DE19547457A1 - Multi-component pourable detergent - Google Patents

Abstract

Multi-component pourable detergent in coarse-grained rounded form, esp. a textile detergent in bead form, which has a high density and good solubility (even in cold water) which allows enhanced freedom of choice of active agents and auxiliaries, comprises an abrasion-resistant material (which is free of powder and fines) comprising a bondingly compressed core of one or more active agents and/or auxiliaries, which are soluble (or insoluble in finely dispersed form) in aq. wash liquors, the core being coated with a mixt. of the same and/or other active agents and auxiliaries with (based on the diameter of the core material) smaller individual particle sizes. The particles of coating substance are bound to one another and to the outer surface of the core material using a organic and/or inorganic binding agent which is soluble or dispersible in cold water and solid at room temp.

Description

The invention relates to improvements to the offer form multicomponent solid coarse-grained pourable and free-flowing Washing and cleaning preparations, in particular laundry detergents. Affected are in particular the at least largely ku gel-rounded solid solid mixtures, also called Textile detergents are known in bead form. The invention wants to make funds of this kind accessible, which - in addition to a we at least largely uniform ball or Per lenform - high density with good solubility even in cold Connect water, are free of dust and fines and there with an increased freedom in the choice of multi-component allow mixture and additives to be used.

The increasing bulk density increase in commercial washing Telegranules are mainly made by an increasingly compact dende grain structure of the granules reached, however - as negative side effect - with an increasing release delay connected. This unwanted release delay will triggered, inter alia, that a number practice-standard anionic and nonionic surfactants and especially entspre surfactant mixtures when dissolved in water for training tend to gel phase. Already at surfactant levels of 10 Wt .-% and above, based on the multi-component mixture,  it can at dissolution in particular cold water to un desired and delays.

EP-B-0486 592 describes granular or extru diert detergents or detergents with bulk densities above 600 g / l, the anionic and / or nonionic surfactants in Men gen of at least 15 wt .-% and up to about 35 wt .-% enthal They are manufactured by a process in which a solid, free-flowing premix containing a plasticizing and / or Lubricant contains, at high pressures between 25 and 200 bar extruded stranded and the strand after leaving the hole shape by means of a cutting device on the vorbe The granulate dimension is tailored and rounded. The produced extrudates can be retrofitted with other Granu laten are mixed, wherein in an advantageous Ausfüh form the proportion of extrudates in the finished washing or Detergents more than 60 wt .-% is.

From the international patent application WO-A-93/15180 is be it is known that the rate of dissolution of extruded agents thereby it can be improved that in the premix short-chain alkylsul fate, in particular C₈-₁₆-alkyl sulfates are used, the introduced a certain way in the premix who the. However, this measure is not always sufficient to: to increase the dissolution rates of the entire agent.

The older German patent application of the applicant according to DE 195 19 139 (H 1795) proposes to resolve the conflict between high Degree of compaction of the valuable mixture, in particular by Ex trusion, on the one hand and the nevertheless required ra particular, gel-free solubility of this value Good material even in the early stages of a washing process before, granular detergents or cleaners with a bulk density above 600 g / l, containing an extruded component and anionic and / or nonionic surfactants in amounts of at least 15 wt .-% to design such that at least two  various granular components in the multi-substance to be used are provided, of which at least one extruded and at least one is not extruded. The extruded Component (s) should thereby in amounts of 30 to 85 wt .-%, bezo be included on the entire remedy, being at the same time the content of the extruded component (s) of surfactants (including soaps) 0 to less than 15 wt .-%, based to the respective extruded component. In the more substance mixture is at least one non-extruded granular and surfactant-containing component in such amounts that by this component at least 1 wt .-%, based on the total Agent provided to surfactants, wherein further before is zugt, non-extruded granular and surfactant-containing Kompo nents in the different mixtures of substances produced provide in such amounts that thereby up to 30 wt .-% and preferably 5 to 25 wt .-% - in each case on the entire Multi-substance mixture - be provided to surfactants. The Ge weight ratio of the surfactant-containing extruded component to non-extruded surfactant-containing granular component preferably in the range from 6: 1 to 2: 1, preferably in Be rich from 5: 1 to 3: 1. The object of the revelation the This older application is hereby expressly also the counter was made the present invention disclosure.

Even though they differ in their way of mixing Substituted multicomponent components, of which at least one with extrusion is highly compressed, to a better compromise between the desired high bulk density of Mehrkomponen mixture and the simultaneously required gel-free sufficiently rapid solubility leads, so nevertheless egg a series of new problems with it. The ideal idea of uniform grain, each containing the entire components of the multicomponent mixture is left. It can handle it Demixing processes and, accordingly, fluctuations in the Reproducibility of the desired washing and cleaning results occur. The extruded material content is not just  high density, which are dried extrudates at the same time comparatively hard. In the conditions of Transport, storage and use of the comparatively white chere Granulatanteil thus exposed to mechanical forces be proportionate to its diminution and thus to Formation of dust and fines by abrasion.

Object of the invention

This is where the concept of the teaching according to the invention begins. The Invention has set itself the task of highly compressed More component mixtures from the field of washing and cleaning medium and especially in the textile sector To make accessible to washing agents, the problem-free Ver Realization of the old wishful imagination, all Kom components of these known highly complex multicomponent mixtures in each to be able to unite only one grain. The new kornför Mige Good is supposed to contradict itself in a certain sense the material properties of the high compression and thus entspre high bulk density on the one hand, but at the same time good Dispersibility and solubility - especially already during the flushing phase with the üb in household washing machines Sometimes cold tap water - connect. The invention However, proper conception is not limited to this. It should also be created the possibility of spherical abge rounded and highly compressed multicomponent mixtures of different Composition in such similar external space form of Offer ball or pearl at comparable densities to be able to virtually any mixes of the under different types of composite storage stable and demii can be offered to the trade free of

The task of the invention goes beyond that. The new range of high-density laundry detergents should also be the possibility of a controllable delay of Solubility of certain proportions of the multicomponent mixture ermögli  in order to do so - especially at the same time Co-use of rapidly soluble components - a multi-level To enable washing and cleaning procedures, as with For example, the subject of the earlier German patent application the applicant according to P 44 38 850.0. The revelation too This earlier application is hereby the subject of made invention disclosure. Described is there in particular a conditioning of the aqueous liquor and / or of the goods to be cleaned in the early phase of the washing process by the use of even in cold water quickly soluble Complexing agents for the polyvalent cations of water hardness and appropriate blends with cold-soluble surfactant compound fertilize.

The concept of the technical described below Teaching is based in particular on the task, which in many cases Respect of highly sensitive mixtures today's conventional textile detergent in a free of dust and fines a to offer a uniform spherical shape, the illustrated Requirements met in total, but at the same time also the possibility There are still modifying changes in each of them permissible recipes of multicomponent mixtures, without fundamental changes in the requested form of the To make multi-substance mixtures. The inventive At the same time, teaching wants access to technical expertise This task is so broad that on the basis of at the respective manufacturer today existing technology the technical realization of wishful thinking without substantive All modifications are possible.

Subject of the invention

The invention accordingly is in a first Embodiment a multicomponent pourable and free-flowing Detergents and cleaning agents in a coarse-grained rounded area botsform, in particular a multi-component laundry detergent in  Pearl shape, which additionally high density with good solubility also in cold water combines and thereby increased freedom in the choice of the value and optionally excipients made possible light. The teaching of the invention is characterized thereby shows that this new offer form of Mehrkomponentengemi As abrasion-resistant, free of dust and fines Good the following grain structure is formed:

• - Each grain contains an adherent ver in its interior sealed core of one or more value and / or Excipients which are soluble in aqueous liquor and / or are finely dispersed insoluble - in the following also referred to as "nuclear material".
• - This core material is sheathed in a blend cher and / or other valuable and / or auxiliary substances whose Solid content has an individual particle size, which is smaller than the diameter of the core material - hereinafter also referred to as "envelope substance".
• - These particles are the shell substance under Mitver Use of a soluble in cold water and at Room temperature solid binder together and to the Outer surface of the core material bound - in the inven description of this binder is also as Called "binder". The binder can be organic and / or inorganic origin.

The teaching according to the invention in the preferred embodiment ment that components that have a resolution of ver sealed spheres in the aqueous liquor, and thereby especially when water is gelling and / or only slowly soluble components of the multicomponent mixtures for at least over are part of the shell substance. Fiction According to these shares each with predeterminable indivi dueller particle size incorporated into the shell substance. Your cooperation  The content is here by at room temperature and in the Practice occurring moderately elevated temperatures solid binder guaranteed. When water enters the binder also dissolves even at the temperatures usual cold tap water. The isolated in the encapsulant by the binder and separated from present each other slowly soluble and possibly ver dispersing particulate matter in the liquor without adding coagulate or otherwise the flushing process and / or to affect the washing process. By the below additional measures described, for example, co-use of dispersing and / or dissolution aids - this Pro the decomposition of the sheath substance into individualized ones Feinstteilchen be promoted almost arbitrarily.

The nature and especially the solubility of the kernma terials, as a highly dense commodity and usually in the The spherical sphere in the form of only one grain - in the following also known as "carrier grain" - present, are chosen so that disabilities of the solubility and dispersion of the More component mixtures are excluded.

In particular, in the shell substance can almost any fine Partial to dust-like components presented and solidified then, after their release through the primary step the dissolution of the binder, the subtask to which it belongs Can fulfill the framework of the washing and cleaning process. It It immediately becomes clear that as components of the encapsulating substance not only selected individual components are suitable for Ein set can here in particular arbitrarily selected and zusam Multicomponent compounds come in the form of supply the preferred spherical dry material of adjacent par separated and thus from an undesirable interaction are protected. Such fine particulate compounds in the Envelope substance can be coordinated so that predetermined technical effects at and / or after their dissolution solution in the wash liquor can run in optimized form.  

The assortment of solid core material - the carrier Kor nes - is also within the framework of the available here Multi-component mixtures in a comparatively broad Be rich variable and selectable. The selection is dominated here the component (s) on the one hand by the requirement of a down reaching solubility in the context of the washing process - without For example, triggering difficulties by gelling sen - on the other by superordinate conceptions of a For example, in terms of the pH of the wash liquor mehrstufi washing and cleaning process. The carrier grain can egg from ner determines selected component, but especially from appropriately selected and compressed together Multicomponent mixtures exist. For details, see in the following details of the invention Teaching.

The present invention relates in another embodiment tion form the process for the preparation of the washing and cleaning in the particular spatial form shown here. In the widest version of the process is characterized net, that the core material in the form of a preformed, adherently compacted carrier grain with the finely divided Good of Shell substance in the presence of the binder in flowable preparation enveloping agglomerated or granulated and solidified the binder. The binder can in particular under Use of a solvent and / or emulsifying agent - preferably as an aqueous solution and / or emulsion - under the same early or subsequent drying used come, but it is preferably the binder in the form of a Melting to use, to be united with one another apply and by subsequent cooling of the coated Good to ensure the solidification of the multicomponent mixture. For details also see this in the following invention description.  

The carrier material or highly compressed carrier grain in the sense of the definition according to the invention is usually a adherently compacted agglomerate of a plurality of smaller pri märteilchen from the field of value and / or auxiliaries for the subject area mentioned here. The carrier grain is - like even his name says - the basis for the training of finished ball - or pearl - shaped offer form of the of dust and fines free material mixture. These Shares are predeterminable by Schalenagglomerati bound on the surface of the carrier grain. In the selection the respective technology for the production of the carrier grain is - in addition to the selection and determination of the carrier grain forming individual components - one of the key points of the he inventive action. Details can be found in the following description of the invention. Here is only briefly together In summary: Produced using high processing pressures put extrudates by blowdown granulation of the extrudate strands, by subsequent rounding and usually out reaching drying can be preferred Support materials or carrier grains within the meaning of he be inventive teaching.

The definition of the carrier grain in the sense of the invention However, teaching does not limit itself to these extrudates. In egg An important modification may be the principles of the invention appropriate action for transfer powdery and / or fine granular multi-component mixtures from the field of washing and Detergent in a coarse-grained, abrasion-resistant, dust and Fines free used well with particular pearl shape become. In particular, those currently available on the market various types of commercial heavy-duty textile detergents with bulk densities above 600 g / l and in particular 700 g / l in the ball or beads defined according to the invention be transformed into shape. It will be in a following teaching a sufficient portion of the pul Verform fine-grained multi-component mixture for adherent compaction  converted carrier grain, which then in the sense of the Invention proper shell agglomeration with the remaining parts of the powdery finely divided recyclable material is coated. last Lich falls here also a free of dust and fines Good in rounded ball or pearl shape with vorbe tunable size and density of the individual balls.

