WO2007014601A1

WO2007014601A1 - Coated core-shell aggregates

Info

Publication number: WO2007014601A1
Application number: PCT/EP2006/006112
Authority: WO
Inventors: Wilfried Rähse
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2005-07-29
Filing date: 2006-06-24
Publication date: 2007-02-08
Also published as: DE102005036346A1; JP2009503156A

Abstract

A description is given of coated aggregates having a core-shell structure and of a method of constructing such aggregates. The aggregates allow fine-tunable release of active ingredient. They can be used with advantage in particular in the detergents sector. The method also allows conventional pulverulent and/or finely particulate multi-component mixtures from the detergents sector to be converted into core-shell aggregates provided with a coating; in other words, it allows the upgrading of conventional laundry detergents. The method involves charging a mixer/granulator with a particulate material (“initial-charge particles”) which is granulated/agglomerated with the addition of granulation aid and of further particulate material (“particles for addition”), the initial-charge particles preferably having a very substantially uniform size, and the particles for addition having a diameter d50 which is not more than a tenth of the diameter d50 of the initial-charge particles but is greater than 2 µm. Even after long storage, the coated aggregates are readily pourable and free-flowing, and do not undergo caking.

Description

"Coated core-shell aggregates"

The present invention relates to coated core-shell aggregates for detergents or cleaners and to a process for the preparation thereof. The aggregates which can be produced by agglomeration can be advantageously used and used in the washing or cleaning agent industry.

Granulation processes are state of the art in a wide variety of industries, and there are a large number of standard monographs and patent literature on this subject. In the context of the present invention, it is important that an important contribution to product design can be made via the granulation process.

Due to the enormous variety of goods offered for all the needs of everyday life, the consumer is often faced with the problem of choosing from a variety of products that is almost unimaginable just what suits his needs the most. Here, product design can make it easier for the consumer to make a purchase decision.

The purchase decision is generally based on very different criteria, but above all on the price of the presented goods and their quality. As an additional criterion for the purchase decision, however, product design is becoming increasingly important. Consumers usually want to use a product that also appeals to their aesthetic sensibilities. For this reason, many products are equipped with visually appealing packaging. The product itself is also of great interest, for example with regard to its color and shape. The shape of the product makes it particularly easy to address consumers' aesthetic sensibilities. As an example, powdery detergents and / or cleaning agents may be mentioned here. A visually very appealing product from this area is, for example, a detergent powder which consists exclusively of almost spherical particles. Due to its high symmetry and homogeneous appearance in the eyes of the consumer, such a detergent powder of almost identical and almost spherical particles indicates great care in the preparation and high competence in the processing of the washing powder, whereas a powder consisting of very irregularly shaped particles exists, the consumer does not trigger corresponding positive associations.

Against this background, the object of the present invention was to provide largely aesthetically pleasing granules.

This object is achieved by the subject matter of the invention, which is a core-shell aggregate for detergents or cleaners, which consists of a core and the core surrounded the particles surrounding the core have a particle diameter d ₅₀ which is at most one tenth of the particle diameter d _{50 of} the core particles, but greater than 2 microns, preferably the core particles in particular less than 75 wt .-% and the zugebenden Particles in particular make up more than 25 wt .-% of the core-shell aggregate forming solids, with the proviso that at least one coating is applied to the core-shell aggregate from the outside.

The particle diameter d ₅₀ of the particles surrounding the core is preferably in the range from 3 to ₅₀ μm, advantageously from 4 to 25 μm, more preferably from 4 to 15 μm, in particular from 5 to 10 μm. This corresponds to a preferred embodiment of the invention.

Advantageously, all three phases (core, shell (s), coating) of the coated core-shell aggregates in the sense of a controlled release effect for delayed release of active ingredient from each of the three phases can be adjusted, with a continuous adjustment of the controlled release effect over very wide areas is possible. This corresponds to a preferred embodiment.

A coated core-shell aggregate in which the ingredients contained in the core are released in a delayed manner corresponds to a preferred embodiment.

