EP1015550B1 - Method for manufacturing washing and detergent particulates - Google Patents

Abstract

The invention aims at providing particulate washing or cleaning agents, compounds or raw materials with apparent densities above 600 g/l for the latter which even with a reduced surface, in particular with a spherical shape disintegrate better when they are dissolved in an aqueous bath. Moreover, the particulate washing or cleaning agents, compounds or treated raw materials should be produced by joining washing or cleaning agent compounds and/or raw materials, at the same time as or after they are shaped. For that purpose, at first an essentially anhydrous premixture is produced, containing individual raw materials and/or compounds which are solid under standard conditions and have a melting or softening point not below 45 DEG C, as well as up to 10 wt % optional non-ionic surfactants which are liquid at temperatures below 45 DEG C and under 1 bar pressure. The mixture is granulated by applying compacting forces at temperatures of at least 45 DEG C, then further processed or conditioned; the premixture contains at least one raw material or compound which is solid under 1 bar pressure and at temperatures below 45 DEG C, but which melts under processing conditions, forming a molten mass which acts as a polyfunctional, water-soluble binder which serves as a lubricant during the production of the washing and cleaning agent and as an adhésive for the solid washing or cleaning agent compounds or raw materials, but which has a disintegrating effect when the washing or cleaning agent is dissolved again in an aqueous bath.

Description

The invention relates to a process for the preparation of particulate detergents or cleaning agents or of multicomponent components which, in admixture with other ingredients, give rise to such agents, with the aid of a specially adapted granulation process and washing or cleaning agents prepared in this way.

Particulate detergents or cleaning agents with bulk densities above 600 g / l have been part of the state of the art for quite some time. In recent years, was associated with the increase in bulk density and a concentration of the washing and cleaning active ingredients, so that the consumer had to dose not only less volume, but also less mass per washing or cleaning process. The increase in bulk density, and in particular the higher concentration of agents on washing or cleaning-active substances was generally paid for by a subjective from the point of view of the consumer subjectively worse solubility, which was caused by the usually slower dissolution rate of the agent used. This undesirable dissolution delay is triggered inter alia by the fact that a number of anionic and nonionic surfactants which are customary in practice and, above all, corresponding surfactant mixtures tend to form gel phases when dissolved in water. Such gelling agents can already occur at surfactant contents of 10% by weight, based on the total agent, that is to say surfactant quantities which are quite customary in detergents or cleaners. Experience has shown that the tendency to form gels also increases with the increasingly compact grain structure of the particles.

European Patent EP 0 486 592 B1 describes granular or extruded detergents or cleaning compositions having bulk densities above 600 g / l and containing anionic and / or nonionic surfactants in amounts of at least 15% by weight and up to about 35% by weight. contain. They are prepared by a process in which a solid, free-flowing premix containing a plasticizer and / or lubricant of preferably aqueous surfactant pastes and / or aqueous polymer solutions, extruded at high pressures between 25 and 200 bar extruded and the strand after leaving the hole shape is cut by means of a cutting device to the predetermined granule dimension and rounded. The premix consists at least partially solid ingredients, which optionally liquid ingredients such as liquid at room temperature nonionic surfactants are mixed. As stated above, aqueous formulations are used as plasticizers and / or lubricants in preferred embodiments. However, there are also relatively high-boiling organic liquids, optionally in turn in admixture with water, in question. However, the patent does not disclose any process conditions to be observed in the case of an anhydrous extrusion. The extrudates produced can either already be used as detergents or cleaners or else subsequently be treated with other granules or powder components to form finished detergents or cleaners. Due to the high compactness of the grain and the relatively high surfactant contents, but also by the consumer desired ball or bead shape, which compared to conventional granules have a much smaller surface, it may depending on the selected surfactant combinations come to the above-mentioned difficulties.

From the international patent application WO-A-93/15180 it is known that the dissolution rate of such extruded agents can be improved by using in the solid premix short-chain alkyl sulfates, in particular C ₈ to maximally C ₁₆ alkyl sulfates, which are based on a specific Way in the pre-mix are introduced. However, this measure is not sufficient in all cases to increase the dissolution rates of the entire agent to the desired extent.

The German patent application DE 195 19 139 A1 proposes to solve the conflict between high degree of compaction of the individual grain, in particular of the extrudate, on the one hand and the nevertheless required rapid and in particular gelgeleverfreien disintegration of the finished detergents or cleaners in aqueous liquors before, particulate wash or detergent having a bulk density above 600 g / l, which contain anionic and / or nonionic surfactants in amounts of at least 15 wt .-%, to be designed such that at least two different granular components are used, of which at least one extruded and at least a non-extruded, wherein the surfactant content of the extruded component, including the soaps, a maximum of 15 wt.%, Based on the respective extruded component should be. Additional surfactant components of the final detergent or cleaning agent are incorporated into the composition by one or more non-extruded component (s). Although this method solves the problem of gelling high-density and high-surfactant detergents or cleaners when used in an aqueous liquor, but also involves a number of new problems. There may be segregation processes and corresponding fluctuations in the reproducibility of the desired washing or cleaning result. In addition, the extruded portion of the agents is not only of high density, but the dried extrudates are also comparatively hard at the same time. Under the conditions of transport, storage and use, the comparatively softer granulate content of the non-extruded component (s) may thus be exposed to mechanical forces which lead in part to its reduction and thus to the formation of dust and fines by abrasion.

Conventional processes generally operate with both solid and room temperature liquid ingredients of detergents; Also aqueous solutions and / or dispersions are widely used as granulating aids or, as in the case of the European Patent EP 0 486 592 B1, as plasticizers and / or lubricants. Such procedures have the risk that even during the preparation of detergents or cleaners gel-like structures may be formed which contribute to the dissolution delay in the redissolution in the aqueous liquor. In addition, in particular, the processes in which water, aqueous solutions or aqueous dispersions are used as Granulierhilfsmittel, the disadvantage that in most cases an energetically unfavorable drying must be followed in order to obtain a free-flowing or storage-stable end product, and also often right coarsely obtained agglomerates must be comminuted and / or screened (see also "Size Enlargement by agglomeration", W. Pietsch, John Wiley & Sons, 1990, page 180). Another disadvantage of this method is that it can come to particle enlargements and crystallizations by the dissolution of solid and water-soluble constituents by the water contained, in particular under the influence of pressure during extrusion, which in turn in turn disadvantageous to the dissolving behavior of the finished. Affect funds.

A method for the production of heavy granules with the aid of an aqueous granulating aid is the two-stage granulation, initially plastic primary agglomerates are produced in a conventional mixer / granulator, which subsequently in apparatuses such as a Verrunder, Rotocoater, Marumerizer etc. with liquid binder and / or subsequently treated with dust and then usually dried become. The granulation and simultaneous rounding can be carried out, for example, in fluidized-bed granulators which comprise a rotating disk. In this case, solid starting materials are first fluidized in the fluidized bed and then with liquid binder which is introduced via tangentially oriented nozzles in the fluidized bed, agglomerated "(Size Enlargement by Agglomeration," W. Pietsch, John Wiley & Sons, 1990, pages 450 to 451). In principle, this method can also be used for non-aqueous processes (melt-coating process), but then the advantage of the apparatus to be able to effect a simultaneous drying, is not exploited.

In the literature ("Size Enlargement by Agglomeration", W. Pietsch, John Wiley & Sons, 1990, pages 440 to 441), only two methods for granulation under high pressure are known, which can be carried out completely anhydrous. These are tabletting in tablet presses and roll compacting, the latter process usually producing slugs which are subsequently broken into granular but irregularly shaped products. For this reason, so-called pre-breakers are used in some systems in order to make the starting material for the actual granulation or grinding step more uniform in shape. Subsequently, unwanted fine and / or coarse grain fractions of the granules thus produced can be screened off and optionally recycled.