Details of the teaching of the invention

Before to the individual determining elements for the invention Acting is taken in closer, is their conceptual Zu first shown below. The selection and Definition in a specific case to be selected combinations the individual elements is then in the light of the general Fachwis sens accessible.

In essence, the invention in one of their important Ausfüh forms the repatriation of the spatial form of a multicomponent Detergent and detergent preparation in the dry state on the 1-grain. This grain-shaped good should be all or include virtually all components for the application. Basically, the principle should be realized, the for example, in the previously cited EP-B-0486 592 is. In particular, the teaching of the invention as kon krete grain form the spherical or cylindrical rounded Anbie enable such solid multicomponent mixtures.

Notwithstanding the just cited document of the prior However, the teaching of the invention now wants a technique Separation of the value and / or excipients within each individual NEN ball in a plurality of separated in the dry state Provide rooms. This is the first one core, the "core material", and enveloping that core ordered "shell substance". The shell substance can - Unab depending on the number of their individual components - single-shelled or be formed mehrschalig. The way this way  resulting storage rooms for the stored in the dry state Multi-material can be in direct contact with one another but they can also be separated by separating layers be separated separately.

The conception according to the invention also provides for the Scha le (n) of the enveloping substance in turn in a plurality of arbitrary to divide many small individual spaces where the ver similarly finely divided value and / or auxiliaries of the envelope substance shell (s) non-contact and yet in a tight package are stored. This is achieved by the inventive Conception, the water-soluble binder as additional to incorporate a soluble component into the shell substance (s).

The binder component according to the invention thus comes a multi functional importance too. Without claim of completeness Here are the following functions listed: The Verfesti coating material on the core material and at the same time finely divided multicomponent mixture of solid value and / or auxiliary fibers; the separation of the individual components from the Hüllsub punch against each other and the separation of the shell substance in total together with the core material; the release of the coating substance including the surface of the core material upon entry already from cold water; the solidification in particular of Kornaußenbereiche against abrasion under the usual conditions conditions of transport, storage, use and the like; the Binder can itself as a recipe component of the total mixture to be selected; The binder can also be additional carrier for dissolving and / or dispersing aids for facilitated and gel free dissolution of the individual components and the recyclable mixture be in its entirety.

As a result, the teaching of the invention enables the Ausbil tion according to the type and size pre-definable solid Mehrstoffgemi in each case the entirety of the multi-substance in one grain mixture included. Here they are in predictable form  separated from each other so that an undesirable interaction does not take place at this stage. At the same time the ge controlled or controllable release of mehrkompo nentigen material mixture in the aqueous liquor possible. per Blemanteile these mixtures of substances can in the state ei ner predictable Feinstdispergierung so stored and the Washing and cleaning process are offered that unwanted Disqualify here. The dry solid material is dust-free and also free of fines. A multi-level Textile laundry becomes possible. Finally, the invention creates the possibility of the visual appearance of the dry-grain nes - in addition to the appealing pearl shape, for example, his Whiteness or its color - to be determined in a predictable way put; all these controlled adjustable effects go thereby from the conception demanded today, highly condensed Recyclable material preparations, for example in the range of 500 to 1300 g / l, in particular 600 or 700 to 1200 g / l, available to make provision in the selection and compilation their value and auxiliaries to the respective conditions of the Washing and cleaning process and / or always changing the ideas for optimizing the individual used Adapt recyclables - for example from an ecological point of view.

In the following, first of all, the three essentials are discussed chen determining elements for the inventive action the nuclear material - also known as "carrier grain" -, the shell substance or the shell substance as ver and finally the binder / bin for the cup-shaped wrapping of the carrier grain.

Nuclear material / carrier grain and its production

This inner core of each individual grain of invented The multicomponent mixture according to the invention can itself be 1-component or be formed mehrkomponentig. As a rule, a sub proportional share - preferably the majority - of the  Whole grain is formed by the carrier grain is its down reaching compression is a determining element. For the Core material are bulk densities of at least 450 g / l and ins particular of at least 500 to 600 g / l preferred. Further be preferred lower limits here are 650 or 700 g / l. Just the possibility of this carrier grain also 1-component, for example play by water-soluble inorganic and / or organic Salts such as soda, alkali silicate, alkali metal salts of polycarboxylic acid ren, such as trisodium citrate, and the like here the way to high bulk densities in this inner sphere core. Upper limit values can be above 1000 g / l, for example se at 1300 to 1500 g / l or even more. Nevertheless, the predictable water solubility is this Core material adjustable secure.

The core material accounts for at least about 15 to 20 weight percent but preferably at least 1/3 and in particular at least et wa 35 to 40 wt .-% of the total mixture. In the most important Embodiments is the amount by weight of Kernmate at least about 50% by weight of the total blend, wherein special meaning the range of about 55 to 80 or 90 Gew .-% zukommen kann - Gew .-% also here as before based on the entire multi-substance mixture.

The core material is 1-component or multi-component forms out and is thereby formed at least substantial proportion of water-soluble and / or finely dispersed in water-insoluble inorganic and / or organic components of conventional detergents and cleaners. By way of example, suitable bulking agents and / or cobuilders, alkalizing agents, temperature-stable bleaching agents based on hydrogen peroxide, such as perborate compounds, may be mentioned here from the field of laundry detergents. Further examples are at least largely gelatin-free soluble surfactant compounds, in particular ent speaking anionic surfactants and / or nonionic surfactants, but also a plurality of other common small components of Textilwaschmit stuffs that can be safely the burden of a sufficient Ver sealing step, for example by extrusion, suspended. In principle, the carrier grain can be constructed in the inventive sense from the group of recyclables, which are pre-see in the aforementioned German Patent Application DE 195 19 139 (H 1795) as components for extrusion and there with non-extruded granular further components of the washing - And detergent mixtures are mixed abge. The individual components should be soluble and / or finely dispersible in the aqueous phase. In the following, a summary of suitable components will be given. First, by way of example only, but as an example for the technical knowledge, a number of suitable components for the construction of the core material / carrier grain are enumerated:
Inorganic soluble or finely disperse Waschmit telbestandteile as Builder main components - for example, zeolite compounds of the zeolite A, X and / or P type, alkali sierungsmittel such as soda and water glass, sufficiently stable carrier salts for hydrogen peroxide, for example, sodium perborate salts, but also inorganic salts as Auxiliary components, for example sodium sulfate. Suitable organic components can be sufficiently soluble antionic surfactants, for example of the alkylbenzenesulfonate type, or else comparatively short-chain (for example C _12-14 ) -alkyl sulfate salts. Nion surfactant compounds in limited amounts, which in particular associate fatty alcohol residues with oligo-EO residues, are also suitable mixing components for the core material. Compounds of this type are usually at room temperature flowable compo th, which are accordingly mixed only in limited quantities in the Fe ste core material. Soap as a further surfactant compound is a suitable component for the construction of the core material.

Other organic compound components of the carrier grain are For example, co-builder components which are blended with the Main Builder component to train the builder system. typical Examples of these are compounds of the type of trisodium citrates and / or polymeric polycarboxylates, such as sodium salts of Polyacrylic acid or polymethacrylic acid, their copolymers and / or their copolymers with maleic acid.

Other components of the core material can be readily dissolved in water che and / or solubilizing organic components with binder function such as polyethylene glycol and / or its Deri vate who, on their part, have multifunctionality in manufacturing ment of the highly compressed preparation forms of the core material and its redissolution in the aqueous liquor can. The concomitant use of such components with Binderfunk tion already in the production of the compressed Trägerkor This is part of a detail below described particular embodiment of the invention Teaching. For a special definition of suitable mixed components Binder function is referred to the following subchapter related to the binders to be used according to the invention refer to the binding of the coating substance to the carrier grain. But also small components whose use under the ver equally severe conditions of compression of the Trägerma terials is harmless, may be part of the nuclear material be as / carrier grain. For example, here are the be knew brighteners from the field of laundry detergents be Nannt.

In an important embodiment of the teaching according to the invention the following modification is provided: component or even also sole creators of the carrier grain can be selected Recyclables about the type of Waschmittelenzyme relationship be their usual form of preparation today, the Detergent enzymes mixed with excipients included in encasing substances. In adaptation to the ever  conditions of the preparation of the carrier grain can there in also blends with other of the previously named Kompo may be considered for the carrier material, insofar as can be referred to the general expertise. The here be Affected special embodiment brings, inter alia, the fol important advantage: for storage and handling of detergent preparations is known to be the safe Ver conclusion possibly used recyclables on enzymati shear base an important basic requirement to unwanted reeak exclusion of direct contact. The incorporation of enzyma valuable materials in the inner core of the spherical More Stratified material reinforces here on the one hand the corresponding Si on the other hand, the approximation of the Outer shell of the spheres in mixture - Hüllsub punch / binder in the sense of the definition according to the invention - the Homogenization of the spherical material and the preservation of the ho Mixture condition substantially relieved. Because of the Expert known specialties of enzymatic preparations However, it may be appropriate according to the invention, such En zymzusätze the carrier material only in a proportion of individu Provide multi-component grains, while the correspond the finished grains in terms of their physical properties so similar to each other that the homogeneous interference the enzyme-containing components in the enzyme-free Korngut si is ensured. The here on the detergent enzymes Darge presented possible embodiment of the teaching of the invention has understandably general validity. In analog form can select other components, isolated from the immediate ren contact with other valuable components of Waschmittelge mixed into the total detergent, without it to undesirable segregation phenomena and / or to a undesirable impairment of the overall aesthetic image comes.

The production of the granular Kernmateri as carrier grain can be in any of the professional world here  knew manner. Especially suitable for multi-substance Mixed in the carrier grain usual compression method simultaneous and / or subsequent shaping to the individual carrier grain. In that regard, the general expertise to get expelled. For example, here are methods named as the wet granulation in particular under additional Introduction of condensing mechanical energy, the melt zagglomeration, the spray agglomeration in particular rotie render fluidized bed, the Walzenkompaktierung and / or others Compacting. The relevant literature is at For example, refer to the manual W. Pietsch "SIZE ENLARGEMENT BY AGGLOMERATION ", John Wiley & Sons, New York / Salle + Sauerland, Frankfurt a. Main, 1991 and the dar in cited relevant literature.

Of particular importance for the production of the compacted multicomponent carrier grain in the sense of the invention Teach the recycling of materials by means of extrusion and rel ter process, such as processing in the pellet press, in each case connected with subsequent comminution of the Extrudate strands, for example by means of knock granulation and if desired, rounding of the still deformable granules. This today also just for textile detergent formulation in the practice world-wide introduced technology is in the beginning cited EP 0 486 592 and related publications Lich described. Suitable extrudate grains have beispielswei se bulk densities in the range of 600 to 1100 g / l and esp densities in the range of 750 to 1000 g / l. Under Be Considering the teaching of the invention, the composition this obtained by extrusion or similar methods high-density agglomerates sufficiently gelled and water Soluble form, here is an optimal access to the Gewin tion of the core material in the formation of the carrier grain gege ben.  

In a second particularly preferred embodiment of he According to the invention, the carrier grain without use of a Extrusion on the below described way of compacting produced by wet granulation. Again, it succeeds, feintei ligeres good in a predeterminable manner according to the invention indi to build up a vidualized carrier grain. It can by a Plurality of working parameters on the one hand the sufficient Ver seal and spatial shape to the carrier grain, on the other hand but also in the practical use then required Wiederauf be ensured solution in the aqueous liquor.

The marketable pourable and pourable preparations today of detergents and cleaning agents, in particular Textilwaschmit tel, are indeed - compared to the formerly common Leicht powders - by increased bulk densities, but they have usually no uniform particle size, but erfas sen the wide range of particles <0.1 mm to coarser Proportions, for example <1.6 mm. By far the predominant The number of marketable products is the individual part chengröße this powdered agglomerates or Granules predominantly at values <0.8 mm and in particular <0.5 mm to 0.6 mm. The coarse fraction with individual particles size above 0.8 mm and in particular greater than 1 mm is included For example, in the range of 10 to 20 wt .-% of the total good or at even lower values.