For details, see below. The three phases differ according to a preferred embodiment in the recipe, i. in their composition. For details, see below. The core material may, according to a preferred embodiment of one, composed of two or more substances, it may be approximately round, but also arbitrarily shaped. For details, see below. For example, the shell may be composed of one, two or more different soluble materials (e.g., tower powders or raw materials / compounds), which corresponds to a preferred embodiment. The coating layer (coating) results for example from anhydrous or low-water mixtures or suspensions, can e.g. but also be water-containing when drying, which corresponds in each case to a preferred embodiment.

It is preferred if the coating is applied without subsequent post-drying, which corresponds to a preferred embodiment.

According to another preferred embodiment, it may also be advantageous if the coating is applied with subsequent drying.

The thickness of the coating is variably adjustable and is preferably in the range of the order of a monomolecular coverage up to 50 microns, but it is highly preferred if the coating thickness is significantly smaller than 5 microns. In the following, when talking about an agent according to the invention, it always means a coated core-shell aggregate. If, on the other hand, only a core-shell aggregate is mentioned, then this does not mean the agent according to the invention but always an uncoated core-shell aggregate.

According to a preferred embodiment, the coating applied is a liquid, preferably water-free, in particular anhydrous, liquid, advantageously containing surfactants, such as e.g. preferably nonionic surfactants, amphoteric surfactants and / or cationic surfactants, brighteners, triglycerides, terpenes, glycerol silicone oil, paraffin (oil), perfume, vitamin E, (co) polymer (solutions) and / or natural oils.

Such a liquid advantageously does not remain liquid on the surface of the core-shell aggregate, but draws on, so that the surface of the core-shell aggregate is advantageously not wet or sticky.

Very preferred here is nonionic surfactant, which is advantageously combined with other components. Preferred are e.g. the following combinations: (a) nonionic surfactant, brightener, optional perfume

(b) nonionic surfactant, silicone oil, optionally paraffin (oil), optionally perfume

(c) silicone oil, whitener, optional perfume, optional nonionic surfactant

(d) nonionic surfactant, vitamin (derivative) such as preferably vitamin E, optional perfume

(e) nonionic surfactant, natural oils, optional perfume

(T) nonionic surfactant, vitamin (derivative), natural oils, optional perfume.

Low-water means in this context that the coating liquid used contains less than 35 wt .-% water, based on the total coating liquid. In preferred embodiments, this upper limit of water content may also be at lower levels, e.g. at a value of preferably 30% by weight, 25% by weight, 20% by weight, 15% by weight, 10% by weight or 5% by weight or between these values, e.g. at a value of preferably 9, 8, 7 or 6 wt .-% based on the total coating liquid. An anhydrous coating liquid contains a maximum of 4 wt .-%, advantageously at most 3 wt .-%, more preferably at most 2 wt .-%, preferably at most 1 wt .-% or in particular no water based on the total coating liquid. This corresponds to a preferred embodiment.

However, according to another preferred embodiment, the coating liquid may also contain larger amounts of water, that is more than preferably 35 wt .-%, based on the total coating liquid. In preferred embodiments, this minimum water content limit may also be at higher values, for example at a value of preferably 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight or 65 Wt .-% or between these Values, that is, for example, at a value such as 41, 42, 43 or 44 wt .-%. based on the entire coating liquid. According to a preferred embodiment, a very water-rich liquid may even have an even higher water content upper limit, for example with a value of preferably 70% by weight, 75% by weight, 80% by weight, 85% by weight, 90% by weight. % or 95 wt .-% water based on the total coating liquid.

According to a preferred embodiment, the coating contains (co) polymers, in particular water-soluble (co) polymers, optionally modified (co) polymers, such as e.g.

