EP0836641A1 - Granules detergents et nettoyants de masse volumique apparente elevee, exempts de poudre et de fractions fines - Google Patents

Granules detergents et nettoyants de masse volumique apparente elevee, exempts de poudre et de fractions fines

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Publication number
EP0836641A1
EP0836641A1 EP96923951A EP96923951A EP0836641A1 EP 0836641 A1 EP0836641 A1 EP 0836641A1 EP 96923951 A EP96923951 A EP 96923951A EP 96923951 A EP96923951 A EP 96923951A EP 0836641 A1 EP0836641 A1 EP 0836641A1
Authority
EP
European Patent Office
Prior art keywords
binder
carrier
mixtures
components
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP96923951A
Other languages
German (de)
English (en)
Other versions
EP0836641B1 (fr
Inventor
Wilfried Rähse
Norbert Kühne
Dieter Jung
Johann-Friedrich Fues
Peter Sandkühler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Priority claimed from DE19524287A external-priority patent/DE19524287A1/de
Priority claimed from DE1995147457 external-priority patent/DE19547457A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0836641A1 publication Critical patent/EP0836641A1/fr
Application granted granted Critical
Publication of EP0836641B1 publication Critical patent/EP0836641B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules

Definitions

  • the invention relates to improvements in the form of multicomponent, solid, coarse-grained, free-flowing and free-flowing detergents and cleaning agents, in particular textile detergents.
  • the invention seeks to make available means of this type which, in addition to a at least largely uniform spherical or pearl shape, combine high density with good dissolvability even in cold water, are free of dust and fine particles and, in doing so, offer greater freedom in the choice of Allow valuable and auxiliary substances to be used in the multi-component mixture.
  • EP-B-0486 592 describes granular or extruded detergents or cleaning agents with bulk densities above 600 g / l, the anionic and / or nonionic surfactants in amounts of at least 15% by weight and up to about 35% by weight. -% contain. They are produced by a process in which a solid, free-flowing premix containing a plasticizer and / or lubricant is pressed in the form of a strand at high pressures between 25 and 200 bar and the strand after exiting the hole shape by means of a cutting device is cut to the predetermined granule size and rounded. The extrudates produced can subsequently be mixed with other granules, The extrudates produced can subsequently be mixed with other granules, in an advantageous embodiment the proportion of extrudates in the finished washing or cleaning agents is more than 60% by weight.
  • German patent application according to DE 195 19 139 proposes to solve the conflict between the high degree of compression of the mixture of valuable materials, in particular by extrusion, on the one hand and the rapid, in particular gelation-free, dissolvability of this valuable material even in the early phase of a washing process
  • Multicomponent mixtures are provided, of which at least one is extruded and at least one is not extruded.
  • the extruded component (s) should be present in amounts of 30 to 85% by weight, based on the total agent, the surfactant content (including soaps) being 0 at the same time to less than 15% by weight, based on the respective extruded component, in the multicomponent mixture there is at least one non-extruded granular and surfactant-containing component in amounts such that at least 1% by weight, based on the total agent, of surfactants is provided, it being further preferred to provide non-extruded granular and surfactant-containing components in the differently prepared substance mixtures in such quantities that up to 30% by weight and preferably 5 to 25% by weight % based on the total multicomponent mixture of surfactants, the weight ratio of the surfactant-containing extruded component to the non-extruded surfactant-containing granular Component is preferably in the range from 6: 1 to 2: 1, preferably in the range from 5: 1 to 3: 1.
  • the invention has set itself the task of making highly compressed multicomponent mixtures from the field of detergents and cleaning agents, and here in particular from the field of textile detergents, which enable problem-free implementation of the old idea, all components of these known highly complex multicomponent mixtures in each case in just one com to be able to unite.
  • the new, comformed material is said to combine, in a certain sense, the material properties of the high compression and thus correspondingly high bulk densities, which are, at the same time, good dispersibility and solubility - in particular also during the washing-in phase with the tap water which is usually cold in domestic washing machines.
  • the conception according to the invention is not restricted to this.
  • the conception of the technical teaching described in the following is based in particular on the task of being able to offer textile detergents which are highly sensitive in many respects in many respects in a uniform spherical shape which is free of dust and fine fractions and which at the same time fulfills the requirements shown, but at the same time the possibility also opens up further modifying changes in the respective recipes of the multicomponent mixtures without having to make fundamental changes in the desired form of supply of the multicomponent mixture.
  • the teaching according to the invention at the same time wants to make the access to the technical realization of this task so broad that on the basis of the technology available at the respective manufacturer today, the technical realization of the desired idea is possible without substantial changes in equipment.
  • the invention relates in a first embodiment to a multicomponent pourable and free-flowing detergent in coarse-grained form, in particular a multicomponent textile detergent in pearl form, which additionally combines high density with good dissolvability even in cold water and thereby increased freedom in the choice of valuable and optionally auxiliary substances.
  • the teaching according to the invention is characterized in that this new form of the multi-component mixture is designed as an abrasion-resistant material of the following grain structure, free of dust and fine particles:
  • Each grain contains an internally compacted core made of one or more valuable and / or auxiliary substances, which are soluble and / or finely dispersed insoluble in an aqueous liquor - hereinafter also referred to as "Kemmateriar".
  • This core material is encased by a mixture of the same and / or further valuable and / or auxiliary substances, the solids content of which has an individual particle size which is smaller than the diameter of the core material - hereinafter also referred to as “coating substance”.
  • binder that is already soluble and / or dispersible in cold water and solid at room temperature - in the description of the invention, this binder is also referred to as a “binder”.
  • the binder can be of organic and / or inorganic origin.
  • the teaching according to the invention provides in the preferred embodiment that components which hinder dissolution of the compacted spheres in the aqueous liquor, and in particular gel-forming and / or only slowly soluble components of the multicomponent mixtures in the presence of water, constitute at least a predominant part of the coating substance are. According to the invention, these portions are incorporated into the coating substance, each with a predeterminable individual particle size. Their cohesion is ensured here by the binder which is solid at room temperature and the moderately elevated temperatures which occur in practice. If water enters the binder, it will dissolve at the usual cold tap water.
  • the slowly soluble and optionally gelling solid particles which are isolated in the coating substance and separated from one another by the binder disperse in the liquor without coagulating or in any other way impairing the washing-in process and / or the washing process.
  • This process of disintegration of the coating substance into individualized fine particles can be promoted almost as desired by the additional measures described below - for example the use of dispersing and / or auxiliary solvents.
  • solubility of the core material which as a highly compressed material and usually in the respective sphere in the form of only one grain - in hereinafter also referred to as “carrier grain”, are chosen so that impediments to the dissolvability and dispersion of the multicomponent mixture are excluded.
  • any fine-particle to dust-like components can be present and solidified, in particular in the coating substance, which, after their release through the primary step of dissolving the binder, can then perform the sub-task that they are assigned in the course of the washing and cleaning process. It is immediately evident that not only selected individual components are suitable as constituents of the coating substance; in particular, arbitrarily selected and combined multicomponent compounds can be used here, which are separated from neighboring particles in the form of the preferably spherical dry material and thus from an undesired one Interaction are protected. Such fine-particle multicomponent compounds in the coating substance can be coordinated with one another in such a way that predetermined technical effects can take place in an optimized form when and / or after their dissolution in the wash liquor.
  • the compilation of the solid core material - the carrier grain - is likewise variable and selectable in a comparatively broad range within the multicomponent mixtures available here.
  • the selection of the component (s) is controlled here on the one hand by the requirement of a sufficient dissolvability in the course of the washing process - without, for example, triggering difficulties due to gelling formation - on the other hand by superordinate concepts of a multi-stage washing process, for example with regard to the pH value of the washing liquor. and cleaning process.
  • the carrier grain can consist of a specifically selected component, but in particular also of appropriately selected and compressed multicomponent mixtures. Further details can be found in the following details on the teaching according to the invention.
  • the present invention relates to the process for producing the detergents and cleaning agents in the particular spatial form shown here.
  • the process is characterized in that the core material is formed in the form of a pre-formed, firmly compressed carrier core with the finely divided material of the coating substance in the presence of the binder in a flowable preparation form, agglomerating or granulating, enveloping and solidifying the binder.