Of these forms of offer or the associated Technology of manufacturing today conventional compacted solid starting from free-flowing detergent granules, sees the inventions teaching according to the invention in the embodiment concerned here, as carrier grain, the granules or agglomerate with individual particle sizes equal to / greater than 0.6 mm and ins special equal / greater than 0.8 mm to use. By simple you tion of a primary accumulating rather powdery good can these coarse fractions abge from the residual amount of the dry matter be separated. This separated coarse fraction can then in the  Affected here embodiment of the teaching of the invention take over the function of the carrier grain.

As stated is usually the amount of these coarse shares in the conventionally prepared solid recyclables too low for the species involved. The inventive Teaching accordingly provides in a modification, in one Precursor the coarse-grained fraction - individual particle sizes equal to / greater than 0.5 mm, preferably equal to / greater than 0.6 mm and in particular equal to or greater than 0.8 mm - to be raised to such values, the processing of the entire material then in erfindungsge According to the meaning of the shell-shaped wrapping of the coarse grained Trä gerkorns with the shell substance with the concomitant use of the binder enable. Accordingly, are preferred in such Precursor the suitable as carrier grain individual Kornantei to levels of at least about 40 to 45 percent by weight, and preferably wise amounts of at least 50 wt .-% - wt .-% each be attracted to the entire multicomponent mixture to be processed, raised.

In particular, for the realization of this approach the below-described method of compacting Wet agglomeration under additional entry of compacting mechanical energy proved suitable. This is all Recently in a further preferred embodiment ge pay attention to the training of shear forces during the compacting keep the agglomeration step as low as possible. In this way, unwanted influences can be directed towards later disturbing release delays of the carrier grain switched off become.

In a further embodiment of this pretreatment used the invention already in this stage of the construction of the Trägerkor nes such components with which - after drying of the Trä gerkornes - Binder function for the structural cohesion of the egg ner variety of smaller particles composite carrier grain  due. Suitable binders are also here in particular as well already in cold water soluble inorganic and / or organi components that are included in a preferred embodiment the drying are capable of film formation. In particular is it thus already in this stage of construction the carrier grain around binder of the kind, as in the following in the Connection with the order and the connection of the shell sub punch (s) are described to the preformed carrier grain. in so far can be on these subsequent information to suitable Bin also for the previous construction of the Trä gerkorns be referenced.

The last described embodiment in the training a carrier grain according to the invention thus creates by a Feature combination the sufficiently adherent compaction of Carrier material: On the one hand, the elements of the Wet agglomeration, preferably with additional entry me chanic energy, for further compression of the agglomerate used in fine grain fractions. On the other hand, additional the solidification of this carrier grain in its Gesamtstruk through the use of selected binders with adhesive fabric character increased. For the dry state of the carrier grain or the multi-layered value built thereon Mixture of substances within the meaning of the invention is thus the full radio secured. At the same time, it is also safe represents that in the dissolution of the granular material in the aqueous liquor the desired sufficiently rapid decay of the spherical or pearl agglomerate not only the detachment of the coating substances from the carrier grain by dissolution the particular cold-water-soluble binder favors, in The embodiment described here occurs a corresponding Disintegration help also regarding the constitution of one Variety of smaller proportions of glued carrier grain. It is clear that in this way additional freedom th in the embodiment also just open the carrier grain. So can be - starting from a commercially available fine-grained  Detergent powder or granules with a granulate grain fraction <0.8 mm of about 15 to 20 wt .-% - by Naßgranu For example, in a Lödigemischer with chopper un ter entry of a limited amount of aqueous binder solution and subsequent drying of the coarsened in the grain Ma terials as a primary product granules with significantly raised Content of granular material with particle sizes above 0.8 mm to adjust. Here can - depending on the used Binder Quantity - the corresponding coarser-grained Gutanteil on Values between 50 and 75 wt .-% of the total increase. Becomes now this proportion as separated dry matter as carrier grain for the connection of the finer residual parts of mehrkomponenti used starting material, then it becomes the Überfüh tion of the overall good in the present invention aspired spatial che shape of comparatively large ball or pearl without making unacceptable changes to the Use of the spatially deformed multicomponent mixture in practice washing process.

The enveloping substance and the way it is applied

The enveloping substance can be immediately adherent to the carrier grain be connected. But it is also possible one or more Separating layers between the carrier grain and the enveloping substance provided. This latter case, however, is only then have meaning when talking about the selection and condition the components of the coating substance have special effects when practi intended to trigger a delay in the dissolution of the carrier grain desirable. Only exemplary here is the multi-stage textile laundry with zeitli mentioned in the introductory working stage (s). release layers of the species affected here can also be quite a have practical significance: with a suitable choice of the Interface material, this can be the resolution of Trägerkor favor or be in the aqueous liquor accelerate. This can be valid in particular for such Trägerma  materials which are not free of gel-forming surfactant ver bonds and in the preparation of the carrier material a Lö inhibiting retarded surfactant layer at least in the Au have formed ßenhülle the carrier grain.

Usually, however, the immediate order is the envelope substance to be provided on the carrier grain. The envelope substance can, as already stated, single-layer or more be applied layered. Again, this is usually the case technically more modest order of the single-layer shell sub punch the preferred embodiment.

The coating substance applied to the carrier grain consists of it on the one hand from the in comparison to the carrier grain usually feintei ligeren solid value and optionally excipients, the so if necessary blended flowable value and / or Excipients and the used as agglomeration, in cold water-soluble and at room temperature solid binder. This last component is in a separate essay described in detail below, so that here only on the value and, if appropriate, auxiliary substances of the coating substance received by means of the binder on the carrier grain be solidified shell-shaped.

As solid components of the coating substance, in particular one or more of the following are present: dust and / or fines or for fineness zer smaller portions of the core material; slowly soluble and / or vergelende components in the form of selected 1-substances and / or in the form of preformed multi-substance compounds; usual ingredients, especially small components of washing and cleaning as far as they are compatible with the conditions of compression of the Nuclear material should not be suspended; possibly even in cold water quickly soluble components for rapid Conditioning the wash liquor and / or the Gu to be purified tes in an early phase of the washing process; reactive components  for subsequent reaction with other reactive components of the multicomponent mixture which is stored in the solid material of the corresponding reactive components with sufficient Security should be stored separately. The here darge put different groups for the solid components th the envelope substance are in the following example he purifies. Taking into account the general expertise he give it further lessons for the construction of he Inventive mixtures of suitable materials.

In a first embodiment, the solid components become the shell substance by the mixed material according to the Nuclear material or at least by substantial portions of Core material values formed. The envelope substance distinguishes to disassociate themselves from the nuclear material by the size of the like solid particles. This embodiment may be like previously described, for example, then get meaning, if known mixtures of detergents and cleaners in the inventive spatial shape of the ball or Per le or similar shaped spatial body to be transferred. Textile detergent mixtures are still overflowing today weighing in the form of pourable and free-flowing powder relationship se partial agglomerates offered a very broad grain spectrum of the individual particles. Textile detergent mixtures this In particular, species often contain substantial amounts of congestion ban parts which, in practical use, give rise to unwanted can lead. The simultaneously present Feinantei le - for example, in conditions of elevated air Moisture - the unwanted clumping process of the dry A mixture of valuable substances, for example, the portioning of household detergents with prolonged use of a Waschmit hamper or complicate telpacking. The invention proposed form of the particular spherical Mehr Substance blends with solid and preferably non-sticky Outer surface with simultaneous choice of the individual ball  in the millimeter range excludes obstructions outlined type.

In the embodiment discussed here so example example agglomerated in a conventional manner and in particular special at least partially compressed mixture corresponding Detergents and cleaning agents with a broad grain spectrum of Ein Particles of a particle size fractionating orders be fed. The particles suitable as core material Size is then in the sense of the invention with the dust and Refined fines of the same product. Perhaps incurred coarser fractions can lead to dust and fines crushed and then zurückge in this form in the product be led. The compression of the multicomponent mixture can in any form using method types, the previously for the inventive production of Kernmateri have been listed as / carrier grain.

The teaching of the invention provides in the next embodiment form the use of problem components, for example, only slowly soluble and / or vergelenden components and / or multi-component compounds as a solid content of the encasing substance. Merely by way of example surfactants of the type of fatty alcohol sulfates with, in particular, straight-chain FA radicals, for example the range C _{14-18, may be mentioned here} . He inventive teaching provides here, on the separate position tion of these problem components in the shell substance and the inven tion according to possible selection and predetermination of the individual particle size of these problem components to ensure the sufficiently fine disperse distribution of these shares in the aqueous liquor even if no additional measures the solubilization or gelation restriction are made. In important embodiments, however, it may also be provided here to work up these problem components with the aid of, for example, the type of fatty alcohol-oligoethoxylates to form multi-substance compounds and then to incorporate them into the shell substance in finely dispersed form and separately from further constituents and to store them here. It is clear that here substantial help for the dispersion and dissolution of such problem components can be given by the teaching of the invention.

A next group of possible blend components of the envelope Substance are other common ingredients, especially Small components of detergents and cleaners, the Ar Beitsbedingungen the compression of the core material is not sufficient should be set. Components of this type often fall in Form of the finest solid products. Your training in the Covering substance eliminates otherwise possibly occurring problems. On a special feature in this context is already here received: Respective particular dusty or very finely divided constituents of the multicomponent Wertstoffgemi can be added to the flowable preparation of the binder and dissolved therein, dispersed and / or emulsified and in of this form are registered in the shell substance.

Another example of possible mixing components of Enveloping substance is given when the washing and cleaning procedure should be carried out in several stages. Such an example Game is about when the textile laundry in a timely manner to be planned for an initial phase, for example, among others pH values of the wash liquor should be carried out as the after following main wash. So it may be desirable that Main wash under comparatively more alkaline conditions a pre-wash under weaker alkaline conditions or even in the neutral range or weakly acidic range turn. By suitable choice of appropriate recyclables for Regulation of the pH in the shell substance, if necessary in combination with a delay in the dissolution of the core material, is the broad variation of the working parameter mentioned here possible. Other examples of these gradual exams staltung lie in a prior conditioning of the wash  liquor and / or of the textile material to be cleaned by Mitverwen tion of particularly fast-acting water hardness binders, the release of particularly strong wetting and de-aerating Surfactant levels in the early phase of the washing process and the like chen. Again, the teaching of the invention opens under Be Consideration of general technical knowledge That's an easy way to implement these variants.

Finally, another example of the disconnected situation tion of individual components in the encasing substance: Important can be a spatial separation of selected resources then also be in the solid multicomponent mixture, if potenti All reactive components in the blend are used together but their reaction only in the aqueous phase to be held. A typical example of this is the one Set of bleaching components based on hydrogen peroxide containing salts, such as the type of perborate compounds and / or percarbonate compounds on the one hand, and the simultaneous use of so-called bleach activator based on components in the wash liquor under Zu occurs from H₂O₂ form peracids. The teaching of the invention sees optimized possibilities for the simultaneous installation of these Reactive components to the exclusion of premature Abreaktion in solid matter.

The amount of shell substance is usually low at least about 5 to 10% by weight and preferably at least 12 to 15 Wt .-%, in particular at least about 20 to 25 wt .-% - wt .-% based on the entire multi-substance mixture. If the envelope substance definitely make up more than half of the total mix may, however, in important embodiments thereof it can be assumed that the coating substance has a maximum of about 50% by weight of the multicomponent mixture forms. In specific embodiments For example, corresponding quantity ranges of Shell substance of about 20 to 45 wt .-% and in particular of et  Were 25 to 35 wt .-% proved to be very advantageous - wt .-% as previously defined.

As stated previously, the solid components of Enveloping substance with average particle sizes - determined as sieve pay - used, which are smaller than the middle part size or the individual particle size of the Core material / carrier grain. In this way it is ensured that in the process of coating the core material, the Aus formation of the shell substance in the sense of a shell agglomeration takes place around the carrier core. Suitable mean particles sizes (screening numbers) for the solid components of the Hüllsub are in agreement with the particle sizes of the Ein next carrier grain - especially the following Values: preferably <0.8 mm, preferably <0.6 mm and in particular <0.5 mm. A limitation of the particle size down for these particles of shell substance schei usually out. Even the finest dust particles can Be be part of the encasing substance and / or by means of the flowable Binders are entered into the shell substance. Here is the for the inventive supply form of the multi-component mixture in ball or pearl form characteristic parameters of freedom from dust and fines ver understandable. Both the fines - for example, in übli Washing powders of today's supply form are still in large quantities Percentages present fines about the range of 0.1 to 0.4 mm individual grain size as well as the Staubantei le with an individual particle size below 0.1 mm almost completely as the best part of the shell substance on the according to the invention multi-layer ball or Per le be bound. The nature of the used and in the following discussed Binders allows in practice the rapid replacement of all these shares in the aqueous liquor.  