(A) synthetic polymers, such as polyethylene glycols, polyvinylpyrrolidones, polyvinyl alcohols, homo- and copolymers of (meth) acrylic acid and its derivatives, the maleic, vinylsulfone, vinylphosphonic, polyethyleneimine and / or PAA ^" (b) nature-based , optionally modified polymers, such as starch, alginates, pectins, vegetable gums,

Caseins, gelatin guar, cellulose, cellulose ethers and / or starch ethers

(c) biotechnology. produced products such as e.g. Pullulan, Curdlan and / or Xanthan.

(d) mixtures of the aforementioned.

According to another preferred embodiment, a melt is applied as coating, preferably melting of (co) polymers, waxes, esters and / or fats. Such a melt advantageously remains on the surface of the core-shell aggregate no melt, but is advantageously solid after pulling and cooling, so that the surface of the core-shell aggregate is advantageously not sticky.

The coating preferably comprises waxes. For waxing, the following may be preferred:

(a) vegetable waxes such as preferably carnauba wax, candelilla wax, espartowax, guarra wax, Japan wax, cork wax, montan wax, ouricury wax, rice germ oil wax and / or sugarcane wax

(b) animal waxes such as preferably beeswax, rumen grease, wool wax, shellac wax and / or spermaceti

(c) mineral waxes such as preferably ceresin and / or ozokerite

(d) chemically modified waxes, preferably hard waxes, in particular hydrogenated jojoba waxes, montan ester waxes and / or sasol waxes

(e) synthetic waxes, such as preferably paraffin waxes (in particular soft paraffin with a melting point of> 38 ° C.), polyalkylene waxes and / or polyethylene glycol waxes

(f) microwaxes, ie preferably higher-melting constituents of the crude oil, which consist in particular of a mixture of saturated hydrocarbons (isoalkanes) and advantageously also alkyl-substituted cycloparaffins and alkyl-substituted or naphthenic-sub- containing substituted aromatic compounds, advantageously petrolatum, plastic microwaxes and hard microwaxes

(g) mixtures of vegetable waxes, animal waxes, mineral waxes, synthetic waxes, microwaxes and / or chemically modified waxes.

The coating preferably comprises esters. For esters, the esters of long-chain fatty acids are advantageously preferred, in particular having at least 22 carbon atoms, such as e.g. Behenic acid, tetracosanoic acid, cerotic acid and / or triacontanoic acid, etc.

The coating preferably comprises fats. By fats is preferably meant the solid or semi-solid products which consist essentially of mixed glycerol esters of higher fatty acids.

The coating preferably comprises (co) polymers. Polyethylene glycols, polyacrylic acids, polyacrylamides, polyvinylpyrrolidones, polyvinyl acetates and polyvinyl alcohols are particularly preferred in the (co) polymers.

Polyethylene glycols having molecular weights of about 200-5000000 g / mol, corresponding polymerization degrees Pn of about 5 to> 100,000 are preferred.

Liquid products with molecular weights <about 25000 g / mol can also be used as coating material.

The higher molecular weight solid polyethylene glycols, also called polyethylene oxides, are also preferred.

In general, it is very preferred if the coating contains lipids and / or silicone oil, which corresponds to a preferred embodiment. Preferred lipids are

(a) lipophilic hydrocarbons (such as triacontane, squalene or carotenoids, etc.),

(b) lipophilic alcohols (such as wax alcohols, retinol or cholesterol, etc.),

(c) ether lipids

(d) lipophilic carboxylic acids (fatty acids),

(e) lipophilic esters [such as neutral fats - i. Mono-, Di- u. Triacylglycerols (triglycerides), sterol esters, etc.]

(f) lipophilic amides (such as ceramides, etc.),

(g) waxes

(h) lipids with more than 2 hydrolysis products, such as glycolipids, phospholipids, sphingolipids and / or glycerolipids etc. (i) lipids in the form of higher molecular weight conjugates with more than 2 hydrolysis products, such as lipoproteins and / or lipopolysaccharides, etc., (j) phosphorus-free glycolipids, such as glycosphingolipids (such as preferably cerebrosides, gangliosides, sulphatides) or, for example, glycoglycerolipids (as preferably Glykosyldi- and -monogly- ceride), etc. (k) carbohydrate-free phospholipids, such as, for example, sphingophospholipids (such as, preferably, sphingomyelin) or, for example, glycerophospholipids (such as preferably lecithins, cephalins, cariolipins, phosphatidylinositols and inositol phosphates, etc.) (I) mixtures of the abovementioned.