  • the binder can be used in particular with the use of a solution and / or emulsifying auxiliary.
  • the carrier material or highly compressed carrier comminut in the sense of the definition according to the invention is generally an agglomerate of a large number of smaller primary particles from the area of valuable and / or auxiliary substances, compacted for adhesion, for the subject matter addressed here.
  • the carrier commodity is the basis for the formation of the finished spherical or pearl-shaped offer form of the mixture of recyclable materials free of dust and fine particles. These portions are bound in a predeterminable manner by shell agglomeration on the surface of the carrier dome.
  • the selection of the respective technology for producing the carrier dome is one of the key points of the action according to the invention. Details can be found in the following description of the invention. To summarize here briefly: Extrudates produced using high processing pressures, which have been obtained by knocking off the extrudate strands, by subsequent rounding and usually sufficient drying, can be preferred carrier materials or carrier grains in the sense of the teaching according to the invention.
  • the definition of the carrier grain in the sense of the teaching according to the invention is not restricted to these extrudates.
  • the principles of the action according to the invention for converting powdery and / or fine-grain multicomponent mixtures from the field of detergents and cleaning agents can be used in a coarse-grained, abrasion-resistant material free of dust and fine particles, in particular in the form of beads.
  • the forms of commercial heavy-duty laundry detergents currently on the market with bulk densities above 600 g / l and in particular 700 g / 1 can be converted into the spherical or pearl shape defined according to the invention.
  • a sufficient proportion of the pulverulent, fine-grained multicomponent mixture is converted into a firmly compressed carrier particle, which in the sense of the shell agglomeration according to the invention is then mixed with the remaining proportions of the pulverulent, finely divided valuable material is enveloped.
  • a product free of dust and fine particles is obtained in a rounded spherical or pearl shape with a predeterminable size and density of the individual spheres.
  • the invention in one of its important embodiments, aims to return the spatial shape of a multicomponent washing and cleaning agent preparation in the dry state to the 1-grain.
  • This comformed material should contain all or practically all of the components for the application. Basically, this is intended to implement the principle described, for example, in EP-B-0486 592 cited above.
  • the teaching according to the invention also wants to enable the spherical or cylindrically rounded form of supply of such solid multi-material mixtures as a specific shape.
  • the teaching according to the invention now wants to provide a separation of the valuable and / or auxiliary substances within each individual sphere into a plurality of rooms separated in the dry state.
  • This is initially the inner core, the “core material”, and the “enveloping substance” that surrounds this core.
  • the coating substance can be single-shell or multi-shell, regardless of the number of its individual components.
  • the storage spaces thus created for the multi-material material to be stored in the dry state can be in direct contact with one another, but they can also be additionally separated from one another by separating layers.
  • the concept according to the invention further provides for the shell (s) of the shell substance to be subdivided into a plurality of any number of small individual rooms in which the comparatively finely divided valuable and / or auxiliary substances of the shell substance shell (s) are contactless and are nevertheless stored in a tight package.
  • This is achieved through the invented Conception in accordance with the invention to incorporate the cold-soluble water binder as an additional component in the coating substance (s).
  • the binder component according to the invention is therefore of multifunctional importance. Without claiming to be complete, the following functions are enumerated here: the solidification of the coating substance on the core material and at the same time the finely divided multicomponent mixture of solid valuable and / or auxiliary substances; the separation of the individual components from the shell substance from one another and the separation of the shell substance as a whole from the core material; the release of the coating substances including the surface of the core material upon entry of cold water; the hardening of the outer areas in particular against abrasion under the usual conditions of transport, storage, use and the like; the binder can be selected as part of the formulation of the overall mixture; however, the binder can also become a carrier for dissolving and / or dispersing aids to facilitate the gel-free dissolution of the individual components and the mixture of valuable substances in its entirety.
  • the teaching according to the invention enables the formation of solid multi-substance mixtures which can be predetermined according to the type and size and which each contain the entirety of the multi-substance mixture in one grain. Here they are present in a predeterminable form separately from one another, so that an undesired interaction does not take place at this stage.
  • the controlled or controllable release of the multicomponent mixture of valuable substances in the aqueous liquor is possible. Problems in these mixtures of valuable substances can be stored in the state of a predeterminable fine dispersion and can be offered to the washing and cleaning process in such a way that undesired disabilities are eliminated here.
  • the dry solid material is dust-free and also free of fine particles. A multi-stage textile wash is possible.
  • the invention makes it possible to adjust the visual appearance of the dry grain - in addition to the appealing pearl shape, for example its degree of whiteness or color - in a predetermined manner; All of these effects which can be adjusted in a controlled manner are based on the design required today to provide highly compressed valuable substance preparations, for example in the range from 500 to 1,300 g / l, in particular 600 or 700 to 1,200 g / l, which are available in adapt the selection and composition of your valuable and auxiliary substances to the respective conditions of the washing and cleaning process and / or the constantly changing ideas for optimizing the individually used valuable substances - for example from an ecological point of view.
  • the core material also referred to as “carrier particle” - the shell substance or the components to be used as shell substance and finally the binder / binder for the shell-shaped Wrapping the carrier com.
  • This inner core of the individual grain of the multicomponent mixture according to the invention can in turn be of 1-component or multicomponent design. Since, as a rule, a substantial proportion - preferably the predominant proportion - of the total grain is formed by the carrier grain, its sufficient compression is a contributing element. Bulk densities of at least 450 g / l and in particular of at least 500 to 600 g / l are preferred for the core material. Further preferred lower limits are 650 or 700 g / l.
  • this carrier component is precisely the possibility of forming this carrier component as a single component, for example by means of water-soluble inorganic and / or organic salts such as soda, alkali silicate, alkali salts of polycarboxylic acids, such as trisodium citrate, and the like, and opens the way to high bulk densities in this interior Kugelkem.
  • Upper limit values can be above 1,000 g / l, for example 1,300 to 1,500 g / l or even higher. Nevertheless, the predeterminable water solubility of this core material is adjustable to ensure.
  • the core material makes up at least about 15 to 20% by weight, but preferably at least 1/3 and in particular at least about 35 to 40% by weight of the total mixture.
  • the amount by weight of the core material is at least about 50% by weight of the total mixture, with particular significance being able to be in the range from about 55 to 80 or 90% by weight - based on weight here as before, too the entire multi-component mixture.
  • the core material is 1-component or multi-component and is formed at least substantially by water-soluble and / or finely dispersed water-insoluble inorganic and / or organic components of conventional detergents and cleaners.
  • Corresponding builders and / or cobuilders, alkalizing agents, temperature-stable substances from the field of textile detergents are merely examples here Bleaching agents based on hydrogen peroxide, such as perborate compounds.
  • Further examples are at least largely gelling-free soluble surfactant compounds, in particular corresponding anionic surfactants and / or nonionic surfactants, but also a large number of other customary small components made of laundry detergents, which can be safely exposed to the stresses of a sufficient compression step, for example by extrusion.
  • the carrier comminute in the sense of the invention can be constructed from the group of valuable substances which are provided as components for the extrusion in the German patent application DE 195 19 139 mentioned at the outset and there with non-extruded granular further components of the detergent and cleaning agent mixtures be mixed.
  • the individual components should be soluble in the aqueous phase and / or finely dispersed insoluble.
  • suitable components for the construction of the core material / carrier grain are listed only by way of example, but as an example for the specialist knowledge:
  • inorganic soluble or very finely dispersed insoluble detergent constituents such as main builder components - for example zeolite compounds of the type zeolite A, X and / or P, alkalizing agents 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 anionic surfactants, for example of the alkylbenzenesulfonate type, or also comparatively shorter-chain (for example C 2 -i 4 -) alkyl sulfate salts.
  • Nonionic compounds in limited quantities which in particular combine fatty alcohol residues with oligo-EO residues, are also suitable mixture components for the core material.
  • Compounds of this type are generally flowable components at room temperature and, accordingly, are only mixed into the solid core material in limited amounts. Soap as a further surfactant compound is also a suitable component for the construction of the core material.
  • organic mixture components of the carrier particle are, for example, cobuilder components which, when mixed with the main builder component, form the builder system.
  • cobuilder components which, when mixed with the main builder component, form the builder system.