According to the invention, it is also provided in particular in the Solid components of the coating substance flow at room temperature to absorb eligible recyclables. Examples are here named corresponding liquid Niotensidverbindungen but also Auxiliaries of a completely different kind. One example here is silicone Oils, which are known as foam brake or part of the Foam brake used in Textilwaschmittelabmischungen who the. According to the invention, it may be preferable to give one early spread of such flowable excipients by their Preparation and incorporation in the form of selected Mehrstoffcom to prevent pounds. This way can be about an undesirable Solution delay of the already slowly soluble and / or under Gelling soluble anionic surfactants are counteracted.

The solid and possibly absorbed therein flowable Values and / or auxiliaries from the shell substance are in the finished preparation of the spherical granules in inni mixture with the solid binder at room temperature and especially of this at least for the most part wrapped together. This bond is the envelope Substance particles together preferably so sufficiently stable designed that a significant abrasion of fines under the conditions of transport, storage and use of the kör austerity. On the other hand, it may be before be zugt, the amount of the solid particles of Hüllsub To limit the application of the binder so that at least proportionally in this outer shell but also a mikropo Rough good structure is preserved, requiring rapid penetration promotes the aqueous phase in the shell substance. This in be voted embodiments preferred embodiment of the envelope However, substance is not mandatory.

The order of the finely divided shell substance components on the Surface of the carrier core and its connection thereto and with each other with the concomitant use of the below Bindersubstanz (s) is suitably in the form that  the finely divided components of the encapsulant under Mitverwen tion of a flowable binder phase by granulation relate As agglomeration applied to the carrier grain and be solidified there. Particularly suitable here is the Implementation of this process step in the sense of a melt agglomeration or melt granulation, wherein the on Higher temperatures heated and melted binder than flowable phase is used. Details will be given specified below. The order procedure of Shell substance, however, is not due to this melt agglomeration restricted on or granulation, also other wet procedures are suitable. The enveloping substance can, for example be formed with the use of a binder phase, in aqueous preparations - solutions and / or emulsions - of Binders are used. Here then closes in the Re gel a subsequent drying step to the training of Coating layer on. For details, see below.

The binder used in the formation of the encasing substance

Two important requirements for the binder have already been defined at the outset: The binder should be a component which is solid at room temperature, but should also be soluble in cold water if possible. Furthermore:
As a binder, certain selected inorganic or orgasmic African components or multi-component mixtures can be used, which meet the polyfunctional and initially described importance of this component. Particularly suitable in this context are organic components with softening and / or melting points not below 45 ° C and preferably before at least 60 ° C, with a further preferred lower limit for the softening and / or melting points of the binder substance at least 75 ° C is.

As organic binders, in particular film-forming or ganic components are particularly suitable as such or in admixture with excipients, such as dispersants and / or solubilizers can be used. The as Binder used components can under normal washing and Detergent mixtures an intrinsic function - beispielswei as an alkalizing agent, as a co-builder or as a solution and Dispersing aids - come, but there are also compo nenten in the context of the invention suitable as a binder, the no usual ingredients of detergents and / or cleaning agents are. An inorganic binder component with intrinsic functionality in Detergent and cleaning agent mixture is for example water soluble water glass, as organic binder, which is not normal Function in detergents and cleaning agents, are suitable For example, sugar or sugar-like components.

A particularly suitable class of organic and preferably film-forming binders are water-soluble and / or water-dispersible oligomer and / or polymer compounds of synthetic, semi-synthetic and / or natural origin. The pertinent literature has specifically dealt with water soluble polymer compounds of recent history with reference to the US patent literature in detail. Reference is made in this connection to the book publication Y. Meltzer "WATER SOLUBLE POLYMERS" Developments Since 1978, NOYES DATA CORPORATION, New Jersey, USA (1981). Reference is made in particular to the summary in the chapter Market Survey supra, pages 5 to 15. For the purpose of disclosure, the main classes of water-soluble Polymerverbindun conditions are summarized here, in principle, in the sense of inventions to the invention use as binder component - taking into account general Expertise - can be used:
Acrylamide polymers; Acrylic acid and / or methacrylic acid polymers and copolymers with further, in particular free carboxy-containing components, such as maleic acid; Ethylene oxide polymers or polyethylene glycols and their reaction products te; Polymer compounds based on carbohydrate compounds of the guar gum type and heteropolysaccharides of the gum arabic or gum tragacanth species; Galacto-mannan polymers of the locust bean gum type; water-soluble cellulose derivatives of, for example, the types of alkylcelluloses, hydroxyalkylcelluloses, carboxymethylcelluloses and the like; Poly ethyleneimines; Polyvinyl alcohol and water-soluble vinyl alcohol copolymers; Polyvinylpyrrolidone and starch and water-soluble starch derivatives. The definition of polymer compounds defined herein includes, in all cases, corresponding oligomer compounds of comparatively lower molecular weight, as far as these components fulfill the requirements of the binder and its properties described in the context of the invention disclosure. In this respect too, general knowledge can be referred to.

Particularly suitable cold water soluble and nonetheless at Room temperature solid binder components may be in the range of co-builders of known (meth) acrylic acid polymer compounds or copolymer compounds with, for example, times Be given a single acid. Another particularly suitable area for the selection of binder or binder components in the According to the invention are poly-EO components relationship se corresponding derivatives with reactive and optionally also oleophilic molecular components, as far as the overall structure of the Poly- or oligo-EO derivatives previously defined Basic conditions for the binder met.

As adhesive liquid are basically melts, Emul ions and in particular aqueous solutions and / or emulsions the binder substances and in particular corresponding orga nischer oligomer or polymer compounds, wherein  Here adherent films forming components special importance is due.

In a further embodiment of the invention can via a Control of the cold water solubility of the binder influence on the Release mechanism of the solid spherical Multi-component mixture are taken. For example In principle, very good water-soluble oligo-EO derivatives - about the type of fatty alcohol ethoxylates with 30 or 40 EO units in the molecule - thereby modifi in their dissolving behavior be blended with more hydrophobic in admixture Components - for example, fatty alcohols - are used. While preserving the expert knowledge, here too is the one Determination of cold solubility and solid state in Raumtem temperature or only slightly elevated temperatures. Nevertheless, the co-use of the oleophilic Mi a control of the cold water solubility and so that the total water solubility possible, so here is a further possibility of targeted influencing of Mehrkompo product in its entirety is possible.

Particular importance can be attached to binders, which are from their mole seen in the field of value and auxiliary substance fe for use in detergents and cleaners. A optionally remaining slight stickiness of the up dried binder component in the room temperature can collected in a simple manner by per se known powdering become. This can be considered, for example, with binders on Ba sis come from oligo- or poly-EO compounds.

As mentioned earlier, the flowable binder can its on the one hand also carrier for finely divided solid and / or dissolved value and / or Excipients, which together with the carrier in the Mehrkomponentengut be introduced. On a special feature be expressly referred to in this context: The flowable preparation of the binder can be used as additives  in particular dissolved and / or dispersed auxiliaries for Influencing the visual appearance of the finished goods added and registered in this form in the shell substance become. Examples include dyes, pigments, on brighter and the like. Here, the technical opens up easy to realize possibility, the spherical dry nen Mehrkomponentengemischen a particularly attractive appearance to rent.

Here also opens up the following modification: Shall For example, soluble and / or ultrafine insoluble color substances or pigments for the color finish of the Outer shell of the multi-material balls are used, so can a corresponding last order envelope of the cold water-soluble Binders ensure this equipment of the ball outside. In this way, it is possible, if necessary pronounced visual effects with a minimum of optically perceived to ensure the remedy. For the practical use of Detergent mixtures here is an important modification ge compared to previously customary detergent preparations with a wide range Grain spectrum and fine particle size before.

In this context, let us look at another parameter for the as thetic manifestation and potential acceptance of the Multicomponent mixture received by the invention provided shell structure using the under Lagerbedin tions of solid binder can be varied largely freely: It It is known that a number of ingredients are commercially available Detergents and cleaners and in particular conventional textile detergent blends burdened with unwanted odor notes are. This parameter is disproportionately important the storage of the multicomponent mixture in tightly sealed Packun to. Will the pack after a longer storage period first opened or reopened, so unwanted Ge smell notes in a disproportionate way and to a substantial disturbance of the aesthetic appearance  of the lead. It is accordingly known and customary, fragrance or odorous substances the finished Mehrkomponentengemi in order to avoid any unwanted To mask odor notes. By the teaching of the invention individual encapsulation ultimately of all components of the Multi-substance mixture with the at room temperature and under übli The storage conditions for solid binders can be a bit too At least substantial reduction of this problem reaches who the. Regardless, the teaching of the invention includes the Mit However, use of fragrances or odors on. From the previously said but it is understandable that Here is another important advantage of the invention Derived structure of the multi-component mixture, the for the practical acceptance may be of crucial importance.

In the dry material constructed according to the invention is the respective Amount of binder to be used inter alia by the Mi ratio of core material and shell substance mitbe Right. Nevertheless, limited quantities are usually sufficient Binder substance, the shell agglomeration of the enveloping substances on the carrier grain. Accordingly, the lie Binder contents in the dry valuable material according to the invention usually at most about 15 to 20 wt .-% and preferably at not more than 10% by weight, in each case be counts as a solid and based on the sum of Kernma material and shell substance. In particularly important Ausführungsfor Again, significantly lower levels of binder in the dry well planned. Exceed the amounts of this substance here generally not values of 5 to 6 wt .-%. You can for example, in the range of about 0.5 to 4 wt .-% - % By weight as defined above. It has been shown that in the Encapsulation of preformed carrier based on extrudate granules with the shell substance in weight ratios of about 2/3 Trä grain on 1/3 shell substance, the peel agglomeration with a Binder melt already with amounts of the binder in the range of about 1 to 3 wt .-% is to be realized. The corresponding ball  shaped solid products are characterized by perfect dust freedom with uniform spherical shape with high abrasion resistance and yet excellent flushability and solubility in the cold or moderately heated wash liquor. more Leading information can be found in the following Be description of the preferred manufacturing processes for the Sphere converted converted multi-component material in the sense the teaching of the invention.

The coarse-grained and especially perlenför invention mig formed solid multicomponent mixtures

The teaching according to the invention creates the possibility of offering of the mixtures of substances concerned put in the realization of all desired self previously difficult or restricted access Lich: The dry multicomponent mixtures are in the form of rounded coarse grains, especially in ball relationship Wise pearl shape with practically arbitrary individual Grain size before. The balls as such, but also their mix gen, characterized by high bulk densities with good Fe Stability of the spherical material opposite the Beanspru transport, application and the like. simultaneously connected with it but the desired good and in particular rapid solubility and / or flushability on entry the still cold aqueous liquor. The dispersion of problem components, such as forgiving shares, in the wash fleet is controllable adjustable. The teaching of the invention allows the combination of all detergent components in the essentially freely determinable mixing ratios in each case in just one grain, but it is also possible, different composite spherical agglomerates in such a way agree that unwanted segregations during storage and Transport does not occur. By suitable shell construction we at least one part of the total coarse grained Good is the realization of the step-by-step washing  process is easy to realize. The coarse-grained solid More component mixture is free from predeterminable extent Dust and fines and thus controllable free of value substance proportions <0.5 mm and in particular <0.4 to 0.2 mm.

The dry coarse-material mixtures can consist of spheres with a very small variation of the individual Ku be composed on the other side, it is on the other side possible targeted balls of different individual through to mix it down without any practical storage, Transport and application to fear demixing are.