International Patent Application WO-A-93/02176 describes a process for the preparation of solid detergents or cleaners having high bulk densities by combining solid and liquid detergent or cleaning agent raw materials with simultaneous or subsequent shaping, wherein as solid components, for example anionic surfactants and builders and as liquid Nonionic surfactants are used, the latter being provided in an intimate mixture with a structure breaker such as polyethylene glycol or polypropylene glycol or ethoxylated C ₈ -C ₁₈ fatty alcohols having 20 to 45 ethylene oxide groups (EO). Preferred liquid nonionic surfactants are ethoxylated linear or 2-methyl-branched alcohols containing from 8 to 20 carbon atoms in the carbon chain and, on average, from 1 to 15 moles of ethylene oxide per mole of alcohol. In addition to such structure-breaking substances and water is described as a principle suitable structure breaker, the use of which is less preferred because the means can be depleted during storage due to the internal drying of the agent in water and thus the desired effect of improved Dissolution rate by using a structure breaker no longer or no longer in full would come to fruition. According to the teaching of this international patent application, the mixtures of nonionic surfactants and structure breakers, which are present either as a solution or as a dispersion, can be used in all known granulation processes in which separately prepared compounds and / or raw materials are used. Use in an extrusion process according to international patent application WO-A-91/02047 (or European patent EP 0 486 592 B1) is also possible and even preferred. Accordingly, the use of aqueous solutions, pastes or aqueous dispersions is suggested, wherein the water is not used as structure breaker as said above and is usually dried away after the extrusion. Extrusion without addition of water is not explicitly suggested; even in the example part, the addition of aqueous solutions takes place additionally and separately from the nonionic surfactant-structure breaker mixture; above all, however, this document does not mention any process conditions under which an anhydrous extrusion can be carried out.

European Patent Application EP 0 337 330 describes a process for increasing the bulk density of a spray-dried detergent by granulation in a mixer with addition of nonionic compounds. These 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, especially nonionic surfactants having 2 to 6 EO and HLB values of 11 or less added in the mixer become. Ethylene glycols and propylene glycols can also be used there as nonionic compounds.

In the European patent application EP 0 71 1828 a process for the production of tablets is described wherein a coated particulate product is pressed. The coating substance is a water-soluble binder or disintegrant with melting temperatures between 35 and 90 ° C. An essential feature is stated here that the compaction / tableting should be carried out at temperatures which are at least 28 ° C, but below the melting temperature of the binder.

International patent application WO-A-96/10071 discloses a process for producing granules having bulk densities of at least 650 g / l and surfactant contents of at least 40 wt .-%, wherein the granulation is carried out in one step in a high shear mixer at temperatures between room temperature and 60 ° C. The solid starting materials are particles having a particle size between 0.1 microns and 500 microns, wherein at least 15 wt -.% Of the particles should have a particle size above 50 microns, but sufficiently small, fine particles are present, so that a particularly large surface of the solid feed. Surfactant mixtures of anionic surfactants and nonionic surfactants in weight ratios of 2: 8 to 8: 2, which may have up to 20% by weight of water, are used as binders. As nonionic surfactants primary C ₁₂ -C ₁₅ alcohols are given with 3 to 7 EO. Surfactant mixtures which contain up to 20% by weight of water are particularly advantageous in the context of the process given, since this increases the viscosity of the mixture and makes the process more controllable. In addition, the surfactant mixture may also contain polyethylene glycols.

US Pat. No. 5,108,646 describes the preparation of builder agglomerates in which 50 to 75 parts by weight of aluminosilicates or crystalline sheet silicates are agglomerated with 20 to 35 parts by weight of a binder. Suitable binders are, above all, high-viscosity anionic surfactant pastes which may contain up to 90% by weight of water. But also polymers such as polyethylene glycols having molecular weights between 1000 and 20,000 come into consideration, as well as mixtures of these and conventional nonionic surfactants such as C ₉ -C ₁₆ alcohols having 4 to 8 EO, as long as their melting range is not below 35 ° C or below 45 ° C begins. The agglomeration takes place in a so-called intensive mixer with a very specific, relatively high energy input. For energy inputs above the specified values, a superagglomeration up to a dough-like mass occurs, at lower energy inputs only finely divided powders or very light agglomerates are obtained with an undesirably wide Komspektrum.

In contrast, the object of the invention was to produce particulate detergents or cleaning compositions or multicomponent components which, when blended with other ingredients, produce such agents which, even with a reduced surface area, in particular with a spherical shape (bead shape), have improved disintegration in the aqueous solution Fleet exhibit. In addition, the process should be economically advantageous and can dispense with costly drying steps.

The invention therefore relates to a process for the preparation of particulate laundry detergents or cleaning agents or multicomponent or treated raw materials which, when blended with other ingredients, provide such compositions with bulk densities above 600 g / l by combining detergent or cleaning agent compounds and / or raw materials with simultaneous or subsequent shaping, initially producing a premix containing individual raw materials and / or compounds which are present as solids at room temperature and a pressure of 1 bar, and then converting this premix into a grain using compaction forces and optionally on it subsequently processed or processed, which is characterized in that the premix is substantially anhydrous and one under the molding conditions, especially at room temperature and a pressure of 1 bar, liquid molding In the form of a swollen in non-aqueous solution polymer.

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

In the context of the invention, particulate detergents or cleaners are preferably understood as meaning those which have no dust-like constituents and in particular no particle sizes of less than 200 μm. In particular, such particle size distributions are preferred which comprise at least 90% by weight of particles having a diameter of at least 400 μm. In a particularly preferred embodiment dough-shaped mass at lower energy inputs only finely divided powders or very light agglomerates are obtained with an undesirably broad particle size range.

In contrast, the object of the invention was to produce particulate detergents or cleaning compositions or multicomponent components which, when blended with other ingredients, produce such agents which, even with a reduced surface area, in particular with a spherical shape (bead shape), have improved disintegration in the aqueous solution Fleet exhibit. In addition, the process should be economically advantageous and can dispense with costly drying steps.

The invention therefore relates to a process for the preparation of particulate laundry detergents or cleaning compositions or multicomponent components or treated raw materials which, in admixture with other ingredients, results in such compositions having bulk densities of above 600 g / l by combining washing or cleaning agent compounds and / or raw materials with simultaneous or subsequent shaping, initially producing a premix containing individual raw materials and / or compounds which are present as solids at room temperature and a pressure of 1 bar, and then converting this premix into a grain using compaction forces and optionally on it subsequently processed or prepared, characterized in that in the premix, the content of liquid water is less than 2 wt.% And in the shaping under the molding conditions, especially at room temperature and a pressure of 1 bar, liquid forming assistant in the form of a swollen in substantially nonaqueous solution polymer, the substantially non-aqueous liquid having not more than 20 wt.% Water containing the substantially non-aqueous liquid component of the forming aid from the liquid at room temperature di- or trihydric alcohols Boiling points (at 1 bar) above 80 ° C, the mixtures and mixtures thereof with liquid at room temperature monohydric alcohols having boiling points (at 1 bar) is selected above 80 ° C, and the system of substantially nonaqueous liquid and polymer at room temperature in the presence of the polymer is at least 20 times higher in viscosity than the substantially non-aqueous liquid alone.