  • Typical examples of this are compounds of the type of trisodium citrate and / or polymeric polycarboxylates, such as sodium salts of polyacrylic acid or polymethacrylic acid, their copolymers and / or their copolymers with maleic acid.
  • Other constituents of the core material can be readily water-soluble and / or solubilizing organic components with a binder function, such as polyethylene glycol and / or its derivatives, which in turn can be multifunctional in the preparation of the highly compressed preparation forms of the core material and its redissolution in the aqueous liquor .
  • constituent or even sole agent of the carrier particle can be selected valuable substances, for example of the type of detergent enzymes or their currently customary preparation forms, which include the detergent enzymes in admixture with carrier substances contained in coating substances.
  • blends with other of the previously mentioned components for the carrier material can also be considered, in this respect reference can be made to the general specialist knowledge.
  • the particular configuration concerned here has the following important advantages, among other things: for the storage and handling of detergent preparations, it is known that the secure closure of any recyclable materials used on an enzymatic basis is an important basic requirement in order to rule out undesirable reactions in direct contact.
  • the incorporation of enzymatic materials into the inner core of the spherical multilayer material reinforces the corresponding safety aspects on the one hand, and on the other hand the homogenization of the spherical one is achieved by adjusting the outer shell of the spheres present in a mixture - shell substance / binder in the sense of the definition according to the invention Good and the maintenance of the homogeneous mixed state substantially facilitated.
  • the core material / carrier granule in the form of a come can be produced in any manner known to those skilled in the art. Compression processes which are customary in multi-component mixtures in the carrier granule with simultaneous and / or subsequent shaping to the individual carrier granule are particularly suitable. In this respect, reference can be made to the general specialist knowledge. Methods are mentioned here merely by way of example, such as wet granulation, in particular with additional introduction of compacting mechanical energy, melt agglomeration, spray agglomeration in a rotating fluidized bed in particular, roller compaction and / or other compaction methods. Regarding the relevant literature, reference is made, for example, to the W. Pietsch manual "SIZE ENLARGEMENT BY AGGLOMERATION", John Wiley & Sons, New York / Salle + Saueriender, Frankfurt a.Main, 1991 and the relevant literature cited therein.
  • Suitable extrudate grains have, for example, bulk densities in the range from 600 to 1,100 g / l and in particular densities in the range from 750 to 1,000 g / l.
  • the composition of these high-density agglomerates obtained by extrusion or comparable processes is sufficiently gelatin-free and water-soluble, there is an optimal access to the extraction of the core material in the formation of the carrier dome.
  • the carrier com is produced without the use of extrusion in the way described below of compacting wet granulation.
  • a plurality of working parameters can ensure adequate compression and spatial shaping on the one hand, and on the other hand the redissolution in the aqueous liquor then required in practical use.
  • the free-flowing and free-flowing preparations of detergents and cleaners, in particular textile detergents, which are customary on the market today are distinguished by increased bulk densities compared to the light powders which were customary in the past, but they generally do not have a uniform particle size, but cover the wide range of Particles ⁇ 0.1 mm to coarser parts, for example> 1.6 mm.
  • the individual particle size of these powdery agglomerates or granules is predominantly at values of ⁇ 0.8 mm and in particular ⁇ 0.5 mm to 0.6 mm.
  • the coarse fraction with individual particle size above 0.8 mm and in particular greater than 1 mm is, for example, in the range from 10 to 20% by weight of the total good or at even lower values.
  • the teaching according to the invention in the embodiment concerned here provides that the granule or agglomerate fractions with individual particle sizes equal to or greater than 0.6 mm are used as carrier particles and in particular to use equal or greater than 0.8 mm.
  • these coarse fractions can be separated from the remaining amount of the dry substance. This separated coarse fraction can then take on the function of the carrier dome in the embodiment of the teaching according to the invention concerned here.
  • the amount of these coarse fractions in the conventionally produced solid valuable substance preparations of the type concerned here is generally too small.
  • the teaching according to the invention accordingly provides for a modification, in a preliminary stage the coarse-grained fraction - individual particle sizes equal to or greater than 0.5 mm, preferably equal to / greater than 0.6 mm and in particular equal to / greater than 0.8 mm - to be increased to values which then allow processing of the entire material in the sense of the invention in the form of a shell-like covering of the coarse-grained carrier granule with the coating substance using the binder.
  • the individual coma parts suitable as carrier coma are preferred in amounts of at least about 40 to 45% by weight and preferably in amounts of at least 50% by weight, based in each case on the total to be processed Multi-component mixture - raised.
  • the invention already uses components at this stage of the construction of the carrier granule, which - after drying of the carrier granule - have a binder function for structural cohesion of the carrier granule composed of a large number of smaller particles.
  • Suitable binders here are in particular likewise inorganic and / or organic components which are already soluble in cold water and, in a preferred embodiment, are capable of film formation during drying.
  • binders of the type described below in connection with the application and the connection of the coating substance (s) to the preformed carrier com it is a matter of binders of the type described below in connection with the application and the connection of the coating substance (s) to the preformed carrier com.
  • suitable binders for the previous structure of the carrier dome concerned here.
  • the embodiment last described here in the formation of a carrier compres- sion according to the invention thus creates a sufficiently adherent compression of the carrier material / carrier grain through a combination of features: on the one hand, the elements of the wet agglomeration, preferably with additional input of mechanical energy, are used for further compression of the agglomerate used from fine coma parts. On the other hand in addition, the solidification of this carrier granule in its overall structure is increased by the use of selected binders with adhesive character. The full functionality is thus ensured for the dry state of the carrier granule or the multilayer material mixture based thereon in the sense of the invention.
  • the sufficiently rapid disintegration of the spherical or pearl-shaped agglomerate not only promotes the detachment of the coating substances from the carrier by dissolving the, in particular, cold water-soluble binder, in the ge here ⁇ described embodiment, a corresponding disintegration aid also occurs with regard to the constitution of the carrier dome glued together from a large number of smaller portions. It is obvious that this also opens up additional freedom in the design of the carrier base.
  • this portion is now used as a separated dry material as a carrier for the connection of the finer residual parts of the multicomponent starting material, then the transfer of the total material into the spatial shape of the comparatively large ball or pearl desired according to the invention is made possible without this unacceptable changes for the use of the spatially deformed multicomponent mixture in the practical washing process would have to be associated.
  • the coating substance can be bonded directly to the carrier com. However, it is also possible to provide one or more separating layers between the carrier and the casing substance. This last-mentioned case will, however, only be of significance if the selection and nature of the components of the coating substance are intended to trigger special effects in practical use which make a delay in the dissolution of the carrier particle desirable.
  • the multi-stage textile washing with timing of the introductory work stage (s) should be mentioned here only as an example.
  • Separating layers of the type concerned here can also have a completely different practical meaning: If the separating layer material is selected appropriately, this can promote or accelerate the dissolution of the carrier grain in the aqueous liquor. This can be particularly valid for those carrier materials that are not free of gel-forming surfactant compounds and that have formed a gelled surfactant layer that hinders the solution in the manufacture of the carrier material, at least in the outer shell of the carrier.
  • the direct application of the coating substance to the carrier commutation will be provided.
  • the coating substance can be applied in one or more layers.
  • the technically less demanding application of the single-layer coating substance is generally the preferred embodiment.
  • the coating substance applied to the carrier granule consists in turn of the solid value substances and optionally auxiliary substances, which are generally more finely divided than the carrier granule, the flowable valuable substances and / or auxiliary substances to be mixed therewith as well as the agglomeration aid that is soluble in cold water and at room temperature fixed binder.
  • This last component is described in detail in a separate treatise below, so that only the valuable and optionally auxiliary substances of the coating substance are discussed here, which are solidified in shell form by means of the binder on the carrier dome.
  • One or more of the following representatives can in particular be present as solid components of the coating substance: dust and / or fine fractions or parts of the core material comminuted to finely divided; slowly soluble and / or gelling components in the form of selected 1 substances and / or multi-component compounds preformed in fo ⁇ n; usual components, in particular also small components of detergents and cleaning agents, insofar as they are not to be exposed to the working conditions of the compaction of the core material; optionally also quickly soluble components in cold water for the rapid conditioning of the washing liquor and / or the items to be cleaned in an early phase of the washing process; Reactive components for the subsequent reaction with further reactive constituents of the multicomponent mixture, which are to be stored separately from the corresponding reactive constituents with sufficient security in the storage in the solid material.