In a further preferred embodiment, the coating comprises unsaponifiable lipid, preferably selected from free fatty acid, isoprenoid lipids, in particular steroids, carotenoids, monoterpenes etc. and / or tocopherols.

In another preferred embodiment, the coating comprises saponifiable lipid, preferably selected from mono-, di-, triacylglycerides, phospholipids (phosphatides), glycolipids, diollipids, waxes and / or sterol esters.

In a further preferred embodiment, the coating comprises at least one unsaponifiable and one saponifiable lipid.

In another preferred embodiment, the coating comprises neutral lipid, preferably selected from fatty acids (> C12), mono-, di-, triacylglycerides, sterols, sterol esters, carotenoids, waxes and / or tocopherols.

In another preferred embodiment, the coating comprises polar lipid, preferably selected from glycerophospholipids, glyceroglycolipids, sphingophospholipids and / or sphingoglycolipids.

In a further preferred embodiment, the coating has at least one polar and one nonpolar lipid.

According to a preferred embodiment, the coating is applied as a dispersion, thus advantageously as a system consisting of several phases, one of which is dispersed continuously (dispersing agent) and at least one further (dispersed) (dispersed phase), preferably as emulsion, aerosol or suspension. Most preferred are suspensions, ie dispersions of insoluble solid particles with particle sizes down to colloidal dimensions (<10 ^{~ 6} cm) in liquids, plastic masses or solidified melts.

Particular preference is given to solvent-containing, advantageously aqueous suspensions of pulverulent components, preferably of a few μm diameter, e.g. aqueous suspensions of pigments. Solvent-containing systems preferably contain dispersants, such as in particular

(a) oligomeric titanates and / or silanes,

(b) amphoteric dispersants such as e.g. Soy lecithin etc.

(c) anionic dispersants, e.g. oligomeric or polymeric carboxylic acids, etc.,

(d) cationic dispersants, e.g. Polyamines etc.,

(e) Electroneutral dispersants, such as e.g. Salts of long-chain polyamines and. Polycarboxylic acids, etc., and / or

(f) amine / amide functional polyesters and / or amine / amide functional polyacrylates.

Aqueous systems preferably contain dispersants, such as in particular

(A) inorganic dispersants, here preferably so-called Pickering dispersants, ie fine-grained, insoluble inorganic compounds such as CaCO ₃ or Ca ₃ (PO ₄ J ₂ , polyphosphates, such as preferably salts of pyro-, meta- or polyphosphoric the general. formula M _{n + 2} P _n O _{3n + 1} or Mn [H ₂ P _n O _{3n + 1]} with M = Na +, K +, NH ^4+;. n = 2-10 oligophosphates, such as pentasodium triphosphate, Na ₅ P ₃ O ₁₀ , n> 10 polyphosphates

(b) modified natural products, e.g. Gum arabic, alginates, casein, gelatin, soy lecithin, tannates and / or ligninsulfonates and / or

(c) synthetic polymers, for example predominantly water-soluble Na ⁺ or NH ⁴⁺ salts of anionic synthetic polymers with carboxylate, sulfate or sulfonate groups, homopolymers, such as preferably polyacrylic acid, polymethacrylic acid,

(d) Copolymers, such as preferably acrylic acid or methacrylic acid with vinyl (ethene), allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), acrylamide or acrylonitrile, maleic anhydride with ethylene or other 1-alkenes, methyl vinyl ether or styrene , Polyaldehydocar- bonsäuren, such as preferably co- or terpolymers of acrylic acid, acrylamide, acrylonitrile, in the presence and incorporation of long-chain, branched or linear mercaptans as regulators, naphthalenesulfonate-formaldehyde condensation products.