Individual ball diameter in the sense of the invention Teaching are preferably at values of at least 0.5 mm and especially at values of at least 0.6 or 0.7 mm. Beson Preferred are coarse balls with diameters of Einzelku gel of at least 0.8 to 1 mm. Upper limits for the ball size can be chosen practically freely and are for example in the range of a few millimeters, in particular up to about 5 mm. Further preferred upper limits are 3 to 4 mm and ins special at values of about 2 mm. Particularly suitable preparation che for the ball or pearl shape in the sense of he According to the invention, the following are: 0.5 to 5 mm before zugt 0.8 to 3 mm and in particular 1 to 2 mm.

The flowability of the spherical material is convenient Any length of storage and also under such storage Conditions under which fine-grained rel example, powdery mixtures of the type in question here lead to caking or sticking. Belästi Conditions due to powdery components are excluded. The Äs Thetics of the spherical outer surface - for example, by color or closed shell structure - is freely adjustable. Gleichzei There is practical freedom in choice or Va  riation of the selection and composition of the components of the Multicomponent mixture.

The preparation of the invention agglomerated relationship granulated multi-layered preparations in spherical form

To apply the order of the coating substance to the carrier grain zende technology falls into the area of shell agglomeration or shell aggregation. In this context can Again, reference is made to the well-known knowledge of in Booklet published and previously cited publication W. Pietsch a.a.O., "SIZE ENLARGEMENT BY AGGLOMERATION".

Generalizing, the appropriate manufacturing processes are there characterized in that the core material in the form of a preformed carrier grain with the finely divided Good of Hüllsub punch in the presence of the binder in a flowable preparation form enveloping agglomerated or granulated and the bin which solidifies. The possible in principle and erfindungsge according to preferred ways of producing the Kernmateri as / Trägerkorns are already in the corresponding subchapter already shown. This information is referenced here. As fluent capable binder phase are on the one hand in particular aqueous Zube preparations of binder substances suitable, in particular insbesonde re solutions and / or emulsions are considered, especially but preferably the use of the binder as a flowable Melt.

In a known manner, the two can speak here NEN process types are performed in the form that the flowable preparation of the binder in the agglomerated or to be granulated Good is sprayed, wherein at the same time core material and the finely divided solid particles added to the cladding substance of the agglomeration zone and here preferably be sufficiently moved. Coating the carrier grains can be in a conventional manner in Ver  rounder, in other mixing devices but also in the vertebrae perform a shift. For example, the core material in a mixer with the sticky flow phase of the binder be sprayed. The finer particles compared to the core material stick to the surface of the core material that is rolling becomes firm, and there form the desired cup cladding. Other suitable devices are Verrunder (Spheronizer), Pounding pears, rotary drums and the vortex already mentioned bed apparatus.

When working with aqueous preparations of the binder, usually joins this wrapping step one Drying stage on. The use of melting the binder be or mixture of compounds can be added to this additional Ar refrain from employment.

For spraying the flowable binder preparation is in a preferred embodiment, the concomitant use of a propellant gas provided by using multi-fluid nozzles. It can in egg ner special embodiment can be worked as follows: To in addition to the particular registered with a propellant gas Binder melt becomes another hot gas phase - usually hot air - blown into the material to be agglomerated. Possible Thus, the short-term attitude and optimization of the Mi kroklimas in the area of solid surfaces and thus the Op trimming and spread of the binder melt the surfaces to be brought into adhesive contact with each other. These Coating the carrier grain with a sprayed flowable Binder, in particular a corresponding binder melt can 1-stage or multi-stage. Geeig net is here, for example, a gradual treatment in on successive roto-coaters.

The temperature control, especially in the solid material in the frame Melt agglomeration is largely due to the tempera ture-sensitivity of the value to be brought into contact with each other  substances or recyclables. In general NEN, the temperature of the solid material is maximum in the range up to 45 or 60 ° C and thus at most in the area of melting held the temperature of the binder. Taking into account the high Sensitivity of at least selected components of the festival However, it is good material in preferred embodiments of the Invention provided, the solid feed approximately at room Tempe temperature or only slightly elevated temperatures and with the setting of the microclimate on a blown Hot gas phase the order and spread of the binder on the To ensure solid surfaces without becoming a substan material increase of the Guttemperatur to come.

In the following, general information on recyclables and Mixtures of valuable substances, which are part of the inventions according to the invention teaching in the carrier material and / or in the Hüllsub can be used.

The content of surfactants including soaps be Overall, preferably 15 to 40 wt .-% and in particular 18 to 30 wt .-%.

As surfactants come here - especially in the carrier grain - both anionic surfactants and anionic and nonionic together niche surfactants into consideration.

As surfactants of the sulfonate type are preferably C₉-C₁₃- Alkyl benzene sulfonates, olefin sulfonates, d. H. Mixtures of alkene and Hydroxyalkansulfonaten and disulfonates, as they are in For example, from C₁₂-C₁₈ monoolefins with end or innenständi ger double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of Sulfonierungsprodukte receives into consideration. Are also suitable Alkanesulfonates, for example, from C₁₂-C₁₈ alkanes Sulfochlorination or sulfoxidation followed by Hy  drolyse or neutralization can be recovered. Furthermore suitable are also the esters of p-sulfo fatty acids (ester sulfonates), z. B. the μ-sulfonated methyl esters of hydrogenated coconut, Palmkernel or tallow fatty acids, as well as their Disalts. So come also sulfated Fettsäureglycerinester into consideration. Under fat acid glycerine esters are the mono-, di- and triesters and de Understand mixtures as they are produced by Esterification of a monoglycerine with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol Glycerol can be obtained. Preferred sulfated fat acid glycerol esters are the sulfonation of saturated th fatty acids having 6 to 22 carbon atoms, for example of caproic acid, caprylic acid, capric acid, myristic acid, lau rinsäure, palmitic acid, stearic acid or behenic acid. The Sul fierprodukte represent a complex mixture, the mono-, di- and Triglyceride sulfonates with μ-stable and / or internal contains a th sulphonic acid grouping. Form as by-products sulfonated fatty acid salts, glyceride sulfates, glycerol fate, glycerin and soaps. If one goes in the sulfation of ge saturated fatty acids or hydrogenated fatty acid glycerin The proportion of μ-sulfonated Depending on the procedure, fatty acid disalts may well be up to about 60 wt .-% amount.

As alk (en) ylsulfate are the alkali and especially the Sodium salts of sulfuric acid half esters of C₁₂-C₁₈-Fettal for example, coconut fatty alcohol, tallow fatty alcohol, Lauryl, myristyl, cetyl or stearyl alcohol or the C₁₀-C₂₀-oxo alcohols and those half-esters of secondary alcohols this chain length is preferred. Further preferred Alk (en) ylsulfates of said chain length, which have a syn thetic petrochemical-based straight kettles Alkyl radical containing an analogous degradation behavior like the adequate compounds based on fat chemistry raw materials. From washing technical interest are C₁₆-C₁₈-  Alk (en) ylsulfate particularly preferred. It can also be used by particular advantage and especially for machine detergents be advantageous, C₁₆-C₁₈-alk (en) ylsulfate in combination with lower melting anionic surfactants and in particular with sol anionic surfactants having a lower Krafft point sen and at relatively low washing temperatures of example wise room temperature to 40 ° C a low crystallisati show a tendency to use. In a preferred embodiment In accordance with the invention, the agents therefore contain mixtures from short-chain and long-chain fatty alkyl sulfates, preferably wise mixtures of C₁₂-C₁₄-Fettalkylsulfaten or C₁₂-C₁₈-fat alkyl sulfates with C₁₆-C₁₈-Fettalkylsulfaten or C₁₂-C₁₆-fat alkyl sulfates with C₁₆-C₁₈ fatty alkyl sulfates. In a white However, not only ge ge embodiment of the invention saturated alkyl sulfates, but also unsaturated alkenyl sulfates having an alkenyl chain length of preferably C₁₆ to C₂₂ set. In particular, mixtures of saturated, predominantly consisting of C₁₆ sulfated fatty alcohols and unsaturated, consisting mainly of C₁₈ sulfonated Fet preferred are talc, for example those which differ from fe or liquid fatty alcohol mixtures of the HD-Ocenol® type (Commercial product of the applicant). Ge are Weight ratios of alkyl sulfates to alkenyl sulfates of 10: 1 to 1: 2 and especially from about 5: 1 to 1: 1 is preferred.

Also 2,3-alkyl sulfates, which, for example, according to the US Patent 3,234,258 or 5,075,041 and as commercial products of Shell Oil Company under the name DAN® can be obtained are suitable anionic surfactants.

Also, the sulfuric acid monoesters of with 1 to 6 moles of ethylene oxide ethoxylated straight or branched C₇-C₂₁ alcohols, such as 2-methyl-branched C₉-C₁₁ alcohols with an average of 3.5 Mol of ethylene oxide (EO) or C₁₂-C₁₈ fatty alcohols containing 1 to 4 EO, are suitable. They are used in detergents because of their high  Foaming behavior only in relatively small amounts, for example in amounts of 1 to 5 wt .-%, used.

Preferred anionic surfactants are also the salts of alkylsulfobern also known as sulfosuccinates or as sulfosurfers are called stearic acid esters and the monoesters and / or Diesters of sulfosuccinic acid with alcohols, preferably Fatty alcohols and in particular ethoxylated fatty alcohols put. Preferred sulfosuccinates contain C₈- to C₁₈-fat alcohol radicals or mixtures of these. In particular be Preferred sulfosuccinates contain a fatty alcohol residue, the is derived from ethoxylated fatty alcohols, the be seeks to represent nonionic surfactants (see description below). Again, sulfosuccinates, their fatty alcohol Residues of ethoxylated fatty alcohols with concentrated Ho derived mologen distribution, particularly preferred. It is the same also possible, alk (en) ylsuccinic acid with preferably 8 to 18 Carbon atoms in the alk (en) ylkette or their salts einzu put.

However, preferred anionic surfactants are alkylbenzenesulfonates and / or both straight-chain 41327 00070 552 001000280000000200012000285914121600040 0002019547457 00004 41208e and branched alkyl sulfates.

In addition to the anionic surfactants, soaps occur preferably in amounts of 0.1 to 5 wt .-%, based on the ge total funds, into consideration. Suitable are, for example, sown fatty acid soaps, such as the salts of lauric acid, myristin acid, palmitic acid, stearic acid, hydrogenated erucic acid and Behenic acid and in particular from natural fatty acids, eg. B. Coconut, palm kernel or tallow fatty acids, derived soap mixtures cal.

The anionic surfactants and soaps may be in the form of their Natri um-, potassium or ammonium salts and as soluble salts orga nischer bases, such as mono-, di- or triethanolamine, are present.  

Preferably, the anionic surfactants are in the form of their Na trium- or potassium salts, in particular in the form of the sodium salts in front.

As nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols preferably having 8 to 18 C atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used in which the alcohol radical linear or preferably in the 2-position methylver may be branched or linear and methyl-branched radicals in Ge May contain mixed, as they usually in oxo alcohol present. In particular, however, are alcohol ethoxylates with linear residues of alcohols of native origin 12 to 18 C atoms, z. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol before Trains t. Among the preferred ethoxylated alcohols include For example, C₁₂-C₁₄ alcohols with 3 EO or 4 EO, C₉-C₁₁-Al alcohols with 7 EO, C₁₃-C₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C₁₂-C₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures from these, such as mixtures of C₁₂-C₁₄-alcohol with 3 EO and C₁₂-C₁₈-alcohol with 5 EO. The specified degrees of ethoxylation represent statistical averages that are appropriate for a particular Product can be a whole or a fractional number. Be preferred alcohol ethoxylates have a restricted Homologenver division (narrow range ethoxylates, NRE). In addition to the Non-ionic surfactants may also contain fatty alcohols with more be used as 12 EO. Examples are tallow fat kohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, as other nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used 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 represents 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 before x is 1.2 to 1.4.

Another class of preferred nonionic Ten side, either as the sole nonionic surfactant or in Combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or Alkylglykosi used, are alkoxylated, preferably ethoxy lated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, In particular, fatty acid methyl esters, as described for example in Japanese Patent Application JP 58/217598 or preferably according to the method described in the international patent message WO-A-90/13533 described who made the.