In the context of this invention, the premix is "essentially anhydrous", which in the context of this invention means a state in which the content of liquid water, that is not in the form of water of hydration and / or water of constitution, is less than 2% by weight. preferably below 1% by weight and in particular even below 0.5% by weight, based in each case on the group-bearing starches or celluloses, phosphated starches such as starch disphosphate, but also inorganic polymers such as phyllosilicates and mixtures thereof. Among the polyvinylpyrrolidones, those having molecular weights of up to 30,000 are preferred. In this case, particular preference is given to relative molecular mass ranges of between 3,000 and 30,000, for example about 10,000. The polymers which are preferably used also include hydroxypropyl starch and starch diphosphate. The concentration of the polymers in the anhydrous liquids is preferably 5% by weight to 20% by weight. in particular about 6 wt .-% to 12 wt .-%.

The content of shaping aids, based on the premix to be compressed, is preferably at least 2% by weight but less than 20% by weight, in particular less than 15% by weight, with particular preference being given to amounts in the range from 3% by weight to 10% by weight. In the further course of the description of this invention, for simplicity's sake, only one or the shaping aid will be mentioned. However, it should be made clear that it is always possible to use several, different shaping aids and mixtures of different shaping aids.

Detergents or cleansers are understood to mean compositions of this type which can be used for washing or cleaning without the need to generally add further ingredients. A multi-substance mixture or compound, however, consists of at least 2 components usually used in detergents or cleaners; However, compounds are normally only used in combination with other ingredients, preferably together with other compounds. A treated raw material in the context of this invention is a relatively finely divided raw material which has been converted by the process according to the invention into a coarser particle. Strictly speaking, a treated raw material in the context of the invention is a compound if the treatment agent is an ingredient commonly used in detergents or cleansers.

The ingredients used in the process of the invention may be prepared separately compounds, but also raw materials which are powdery or particulate (finely divided to coarse), but in any case at room temperature and a pressure of 1 bar - with the exception of those optionally present at temperatures below 45 ° C and a pressure of 1 bar liquid nonionic surfactants - in solid form. As a particulate mm. For the purposes of the present invention, particulate detergents or cleaners may also be tablets having customary dimensions for washing or cleaning agent tablets for household use, for example with weights of 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of about 35 mm to 40 mm, act.

Swollen polymers used in the context of the present invention as a component of the formulating aid are those which lead to gelatinous states in essentially non-aqueous liquids. Suitable systems are those of essentially nonaqueous liquid and polymer which have at room temperature in the presence of the polymer at least 20 times, in particular 300 times to 5000 times higher viscosity than the substantially nonaqueous liquid alone. The viscosity of the forming aid, that is, the combination of substantially non-aqueous liquid and polymer, is preferably in the range of from 200 mPas to 100,000 mPas, especially from 400 mPas to 50,000 mPas, as measured, for example, by means of a Brookfield rotary viscometer. At a higher temperature, for example 60 ° C., the viscosity preferably deviates only relatively little from the values at room temperature and is preferably in the range from 250 mPas to 40,000 mPas. The suitable constituents of the liquid component of the shaping assistant include liquid at room temperature, di- or trihydric alcohols having boiling points (at 1 bar) above 80 ° C, especially above 120 ° C, their mixtures and mixtures thereof with liquid at room temperature single-grade alcohols having boiling points (at 1 bar) above 80 ° C, especially above 120 ° C; such as, for example, n-propanol, isopropanol, n-butanol, s-butanol, isobutanol, ethylene glycol, 1,2- or 1,3-propylene glycol, glycerol, di- or triethylene or -propylene glycol or mixtures thereof, in particular glycerol and / or ethylene glycol. As outlined above, these liquids, which are referred to as essentially nonaqueous, may also contain water, as long as it is observed that the molding agent is used only in amounts such that the above limit of 2% by weight of additional liquid water in the premix is not used is reached. A substantially non-aqueous liquid in this sense contains not more than 20% by weight, in particular not more than 15% by weight of water, in one particularly preferred embodiment liquids having water contents below 1% by weight, in particular at most 2 to 5 wt .-% is. It is particularly advantageous if the premix contains no water that is not bound to the builders. This is technically difficult to realize; As a rule, at least always traces of water are introduced by the raw materials and compounds.

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

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

In a preferred embodiment of the invention, at least 80% by weight, in particular at least 85% by weight and with particular preference at least 90% by weight of all compounds and individual raw materials used in the premix, with the exception of the molding aid liquid at room temperature, have a substantially higher softening point or Melting point than the temperatures that are achieved under the molding process conditions. In practice, the molding temperatures alone, for economic reasons, not above 150 ° C, preferably not above 120 ° C. Thus, at least 80% by weight of the used compounds and individual raw materials have a softening point or melting point above 150 ° C at atmospheric pressure (1 bar).

The premix, in addition to the solid constituents and the molding aid liquid at room temperature, may contain up to 10% by weight of liquid nonionic surfactants at temperatures below 45 ° C. and a pressure of 1 bar, in particular the alkoxylated alcohols customarily used in detergents or cleaners. such as fatty alcohols or oxo alcohols having a C chain length of between 8 and 20 and especially an average of 3 to 7 ethylene oxide units per mole of alcohol. The addition of the liquid nonionic surfactants can be carried out in the amounts which still ensure that the premix is in free-flowing form. If such liquid nonionic surfactants are incorporated into the premix, it is preferred that liquid nonionic surfactants and the disintegrating styling aid be incorporated separately into the process. In a preferred embodiment of the invention, the liquid surfactants are applied to the powder stream in a continuous production process, in particular by means of nozzles, and are absorbed by the latter.

However, the premix also contains at least one raw material or at least one compound which, as stated above, serves as a shaping aid. The shaping aid in the form of the anhydrous swollen polymer can be mixed with the remaining constituents of the premix before the shaping step. This is particularly preferred when the shaping takes place by an extrusion step or by means of a tableting or other pressing operation. It can also be sprayed onto the premix during shaping or added dropwise to the premix, which is particularly preferred in shaping by build-up granulation. The temperature during the shaping step is preferably in the case of room temperature or the temperature resulting from the energy input of the molding device, but it is also possible to increase the premix and, if appropriate, the molding aid to be added separately during molding to higher temperatures, for example 35 ° C. to 80 ° C. to heat, with temperatures in the range of 45 ° C to 65 ° C may be particularly advantageous.

It has also proved to be advantageous if the shaping aid in the process step of the compacting shaping as homogeneous as possible in the compacted Well distributed. Without wishing to be limited to this theory, the Applicant is of the opinion that by a homogeneous distribution of the shaping aid in the sense of a binder within the premix under the process conditions of compression, the solid compounds and the optionally present individual raw materials so enclosed by the binder and then together be glued that the finished end products are composed almost exactly of these many small individual particles, which are held together by the binder, which performs the task of a preferred thin partition between these individual particles. In the idealized form can be assumed that a honeycomb-like structure, these honeycombs are filled with solids (compounds or Einzelrohstofien). Upon contact with water, even with cold water, so for example at the beginning of a machine wash, dissolve or disintegrate these thin partitions almost instantaneously; Surprisingly, this is also the case when the forming aid per se is not rapidly soluble in water at room temperature. Preferably, however, such shaping aids are used, which can be almost completely dissolved within 90 seconds in a test method as indicated below in a concentration of 8 g molding aid to 1 liter of water at 30 ° C. In some cases, however, it may be advantageous to use an additive to adjust the solubility in a controlled manner, that is to delay it.