  • the different groups shown here for the solid components of the Hüilsubstanz are exemplified in the following explained. Taking into account the general specialist knowledge, further teachings result from this for the structure of the mixtures of recyclable materials according to the invention.
  • the solid components of the coating substance are formed by the mixture of resources corresponding to the core material or at least by substantial portions of the core materials.
  • the shell substance differs from the core material in the size of the solid particles to be compared with one another.
  • this embodiment can become important, for example, if mixtures of detergents and cleaning agents known per se are to be converted into the spatial shape according to the invention of the ball or pearl or a similarly shaped spatial body.
  • Textile detergent mixtures are still largely offered today in the form of pourable and free-flowing powders or partial agglomerates, which comprise a very wide range of particles. Textile detergent mixtures of this type in particular frequently contain substantial amounts of dust components which, in practical use, can lead to undesirable nuisance.
  • the fines present at the same time for example under conditions of increased air humidity - promote the undesired clumping process of the dry material mixture, which can, for example, hinder or complicate the portioning of household detergents when a detergent package is used for a long time.
  • the form of supply provided according to the invention of the spherical multi-material mixtures in particular with a solid and preferably non-sticky outer surface with simultaneous selection of the individual ball diameter in the millimeter range excludes disabilities of the type described.
  • a mixture of appropriate detergents and cleaning agents with a broad grain spectrum of the individual particles which is agglomerated in a known manner and in particular at least partially compressed, can be fed to a fractional fractionation according to particle sizes.
  • the particle size suitable as core material is then worked up in the sense of the invention with the dust and fine fractions of the same product. Possibly coarser parts can be crushed into dust and fine parts and then returned to the product in this form.
  • the multicomponent mixture can be compressed in any form using the types of processes which have been enumerated previously for the production of the core material / carrier granulate according to the invention.
  • the teaching according to the invention provides for the use of problem components, for example only slowly soluble and / or gelling components and / or multi-component compounds as a solid component of the coating substance.
  • problem components for example only slowly soluble and / or gelling components and / or multi-component compounds
  • surfactants of the type of fatty alcohol sulfates with, in particular, straight-chain FA residues, for example in the Cnns range, are mentioned here as examples.
  • the teaching according to the invention provides here to ensure the sufficiently finely dispersed distribution of these parts in the aqueous liquor even if none of them are stored separately in the coating substance and the selection and predetermination according to the invention of the individual particle size of these problem parts is possible additional measures for mediating solutions or restricting retaliation are taken.
  • a next group of possible mixture components of the coating substance are further usual components, in particular also micro components of detergents and cleaning agents, which should not be exposed to the working conditions of the compaction of the core material.
  • Components of this type are often obtained in the form of the finest solid products. Their incorporation into the coating substance eliminates any other problems that may arise. A peculiarity in this connection is already discussed here: Corresponding in particular dusty or very finely divided components of the multicomponent mixture of valuable substances can be added to the flowable preparation of the binder and dissolved therein, dispersed and / or emulsified and in this form into the Envelope are registered.
  • Another example of possible mixture components of the coating substance is given when the washing and cleaning process is to be carried out in several stages.
  • An example of this is when the textile washing is to be carried out in an initial phase to be predetermined, for example, under different pH values of the washing liquor than the subsequent main wash cycle. It may be desirable to pre-wash the main wash under comparatively more alkaline conditions upstream under weakly alkaline conditions or even in the neutral range or weakly acidic range.
  • step-by-step configuration lie in a prior conditioning of the wash liquor and / or the textile goods to be cleaned by using particularly quickly effective binders for the water hardness, the release of particularly strongly wetting and deaerating surfactant components in the early phase of the washing process and the like.
  • teaching according to the invention taking into account the general specialist knowledge, opens up the technically particularly simple possibility of realizing these variants.
  • the amount of the coating substance is usually at least about 5 to 10% by weight and preferably at least 12 to 15% by weight, in particular at least about 20 to 25% by weight, based on the overall multicomponent mixture. If the coating substance can also make up more than half of the total mixture, it can nevertheless be assumed in important embodiments that the coating substance forms a maximum of about 50% by weight of the multicomponent mixture. In specific embodiments, for example, corresponding amount ranges of the coating substance of approximately 20 to 45% by weight and in particular approximately 25 to 35% by weight have proven to be very advantageous -% by weight as previously defined. As already stated above, the solid components of the coating substance are used with average particle sizes - determined as sieve numbers - which are smaller than the average particle size or the individual particle size of the core material / carrier grain.
  • Suitable average particle sizes (sieve numbers) for the solid components of the coating substance are - in coordination with the particle sizes of the carrier granules used - in particular the following values: preferably ⁇ than 0.8 mm, preferably ⁇ than 0.6 mm and in particular ⁇ as 0.5 mm.
  • a downward limitation of the particle size for these solid particles of the coating substance is generally ruled out. Even the finest dust particles can be part of the coating substance and / or can be introduced into the coating substance using the flowable binder.
  • fractions of recyclable material which are flowable at room temperature into the solid components of the coating substance.
  • examples here are corresponding liquid nonionic surfactant compounds, but also auxiliaries of a completely different kind.
  • One example here is silicone oils, which are known to be used as a foam brake or as a component of the foam brake in textile detergent mixtures.
  • the solid and optionally flowable valuable and / or auxiliary substances from the coating substance are intimately mixed in the finished preparation form of the spherical granulate in intimate admixture with the binder which is solid at room temperature and in particular at least for the most part encased with one another.
  • This binding of the shell substance particles to one another is preferably designed to be sufficiently stable that a significant abrasion of fine material is eliminated under the conditions of transport, storage and use of the granular material.
  • this preferred embodiment of the coating substance in certain embodiments is not mandatory.
  • the application of the finely divided coating substance components to the surface of the carrier core and their connection thereon and to one another, with the use of the binder substance (s) described below, is expediently carried out in such a way that the fine-particle components of the coating substance pass through with the use of a flowable binder phase Granulation or agglomeration are applied to the carrier com and solidified there. It is particularly suitable here to carry out this process step in the sense of melt agglomeration or melt granulation, the binder heated and melted to higher temperatures being used as the flowable phase. Details of this are given below.
  • the application method of the coating substance is, however, not restricted to this melt agglomeration or granulation; other wet methods are also suitable.
  • the coating substance can be formed, for example, with the use of a binder phase in which aqueous preparations - solutions and / or emulsions - of the binder are used.
  • a subsequent drying step then usually follows the formation of the coating layer. See the details below.
  • the binder used in the formation of the coating substance is the binder used in the formation of the coating substance
  • the binder should be a component that is solid at room temperature, but at the same time should be soluble and / or dispersible in cold water if possible.
  • Certain selected inorganic or organic components or also multicomponent mixtures can be used as binders, which do justice to the polyfunctional and initially described meaning of this component.
  • film-forming organic components can be particularly suitable as organic binders, which can be used as such or as a mixture with auxiliaries, such as dispersants and / or solubilizers.
  • the components used as binders can have their own function in the context of conventional detergents and cleaning agents - for example as alkalizing agents, as cobuilders, as dissolving and dispersing auxiliaries or as surfactant components, but components in the sense of the invention are also suitable as binders which are not conventional constituents of detergents and / or cleaning agents.
  • An inorganic binder component with its own function in the detergent and cleaning agent mixture is, for example, water-soluble water glass.
  • an organic binder which has no normal function in detergents and cleaning agents, sugar or sugar-like components are suitable.
  • a particularly suitable class of organic and preferably film-forming binders or binder components are water-soluble and / or water-dispersible oligomer and / or polymer compounds of synthetic, semisynthetic and / or natural origin.
  • the relevant literature has dealt in particular with water-soluble oligomer and / or polymer compounds from the recent past with reference to the US patent literature.