Also nonionic surfactants of the type of amine oxides, beispielswei N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-di hydroxyethylamine oxide, and the fatty acid alkanolamide be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of Formula (I),

in the R²CO for an aliphatic acyl radical having 6 to 22 Koh lenstoffatomen, R³ is hydrogen, an alkyl or Hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] for ei  NEN linear or branched polyhydroxyalkyl having 3 to 10 Carbon atoms and 3 to 10 hydroxyl groups. Both Polyhydroxy fatty acid amides are known substances, usually by reductive amination of a redu ornamental sugar with ammonia, an alkylamine or an Al kanolamine and subsequent acylation with a fatty acid, ei a fatty acid alkyl ester or a fatty acid chloride can be. Preferably, the poly is derived hydroxy fatty acid amides of reducing sugars with 5 or 6 Carbon atoms, in particular from the glucose.

As already shown above, the invention covers the Ausfüh approximately form that the composition of the carrier material on the one hand and the shell substance (s) are identical or practically the same and differ only by the particle sizes of the present in the respective material content solid particles. In important and preferred embodiments, however, there are certainly differences in the composition of the valuable substances or mixtures of useful substances - on the one hand in the carrier grain, on the other hand in the shell substance - before. For example, here is the following:
In a preferred embodiment of the invention, the granular agents comprise an extrudate-based carrier grain, the proportion of the extruded component (s) being from 50 to 80% by weight, based on the total agent. It is further preferred that this extruded component contains surfactants, wherein the content of the extruded component of surfactants is not more than 14 wt .-% and preferably 6 to 13 wt .-%, based on the extruded component. In a further preferred embodiment of the invention, the agents contain surfactant-containing extruded carrier components in the amounts that thereby 0.5 to 10 wt .-%, based on the total agent, of surfactants are provided.

The extruded components can be after each of the be knew procedures were produced. Preference is ever here but a method according to the teaching of the European patent EP-B-0 486 592 or the teaching of the international patent application WO-A-94 / 09,111th The size of the preferred, nearly spherical Carrier extrudates is advantageously between 0.8 and 2 mm.

The shell substance (s) contains anionic surfactants or anionic and nonionic surfactants preferably in amounts of from 30 to 95 Wt .-%, based on the shell substance. In particular, it may be It is preferable that the encapsulant contain anionic surfactants, but is free of nonionic surfactants. Advantageously as anionic surfactants alkylbenzenesulfonates and / or straight-chain and / or branched alkyl sulfates used. Not extruded granular and surfactant-containing components are there preferably contained in the amounts in the agents through them 2 to 30% by weight, in particular 5 to 25% by weight, each because of the total amount of surfactants available be presented.

In a further preferred embodiment of the invention Surfactant-containing extruded carrier components and surfactant containing non-extruded coating substances, wherein the Weight ratio of surfactant-containing extruded component: not extruded surfactant-containing component 6: 1 to 2: 1 and in particular 5: 1 to 3: 1.

The non-extruded components, especially the tensidhal Components can be determined by any of the Ver drive, for example by spray drying, superheated steam drying, spray neutralization or granulation have been. In particular, anionic surfactant-containing com preferred components obtained by spray neutralization according to the äl German Patent Application P 44 25 968.9 or by Granu  lation and possibly simultaneous drying in a fluidized bed according to the teaching of international applications WO-A-93/04162 and WO-A-94/18303. The particle size distribution of non-extruded tenside-containing recyclables - also in the form of granules - should the previously specified claim ent speak: At least on average smaller than the carrier grain to to ensure its serving. Especially after the lesson WO-A-93/04162, for example, granules in the Fluidized bed of almost any grain size and grain sizes distribution. The same applies to the grain size distribution of other granular components, for example an enzyme granules, a foam inhibitor granules, a Bleach activator granules for their incorporation into the shell substance.

Enzymes are those from the class of proteases, lipases or lipolytic enzymes, amylases, cellulases or their mixtures in question. Especially suitable are from Bak strains or fungi, such as Bacillus subtilis, Bacillus li cheniformis, Streptomyces griseus and Humicola insolens won nene enzymatic agents. Preferably, proteases are from Subtilisin type and in particular proteases derived from Bacillus lentus are used. These are enzyme mixtures, for example from protease and amylase or protease and lipa se or lipolytic enzymes or protease and Cellu lase or from cellulase and lipase or lipolytic acting Enzymes or protease, amylase and lipase or lipolytic acting enzymes or protease, lipase or lipolytic we kenden enzymes and cellulase, but in particular protease and / or Lipase-containing mixtures or mixtures with lipoly table-acting enzymes of particular interest. examples for Such lipolytic enzymes are the known cuti noses. Peroxidases or oxidases have also been found in some Cases proved to be suitable. The enzymes are preferably on Carriers adsorbed and / or in coating substances bedded to protect them against premature decomposition. The  Proportion of enzymes, enzyme mixtures or enzyme granules can for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-% amount.

When used in machine washing it can be beneficial be added to the means conventional foam inhibitors. When Foam inhibitors are, for example, soaps of natural or synthetic origin containing a high proportion of C₁₈-C₂₄-fat have acids. Suitable non-surfactant foam inhibitor gates are, for example organopolysiloxanes and mixtures thereof with microfine, possibly silanized silica and paraffins, Waxes, microcrystalline waxes and their mixtures with silanes ter silica or bistearyl ethylene diamide. With advantages who which also mixtures of different foam inhibitors verwen det, z. As those of silicones, paraffins or waxes. before Preferably, the foam inhibitors, in particular silicone and / or Paraffin-containing foam inhibitors, to a granular, bound in water or dispersible carrier substance. In particular, mixtures of paraffins and Bi are stearyl-ethylene-diamides and mixtures of paraffins and sili Konen on inorganic carriers preferred. Granules which Blends of paraffins and silicones in weight ratio from 1: 1 to 3: 1, are particularly preferred.

When washing at temperatures of 60 ° C and below one To achieve improved bleaching action, bleach activators can be used be incorporated into the preparations. Examples of this are with H₂O₂ organic peracids forming N-acyl or O-acyl compounds, preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, also carboxylic acid anhydrides and Esters of polyols such as glucose pentaacetate. Other well-known Bleach activators are acetylated mixtures of sorbitol and Mannitol, as described, for example, in the European patent application EP-A-0 525 239. Especially before ferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine  (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN). The Ge halt the bleach-containing agent is due to bleach activators in the usual range. In particular, the bleaching agents become tors in the inventive agents in the amounts has the means 1 to 10 wt .-% and preferably 3 to 8 % By weight, based in each case on the total agent, of bleaching acti vator included.

Other ingredients of the compositions of the invention are present preferably inorganic and organic builders, Bleaching agents, substances which are the oil and grease washable influence positively, graying inhibitors, given if substances, the solubility and the dissolution rate of the individual granular components and / or the ge improve velvet remedies, fabric softening fabrics, optical Brightener, dyes and fragrances as well as alkaline and / or new tral salts in the form of their sodium and / or potassium salts.

As the inorganic builder substance, for example, is suitable fine crystalline, synthetic and bound water enthal detergent grade zeolite. Are suitable in particular zeolite A and / or P and optionally zeolite X and mixtures from A, X and / or P. The zeolite can be spray-dried Powder or even as undried, from their preparation yet moist, stabilized suspension are used. For the If the zeolite is used as a suspension, the se minor additions of nonionic surfactants as Stabili contain, for example, 1 to 3 wt .-%, based on Zeolite, ethoxylated C₁₂-C₁₈ fatty alcohols with 2 to 5 Ethylene oxide groups, C₁₂-C₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable Zeo Lithe have an average particle size of less than 10 microns (Volume distribution, measurement method: Coulter Counter) on and ent preferably hold 18 to 22 wt .-%, in particular 20 to 22  Wt .-% of bound water. Zeolites can be found both in the ex truded components as well as in the non-extruded Kom be included.

Suitable substitutes or partial substitutes for phosphates and Zeo lithe are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} · yH₂O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number of 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline crystalline layer 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 is 2 or 3. In particular, both β- and d-sodium disilicates Na₂Si₂O₅ · yH₂O are preferred, wherein β-sodium disilicates can be obtained for example by the method described in International Patent Application WO-A-91/08171. Crystalline layered sodium silicates may be included in both the extruded and non-extruded components.

Also amorphous silicates, so-called X-ray amorphous silicates, wel In X-ray diffraction experiments, no sharp X-ray reflections were observed xe, as they are typical for crystalline substances, but at most one or more maxima of the scattered Röntgen radiation of a width of several degrees of Having diffraction angle, secondary washing ability can besit zen and be used as builders. It can even lead to very good builder properties, if the sili fuzzy or fuzzy particles in electron diffraction experiments even deliver sharp diffraction maxima. This is so interpre that the products size 10 microcrystalline areas up to several hundred nm, with values up to max. 50 nm and especially up to max. 20 nm are preferred. Especially preferred are silicates and silicate compounds according to the cold  ren German Patent Application P 44 00 024.3 or silicates and Silicate compounds, for example those that are commercially available Nabion 15® and Britesil® (Akzo-PQ) are available. Particularly preferred are also spray-dried Sodium carbonate-sodium silicate compounds, which in addition Tensi de, in particular anionic surfactants such as alkylbenzenesulfonates or Al Contain kylsulfate including the 2,3-alkyl sulfates Kings NEN. Amorphous silicates and silicate compounds such as those mentioned Silicate carbonate compounds can also be found in carrier grain also be contained in the coating substance.

In addition to the alkali carbonates or instead of Alkalicar Bonates, in particular of the sodium carbonates, may also be bicarbo nate, in particular sodium bicarbonates contained in the agents his. As amorphous silicates are mainly sodium silicate with a molar ratio of Na₂O: SiO₂ from 1: 1 to 1: 4.5, as amorphous silicates with secondary washing power preferably of 1: 2 used up to 1: 3.0. The content of the sodium carbonate and / or sodium bicarbonate is preferably up to 20 Wt .-%, advantageously between 5 and 15 wt .-%. The salary the level of sodium silicate is generally up to 30 Wt .-%, and preferably between 2 and 25 wt .-%.

Useful organic builders are, for example, the preferably used in the form of their sodium salts polycarbon acids, such as citric acid, adipic acid, succinic acid, glutar acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilo triacetic acid (NTA), provided such use of ecologi is not objectionable, as well as blends this. Preferred salts are the salts of the polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids and mixtures of these.

Suitable polymeric polycarboxylates are, for example, the Na triumsalze of polyacrylic acid or polymethacrylic acid, at  For example, those having a molecular weight of 800 to 150 000 (based on acid). Suitable copolymeric polycarboxyls te are in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As be Copolymers of acrylic acid with Mal have particularly suitable proved to be acidic, the 50 to 90 wt .-% of acrylic acid and 50 to 10 wt .-% maleic acid. Your molecular weight, based on free acids, is generally 5000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. Particularly preferred are Ter- and Quadropo polymers, for example those described in DE-A-43 00 772 as Monomeric salts of acrylic acid and maleic acid as well Vinyl alcohol or vinyl alcohol derivatives or according to the DE-C-42 21 381 as monomers salts of acrylic acid and 2-Al kylallylsulfonsäure and sugar derivatives.

Other suitable builder systems are oxidation products of carboxyl-containing polyglucosans and / or their water soluble salts, such as those in the international Patent application WO-A-93/08251 are described or their Production for example in the international patent application WO-A-93/16110.

Likewise, as further preferred builders, the known polyaspartic acids or their salts and derivatives call.

Further suitable builder substances are polyacetals, which by reaction of dialdehydes with polyolcarboxylic acids, which Have 5 to 7 C atoms and at least 3 hydroxyl groups, for example, as in the European patent application EP-A-0 280 223 can be obtained. Preferred polyacet tals are made from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and of polyolefin acids such as gluconic acid and / or glucoheptonic acid.  

The organic builder substances can be used both in the carrier grain as well as in the shell substance, wherein the Ein Set in the carrier grain may be preferred.

Among those serving as bleach, in water H₂O₂ supplying Compounds have the sodium perborate tetrahydrate and the Na triumperborate monohydrate of particular importance. Other useful Bleaching agents are, for example, sodium percarbonate, peroxypy rophosphate, citrate perhydrates and H₂O₂ supplying persaure Salts or peracids, such as perbenzoates, peroxophthalates, dipera zelaic acid or diperdodecanedioic acid. The content of the funds Bleaching agents is preferably 5 to 25 wt .-% and esp especially 10 to 20 wt .-%, wherein advantageously Per borate monohydrate is used. The bleaches can both contained in the carrier grain as well as in the encapsulant of the agent be. It is preferred, perborates on the carrier grain in the agent, while percarbonates preferably be used in the envelope substance.