The forming aid must therefore be of the type that the adhesive properties come into play at the molding temperatures. On the other hand, it is also essential for the choice of the type and amount of forming aid used, that although the binding properties are not lost after the forming step within the final product, the cohesion of the final product is thus secured, but that the final product itself under normal storage and transport conditions not glued. It must be surprising that when using the molding aid at room temperature, a final product is still obtained which neither at room temperature nor at slightly elevated temperatures by 30 ° C, ie at summer temperatures and under storage or transport conditions, tends to stick.

The joining together of the washing or cleaning agent compounds and / or raw materials with simultaneous or subsequent shaping can be achieved by conventional methods in which compaction forces are applied, such as granulating, compacting, for example Roll compacting or extruding, or tableting, optionally with the addition of conventional disintegrants, and pelletizing done. In this case, spray-dried granules can be used as prefabricated compounds in the premix, but the invention is by no means limited thereto. Rather, in the process according to the invention, it is not advisable to use spray-dried granules, since even finely divided raw materials with dust-like proportions can be easily processed according to the invention without being precompounded beforehand, for example spray-dried.

The substantially anhydrous process allows not only that peroxy bleach can be processed without loss of activity, it is thereby also possible to process peroxy bleach and bleach activators together in a particle without having to fear serious loss of activity.

In a preferred embodiment of the invention, the compacting shaping of the process is carried out with the aid of an agglomeration step, wherein the premix is agglomerated in a suitable device and the shaping aid defined above assumes the role of a binder. The granulation process can be carried out continuously or discontinuously. In this case, the procedure is preferably such that the solid constituents of the premix to be compressed are introduced into a granulator in which a mixer may also be used, if appropriate by addition of a liquid nonionic surfactant and any dusts present, and the shaping assistant is introduced into the granulator , The desired average particle size of the granules can be adjusted by the type and amount of forming aid and by the machine and operating parameters, such as speed and residence time, and temperature. Pelletizers, rotary drums, ploughshare mixers with chopper from Lödige®, high-performance mixers with rotating mixing vessels and swirlers, for example from Laeis Bucher® or Eirich®, intensive mixers with shaving heads, for example from LIPP Mischtechnik® or Imcatec®, Drais, can be used as suitable granulators ®, Fukae® or Forberg® mixers and the so-called Rotorcoater® from Glatt® with horizontal and inclined turntables up to 50 °. Less suitable are Lödige® CB mixers, PK-Niro® zig-zag mixers, a Ballestra® warp mix and Hosokawa® or Schugi® mixers. A fluid bed or a horizontal mixer, for example a Nautamixer®, is also less suitable. In the context of this embodiment of the invention It is preferred to process at room temperature or the temperature resulting from the energy input of the mixer or granulator, that is to say without a separate heating step, as described, for example, in international patent application WO 94/13779 and the prior art cited therein. It is to be regarded as an advantage of the process according to the invention that one does not refer to a two-stage granulation process described, for example, in European Patent Application EP 0 367 339, in which granules are first compressed in a high-speed mixer and then in a low-speed mixer and granulator. but using the anhydrous swollen polymer can perform the compacting granulation in only one step.

Compositions according to the invention in tablet form can be produced by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressing pressures in the range of, for example, 200 × 10 ⁵ Pa to 1 500 × 10 ⁵ Pa.

In a further preferred embodiment of the process according to the invention, the solids for the preparation of the solid and free-flowing premix are first mixed together at room temperature to slightly elevated temperatures, which are preferably in the range of room temperature to 35 ° C in a conventional mixing and / or granulating. The compaction step of the process according to the invention is then carried out by means of an extrusion of the premix thus obtained, as described, for example, in European Patent EP 0 486 592 B1 or International Patent Applications WO-A-93/02176 and WO-A-94/09111. In this case, the pre-mixture is extruded under pressure and cut the strand after exiting the hole shape by means of a cutting device to the predeterminable granule dimension. The homogeneous and solid premix usually contains a plasticizer and / or lubricant, which causes the premix under the pressure or under the entry of specific work plastically softened and extrudable. According to European Patent EP0486592B1, anionic surfactants such as alkylbenzenesulfonates and / or (fatty) alkyl sulfates, but also polymers such as polymeric polycarboxylates, are included. With the aid of the method according to the invention, however, it is possible to completely dispense with such solidified plasticizing and / or lubricating agents, since the function of a lubricant can be perceived by the shaping aid defined above. The forming aid prevents or at least reduces the sticking of adhesions Apparatus walls and Verdichtungswerk-Leugen. This applies not only to the processing in the extruder, but equally also to processing, for example, in continuous mixers / granulators or rollers.

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

It is further preferred to supply the still plastic primary granules to a further shaping processing step; In the process, any edges present on the primary granulate are rounded off after the compaction step, so that finally spherical to approximately spherical grains can be obtained, if these do not already arise in the first compacting shaping step. If desired, small amounts of dry powder, for example, zeolite powder, such as zeolite NaA powder, may be included in this stage.

This shaping can be done in commercially available Rondiergeräten. It is important to ensure that only small amounts of Feinkomanteil arise in this stage. Drying, which is described in the abovementioned documents of the prior art as a preferred Ausfühnmgsform, but is unnecessary in the context of the present invention, since the method according to the invention is substantially anhydrous, ie without the addition of free, unbound water.

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

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

It has been found that the Wiederauflöseverhalten of detergents or cleaning agents according to the invention, in contrast to conventionally prepared means now essentially depends only on the release behavior of the individual components; the more components that are relatively quickly soluble, the faster the finished agents are soluble; the more relatively slowly soluble components are contained, the slower the funds dissolve. Adverse interactions during re-dissolution, such as gelling etc., in the process according to the invention also appear to play no role in detergents or cleaners with very high densities, for example above 750 and 800 g / l. The thus prepared agents, compounds and treated raw materials thus have an improved dissolution rate compared to such agents, compounds and treated raw materials, although the same final composition but were not prepared by the process according to the invention, ie were not prepared under anhydrous conditions using an anhydrous swollen polymer as a shaping aid:

Accordingly, another object of the invention is a particulate detergent or cleaning agent, which was prepared by the process according to the invention and whose release behavior is dependent only on the dissolution behavior of the individual raw materials and compounds used. Without wishing to be limited to this theory, Applicant believes that this particular release behavior is effected by a honeycomb-like structure of the particles, these honeycombs being filled with solids.

Another object of the invention are compounds prepared by the process of the invention and treated raw materials, such as builder granules, bleach activator granules or enzyme granules. In particular, treated raw materials show a surprisingly high rate of dissolution in water, especially when the raw material was used in itself in very finely divided, optionally ground form.

With particular preference, base granules, compounds and treated raw materials are provided which have spherical shape or pearl shape.

The bulk density of process end products prepared according to the invention is preferably above 700 g / l, in particular between 750 and 1000 g / l. Even if the granules are treated with other ingredients which have lower bulk densities, the bulk density of the final product does not decrease to the extent that would normally have been expected. It is believed that approximately spherical means, and particularly extrudates made by the process of the invention, are more like the ideal shape of a sphere with a smooth, "smeared" surface than the agents and extrudates made by conventional and, in particular, aqueous processes. As a result, better space filling is achieved, which leads to a higher bulk density, even if components are admixed, which have neither spherical structure nor such a high bulk density.

The resulting particulate process end products can either be used directly as detergents or cleaning agents or aftertreated by conventional methods and / or be prepared. The usual aftertreatments include, for example, powdering with finely divided ingredients of detergents or cleaners, for example zeolites, whereby the bulk density is optionally further increased. However, a preferred after-treatment is also the procedure according to the German patent applications DE 195 24 287 and DE 195 47 457, wherein dust-like or at least finely divided ingredients (the so-called fines) are adhered to the particulate process end products according to the invention, which serve as a core, and thus Means arise, which have these so-called fines as an outer shell. Advantageously, this in turn is done by an agglomeration step, wherein as a binder, the shaping aids of the method according to the invention can be used. For the likewise possible melt agglomeration of the fines on the base granules according to the invention and produced according to the invention, reference is expressly made to the disclosure in the German patent applications DE 195 24 287 A1 and DE 195 47 457 A1.