In a further preferred embodiment, the coating comprises pigments, advantageously in the nanoscale range or in the micrometer range, preferably white pigments, in particular selected from titanium dioxide pigments, in particular anatase pigments and / or rutile pigments, zinc sulfide pigments, zinc oxide (zinc white) , Antimony trioxide (antimony white), basic lead carbonate (lead white) 2PbCO ₃ ^■ Pb (OH) ₂ , lithopone ZnS + BaSO ₄ . Preferably also white auxiliaries, such as preferably calcium carbonate, talc 3MgO ^• 4SiO ₂ ^• H ₂ O and / or barium sulfate may be included.

In another preferred embodiment, the pigments may be um

(a) colored pigments (preferably inorganic colored pigments, in particular iron oxide pigments, chromate pigments, iron blue pigments, chromium oxide pigments, ultramarine pigments, mixed oxide phase pigments and / or bismuth vanadate pigments),

(b) black pigments (e.g., aniline black, perylene black, iron oxide pigments, manganese black and / or spinel black),

(c) luster pigments (preferably platelet-shaped effect pigments, metallic effect pigments such as aluminum pigments (silver bronze), copper pigments and copper / zinc pigments (gold bronze) and zinc pigments, pearlescent pigments such as magnesium stearate, zinc stearate, lithium stearate or ethylene glycol distearate or Polyethylene terephthalate, interference pigments such as metal oxide mica pigments) and / or

(d) luminescent pigments such as e.g. Azomethine fluorescence yellow, silver-doped and / or copper-doped zinc sulfide pigments act.

The coating may preferably also comprise the following substances:

(a) carbonates, such as preferably chalk, limestone, calcite and / or precipitated calcium carbonate, dolomite and / or barium carbonate

(b) sulphates, such as preferably barite, blanc-fixed and / or calcium sulphates

(c) silicates, such as preferably talc, pyrophyllite, chlorite, hornblende, mica, kaolin wollastonite, slate, precipitated Ca, Al, Ca / Al, Na / Al silicates, feldspars and / or mullite

(d) silicas such as, preferably, quartz, fused silica, cristobalite, diatomaceous earth, Neuburg Siliceous Earth, precipitated silica, fumed silica, glass flour, pumice, perlite, Ca-metasilicates and / or fibers from melts of glass, basalt, slags

(E) oxides, in particular aluminum hydroxide and / or magnesium hydroxide

(T) organic fibers, such as in particular textile fibers, cellulose fibers, polyethylene fibers, polypropylene fibers, polyamide fibers, polyacrylonitrile fibers and / or polyester fibers, preferably with lengths in the nanometer or micrometer range and / or

(g) flours, e.g. Starch flours.

In a preferred embodiment, the coating reduces the rate of dissolution of the total particle to 5% based on 20 ° C cold water, ie, that the coated core-shell units corresponding to require more time to dissolve completely in 2O ⁰ C cold water, based Dissolve 60 grams of the particles in one liter of tap water in a 2 liter beaker stirring with a stirrer / magnetic stirrer (250 rpm) at 20 ° C. In further preferred embodiments, the reduction of the dissolution rate of the total 10 particles, preferably 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75,% 80 %, 85%, 90%, 95% or 100% are at a value of 100% so the complete particle dissolution takes twice as long as without coating According to another preferred embodiment, the lowering of the reading speed of the entire particle even at an even higher value 150%, 200%, 250%, 300%, 350%, 400%, 450% or 500%, preferably

Thus, if the uncoated particle is already dissolved after 1 hour, the coated tablet would be dissolved after 5 minutes at a value of 500%

In a preferred embodiment, the 3 phases (core / shell / coating) of the agent according to the invention differ in their lot speed

In a preferred embodiment, effervescent or effervescent components are contained in the coated core-shell aggregate, preferably in the core and / or in the shell