In addition, the agents may also contain components which the oil and Fettauswaschbarkeit from textiles positively impressed influence. This effect becomes particularly apparent when a textile contaminated, which already before several times with an invented To detergent according to the invention, this oil and fat dissolving Kompo contains, is washed. To the preferred oil and fat Solvent components include, for example, nonionic Cellu loose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and to hydroxypropoxyl groups of 1 to 15 wt .-%, respectively on the nonionic cellulose ethers, as well as those from the state known in the art polymers of phthalic acid and / or the Terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalate and / or polyethylene glycol terephthalates or anionic and / or nonionic modifi  ornamented derivatives of these. These substances can both in the Core as well as contained in the shell, with their content in the shell is preferred.

Grayness inhibitors have the function of removing the fiber to keep dissolved dirt suspended in the liquor and so on Prevent the dirt from rebuilding. These are what serlösliche colloids mostly organic nature suitable, at For example, the water-soluble salts of polymeric carboxylic acids, Glue, gelatin, salts of ether carboxylic acids or ether sulfide acids of starch or cellulose or salts of acids Sulfuric acid esters of cellulose or starch. Also what Serosoluble, acidic groups containing polyamides are for sen purpose suitable. Furthermore, soluble starch prepa can be obtained rate and other than the above-mentioned starch products, z. B. degraded starch, aldehyde levels, etc. , Also polyvinyl pyrrolidone is useful. However, cellulose is preferred ethers, such as carboxymethyl cellulose (Na salt), methyl cellulose, Hydroxyalkyl-cellulose and mixed ethers, such as methyl hydroxyethylcellulose, methylhydroxypropylcellulose, methylcar boxymethylcellulose and mixtures thereof, as well as poly vinylpyrrolidone, for example, in amounts of from 0.1 to 5% by weight, based on the funds used. These substances Kings NEN both in the core and in the shell, but especially also be included in the binder.

The agents may also contain ingredients which the Dissolution rate of the individual components and / or ge increase the total agent. Among the preferred used inventory parts include in particular C₈-C₁₈ alcohols having 10 to 80 mol Ethylene oxide per mole of alcohol, such as tallow fatty alcohol with 30 EO and tallow fatty alcohol with 40 EO, but also fatty alcohols with 14 EO, as well as polyethylene glycols with a relative molecule between 200 and 2000. Other suitable substances who  the international patent application WO-A- 93/0217 6 described.

The agents can be used as optical brightener derivatives of Diamino stilbene disulfonic acid or its alkali metal salts. Suitable z. B. salts of 4,4'-bis (2-anilino-4-morpholino 1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or the like structured compounds which replace the morpholino Group a diethanolamino group, a methylamino group, a Anilino group or a 2-Methoxyethylaminogruppe wear. Wei terhin can brighteners of the type of substituted Diphenylsty ryle be present, eg. As the alkali metal salts of 4,4'-bis (2-sulfo styryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) - diphenyls, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. It is also possible to use mixtures of the abovementioned brighteners the.

As neutral salts, especially sulfates, optionally and especially in detergents also be contained chlorides.

Some fine-grained components can also be used to Expend existing granules, thereby for example adhesive reduce the granularity and the bulk density of the granules to increase individual granules and the entire agent. Suitable such surface modifiers are known in the art known to the art. In addition to other suitable are fine Particulate zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts, for example calcium stearate, esp However, precipitated silicas, mixtures of zeolite and Kie selsäuren or mixtures of zeolite and calcium stearate before Trains t. Interesting results - and possibly even Improvements in the re-dissolvability of agglomerates te in aqueous liquor - have also in the use of Ent foaming component as optionally additional Abpuderungs mediate. Finely divided solid preparations based on  Silicone oil as a component with defoaming effect can in the stored in the outer shell of the granules balls and of an undesirable interaction with already solution-impaired Shielding components of the envelope substance are shielded.

Examples

Using the listed in Table 1 below Recyclable ingredients of a laundry detergent mixture becomes according to the specifications of EP-B 0 486 592 by means of extrusion, Ab Schlaggranulation, rounding and subsequent drying Rohextrudat produced whose particle size distribution - be is true as Siebzahlen-wt .-% - in the following Table 3 is summarized.

The composition of this crude extrudate is as follows:

Composition of raw extrudate Wt .-% Zeolite A 27.1 soda 11.4 Na perborate monohydrate 17.4 Na sulfate 5.1 C₉-C₁₃ alkyl benzene sulfonate 9.6 Tallow fatty alcohol with 5 EO 0.7 C₁₂-C₁₈ fatty alcohol with 7 EO 4.3 Copolymer sodium salt of acrylic acid 7.1 C₁₂-C₁₈ fatty acid soap 1.2 PEG 400 3.0 Sodium silicate (Na₂O: SiO₂ 1: 2.0) 2.1 brighteners 0.4 water 10.1 salts 0.5

The granular raw extrudate is in the subsequent step as carrier material (carrier grain) together with those in Table 2 summarized other valuable and auxiliary substances (shell substance) under Use of binders still identified below in the sense associated with a shell agglomeration. In Table 2 are there in addition, the proportions - in wt .-%, based on  the sum of carrier grain and coating substances - for those in the Agglo specified merationsprozeß used components.

Composition of finished product Wt .-% extrudate 66.8 Granules of 85% by weight of the sodium salts of coconut oil fatty alcohol sulphate and tallow fatty alcohol sulphate in a weight ratio of 1: 1, 12% by weight of sodium sulphate, the remainder unsulphured portions and water; produced by granulation and at the same time drying in the fluidized bed 15.8 Tetraacetylethylenediamine granulate 8.2 Defoamer granules based on a mixture of silicone oil, starch and fatty alcohol 3.64 Soil repellent 2.0 Enzyme mixture 1.56 powdering 1.5 fragrances 0.42

Table 3 below summarizes the particle size distribution - be in accordance with sieving numbers in% by weight - for the raw extrudate (Carrier grain) and the additives (enveloping substances) together. Taking into account the proportions according to Table 2 to the proportion of raw extrudate / carrier grain on the one hand and to additionally used as coating substance mixture components It will be seen that in the vast majority of ge Spherical granules formed the carrier grain by Rohextru Particles of a particle diameter <1.0 mm is formed.

The dissolution behavior of the respective agglomerate balls is determined by means of the "L-test". For this purpose, the respective agglomerate to be analyzed is dissolved in water under the conditions indicated below and the residue is determined gravimetrically. The residue is measured (in% by weight) after a dissolution time of 1.5 minutes under standard conditions and in a second determination of the residue in% by weight after a quenching time of 5.0 minutes. Specifically, this L test applies to carry out:
City water with a water hardness of 16 ° dH ± 2 ° dH is used.

The devices used are defined as follows:
Laboratory stirrer with digital display
Stirring shaft length 350 mm
Propeller mixing head ⌀ 50 mm
Hand wash test sieves 0.2 mm mesh size
usual laboratory device.

The test is carried out in detail as follows:
1000 ml of city water are added to a 2000 ml beaker and the propeller stirring head is inserted approximately 1.5 cm from the beaker bottom. The stirring motor is switched on and at 800 rpm. ± 10 rpm set. Then 8 g of the detergent to be examined are entered and stirred for 90 seconds or 5.0 minutes. The stirrer is removed and cleaned with water. Thereafter, the wash liquor is poured wild through the previously tared sieve and rinsed out the beaker with a little water. The sieve with the residue is dried to constant weight in a drying oven at 40 ° C ± 5 ° C and weighed. It is always worked with a double determination.

The residue value (wt .-%) is calculated as

For larger differences, a triple determination is carried out leads. From the double or triple regulations an average is calculated.

In addition, the dissolution behavior is determined in the so-called bowl test. The execution of this test is carried out as follows:
In a wash bowl made of dark plastic (for example, dark red), 25 g of the test agent are added to 5 l tap water (30 ° C). After 15 seconds, the product is distributed by hand in the bowl. After another 15 seconds, a terry towel is placed in the wash liquor and moved as in a typical hand wash. After 30 seconds, the wall of the bowl is wiped off with the towel. After another 30 seconds of washing, the towel is removed and wrung out.

The wash liquor is decanted from the bowl and the remaining residue after treatment with 5 to 10 ml visu ell graded, mean:
+ impeccable, no identifiable residues
± isolated but recognizable residues that are already disturbing when critically assessed
- Clearly recognizable and disturbing residues in increasing number and amount, agglomerate to lumps.

The following examples 1 to 5 give the details to select the binder according to type and quantity, to the type of each used agglomeration process and to get it NEN characteristics according to the evaluation criteria of the L-test and the Bowl test and the particle size distribution of the agglomerates according to the invention.

To carry out the respective agglomeration processes, the following general information applies:
All mixing components which are to be combined with one another in the agglomeration stage are to be weighed together in accordance with the mixing formulation and introduced together into the selected coating or agglomeration apparatus.

The binder used is also according to the selected recipe - either as a melt or as an aqueous Zu preparation - balanced and filled in the pump template. The Coating or agglomeration apparatus is started and started the spraying at the same time. The flowable Binder preparation is based on the agglomerated content sprayed onsapparatur. The spraying process is within one minutes, preferably in 1 to 2 minutes and at the most completed within 5 minutes. After completion of spraying a short aftermix for about 0.5 to 1 minutes, then the agglomerate is removed. Is for spraying , a melt has been used, so that the process is finished. When using aqueous binder preparations closes from a closing drying step. For this, the removed Ag glomerate in a fluidized bed apparatus by means of hot air from dried about 90 ° C for the period of about 5 minutes, the Ma temperature must not exceed 65 ° C (maximum 70 ° C) stride.  

example 1

As agglomeration device is worked in a mixer, in which the solid material moves and sprayed with the binder phase becomes. The binder liquid phase is a 30% aqueous Zuberei tion of used in laundry detergents as a co-builder and sold under the trade name "SOKALAN" product used (sodium salt of an acrylic acid copolymer). These Aqueous binder preparation is used in an amount of 4% by weight. based on the solid material to be agglomerated - sprayed on. Here, without adding the defoamer to the Ag worked glomeration stage.

Example 2

In a modification of the technology of Example 1 will be the same Recyclable material mixture now in the fluidized bed using a Melt of PEG 4000 subjected to agglomeration as a binder. This solid at room temperature and cold water-soluble bandage agent comes in an amount of 2 wt .-% - based on ag glomerating solids are used.

Example 3

The technical teaching of Example 1 is repeated. The Ent foaming component based on a mixture of silicone oil, However, starch and fatty alcohol are now being added to the formed spherical agglomerate and there by Ein solidified.

Example 4

The teaching of Example 1 is repeated, but here - in deviation from the teaching of example 3 - the defoamer granules based on silicone oil directly to the multi-substance mixture in the Mixer added and mixed with the other components of the Enveloping substance by means of the sprayed binder in Mehrstoffgut bound.  

On the products of Examples 1 to 4 are determined: the ever grain spectrum, the L test values after 1.5 min. and 5.0 Min. As well as the evaluation in the bowl test. The, in each case be agreed values or ratings are in the following Table 4 summarized.

The numerical values for the grain spectrum from Table 4 show - in Ver equal to the screening numbers of Table 3 - the grain size increase and unification with simultaneous almost complete Be Clearing of fine and dust components.

The bowl test in all the batches of Examples 1 to 4 is optimized. The solubility values are also significantly improved or at least sufficient.

The following Examples 5 and 6 are from 2 Handelsproduk market, which is used as a universal laundry detergent in Nowadays usual granule form are sold. The sieve analysis of these two free flowing solid formulations is in the Table 5 below.

Table 5

Sieve analysis of feedstock raw materials

As can be seen from Table 5, in the granules according to Bei play 5 the proportion of coarse granules with particle sizes <0.8 mm already over 50 wt .-%. This product is using egg ner aqueous surfactant solution in Lödige mixer with chopper ago and then dried.

In contrast, the coarse-grained fraction is in the feedstock Example 6 (<0.8 mm) under 20 wt .-%.

Example 5

The powdery pourable and free flowing Textilwaschmittelge mixed trade with its particle size distribution according to the table 5 is using a melt of polyethylene glycol with average molecular weight 4000 (PEG 4000) as binder the Melt agglomeration process in the sense of the invention Subject to teaching. In successive approaches will be included the amount of binder of 1 wt .-% increased to 5 wt .-%.