By treatment, it is generally understood that the particulate process end products of the present invention serve as a compound to which other ingredients, and optionally other compounds, are added. Here, reference is made to the descriptions of the cited patent applications and patents, in particular to the European patent EP 0 486 592 B1 and the German patent applications DE 195 19 139, DE 195 24 287 and DE 195 47 457. In addition to enzymes, bleach activators and foam inhibitors, especially salts such as silicates (crystalline or amorphous) including metasilicate, carbonate, bicarbonate, sulfate, bisulfate, citrate or other polycarboxylates, but also organic acids such as citric acid are mixed in the treatment. It is particularly preferred that the admixing components are used in granular form and with a particle size distribution which is tailored to the particle size distribution of the compositions and compounds according to the invention.

In a preferred embodiment of the invention, a particulate detergent is provided which consists of at least 80% by weight of compounds prepared according to the invention and / or treated raw materials. In particular, it consists of at least 80 wt .-% of a base granules according to the invention. The remaining ingredients may have been prepared and admixed by any known method. It is, however preferably that these remaining constituents, which may be compounds and / or treated raw materials, were prepared by the process according to the invention. In particular, this makes it possible to produce base granules and remaining constituents with approximately the same flowability, bulk density, size and particle size distribution. It is also possible to produce larger shaped articles, for example tablets, from the blend of the compounds according to the invention and / or treated raw materials with the said remaining constituents. However, a particular advantage is that it is possible with the aid of the method according to the invention to actually use all components of a complete washing or cleaning agent as a premix and to granulate anhydrous to give beads.

There now follows a detailed description of the possible ingredients of the compositions according to the invention and the constituents used in the process according to the invention.

Important ingredients of the agents and ingredients of the invention, which are used in the process according to the invention are surfactants, in particular anionic surfactants, which are preferably at least in amounts of 0.5 wt .-% in the inventive compositions or the inventively prepared compositions. These include in particular sulfonates and sulfates, but also soaps.

As surfactants of the sulfonate type are preferably C ₉ -C ₁₃ alkylbenzenesulfonates, Olefinsulfonate, that is, mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are, for example, from C ₁₂ -C ₁₈ monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C ₁₂ -C ₁₈ -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids obtained by α-sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 C Atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are prepared, into consideration. These are preferably the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, with sulfonation of unsaturated fatty acids, such as oleic acid, in small Quantities, preferably in amounts not above about 2 to 3 wt .-%, may be present. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with not more than 4 C atoms in the ester group, for example, methyl ester, ethyl ester, propyl ester and butyl ester. With particular advantage, the methyl esters of α-sulfo fatty acids (MES), but also their saponified disalts are used. Other suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof, as in the preparation by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained. Examples of alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. From the washing are C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C _14- C ₁₅ alkyl sulfates are particularly preferred. 2,3-Alkyl sulfates, which are prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants. Also, the sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ -alcohols having on average 3.5 mol of ethylene oxide (EO) or C ₁₂ -C ₁₈ Fatty alcohols containing 1 to 4 EO are suitable. Due to their high foaming behavior, they are normally only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight. Further preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants. Again, sulfosuccinates whose fatty alcohol residues are of ethoxylated fatty alcohols with narrow homolog distribution derive, more preferably. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides). Particularly preferred are the sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate. As further anionic surfactants are in particular soaps, preferably in amounts of 0.2 to 5 wt.%, Into consideration. Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts.

The anionic surfactants (including the soaps) may be in the form of their sodium, potassium or ammonium salts, as well as soluble salts of organic bases such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts. The anionic surfactants are contained or used in the compositions according to the invention or in the process according to the invention preferably in amounts of from 1 to 30% by weight and in particular in amounts of from 5 to 25% by weight.

In addition to the anionic surfactants and the cationic, zwitterionic and amphoteric surfactants, especially nonionic surfactants are preferred.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₂ -alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ -alcohols with 7 EO, C ₁₃ -C ₁₅ -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ -C ₁₄ -alcohol with 3 EO and C ₁₂ -C ₁₈ -alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

The nonionic surfactants also include alkyl glycosides of the general formula RO (G) x, in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4. Also suitable are polyhydroxy fatty acid amides of the formula (I) in which R ² CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{3 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.

in der R⁴ für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R⁵ für einen linearen, verzweigten oder cyclischen Alkylenrest oder einen Arylenrest mit 2 bis 8 Kohlenstoffatomen und R⁶ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C₁-C₄-Alkyl- oder Phenylreste bevorzugt sind, und [Z] für einen linearen Polyhydroxyalkylrest, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielsweise nach der Lehre der internationalen Patentanmeldung WO-A-95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden. Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden, insbesondere zusammen mit alkoxylierten Fettalkoholen und/oder Alkylglykosiden, eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester, wie sie beispielsweise in der japanischen Patentanmeldung JP 58/217598 beschrieben sind oder die vorzugsweise nach dem in der internationalen Patentanmeldung WO-A-90/13533 beschriebenen Verfahren hergestellt werden. Als Niotenside sind C₁₂-C₁₈-Fettsäuremethylester mit durchschnittlich 3 bis 15 EO, insbesondere mit durchschnittlich 5 bis 12 EO bevorzugt. Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N.N-dihydroxyethylaminoxid, und der Fettsäurealkanol-amide können geeignet sein. Die Menge derartiger nichtionischer Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon.The polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in the R ^{4 is} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{5 is} a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R ^{6 is} a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C ₁ -C ₄ alkyl or phenyl radicals are preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group. [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides, for example according to the teaching of international patent application WO-A-95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described for example in Japanese Patent Application JP 58/217598 or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533. Preferred nonionic surfactants are C ₁₂ -C ₁₈ fatty acid methyl esters having an average of from 3 to 15 EO, in particular having an average of from 5 to 12 EO. Also, nonionic surfactants of the amine oxide type, for example, N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may be suitable. The amount of such nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is usually a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE 43 21 022 A1 or dimer alcohol bis- and trimer alcohol tris sulfates and ether sulfates according to German patent application DE 195 03 061 A1. End group-capped dimeric and trimeric mixed ethers according to the German patent application DE 195 13 391 are distinguished in particular by their bi-and multifunctionality. Thus, the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes. However, it is also possible to use gemini polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO95-A- / 19955.

In addition to the surfactants, inorganic and organic builders are among the most important ingredients of detergents and cleaners.

The zeolite containing fine-crystalline, synthetic and bound water is preferably zeolite A and / or P. The zeolite P used is, for example, zeolite MAP® (commercial product from Crosfield). However, zeolite X and mixtures of A, X and / or P are also suitable. The zeolite can be used as spray-dried powder or else as undried, still moist, stabilized suspension of its preparation. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt.%, Based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups, C ₁₂ -C ₁₄ fatty alcohols containing 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} . yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4. Such crystalline sheet silicates are described, for example, in European Patent Application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred. The preferred builder substances also include amorphous sodium silicates having a modulus Na ₂ O: SiO _{2 of} from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delay-delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of 10 nm to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in German patent application DE 44 00 024 A1. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates. Their content is generally not more than 25 wt .-%, preferably not more than 20 wt .-%, each based on the finished composition. In some cases it has been found that in particular tripolyphosphates already in small amounts up to a maximum of 10 wt .-%, based on the finished composition, in combination lead with other builders to a synergistic improvement of the secondary washing ability.