  • the most important classes of water-soluble polymer compounds are summarized here, which in principle also apply to the use according to the invention as a binder component - taking into account general specialist knowledge - can be used:
  • Acrylamide polymers Acrylic acid and / or methacrylic acid polymers and copolymers with further components containing, in particular, free carboxy groups, such as maleic acid; Ethylene oxide polymers or polyethylene glycols and their reaction products; Polymer compounds based on carbohydrate compounds of the type of guar gum and heteropolysaccharides of the type of gum arabic or gum tragacanth; Galacto-mannan polymers of the Locust Bean Gum type; water-soluble cellulose derivatives, for example of the type of alkyl celluloses, hydroxyalkyl celluloses, carboxymethyl celluloses and the like; Polyethyleneimines; Polyvinyl alcohol and water-soluble vinyl alcohol copolymers; Polyvinylpyrrolidone and starch and water-soluble starch derivatives.
  • free carboxy groups such as maleic acid
  • Ethylene oxide polymers or polyethylene glycols and their reaction products Polymer compounds based on carbohydrate compounds of the type of guar gum and heteropol
  • polymer compounds defined here includes corresponding oligomer compounds of comparatively lower molecular weight in all cases, insofar as these components meet the requirements for the binder and its properties described in the context of the disclosure of the invention. In this respect, too, reference can be made to the general specialist knowledge.
  • binder components which are soluble in cold water and nevertheless solid at room temperature can be present in the region of the (meth) acrylic acid polymer compounds or copolymer compounds known as cobuilders, for example with maleic acid.
  • cobuilders for example with maleic acid.
  • Another particularly suitable area for the selection of binders or binder components in the sense of the invention are poly-EO components and corresponding derivatives with reactive and optionally also oleophilic molecular components, insofar as the overall structure of the poly- or oligo-EO derivative meets the previously defined basic conditions fulfilled for the binder.
  • Suitable adhesives are in principle melts, emulsions or dispersions and solutions, in particular aqueous solutions and / or emulsions of the binder substances, and here in particular corresponding organic oligomer or polymer compounds and / or mixtures thereof with other components, components and Substance mixtures are of particular importance.
  • Binder or binder components which are particularly suitable according to the invention are oligo- and / or poly-EO compounds which, in particular, as melt binders with high cold water solubility can also be used in the solid state.
  • Two classes of these poly-EO-based binder types, which can also be used in a mixture with one another, are particularly suitable here: polyethylene oxides with average molecular weights of at least 1500 to 20,000, preferably corresponding poly-EO compounds in the range from at least about 2500 to 10,000 and in particular the corresponding molecular weight range from 3000 to 8000.
  • Polyethylene oxides of this type melt in the aforementioned temperature range, form adhesive films when cooled and are nevertheless readily and rapidly soluble in cold water even in the solid state.
  • the second class of recyclable material which is particularly suitable for use as a binder is derived from the oligo or poly-EO compounds of the type mentioned above.
  • end group modification in particular etherification and / or esterification with oleophilic radicals, is now provided in at least one end of the poly-EO chain in a manner known per se.
  • poly-EO derivatives of this type are distinguished by an increased dispersing and / or emulsifying action. This can be used to influence the solubility of the binder in cold water.
  • a suitable molecular structure - in particular sufficiently long poly-EO chains - can also be used to adjust the substance class concerned here in its substance parameters, in particular in its melting point, so that they correspond to the requirements according to the invention.
  • Known examples here are, for example, polyethoxylates of fatty alcohols or of alkylphenols with poly-EO residues composed of an average of 20 to 100, in particular 20 to 80, EO units in the molecule. Mixtures of selected representatives in their end groups of unmodified poly-EO compounds and end group-modified EO derivatives of the type mentioned here make it possible to set up optimized combinations of the varied substance parameters of the binder component.
  • the solubility or dispersibility of the binder in cold water by controlling the solubility or dispersibility of the binder in cold water, it is possible to influence the dissolving mechanism of the solid spherical multicomponent mixture according to the invention.
  • very readily water-soluble oligo-EO derivatives - for example of the type of fatty alcohol ethoxylates with 30 or 40 EO units in the molecule - can be modified in their dissolving behavior by mixing them with more hydrophobic components - for example fatty alcohols or surfactant compounds - are used.
  • the setting of the cold solubility and the solid state at room temperature or only slightly increased temperature ensure doors.
  • the use of the oleophilic mixture component makes it possible to control the solubility in cold water and thus the solubility in water as a whole, so that a further possibility of specifically influencing the multicomponent product as a whole is possible here.
  • Binders are particularly important because, in terms of their molecular structure, they fall into the area of valuable and auxiliary substances for use in detergents and cleaning agents. Any remaining slight stickiness of the dried binder component in the region of room temperature can be compensated for in a simple manner by means of a known per se.
  • binders based on oligo- or poly-EO compounds and / or corresponding PO compounds are suitable.
  • individually selected components as such or mixtures of 2 or more valuable and / or auxiliary substances can be used as binders in the sense of the invention, insofar as the individual substance or the substance mixture meets the requirements presented fulfill.
  • mixtures of substances are also suitable which are composed of components which are solid at room temperature and those which are liquid at room temperature, but are then solid in the mixture used at room temperature and only fuse at the sufficiently elevated temperatures.
  • the flowable binder can in turn also be a carrier for finely divided and / or dissolved valuable and / or auxiliary substances which are introduced into the multicomponent material together with the carrier.
  • a special feature in this context is expressly referred to here: in particular, dissolved and / or dispersed auxiliaries can also be added to the flowable preparation of the binder as additives, in order to influence the visual appearance of the finished goods, and be added to the coating substance in this form . Examples include dyes, pigments, brighteners and the like. This opens up the technically easy to implement option of giving the spherical, dry multi-component mixtures a particularly attractive appearance.
  • the following modification also opens up here: If, for example, soluble and / or finely insoluble dyes or pigments are to be used to color the outer shell of the multi-material balls, a corresponding last application shell of the cold water-soluble binder can be used to protect the outer surface of the ball. create. In this way it is possible to ensure strongly pronounced visual effects with a minimum addition of optically perceptible auxiliary material. For the practical use of the detergent mixtures, there is an important modification here compared to previously customary detergent preparations with a broad grain spectrum and fine particle size.
  • the respective amount of the binder to be used is also determined, inter alia, by the mixing ratio of the core material and the coating substance. Nevertheless, generally limited amounts of binder substance are sufficient to ensure the shell agglomeration of the coating substances on the carrier grain. Accordingly, the binder contents in the dry valuable substance preparations according to the invention are usually at most about 15 to 20% by weight and preferably not more than 10% by weight, in each case calculated as the solid substance and based on the sum of core material and shell substance. In particularly important embodiments, significantly lower binder contents are again provided in the dry material. The amounts of this substance generally do not exceed values of 5 to 6 or 7% by weight.
  • the shell agglomeration with a binder melt already with amounts of the binder in the range of about 1 to 3% by weight. -% is to be realized.
  • the corresponding spherical solid products are distinguished by their complete absence of dust with a uniform spherical shape with high abrasion resistance and, nevertheless, excellent washability and solubility in the cold or only moderately heated washing liquor. Further information on this can be found in the following description of the preferred production processes for the multicomponent valuable material converted into a spherical shape in the sense of the teaching according to the invention.
  • the dry multi-substance mixtures lie in the form of rounded coarse grains, in particular in spherical form. or Perienform with practically freely selectable individual grain size.
  • the balls as such, but also their mixtures, are characterized by high bulk densities with good strength of the spherical material in relation to the stresses during transport, use and the like.
  • the desired good and, in particular, rapid solubility and / or flushability is associated with the entry of the still cold aqueous liquor.
  • the dispersion of problem components, for example gelling components, in the wash liquor is controllably adjustable.
  • the teaching according to the invention enables all detergent components to be combined in essentially freely definable mixing ratios in each case in just one grain, but it is also possible to match spherical agglomerates of different compositions in such a way that undesired segregation does not occur during storage and transport.
  • a suitable shell structure of at least a portion of the total coarse-grained material By means of a suitable shell structure of at least a portion of the total coarse-grained material, the gradual process can be realized Washing process easy to implement.
  • the coarse-grained, solid multicomponent mixture is to a predeterminable extent free of dust and fine particles and thus controllably free of valuable substances in the range ⁇ 0.5 mm and in particular in the range ⁇ 0.4 to 0.2 mm and below.
  • the dry, coarse-grained mixtures of valuable substances can be composed of spheres with a very small variation in the individual sphere size, on the other hand it is possible to specifically mix spheres of different individual diameters without fear of separation processes for practical storage, transport and use are.
