'j is an optionally alkoxylated linear polyhydroxyalkyl a residue whose alkyl chain is substituted with at least two hydroxyl groups and mixtures thereof. Method according to claim 4, characterized in that the water content not bound to zcolites and / or silicates is not higher than 10% by weight and in particular lower than 7% by weight. 6. The method of claim 4 or 5, characterized in that the pre-mix in addition to the solid constituents comprising the 10% by weight of nonionic surfactants, which are at a pressure of 10 ⁵ Pa and a temperature below 45 ° C the liquid, in particular to detergent tablets usually the alkoxylated alcohols used, such as fatty alcohols or oxoalcohols having a carbon chain length of between 8 and 20 carbons and in particular with an average of 3 to 7 ethylene oxide units per mole of alcohol, the liquid nonionic surfactant and the disintegrating binder being added separately. Method according to one of Claims 4 to 6, characterized in that the melting point of the individual substances used or the softening point of the mixtures used is higher than 45 ° C, preferably at least 50 ° C. Process according to any one of claims 4 to 7, characterized in that mixtures and raw materials having at least 80% by weight, preferably at least 85% by weight, are used in the masterbatch. % and most preferably at least 85 wt. a substantially higher softening or melting point than that obtained under the conditions of the process. Method according to one of Claims 4 to 8, characterized in that in the compaction working step several stages are carried out in the temperature range, for example 2 to 20 ° C above the melting point or above the softening point. Method according to any one of claims 4 to 9, characterized in that one or more binders are used which are almost completely dissolved at a concentration of 8 g of binder per 1 dm ^{3 of} water at 30 ° C within 90 seconds. Method according to one of Claims 4 to 10, characterized in that a binder is used which, at temperatures not exceeding 130 ° C, preferably not more than 100 ° C and in particular up to 90 ° C, is completely in the molten state. Method according to one of Claims 4 to 9, characterized in that the solid components for preparing the solid and free-flowing premix are initially at room temperature up to slightly elevated temperatures, preferably below the melting point or below the melting point of the binder and in particular below 35 [deg.] C., are fed to a conventional mixer and / or granulation apparatus. Method according to any one of claims 4 to 12, characterized in that a binder is added as the last component to the mixture, admixing is carried out under processing conditions such that the highest possible uniform, homogeneous distribution of the binder in the mixture of solids is achieved as solidifying melt, or as a powder. Method according to one of Claims 4 to 13, characterized in that the binder incorporation takes place at temperatures at which the binder is in the form of a melt, the preferred melt temperatures being at 60 to 150 ° C, in particular temperatures in the temperature range from 80 to 150 ° C. 120 [deg.] C. Method according to one of claims 4 to 14, characterized in that the mixing process is carried out until the melt solidifies and the premix is in a solid, free-flowing state. Method according to one of Claims 4 to 15, characterized in that a masterbatch is used in which the binder or binder content is at least 2% by weight but less than 15% by weight, preferably less than 10% by weight, and most preferably 3 to 6% by weight, in each case based on the weight of the masterbatch. Method according to one of Claims 4 to 16, characterized in that the processing temperature in the actual granulation, compression, tabletting, pelletizing or extrusion process is set above the melting point or the temperature of the binder (s) as the melt, being however, it is preferred that the processing temperature is not more than 20 ° C higher than the melting point or the lower temperature of the binder melting temperature range. Method according to any one of claims 4 to 17, characterized in that the binder has a melting point or a melting temperature range of up to 150 ° C, preferably up to 100 ° C and most preferably up to 75 ° C, and the processing temperature is 10 ° C and preferably no more than 5 ° C above the melting point or above the upper limit of the binder melting temperature range. Method according to one of Claims 4 to 18, characterized in that the duration of the application of the temperature between the mixing / homogenization of the masterbatch and the shaping, i.e. in the compaction region, is between 10 seconds and at most 5 minutes, preferably at most 3 minutes. Method according to one of Claims 4 to 19, characterized in that the preparation is carried out by extrusion, wherein the masterbatch is compacted, plasticized, extruded in the form of fine bundles through the orifice in the extruder head and finally crushed by means of a rotary cutter, preferably spherical or the bead shape to the cylindrical shape of the granulate grains and the temperature regime in the transition region of the extrusion screws, upstream of the distributor and the orifice head are set to at least reach the temperature of the upper melting range of the binder, but preferably higher. Method according to claim 21, characterized in that the duration of the application of the temperature in the compression zone of the extrusion is at most 2 minutes and preferably in the range between 30 seconds and 1 minute. Method according to one of Claims 4 to 21, characterized in that the compacted mass has a temperature of not more than 80 ° C, preferably between 35 and 75 ° C and most preferably between 40 and 70 ° C just after leaving the production plant. The process according to any one of claims 4 to 22, characterized in that a premix having a relatively broad particle size distribution and relatively high fine grain fractions is converted into an end product with a relatively narrow particle size distribution and relatively small fine grain fractions.