Suitable substitutes or partial substitutes for the zeolite are also phyllosilicates of natural and synthetic origin. Such sheet silicates are known for example from the patent applications DE 23 34 899, EP 0 026 529 and DE 35 26 405. Their usability is not limited to a specific composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable phyllosilicates which belong to the group of water-swellable smectites are, for example, montmorillonite, hectorite or saponite. In addition, small amounts of iron may be incorporated in the crystal lattice of the phyllosilicates according to the above formulas. Furthermore, because of their ion-exchanging properties, the layered silicates may contain hydrogen, alkali, alkaline earth metal ions, in particular Na ⁺ and Ca ⁺⁺ . The amount of water of hydration is usually in the range from 8 to 20% by weight and depends on the swelling state or on the type of processing. Useful sheet silicates are known, for example, from US Pat. No. 3,966,629, EP 0 026 529 and EP 0 028 432. Preferably, phyllosilicates are used, which are largely free of calcium ions and strong coloring iron ions due to an alkali treatment.

Useful organic builders are, for example, usable in the form of their sodium salts polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for environmental reasons, and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here. Preferably, these acids, when used in the premix according to the invention and are not subsequently added, used anhydrous. Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The Hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preference is given to hydrolysis products having average molecular weights in the range from 400 to 500,000. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose which has a DE of 100. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2000 to 30,000. A preferred dextrin is described in the European patent application EP 0 703 292 A1 , The oxidized derivatives of oligosaccharides for example of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are described, for example, in European patent applications EP 0 232 202, EP 0 427 349, EP 0 472 042 and EP 0 542 496 and in international patent applications WO 92/18542, WO 93/08251, WO 94/28030 , WO 95/07303, WO 95/12619 and WO 95/20608. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous. Other suitable co-builders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Also particularly preferred in this connection are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP 0 150 930 and Japanese Patent Application JP 93/339896. Suitable amounts are in zeolite-containing and / or silicate-containing Fonnulierungen at 3 to 15 wt.%. Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such co-builders are described, for example, in International Patent Application WO 95/20029. Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. To be particularly suitable Copolymers of acrylic acid with maleic acid containing 50 to 90 wt .-% of acrylic acid and 50 to 10 wt .-% of maleic acid. Their relative molecular mass, based on free acids, is generally from 5000 to 200,000, preferably from 10,000 to 120,000 and in particular from 50,000 to 100,000. The content of (co) polymeric polycarboxylates in the usual range is preferably from 1 to 10% by weight. %. Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those according to the German patent application DE 43 00 772 as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to German Patent DE 42 21 381 as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives. Further preferred copolymers are those which are described in the German patent applications DE 43 03 320 and DE 44 17 734 and preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate. Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives, of which German Patent Application DE 195 40 086 discloses that they are co-builders. Properties also have a bleach-stabilizing effect. Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0 280 223. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

In addition, the compositions may also contain components that positively affect oil and grease washout from fabrics. This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component. The preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxy-propylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt.%, In each case on the nonionic cellulose ether, as well as the known from the prior art polymeric esters of phthalic acid and / or terephthalic acid with monomeric and / or polymeric diols or their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

Other suitable ingredients of the compositions are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates such as the above-mentioned dissolving silicates or mixtures thereof; in particular, alkali metal carbonate and amorphous alkali metal silicate, above all sodium silicate with a molar ratio of Na ₂ O: SiO _{2 of} from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used. The content of the sodium carbonate agent is preferably up to 20% by weight, advantageously between 5 and 15% by weight. The content of the sodium silicate agent, if it is not to be used as a builder, is generally up to 10% by weight and preferably between 2 and 8% by weight, but may otherwise be higher. According to the teaching of the international patent application WO 94/01222, alkali metal carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and optionally a further carboxyl and / or amino group-containing amino acids and / or salts thereof. In the context of this invention, it is possible that a partial to complete replacement of the alkali metal carbonates by glycine or glycinate takes place.

The other detergent ingredients include grayness inhibitors, foam inhibitors, bleach and bleach activators, optical brighteners, enzymes, fabric softening substances, dyes and fragrances and neutral salts such as sulfates and chlorides in the form of their sodium or potassium salts.

To reduce the pH of detergents or cleaners, it is also possible to use acidic salts or slightly alkaline salts. Bisulfates and / or bicarbonates or the abovementioned organic polycarboxylic acids, which can also be used simultaneously as builders, are preferred as the acidifying component. Particularly preferred is the use of citric acid, which is either added subsequently (customary procedure) or - in anhydrous form - is used in solid premix.

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. The content of the bleaching agents is preferably from 5 to 25% by weight and in particular from 10 to 20% by weight, with perborate monohydrate or percarbonate being advantageously used.

As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoyisuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and the enol esters known from German patent applications DE-A-196 16 693 and DE-A-196 16 767 and acetylated sorbitol and mannitol or their mixtures described in European patent application EP-A-0 525 239 (SORMAN ), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-al alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzylcapralactam, disclosed in International Patent Applications WO-A-94/27970, WO-A-94/28102, WO-A-94/28103, WO-A No. 95/00626, WO-A-95/14759 and WO-A-95/17498. The hydrophilic substituted acyl acetals known from German patent application DE-A-196 16 769 and the acyllactams described in German patent application DE-A-196 16 770 and international patent application WO-A-95/14075 are likewise preferably used. The combinations of conventional bleach activators known from German patent application DE-A-44 43 177 can also be used. Such bleach activators are in the usual amount range, preferably in Amounts of 1 wt .-% to 10 wt .-%, in particular 2 wt .-% to 8 wt.%, Based on total agent included.

When used in automatic washing processes, it may be advantageous to add conventional foam inhibitors to the compositions. As foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide. It is also advantageous to use mixtures of different foam inhibitors, for example those of silicones, paraffins or waxes. The foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamides are preferred.

The salts of polyphosphonic acids used are preferably the neutral-reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediamine tetramethylenephosphonate in amounts of from 0.1 to 1.5% by weight.

Suitable enzymes are in particular those from the class of hydrolases, such as proteases, lipases, cutinases, amylases, cellulases or mixtures thereof in question. Oxireductases are also suitable. Particularly suitable are enzymatic agents obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. Enzyme mixtures, for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase are of particular interest. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof used. Since the different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of cellulases can be used desired activities are set. The enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation. The proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.

In addition to the above-mentioned phosphonates, the agents may contain other enzyme stabilizers. For example, 0.5 to 1 wt .-% sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. In addition to calcium salts, magnesium salts also serve as stabilizers. However, it is particularly advantageous to use boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyroboric acid (tetraboric acid H ₂ B ₄ O ₇ ).

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful. However, preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of from 0.1 to 5% by weight, based on the compositions ,

The agents may contain as optical brighteners derivatives of Diaminostilbendisulfonsäure or their alkali metal salts. Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which are used in place of the morpholino Group a Diethanolaminogruppe, a methylamino group, an anilino group or a 2-Methoxyethylaminogruppe carry. Furthermore you can Aufhelier the type of substituted Diphenylstyryle be present, for example, the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyls, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyls, or 4- (4 -Chlorstyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brightener can be used.