  • Individual ball diameters in the sense of the teaching according to the invention are preferably at least 0.5 mm and in particular at least 0.6 or 0.7 mm. Coarse balls with diameters of the single ball of at least 0.8 to 1 mm are particularly preferred.
  • 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 in particular values of about 2 mm.
  • Particularly suitable ranges for the spherical or pearl shape in the sense of the teaching according to the invention are the following: 0.5 to 5 mm, preferably 0.8 to 3 mm and in particular 1 to 2 mm.
  • the free-flowing properties of the spherical material are guaranteed for virtually any period of storage and also under conditions under which fine-grained or powdery mixtures of the materials concerned lead to caking or sticking. Annoyances caused by powdery particles are excluded.
  • the aesthetics of the outer surface of the sphere - for example according to color or closed shell structure - can be freely adjusted. At the same time, there is practical freedom in the choice or variation of the selection and composition of the components of the multicomponent mixture.
  • the suitable production processes are characterized in that the core material is agglomerated or granulated in the form of a pre-formed carrier granule with the finely divided material of the coating substance in the presence of the binder in a flowable preparation form and granulated and the binder is solidified.
  • the ways that are possible in principle and preferred in accordance with the invention for producing the core material / carrier core have already been presented in the associated subchapter. Reference is made to this information here.
  • aqueous preparations of the binder substances are particularly suitable, with solutions and / or emulsions being particularly suitable here, but the use of the binder as a flowable melt is particularly preferred.
  • the two types of process mentioned here can be carried out in such a way that the pourable preparation of the binder is sprayed into the material to be agglomerated or granulated, core material and the finely divided solid particles of the coating substance being added to the agglomeration zone at the same time and here preferably be moved sufficiently.
  • the support grains can be coated in a round manner in a manner known per se, in other mixing devices but also in the fluidized bed.
  • the core material is sprayed with the sticky flow phase of the binder in a mixer.
  • the particles, which are finer than the core material stick to the surface of the core material, which is moved in a rolling manner, and form the desired shell covering there.
  • Other suitable devices are rounders (spheronizers), coating pears, rotating drums and the fluidized bed apparatuses already mentioned.
  • this coating step is generally followed by a drying step.
  • the use of melts of the binder or binder mixture can dispense with this additional work step.
  • the procedure can be as follows: in addition to the binder melt introduced in particular with a propellant gas, a further hot gas phase - usually hot air - is blown into the material to be agglomerated.
  • a further hot gas phase usually hot air - is blown into the material to be agglomerated.
  • This coating of the carrier coma with a sprayed flowable binder, in particular a corresponding binder melt can be carried out in one or more stages.
  • a step-by-step treatment in successive roto-coaters is suitable, for example.
  • the temperature control in particular in the solid material in the course of a melting agglomeration, is largely determined by the temperature sensitivity of the materials or parts of materials to be brought into contact with one another.
  • the temperature of the solid material is kept at a maximum in the range up to 45 or 60 ° C. and thus at most in the range of the melting temperature of the binder.
  • the total surfactant content of the agents, including the soaps, is preferably 15 to 40% by weight and in particular 18 to 30% by weight.
  • Suitable surfactants are, in particular also in the carrier, both anionic surfactants and together anionic and nonionic surfactants.
  • Suitable surfactants of the sulfonate type are preferably C9-C 13 come alkylbenzenesulfonates, sulfonates olefin, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example from CirCi ⁇ monoolefins with a terminal or internal Doppelbin ⁇ dung by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which are derived from C -C 18 alkanes, for example by sulfochlorination or sulfonation.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, and their salts.
  • Sulfated fatty acid glycerol esters are also suitable.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters as well as their mixtures obtained in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • the sulfonation products are a complex mixture which contains mono-, di- and triglyceride sulfonates with a ⁇ - and / or internal sulfonic acid grouping.
  • Sulfonated fatty acid salts, glyceride sulfates, glycerol sulfates, glycerol and soaps are formed as by-products.
  • the proportion of the ⁇ -sulfonated fatty acid disalts can be up to about 60% by weight, depending on the procedure.
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid half-esters of the Ci 2 .C ⁇ 8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ⁇ o-C 2 o- Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • Ci 6 -C ⁇ rAlk (en) yl sulfates are particularly preferred for washing technology reasons. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use Ci 6 -Ci 8 -alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and at relatively low washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize.
  • the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C 2 -C 4 -fatty alkyl sulfates or C 1 -C 8 -fatty alkyl sulfates with C 1 -C 8 fatty alkyl sulfates or C 12 -C16- Fatty alkyl sulfates with Ci ⁇ -Ci ⁇ fatty alkyl sulfates.
  • saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used.
  • 2,3-Alkyisulfate which are prepared for example according to US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched CrC 2 ⁇ alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide (EO) or drCi ⁇ fatty alcohols with 1 up to 4 EO are suitable. Because of their high foaming behavior, they are used in washing agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain Cr to -C 8 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • preferred anionic surfactants are alkyl benzene sulfonates and / or both straight-chain and branched alkyl sulfates.
  • soaps can also be used, preferably in amounts of 0.1 to 5% by weight, based on the total agent.
  • saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants and soaps can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols for example C ⁇ 2 -C 14 alcohols with 3 EO or 4 EO, C 8 -C ⁇ include alcohols containing 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include taigfett alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms can also be used as further nonionic surfactants means and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the oligomerization grad x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; x is preferably 1.2 to 1.4.
  • a further class of preferably used nonionic surfactants which are used either as sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or preferably according to the process described in international patent application WO-A-90/13533 getting produced.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride the polyhydroxy fatty acid amides are derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the invention covers the embodiment that the composition of the carrier material on the one hand and that of the coating substance (s) are identical or practically the same and differ only in the particle sizes of the solid particles present in the respective material portion. In important and preferred embodiments, however, there are definitely differences in the composition of the valuable substances or the mixtures of valuable substances - on the one hand in the carrier particle and on the other hand in the coating substance.
  • the granular compositions contain an extrudate-based carrier, the proportion of the extruded component (s) being 50 to 80% by weight, based on the overall composition. It is further preferred that this extruded component contains surfactants, the surfactant content in the extruded component not exceeding 14% by weight and preferably 6 to 13% by weight, based on the extruded component. In a further preferred embodiment of the invention, the compositions contain surfactant-containing extruded carrier components in such quantities that 0.5 to 10% by weight, based on the total composition, of surfactants is thereby provided.
  • the extruded components can be produced by any of the known methods. However, 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-94/09111 is preferred.
  • the size of the preferred, almost spherical carrier extrudates is advantageously between 0.8 and 2 mm.
  • the coating substance (s) contains anionic surfactants or anionic and nonionic surfactants, preferably in amounts of 30 to 95% by weight, based on the coating substance.
  • the shell substance contains anionic surfactants but is free of nonionic surfactants.
  • Alkylbenzenesulfonates and / or straight-chain and / or branched alkyl sulfates are advantageously used as anionic surfactants.
  • the non-extruded granular and surfactant-containing components are preferably contained in the compositions in such a way that they provide 2 to 30% by weight, in particular 5 to 25% by weight, based on the total composition, of surfactants .
  • surfactant-containing extruded carrier components and surfactant-containing non-extruded coating substances are used, wherein the weight ratio of extruded component containing surfactant: non-extruded component containing surfactant is 6: 1 to 2: 1 and in particular 5: 1 to 3: 1
  • non-extruded components in particular the surfactant-containing components
  • components containing anionic surfactants are preferred which are obtained by spray neutralization according to German patent application DE-A-4425968 or by granulation and, if appropriate, simultaneous drying in a fluidized bed in accordance with the teaching of international applications WO-A-93/04162 and WO-A-94/18303 can be obtained.
  • the grain size distribution of the non-extruded surfactant-containing valuable substances - also in the form of granules - should meet the requirement specified above: at least smaller on average than the carrier grain in order to ensure its encapsulation.
  • granules of almost any particle size and particle size distribution can be produced in the fluidized bed.
  • other granular components for example an enzyme granulate, a foam inhibitor granulate, a bleach activator granulate for their incorporation into the coating substance.