An aggregate for the purposes of this invention is an aggregate of particles. It may be a conglomerate, agglomerate or granules, ie a solid comprising particles, a cluster of particles or an aggregate of interconnected particles, which macroscopically advantageously form a unit It is preferably such particle associations in which the original particles are advantageously but not completely fused together, so that z. By (electron) mιkroskopιsche investigations, the outer Umπßlinien the individual parts are advantageously at least partially still recognizable

Konk ret there is a core-shell aggregate of a core and particles that surround this core This does not necessarily mean that the particles surrounding the core must completely cover this It is only necessary that the particles surrounding the core at least partially surrounded or preferably at least 10%, more preferably at least 15%, even more advantageously at least 20%, advantageously at least 25%, more preferably at least 30%, most preferably at least 35%, in a substantially advantageous manner, at least 40%, most preferably at least 45%, in particular at least 50%, of the outer visible surface of the core is covered by the surrounding particles (= degree of coverage), which corresponds to a preferred embodiment

However, according to another preferred embodiment, the degrees of coverage should not exceed certain maximum values, such maximum values being in particular at a value of 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100%, but can also be at a lower value, such as 10%, 15%, 20%, 25%, 30%, 35%, 40% or 45% According to another preferred embodiment, however, it may also be desirable for the degree of coverage to reach very high levels, preferably the degree of coverage may be at values of at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100%.

Consequently, if the term "shell" is used in the following, this does not mean that it must be a completely coherent shell that surrounds the entire core, just as, for example, a hazelnut is surrounded by a nutshell Meaning means eg also only 10% coverage of the outer surface of the core with the core surrounding particles, i. from the concept of the shell here also incomplete shells are included.

The core, in a preferred embodiment, may be a primary agglomerate, i. the core itself may be composed of a multiplicity of interconnected particles which may be completely fused together, not completely fused together or may not be fused together, but preferably held together only by a cement, a binder, a drying process or the like , The particles can also be connected to one another via crystal bridges. According to a preferred embodiment, the core can also be a single grain, ie a grain which has no subparticles, for example a crystal. Of course, it may also be a granulate or a spray-drying product, as well as extrudates.

According to a preferred embodiment of the invention, the core particles of the core-shell aggregate and / or the particles surrounding the core are spray-drying products and / or (raw products of non-tower technologies, preferably resulting from the granulation in drum, plate, mixer and fluidized bed granulators or they have emerged from these.

According to another preferred embodiment of the invention, the core of the core-shell aggregate via compression methods such as wet granulation, preferably with simultaneous entry of mechanical energy, melt agglomeration, spray agglomeration in particular rotating fluidized bed, spray drying, roll compaction, but especially by extrusion and related compression methods - so far required in each case with enclosed shaping to the individual core - manufactured.

According to a further preferred embodiment of the invention, the core of the core-shell aggregate of a plurality of smaller particles, in particular with the concomitant use of a, preferably soluble in cold water, binder is constructed.

According to another preferred embodiment of the invention, the core of the core-shell aggregate is predominantly water-soluble and / or very finely dispersed in water. soluble inorganic and / or organic components of conventional detergents and cleaners formed - for example, Textilwaschmittelbuilder and / or cobuilders, alkalizers, temperature stable bleach on hydrogen peroxide such as perborate - but also ingredients of organic origin, for example at least largely gelatin-free soluble surfactant compounds, in particular corresponding anionic surfactants and / or nonionic surfactants, co-builders, brighteners and the like, may be constituents of the core.

According to a preferred embodiment of the invention, the core as such is uniform, preferably almost spherical or ellipsoidal. The ellipsoid is similar to the sphere, but the longitudinal axis and the transverse axis are different. However, the core can also be other embodiments

(a) cubic (cube-shaped) or at least approximately cubic-shaped or

(b) shaped parallelepiped (e.g., cuboid) or at least approximately parallelepiped shaped or

(c) lamellar (platy and the like) or at least approximately lamellar or

(d) needle-like or fibrous-shaped, or at least approximately needle-like or fibrous, or

(e) be strand-like or at least approximately strand-like.