Examples example 1

The means E1 to E5 as well as for comparison the means V1 and V2 not according to the invention (composition see Table 1) were prepared as follows:

In a batch mixer (Lödige® ploughshare mixer 20 liters) equipped with a cutterhead chopper, a premix of the ingredients shown in Table 1 was added, with the addition of the nonionic surfactant into the powder stream being made by spraying through nozzles, produced. Thereafter, the mixture was homogenized for 2 minutes and then fed to a 2-screw extruder, the granulating head was preheated to temperatures between 50 ° C and 65 ° C. Under the shear action of the extruder screws, the premix was plasticized and extruded through the extruder head hole die plate into fine strands with a diameter of 1.4 mm at the pressure indicated in Table 1, which were comminuted to approximately spherical granules by means of a doctor blade after nozzle exit ( Length / diameter ratio about 1, hot break). The resulting warm granules were rounded for one minute in a commercially available Rumerier Marumerizer® type and optionally coated with a finely divided powder.

The bulk density of the extrudates produced as well as their respective values in the solubility test (L-test) described below are also given in Table 1.

It can be seen that when using the water-swollen polymers WQP1 to WQP 4 according to the invention, even if they are used in smaller amounts than a conventional plasticizing auxiliaries, high-quality products are obtained at significantly (at least 30%) lower extrusion pressures.

To determine the residue or solubility behavior (L test), 8 g of the test agent were sprinkled in a 2 l beaker with stirring (800 rpm with laboratory stirrer / propeller stirring head centered 1.5 cm from the beaker bottom) and 1 , Stirred at 30 ° C for 5 minutes. The test was carried out with water of a hardness of 16 ° d. The wash liquor was then poured off through a sieve (80 μm). The Beaker was rinsed with very little cold water over the sieve. The sieves were dried in a drying oven at 40 ° C ± 2 ° C to constant weight and the detergent residue was weighed out. There was a 2-fold determination; the residue is given as a percentage of the two individual determinations. Deviations of the individual results by more than 20% from each other usually further experiments are carried out; but this was not necessary in the present investigations.

For comparison, another agent V3 was prepared, which contained the same ingredients in the final product as E2 , but in which the copolymer was not introduced in anhydrous swollen form, but as about 30 wt .-% aqueous solution in the process. The excess water was then dried away in a fluidized bed. The bulk density of the extrudate V3 was 770 g / l, the L-test gave a value of 28%.

Compositions of spray-dried powders SP1 and SP2:

Spray dried powder 1: 26.00% by weight of C ₉ -C ₁₃ -alkylbenzenesulfonate 8.50% by weight of sodium carbonate 41.33% by weight of zeolite A, based on anhydrous active substance punching 9.50 wt .-% copolymeric sodium salt of acrylic acid and maleic 1.00% by weight of phosphonate 12.00% by weight of water 0.42% by weight of optical brightener Residual salts from solutions Spray dried powder 2: 26.00 wt .-% C ₉ -C ₁₃ alkylbenzenesulfonate 42.83% by weight of zeolite A, based on anhydrous active substance punching 5.50 wt .-% copolymeric sodium salt of acrylic acid and maleic 1.00% by weight of phosphonate 5.00% by weight of sodium carbonate 6.00% by weight sodium sulfate 12.00% by weight of water 0.42% by weight of optical brightener Residual salts from solutions Table 1 composition E1 E2 E3 E4 E5 V1 V2 Spray dried powder 1 62 - 62 62 64 62 - Spray dried powder 2 - 62 - - - - 62 C _12/18 fatty alcohol + 7 EO 6 6 6 6 5 6 6 sodium perborate 20 20 20 20 20 20 20 C _12/18 fatty alkylsulfate ^a) 7 7 7 7 6 7 7 Salt compound ^b ) - - - - 7 - - WQP 1 ^c) 5 - - - - - - WQP 2 ^d) - 5 - - - - - WQP 3 ^e) - - 5 - - - - WQP 4 ^f) - - - 4 6 - - Polyethylene glycol (4000) - - - - - 7.5 7.5 Extrusion pressure [bar] 70 70 70 60 50 120 100 Bulk density [g / l] 780 790 780 810 800 780 790 L-test 8th 7 4 12 9 7 5 a) 92% by weight of active substance, 3.70% by weight of sodium sulfate, 2.80% by weight of other salts of raw materials and unsulfurised portions, 1.50% by weight of water b) Composition 42.5% by weight of sodium carbonate, 2.5% by weight of sodium silicate module 3.3, 45% by weight of sodium sulfate, 10% by weight of water c) Mixture of 10% by weight of polyvinylpyrrolidone (Luviskol® K30, manufacturer BASF) and 90% by weight of glycerol d) Mixture of 10% by weight of acrylic acid / maleic acid copolymer Na salt (Sokalan® CP5, manufacturer BASF) and 90% by weight of glycerol e) Mixture of 10% by weight of starch diphosphate and 90% by weight of glycerol f) Mixture of 6% by weight of hydroxypropyl starch and 94% by weight of ethylene glycol

Example 2

In a ploughshare mixer with chopper (manufacturer Lödige), the ingredients listed in Table 2 (with the exception of the anhydrous swollen polymers, WQP) at the temperature indicated in Table 2 (temperature "remainder") were presented and mixed together, for dust bonding, the liquid nonionic surfactant was entered as the last component. The respective anhydrous swollen polymer, which had the temperature (temperature WQP) also indicated in Table 2, was subsequently mixed, whereupon the agglomerating granulation of the material began after about 2 minutes. After a further mixing time of 8 minutes to 10 minutes, the granules G1 to G11 listed in Table 2 were obtained with the apparent bulk densities and solubilities (determination as in Example 1) and with the particle size distributions given in Table 3. Most notably, all components of common detergent formulations, including enzyme, soil release polymer, foam regulator and bleach activator (TAED) granules, can be incorporated ( G10 and G11 ). <u> Table 2 </ u> composition G1 G2 G3 G4 G5 G6 G7 G8 G9 G10 G11 SP 1 ^a ) 55 56 60 58 60 58 59 52 52 45 45 Na-perborate · 1H ₂ O 19 19 20 20 20 20 20 17 18 15 15 C _12/18 fatty alkylsulfate ^a) 7 7 7 7 7 7 7 7 7 8th 8th Fatty alcohol + 7 EO ^a) 5 5 6 5 6 5 6 5 5 5 5 Zeolite Na-A (powder) 3 3 - - - - - 3 3 3 3 enzyme granules - - - - - - - - - 2 2 Soil release polymer - - - - - - - - - 1 1 foam regulator - - - - - - - - - 4 4 bleach - - - - - - - - - 7 7 Perfume - - - - - - - - - 1 1 WQP 5 ^b ) - - - - - 10 - - - - - WQP 4 ^c ) 11 - 7 9 7 - - 16 - - - WQP 6 ^d ) - - - - - - 8th - - - - WQP 7 ^e ) - 10 - - - - - - 15 9 9 Temperature WQP 20 20 59 40 20 20 20 20 20 20 68 Temperature "rest" 20 20 20 20 58 20 20 45 45 20 68 Bulk density [g / l] 661 650 710 690 740 680 690 783 790 748 730 L-test 7.6 15.9 3.9 7.9 7.6 4.3 6.8 5.4 5.4 10.0 5.5 a) Composition as in Example 1 b) Mixture of 4% by weight of hydroxypropyl starch and 96% by weight of ethylene glycol c) Mixture of 6% by weight of hydroxypropyl starch and 94% by weight of ethylene glycol as in Example 1 d) Mixture of 8% by weight of hydroxypropyl starch and 92% by weight of ethylene glycol e) Mixture of 10% by weight of hydroxypropyl starch and 90% by weight of ethylene glycol G1 G2 G3 G4 G5 G6 G7 G8 G9 G10 G11 on sieve 1.6 mm [%] 16 16 3 6 7 7 8th 9 5 5 5 on sieve 1.25 mm [%] 24 27 11 16 14 19 16 13 10 15 8th on sieve 1.0 mm [%] 16 22 11 14 12 16 12 13 13 29 18 on screen 0.8 mm [%] 21 21 23 22 22 24 24 22 16 28 26 on sieve 0.4 mm [%] 19 13 47 38 41 29 38 39 49 22 40 through sieve 0.4 mm [%] 4 1 5 4 4 5 2 4 7 1 3