  • Enzymes in particular include those from the class of hydrolases, such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can contribute to color retention and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.
  • hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and microf
  • Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or of cellulase and lipase or lipolytically active enzymes or of protease, amylase and lipase or lipolytically active.
  • the enzymes or protease, lipase or lipolytically active enzymes and cellulase are examples of such lipolytically active enzymes.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin which have a high proportion of Ci8-C24 " fatty acid .
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally signed silica, and paraffins, waxes, microcrystalline waxes and their mixtures with signed silicic acid or bis-arylethylenediamide. Mixtures of different foam inhibitors, for example those made of silicones, paraffins or waxes, are also advantageously used.
  • foam inhibitors in particular foam inhibitors containing silicone and / or paraffin, are preferred a granular, water-soluble or dispersible carrier substance, in particular mixtures of paraffins and bis-stearyl-ethylenediamides and mixtures of paraffins and silicones on inorganic carriers are preferred, granules which mixtures of paraffins and silicones in weight ratio of 1: 1 to 3: 1 are particularly preferred.
  • bleach activators can be incorporated into the preparations.
  • N-acyl or O-acyl which form organic peracids with H_P 2
  • Compounds preferably N.N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, also carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239.
  • bleach activators are NNN'.N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
  • TAED NNN'.N'-tetraacetylethylene diamine
  • DADHT 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine
  • SORMAN acetylated sorbitol-mannitol mixtures
  • ingredients of the agents according to the invention are preferably inorganic and organic builder substances, bleaching agents, substances which have a positive influence on the washability of oil and fat, graying inhibitors, optionally substances which have the solubility and the dissolving rate of the individual granular components and / or the entire agent improve, fabric softening substances, optical brighteners, dyes and fragrances as well as alkaline and / or neutral salts in the form of their sodium and / or potassium salts.
  • Suitable inorganic builder substance is, for example, fine crystalline, synthetic and bound water-containing zeolite in detergent quality.
  • Zeolite A and / or P and, if appropriate, zeolite X and mixtures of A, X and / or P are particularly suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production come.
  • Ten ⁇ ⁇ iden as stabilizers include, for example, 1 to 3 wt .-%, based on zeolite, of ethoxylated C ⁇ -C- j ⁇ ' ⁇ ' ⁇ ohol with 2 to 5 ethylene oxide groups, C -C fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • Zeolites can be contained both in the extruded components and in the non-extruded components.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi O x + ⁇ j -yH O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline sheet silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • ⁇ -sodium disilicate can be obtained, for example, by the process described in international patent application WO-A-91/08171. Crystalline layered sodium silicates can be contained both in the extruded and in the non-extruded components.
  • amorphous silicates so-called X-ray amorphous silicates, which in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle, can be se ⁇ possess secondary washing ability and are used as builder substances. It can even lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Silicates and silicate compounds according to German patent application DE-A-44 00 024 or silicates and silicate compounds are particularly preferred.
  • Spray-dried sodium carbonate-sodium silicate compounds are also particularly preferred, which can additionally contain surfactants, in particular anionic surfactants such as alkylbenzenesulfonates or alkyl sulfates, including the 2,3-alkyl sulfates.
  • surfactants in particular anionic surfactants such as alkylbenzenesulfonates or alkyl sulfates, including the 2,3-alkyl sulfates.
  • Amorphous silicates and silicate compounds such as the above-mentioned silicate-carbonate compounds can also be contained in the carrier grain as well as in the coating substance.
  • Sodium silicate with a molar ratio Na 2 O: SiO of 1: 1 to 1: 4.5 is primarily used as amorphous silicate, and amorphous silicate with secondary washing power preferably used from 1: 2 to 1: 3.0.
  • the sodium carbonate and / or sodium bicarbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
  • the sodium silicate content of the compositions is generally up to 30% by weight and preferably between 2 and 25% by weight.
  • Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures from these.
  • Preferred salts are the salts of 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 sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • Terpolymers and quadropolymers for example those which are described as monomers according to DE-A-43 00 772, are also particularly preferred Salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomers contain salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
  • oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts are described, for example, in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application WO-A-93/16110 .
  • polyaspartic acids or their salts and derivatives are also to be mentioned as further preferred builder substances.
  • suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the organic builder substances can be used both in the carrier granule and in the coating substance, the use in the carrier granule being preferred.
  • Sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphate, citrate perhydrates and HO-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used.
  • the bleaching agents can be contained both in the carrier and in the coating substance of the agent. It is preferred to introduce perborates into the agent via the carrier coma, while percarbonates are preferably used in the coating substance.
  • the agents can also contain components which have a positive effect on the oil and fat washability from textiles. This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic Cellulose ethers, as well as the polymers of phthalic acid and / or terephthalic acid or of their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. These substances can be contained both in the core and in the shell, their content in the shell being preferred.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • water-soluble colloids of mostly organic nature are suitable, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, are preferred. , based on the funds used. These substances can also be contained both in the core and in the shell, but in particular also in the binder.
  • the agents can also contain constituents which increase the dissolution rate of the individual components and / or of the entire agent.
  • the components preferably used include, in particular, C 8 -C 18 alcohols with 10 to 80 moles of ethylene oxide per mole of alcohol, for example tallow fatty alcohol with 30 EO and tallow alcohol with 40 EO, but also fatty alcohols with 14 EO and polyethylene glycols with a relative molecule ⁇ mass between 200 and 2000.
  • Other suitable substances are described for example in international patent application WO-A-93/02176.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-mo ⁇ holino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyrene type may be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl.
  • Mixtures of the aforementioned brighteners can also be used.
  • sulfates may be present as neutral salts, and chlorides may also be present, if appropriate and in particular in cleaning agents.
  • Some fine-grained components can also be used to diminish existing granules, thereby, for example, reducing stickiness of the granules and increasing the bulk densities of the individual granules and of the entire agent.
  • Suitable surface modifiers of this type are known from the prior art.
  • suitable, finely divided zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts for example calcium stearate, but in particular precipitated silicas, mixtures of zeolite and silicas or mixtures of zeolite and calcium stearate are preferred.
  • Finely divided solid preparations based on silicone oil as a component with a defoamer effect can be stored in this form in the outer shell of the granule spheres and can be shielded from undesired interaction with mixture constituents of the coating substance which are already impeded by the solution.
  • composition of this crude extrudate is as follows:
  • Zeolite A (anhydrous active substance) 27.1
  • carrier material carrier granule
  • other valuable and auxiliary substances coating substance
  • Table 2 also shows the quantitative ratios - in% by weight, based on the sum of carrier granules and coating substances - for the components used in the agglomeration process.
  • Table 3 summarizes the grain size distribution - determined according to the number of sieves in% by weight - for the crude extrudate (carrier granule) and the additives (coating substances). Taking into account the quantitative ratios according to Table 2 on the proportion of the crude exudate / carrier particle on the one hand and the mixture components additionally used as coating substance, it can be seen that in the vast majority of the spherical granules formed, the carrier particle is made up of crude extrudate particles with a particle diameter> 1.0 mm is formed.
  • the dissolution behavior of the respective agglomerate spheres is determined by means of the “L test”.
  • the agglomerate to be examined is dissolved in water under the conditions specified below and the residue is determined gravimetrically.
  • the devices used are defined as follows: laboratory stirrer with digital display stirrer shaft length 350 mm propeller stirrer 0 50 mm hand wash test sieves 0.2 mm mesh size usual laboratory device
  • 1,000 ml of city water are placed in a 2,000 ml beaker and the propeller stirring head is inserted approximately 1.5 cm from the center of the beaker.
  • the agitator motor is switched on and set to 800 rpm. ⁇ 10 rpm. set.
  • 8 g of the detergent to be examined are added and stirred for 90 seconds or 5.0 minutes.
  • the stirrer is removed and cleaned with water.
  • the wash liquor is then poured through the previously tared sieve and the beaker is rinsed with a little water.
  • the sieve with the residue is dried to constant weight in a drying cabinet at 40 ° C ⁇ 5 ° C and weighed. A double determination is used in each case.
  • the residue value (% by weight) is calculated as
  • a triple determination is carried out for larger differences.
  • An average is calculated from the double or triple determinations.