According to a further preferred embodiment, the core is designed as such uneven, preferably not spherical or ellipsoidal, but of irregular shape. Such a shape is characterized, for example, by the irregular presence of corners, points, points and edges, bulges and indentations, tears or bubbles. From the center of the core, therefore, the majority of the points of the surface are substantially at an unequal distance. Such a shape may, for example, taper to one side, have a dent or have a flat side.

A collective of coated core-shell aggregates, for example a washing powder consisting of core-shell aggregates, can now be characterized in that

(A) the majority, preferably at least 75%, in particular the total number, the cores of the coated core-shell aggregates is substantially uniform, preferably formed almost spherical or ellipsoidal, or

(b) the majority, preferably at least 75%, in particular the total number, of the cores of the coated core-shell aggregates is uneven, or (C) mixtures of substantially uniformly and non-uniformly formed cores are present, preferably in the ratio of 200: 1 to 1: 200. This corresponds to a preferred embodiment.

The collective of coated core-shell aggregates may also be a sub-collective of a larger total collective, i. the collective of coated core-shell aggregates together with other particles forms a collective.

A collective of coated core-shell aggregates, for example a washing powder consisting of core-shell aggregates, may be distinguished by the fact that the cores of the collective

(a) in the majority, preferably at least 75%, in particular the total number of cores, have a more uniform grain size, or

(b) in the majority, preferably at least 75%, in particular the total number of cores, have a rather non-uniform grain size, or

(c) represent a mixture of cores of very uniform grain size with cores of very non-uniform grain size, preferably in the ratio of 200: 1 to 1: 200. This corresponds to a preferred embodiment.

A rather uniform grain size is preferably present when the cores are present substantially in the most uniform particle size distribution, in which the ratio of d ₅₀ to d ₉₀ at least 0.50, preferably at least 0.6, advantageously at least 0.75, in further advantageously, at least 0.80.

(a) in the majority, preferably at least 75%, in particular the total number of cores, have a more uniform density, or

(b) in the majority, preferably at least 75%, in particular the total number of cores, have a rather different density, or

(c) represent a mixture of nuclei of very uniform density with nuclei of very non-uniform density, preferably in the ratio of 200: 1 to 1: 200. This corresponds to a preferred embodiment. The collective of the coated core-shell aggregates can also be a sub-collective of a larger total collective, ie the collective of the coated core-shell aggregates together with further particles forms a total collective.

(a) in the majority, preferably at least 75%, in particular the total number of cores, have a more uniform structural configuration, i. e.g. either single grains, extrudates or agglomerates, etc., or

(b) in the majority, preferably at least 75%, in particular the total number of cores, have a rather different structural configuration, i. both as extrudates, agglomerates, single grains, etc., or

(c) represent a mixture of cores of very uniform structural composition with nuclei of very inconsistent density. This corresponds to a preferred embodiment.

(a) in the majority, preferably at least 75%, in particular the total number of cores, have a more uniform chemical composition, relative to the collective, or

(b) in the majority, preferably at least 75%, in particular the total number of cores, have a rather non-uniform chemical composition relative to the collective, or

(c) a mixture of cores of very uniform chemical composition with cores of a very non-uniform chemical composition, relative to the collective. This corresponds to a preferred embodiment.

Further, the following cases (i) to (iv) represent preferred embodiments of the invention: (i) A group of coated core-shell aggregates, for example, a washing powder consisting of core-shell aggregates, may be characterized in that the cores of the core-shell aggregates collective as individual objects, in each case have a homogeneous distribution of at least one (preferably one and the same) active substance contained in them (eg surfactant or builder, etc.), the collective oc) formed by the same coated core-shell aggregates likewise having a homogeneous distribution of the ( the active substance (s) concerned is given through the collective, or (b) there is a heterogeneous distribution of the active substance (s) concerned through the collective.