In all experiments, the cup - shaped agglomeration of the Fine particles under ball education to the coarser cores instead, wherein the mean ball diameter with increasing amount of used binder material also increases. The following Table 6 summarizes the product properties of each manufactured th, at least largely spherical agglomerates in the sense the teaching of the invention on the basis of the Siebzahlverteilung together. In all cases, well-soluble granular Agglo Merate obtained when using the binder in a crowd of 5% by weight, a particle fraction <0.8 mm of about 85% by weight point.  

Table 6

Example 6

The used here UWM commercial product with ver similar finer grain size - see the sieve analysis of Ta belle 5 - is in a first step in a Lödige Mixer with chopper with an aqueous solution of a cobuil for laundry detergents (commercial product "Sokalan" on Copo lymerbasis) sprayed in increasing amounts of this binder, ver seals and then dried. In the following Ta belle 7 are the sieving numbers of each product obtained the assigned to "Sokalan" -based binder amounts. It shows that the grain size with increasing amounts of binder can be shifted upward, nevertheless, is the Grain size still present in a broad distribution.  

Table 7

Commercially available UWM granules in the mixer with chopper nachgranuliert

For further processing, the intermediate product is selected, using 3% by weight of the polymer-based binder has been prepared and a grain fraction <0.8 mm of 55 % By weight.

In a series of subsequent experiments this Einsatzmate rial as previously described in the mixer with different amounts a melt of polyethylene glycol with a medium mole Kulargewicht of 6000 (PEG 6000) sprayed and erfindungsge in the regranulated according to the senses.

Table 8 below shows that here too a scha lenförmiger structure of the fines on the outer surfaces of the grö ßeren particles occurs. All agglomerates are dust-free, the fines content increases as the amount of PEG 6000 binder increases  from. The product is predominantly spherical molded granules formed.

Table 8

Post-granulated commercial UWM granules

Claims (32)

1. Multicomponent pourable and free-flowing detergent and cleaning agent in grobkörnig rounded offer form, especially textile detergent in the form of beads, the additional Lich high density with good solubility even in cold water combines and thereby allows increased freedom in the choice of value and optionally excipients, characterized characterized in that it is formed as abrasion-resistant, free of dust and fines Good of the following grain structure:

• Adhesively compacted core of one or more valuable and / or auxiliary substances which are soluble and / or finely dispersed in aqueous liquor (core material)
• coated with a mixture of equal and / or further values and / or auxiliaries with - based on the diameter of the core material - lower individual particle size (shell substance)
• - Wherein these particles of the coating substance with Mitver use of a soluble in cold water and solid at room temperature organic and / or anorgani's binder together and to the Außenflä surface of the core material are bound (binder).

2. mixed material according to claim 1, characterized in that that the dissolution in the aqueous liquor obstructing, ins special in water access gelbildende and / or only long sam soluble components of multi-component mixtures for little at the most predominant part of the encasing substance  with predeterminable individual particle size of this An parts are. 3. Recyclable mixture according to claims 1 and 2, characterized marked records that its grains at least approximately spherical shape own, whose size (ball diameter) preferably inner half of the following ranges: 0.5 to 5 mm, preferably 0.8 to 3 mm and especially 1 to 2 mm, where it continues may be preferred that within a product batch the spherical good in its entirety substantially same ball size. 4. mixed material according to claims 1 to 3, characterized marked characterized in that the compacted core material is at least 15 to 20 wt .-%, preferably at least 35 to 40 wt .-% and in particular more than 50 wt .-%, makes up - wt .-% each based on the entire multi-substance mixture - during the Amount of shell substance preferably at least 10 to 15% by weight and in particular at least 20 to 25% by weight, is (wt .-% as defined above). 5. Recyclable mixture according to claims 1 to 4, characterized marked records that the compacted core material inside the ball (Carrier grain) in at least the majority of the pourable and free-flowing solids through only one Carrier grain is formed, which in turn one or more be formed component and in particular in last case by means of compression method of a more substance mixture with simultaneous and / or subsequent Shaping to individual carrier grain has been established is. 6. Recyclable mixture according to claims 1 to 5, characterized marked records that the multicomponent carrier grain of Kernma materials via compaction processes such as wet granulation, be preferably with simultaneously compacting entry mechani  shear energy, melt agglomeration, spray agglomeration in in particular rotating fluidized bed, roller compact tion, but especially by extrusion and related ver sealing method - if necessary in each case with one closed shape to the individual carrier grain - has been produced. 7. recyclables mixtures according to claims 1 to 6, characterized marked characterized in that the compressed carrier grain from a Mehr Number of smaller particles with the use of a particular specially constructed in cold water soluble binder is. 8. mixtures of materials according to claims 1 to 7, characterized marked records that the carrier material to at least substanti ellen proportion by water-soluble and / or finely dispersed water-insoluble inorganic and / or organic com Components of conventional detergents and cleaning agents is formed For example, laundry detergent builder and / or Cobuil the alkalizing agent, temperature-stable bleaching agent hydrogen peroxide-based compounds such as perborate compounds - but also - preferably in minor amounts - Ingredients of organic origin, for example, little at least largely gel-free soluble Tensidverbindun gene, in particular corresponding anionic surfactants and / or Nio surfactants, cobuilders, brighteners and the like, inventory Part (s) of the carrier material can be. 9. recyclables mixtures according to claims 1 to 8, characterized marked records that, also washing and cleaning-active enzymes and Enzyme preparations as part of the carrier material be present, wherein it may be preferred that only in ei a minor proportion of the solid spheres enzyme-containing ges carrier material is present in the carrier grain.   10. recyclables mixtures according to claims 1 to 9, characterized marked characterized in that the enveloping substance directly on the carrier grain or indirectly via (a) separating layer (s) adherent with the carrier grain is connected. 11. mixtures of substances according to claims 1 to 10, characterized in that as solid components of Hüllsub punch one or more of the following representatives are present:

• - Dust and / or fines or finely divided crushed parts of the core material
• Slowly soluble and / or forgiving components and / or multi-component compounds
• - Customary components, especially small components, of detergents and cleaners, as far as they should not be exposed to the working conditions of the compression of the core material
• - If necessary, in cold water quickly soluble components for rapid conditioning of the washing fleet and / or the goods to be cleaned
• Reactive components for the subsequent reaction with further reactive constituents of the multicomponent mixture after their dissolution in the aqueous liquor.

12. mixtures of materials according to claims 1 to 11, characterized ge indicates that the solid components of the Hüllsub punch with average particle sizes (screening numbers) <0.8 mm, preferably <0.6 mm and in particular <0.5 on the support material are applied.   13. mixtures of materials according to claims 1 to 12, characterized ge indicates that at room temperature liquid portions of Multi-component mixtures in the core material and / or in the Covering substance are included, it being preferred can, nonionic surfactants - especially from the class the fatty alcohol ethoxylates - for the most part Share with the nuclear material. 14. mixtures of materials according to claims 1 to 13, characterized ge indicates that the enveloping substance is 1-shelled or more coated on the carrier core. 15. mixtures of materials according to claims 1 to 14, characterized ge indicates that the coating substance contains further additives, for example, to influence the visual appearance form of the finished good - for example, dyes, pigmen te, brightener and the like - have been added. 16. mixtures of materials according to claims 1 to 15, characterized ge indicates that the solid at room temperature binder the individual solid components of the shell substance for little most of them are wrapped and connected with each other and this bond of the shell substance particles aneinan which is preferably designed so sufficiently stable that significant abrasion of fines under the conditions of Transport, storage and application of the coarse-grained ready good exits. 17. recyclables according to claims 1 to 16, characterized ge indicates that the enveloping substance using the Bin ders as part of a wet agglomeration or Granulation or melt agglomeration or Granulation applied to the carrier grain and there verfe has been stigt.   18. mixtures of materials according to claims 1 to 17, characterized ge indicates that the binder in amounts of at most about 15 to 20% by weight, preferably not more than 10% by weight Binder contents in the range up to 5 wt .-%, for example 0.5 to 4% by weight, may be preferred - Wt .-% in each case calculated as solid substance based on the Sum of core material and shell substance. 19. Recyclable mixtures according to claims 1 to 18, characterized ge indicates that as a binder in particular film-forming or ganic components with softening and / or melting do not score below 45 ° C, preferably at least 60 ° C and in particular of at least 75 ° C, the also with excipients, such as dispersants and / or Lö may be mixed. 20. Recyclable mixtures according to claims 1 to 19, characterized ge indicates that the binder is water-soluble and / or what water-dispersible oligomer and / or polymer compounds synthetic, semi-synthetic and / or natural ur present. 21. mixtures of materials according to claims 1 to 20, characterized ge indicates that binder or binder mixtures used be at least partially value and / or auxiliary are substances from the field of laundry detergents. 22. mixtures of materials according to claims 1 to 21, characterized ge indicates that the outer shell of the spherical material - ge if necessary with the concomitant use of finely divided Abpude tion aids - in the area of room temperature, essentially Chen is formed tack-free. 23. Process for the preparation of detergents and cleaners according to claims 1 to 22, characterized in that one the core material in the form of a preformed compacted  Carrier grain with the finely divided material of the shell substance in Presence of the binder in a flowable formulation enveloping agglomerated or granulated and the Binder solidified. 24. The method according to claim 23, characterized in that with a particular aqueous preparation of the binder and subsequent drying, but preferably with a Melting of the binder and subsequent cooling of the be stratified good work. 25. Process according to claims 23 and 24, characterized gekennzeich net, that the flowable preparation of the binder in the too Agglomerating or to be granulated Good ver is sprayed, preferably with the concomitant use of a Propellant gas is worked. 26. The method according to claims 23 to 25, characterized net, that in particular when entering a binder melt with the addition of an additional hot gas phase in the Agglomerating Good for the adjustment and optimization of the Microclimates in the area of solid surfaces gearbei tet, wherein preferably the temperature of these addi Chen gas phase above the temperature of the solid material lies. 27. The method according to claims 23 to 26, characterized net, that in a melt agglomeration the temperature of Solid material maximum in the range of 45 to 60 ° C and there with at most, in the range of the melting temperature of the binder but it is preferred with tempera acids of the solid material in the melt agglomeration un to work below the melting temperature of the binder. 28. The method according to claims 23 to 27, characterized gekennzeich net, that a core material is a multicomponent  Carrier grain, which by extrusion of Mehrkomponen mixtures under the influence of elevated pressures - preferably wise pressures up to 200 bar and in particular in the range of 15 to 150 bar - with subsequent granulation and Ver rounding of the particular strand-shaped extrudate, or by adherent compression of the finely divided in approach Multi-component mixture by means of agglomeration / granulation - optionally with the concomitant use of a water-soluble Binders - on carrier grain sizes of at least 0.5 mm, preferably at least 0.6 mm and in particular equal to or greater than 0.8 mm has been produced. 29. Application of the method according to claims 23 to 28 for Transfer of pulverulent and / or fine-grained Mehrkom component mixtures from the field of washing and cleaning (feedstock), especially in the Ange botsform commercial textile heavy duty detergent (Bulk densities above 600 g / l and especially above 700 g / l), in a coarse-grained abrasion-resistant, dust and Fines free good with particular pearl shape. 30. Application of the method according to claim 29, characterized records that in the feed optionally before coarse-grained material (particle size equal / greater 0.5 mm, preferably equal to / greater than 0.8 mm) as Kernmateri al used and with the finer Goodanteil as Hüllsub wrapped with the concomitant use of a binder and / or a sufficient proportion of finely divided good for coarse-grained core material tightly compacted and then with the remaining remainder of the finely divided material wrapped. 31. Application of the method according to claims 29 and 30, since characterized in that in a firmly adhering compression more finely divided good parts to the core material (carrier grain) worked without additional use of shear forces is, wherein the bonding of the finely divided material with  a binder which is also soluble in cold water as far as possible to preserve the respective fine grain structure is preferred in the compressed core material. 32. Application of the method according to claims 29 to 31, since characterized in that feedstocks with Gutantei len in the size range of the carrier grain of at least 45 to 50 wt .-% of the conversion to the spherical rounded Good be subjected in bead form, with required if appropriate proportions of a finer use materials first for adherent compacted carrier grain be worked up.