Example 3

For the preparation of other granular detergent G12 to G14 was worked as in Example 2, but using instead of the plowshare mixer an intensive mixer with inclined plate and a swirler (manufacturer Fa. Eirich) as Granulationsvorrichtung. <u> Table 4 </ u> composition G12 G13 G14 SP 1 ^a ) 47 47 45 Na-perborate · 1H ₂ O 16 16 15 C _12/18 fatty alkylsulfate ^a) 8th 8th 8th C _{12/18 fatty} alcohol + 7 EO ^a) 6 6 6 Zeolite Na-A (powder) 3 3 4 enzyme granules 3 3 3 Soil release polymer 1 1 1 foam regulator 4 4 4 Bleach activator TAED 7 7 - Bleach activator TAED ^b ) - - 7 WQP 7 ^c ) 5 5 7 Temperature WQP 20 48 20 Temperature "rest" 20 48 20 Bulk density [g / l] 813 784 737 L-test 3.8 3.6 4.9 a) Composition as in Example 1 b) admixture in the treatment c) Composition as in Example 2 G1 G2 G3 on sieve 1.6 mm [%] 4 5 5 on sieve 1.25 mm [%] 8th 10 13 on sieve 1.0 mm [%] 12 15 20 on screen 0.8 mm [%] 17 17 20 on sieve 0.4 mm [%] 47 41 35 through sieve 0.4 mm [%] 12 12 7

Claims (17)

1. Process for the preparation of particulate detergents or cleaners or multi-substance components or treated raw materials which, in a mixture with further ingredients, produce compositions of this type, with bulk densities above 600 g/l by combining detergent or cleaner compounds and/or raw materials with simultaneous or subsequent shaping, where a premix is firstly prepared which comprises individual raw materials and/or compounds which are in the form of solids at room temperature and a pressure of 1 bar, and then this premix is converted to a particle with the use of compaction forces, and is optionally subsequently further treated or processed, characterized in that in the premix the content of liquid water is less than 2% by weight and, during the shaping, a shaping auxiliary which is liquid under the shaping conditions, in particular also at room temperature and a pressure of 1 bar in the form of a polymer swollen in essentially nonaqueous solution, where the essentially nonaqueous liquid has not more than 20% by weight of water, the essentially nonaqueous liquid component of the shaping auxiliary is chosen from the di- or trihydric alcohols which are liquid at room temperature and have boiling points (at 1 bar) above 80°C, mixtures thereof and mixtures thereof with monohydrate alcohols which are liquid at room temperature and have boiling points (at 1 bar) above 80°C, and the system of essentially nonaqueous liquid and polymer at room temperature in the presence of the polymer has an at least 20-fold higher viscosity than the essentially nonaqueous liquid on its own.
2. Process according to Claim 1, characterized in that the polymer swollen in essentially nonaqueous solution is a system of essentially nonaqueous liquid and polymer which, at room temperature, in the presence of the polymer has a 300-fold to 5000-fold higher viscosity than the essentially nonaqueous liquid on its own.
3. Process according to Claim 1 or 2, characterized in that the viscosity of the shaping auxiliary at room temperature is in the range from 200 mPas to 100 000 mPas, in particular from 400 mPas to 50 000 mPas.
4. Process according to Claim 3, characterized in that, at elevated temperature the viscosity of the shaping auxiliary deviates only relatively slightly from the values at room temperature and, at 60°C, is in the range from 250 mPas to 40 000 mPas.
5. Process according to one of Claims 1 to 4, characterized in that the essentially nonaqueous liquid component of the shaping auxiliary is chosen from the di- or trihydric alcohols which are liquid at room temperature and have boiling points (at 1 bar) above 120°C, mixtures thereof and mixtures thereof with monohydric alcohols which are liquid at room temperature and have boiling points (at 1 bar) above 80°C, in particular above 120°C.
6. Process according to Claim 5, characterized in that the essentially nonaqueous liquid component of the shaping auxiliary is chosen from n-propanol, isopropanol, n-butanol, s-butanol, isobutanol, ethylene glycol, 1,2- or 1,3-propylene glycol, glycerol, di- or triethylene or -propylene glycol or mixtures thereof.
7. Process according to one of Claims 1 to 6, characterized in that the essentially nonaqueous liquid comprises no more than 15% by weight of water.
8. Process according to one of Claims 1 to 7, characterized in that the polymer which leads to a swollen system in the essentially nonaqueous liquid is chosen from polyvinylpyrrolidone, polyacrylic acid, the copolymers of acrylic acid and maleic acid, polyvinyl alcohol, xanthan, partially hydrolyzed starches (maltodextrins), alginates, amylopectin, celluloses or starches carrying methyl ether, hydroxyethyl ether, hydroxypropyl ether and/or hydroxybutyl ether groups, phosphated starches, such as starch diphosphate, and inorganic polymers, such as sheet silicates, and mixtures thereof.
9. Process according to one of Claims 1 to 8, characterized in that, in the shaping auxiliary, the concentration of the polymers in the essentially nonaqueous liquids is 1% by weight to 80% by weight, in particular 2% by weight to 60% by weight.
10. Process according to one of Claims 1 to 9, characterized in that the content of shaping auxiliaries, based on the premix to be compacted, is from 2% by weight to less than 25% by weight, in particular from 3% by weight to 15% by weight.
11. Process according to one of Claims 1 to 10, characterized in that a shaping auxiliary is used which dissolves completely in a concentration of 8 g per 1 litre of water at 30°C within 90 seconds.
12. Process according to one of Claims 1 to 11, characterized in that the premix has a total water content of not more than 20% by weight, where the content of water not bonded to zeolite and/or silicates is not more than 15% by weight and in particular less than 12% by weight.
13. Process according to one of Claims 1 to 12, characterized in that the compacting shaping is carried out using an agglomeration step, where the premix is granulated by agglomeration in a device suitable for this purpose and the shaping auxiliary, in the form of the polymer swollen in essentially nonaqueous liquid, takes on the role of a binder.
14. Process according to Claim 13, characterized in that the solid constituents of the premix to be compacted are initially introduced into a granulator, as which a mixer may also be used, any dusts present are bound, where necessary by adding a liquid nonionic surfactant, and the shaping auxiliary is introduced into the granulator.
15. Process according to one of Claims 1 to 12, characterized in that the shaping takes place by extrusion, where the premix is compacted under pressure, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally comminuted by means of a rotating chopping knife, preferably to give approximately spherical (bead-like) to cylindrical granulate particles.
16. Granulated or extruded detergent prepared by the process according to one of Claims 1 to 15, where its dissolution behaviour is dependent on the dissolution behaviour of the individual raw materials and compounds used, characterized in that it consists, in an amount of at least 50% by weight, of compounds and/or treated raw materials prepared according to the invention and consists, in particular in an amount of at least 60% by weight, of a base granulate or base extrudate prepared according to the invention, where it is particularly advantageous if the remaining constituents are likewise compounds or treated raw materials which have been prepared by the process according to one of Claims 1 to 15.
17. Composition according to Claim 16, characterized in that it has, as outer shell, dust-like or at least finely divided ingredients (the so-called fines) which have been stuck on by melt agglomeration.