  • the dissolution behavior is determined in the so-called bowl test. This test is carried out as follows:
  • test agent 25 g are placed in 5 l of tap water (30 ° C). After 15 seconds, the agent is distributed in the bowl by hand. After a further 15 seconds, a terry towel is added to the wash liquor and moved as in a typical hand wash. After 30 seconds, the wall of the bowl is wiped with the towel. After another 30 seconds of washing, the towel is removed and wrung out.
  • dark plastic e.g. dark red
  • wash liquor is decanted from the bowl and the remaining residue is visually graded after treatment with 5 to 10 ml, where:
  • Examples 1 to 5 below provide more detailed information on the selection of the binder by type and amount, on the type of agglomeration process used and on the characteristic data obtained in accordance with the evaluation criteria of the L test and the Schüssel test, and on the particle size distribution of the agglomerates according to Invention.
  • All the mixing components to be combined with one another in the agglomeration stage are weighed together in accordance with the mixing recipe and are filled together into the selected coating or agglomeration apparatus.
  • the binder used is also weighed out according to the selected recipe - either as a melt or as an aqueous preparation - and poured into the pump feed.
  • the coating or agglomeration apparatus is started and started spraying at the same time.
  • the flowable binder preparation is sprayed onto the moving contents of the agglomeration apparatus.
  • the spraying process is completed within a few minutes, preferably in 1 to 2 minutes and at most within 5 minutes. After spraying is complete, the mixture is briefly mixed for about 0.5 to 1 minutes, after which the agglomerate is removed. If a melt has been used for spraying, the process is ended.
  • aqueous binder preparations are used, a final drying step follows.
  • the agglomerate removed is dried in a fluidized bed apparatus by means of warm air of approx. 90 ° C. for a period of approx. 5 minutes, the material temperature may not exceed 65 ° C. (maximum 70 ° C.).
  • the agglomeration device is operated in a mixer in which the solid material is moved and sprayed with the binder phase.
  • a 30% by weight aqueous preparation of the product used as a cobuilder in textile detergents and sold under the trade name "SOKALAN" (sodium salt of an acrylic acid copolymer) is used as the binder liquid phase.
  • SOKALAN sodium salt of an acrylic acid copolymer
  • This aqueous binder preparation is used in an amount of 4% by weight. % - based on the solid material to be agglomerated - sprayed in.
  • the procedure here is without adding the defoamer component to the agglomeration stage.
  • Example 2 In a modification of the technology of Example 1, the same material mixture is now subjected to agglomeration in the fluidized bed using a PEG 4000 melt as a binder.
  • This binder which is solid at room temperature and soluble in cold water, is used in an amount of 2% by weight, based on the solid material to be agglomerated.
  • Example 1 The technical teaching according to Example 1 is repeated. However, the defoamer component based on a mixture of silicone oil, starch and fatty alcohol is now added to the spherical agglomerate formed and solidified there by rolling it in.
  • Example 1 The teaching of Example 1 is repeated, but here - in deviation from the teaching of Example 3 - the defoamer granulate based on silicone oil is added directly to the multi-substance mixture in the mixer and bound together with the other components of the coating substance in the multi-material material by means of the sprayed-in binder .
  • Examples 1 to 4 are used to determine: the respective grain spectrum, the L-test values after 1, 5 minutes and 5.0 minutes and the assessment in the bowl test.
  • the respectively determined values or evaluations are summarized in Table 4 below.
  • Example 6 In contrast, the coarse-grained fraction in the feed of Example 6 (> 0.8 mm) is below 20% by weight.
  • the powdery, free-flowing and free-flowing commercial laundry detergent mixture with its particle size distribution according to Table 5 is subjected to the melt agglomeration process according to the teaching of the invention using a melt of polyethylene glycol with an average molecular weight of 4,000 (PEG 4,000) as a binder.
  • PEG 4,000 polyethylene glycol with an average molecular weight of 4,000
  • the amount of binder is increased from 1% by weight to 5% by weight.
  • the intermediate product is selected, which has been produced using 3% by weight of the polymer-based binder and has a coma fraction> 0.8 mm of 55% by weight.
  • this feedstock is sprayed in the mixer with various amounts of a melt of polyethylene glycol with an average molecular weight of 6,000 (PEG 6000) and subsequently granulated in the sense of the invention.
  • PEG 6000 polyethylene glycol with an average molecular weight of 6,000
  • Table 8 below shows that here too a shell-like structure of the fine particles occurs on the outer surfaces of the larger particles. All agglomerates are dust-free, the fine fraction decreases with increasing amount of PEG 6000 binder. The product is predominantly formed by spherically shaped granules.
  • Example 7 to 14 summarize in tabular form the results which are determined with regard to the solubility and the spectrum of comics in the case of textile detergent mixtures which are perien-shaped in the sense of the teaching according to the invention.
  • a raw textile detergent mixture is assumed which is the subject of Example 7 (comparative example) in a form which has not been aftertreated in accordance with the invention.
  • This crude mixture is composed of a crude extrudate produced by extrusion in accordance with the specifications of EP-B-0486592 (in the sense of the at the beginning of this Example given Table 1) and other detergent active ingredients (in the sense of Table 2) together.
  • This multicomponent mixture of Comparative Example 7 is agglomerated with different binders in the sense of the teaching according to the invention in Examples 8 to 14 to form the Perienfonm.
  • the crude extrudate is again the carrier commodity, which is coated with the further detergent constituents as coating substances using the respective binders or binder mixtures.
  • the binder or the binder mixture was introduced as a melt with a melting temperature of 100 ° C. into the multi-substance mixture to be agglomerated by means of a multi-substance nozzle.
  • a Roto-Granulator (Glatt) was used.
  • the tabular summary of the work results identifies the binders or binder mixtures used by type and quantity (percent by weight based on the laundry detergent mixture) and then summarizes the numerical values relating to the solubility behavior and the grain spectrum.
  • Binder (% by weight) comparison [without 5% TA 6% TA 7% TA40
  • TA 40 tallow alcohol ethoxylate with 40 EO.
  • Eumulgin B2 fatty alcohol (C ⁇ -i8) + 20 EO
  • Eumulgin B3 fatty alcohol (C16- 1 8) + 30 EO
  • PEG 4000 polyethylene glycol with medium MG 4000

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP96923951A 1995-07-06 1996-06-27 Granules detergents et nettoyants de masse volumique apparente elevee, exempts de poudre et de fractions fines Expired - Lifetime EP0836641B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19524287 1995-07-06
DE19524287A DE19524287A1 (de) 1995-07-06 1995-07-06 Von Staub- und Feinanteilen freie granulare Wasch- und Reinigungsmittel hoher Schüttdichte
DE19547457 1995-12-19
DE1995147457 DE19547457A1 (de) 1995-12-19 1995-12-19 Von Staub- und Feinanteilen freie granulare Wasch- und Reinigungsmittel hoher Schüttdichte
PCT/EP1996/002806 WO1997002339A1 (fr) 1995-07-06 1996-06-27 Granules detergents et nettoyants de masse volumique apparente elevee, exempts de poudre et de fractions fines

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EP0836641A1 true EP0836641A1 (fr) 1998-04-22
EP0836641B1 EP0836641B1 (fr) 1999-08-25

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US6673766B1 (en) 1998-09-25 2004-01-06 The Procter & Gamble Company Solid detergent compositions containing mixtures of surfactant/builder particles
EP1752527A3 (fr) * 1998-09-25 2010-05-05 The Procter & Gamble Company Compositions detergents solides
JP2002525422A (ja) * 1998-09-25 2002-08-13 ザ、プロクター、エンド、ギャンブル、カンパニー 洗剤組成物

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DE3617756C2 (de) * 1985-05-29 1995-01-19 Lion Corp Verfahren zum Herstellen einer granularen Detergentien-Zusammensetzung mit hoher Schüttdichte
JPS62228000A (ja) * 1986-03-28 1987-10-06 花王株式会社 高密度粒状洗剤組成物
GB8728959D0 (en) * 1987-12-11 1988-01-27 Unilever Plc Soap based compositions
DE4435743C2 (de) * 1994-02-17 1998-11-26 Chemolux Sarl Verfahren zur Herstellung eines Mehrkomponenten-Granulates

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GR3031562T3 (en) 2000-01-31
ES2137011T3 (es) 1999-12-01

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