In simple terms, this means that there is a particle collective ψ. In all particles of this collective ψ at least one (preferably one and the same) active substance is homogeneously distributed. In the case α), all particles of the collective ψ also contain the same amount of the active substance in question. This is the case of a homogeneous individual distribution in a homogeneous collective. In the case β), however, the particles contain different amounts of the active substance in question, although the different amounts in each individual particles are homogeneously distributed. This is the case of a homogeneous individual distribution in a heterogeneous collective. The collective of coated core-shell aggregates may also be a sub-collective of a larger total collective, i. the collective of coated core-shell aggregates together with other particles forms a collective.

(ii) A collective of coated core-shell aggregates, for example a washing powder consisting of core-shell aggregates, may be characterized in that the cores of the collective as individual objects each have a heterogeneous distribution of at least one (preferably one and the same) active substance (eg surfactant or builder etc.) contained in them (ie having a concentration gradient of the active substance via a particle or local accumulations of the active substance occur), the collective χ formed by the same coated core-shell aggregates likewise having a heterogeneous distribution of the (s) of the active substances (s) concerned through the collective, or δ) a homogeneous distribution of the relevant active substance (s) through the collective.

In simple terms, this means that there is a particle collective ξ. In all particles of this collective ξ at least one (one and the same) active substance is distributed heterogeneously. In the case χ) all particles of the collective ξ also contain different amounts of the active substance in question. This is the case of a heterogeneous individual distribution in a heterogeneous collective. In the case δ), however, the particles contain equal amounts of the active substance in question, although the same amounts are distributed inhomogeneous in each individual particles. This is the case of a heterogeneous individual distribution in a homogeneous collective. The collective of the coated core-shell aggregates can also be a sub-collective of a larger total collective, ie the collective of the coated core-shell aggregates together with further particles forms a total collective.

(iii) A collective of coated core-shell aggregates, for example a washing powder consisting of core-shell aggregates, can be characterized in that the cores of the collective as individual objects each have a homogeneous mass distribution (ie there is no density gradient in the individual) Nucleus), wherein the collective ε) formed by the same coated core-shell aggregates also gives a homogeneous mass distribution over the collective (ie there is no

Density gradient over the collective as a whole before, so that all the collective forming part chen have almost the same density), or φ) is given a heterogeneous mass distribution over the collective (ie there is a density level over the collective before as a whole, so that that is, the particles forming the collective do not have nearly the same densities).

In simple terms, this means that a particle collective θ is present. In none of the particles of this collective θ is there a density gradient. In the case ε) all particles of the collective θ also have the same density. This is the case of a homogeneous individual distribution in a homogeneous collective. In the case φ), not all particles of the collective 9 have the same density. This is the case of a homogeneous individual distribution in a heterogeneous collective. The collective of coated core-shell aggregates may also be a sub-collective of a larger total collective, i. the collective of coated core-shell aggregates together with other particles forms a collective.

(iv) A collective of coated core-shell aggregates, for example a washing powder consisting of core-shell aggregates, may be distinguished by the fact that the cores of the collective each have a heterogeneous mass distribution as individual objects (ie there is a density gradient in each case) individual nucleus), in which group γ) formed by the same coated core-shell aggregates is likewise given a heterogeneous mass distribution over the collective (ie, it is present

Density gradient over the collective as a whole before, so that the collective forming part chen not all have the same density), or η) a homogeneous mass distribution over the collective is given (ie there is no density level over the collective before as a whole, so that is, that the particles forming the collective have the same densities). In simple terms, this means that a particle collective π is present. The individual particles of this collective π have a density gradient. In the case of γ), the particles of the collective π also have different densities in comparison with each other. This is the case of a heterogeneous individual distribution in a heterogeneous collective. In the case η), the particles of the collective π have identical densities in comparison with one another. This is the case of a heterogeneous individual distribution in a homogeneous collective.

According to the invention, at least one coating is applied externally to the core-shell aggregate of core and surrounding particles, for example by spraying the core-shell aggregate with a coating agent which is preferably solid at room temperature and which contains in particular nonionic surfactant. Preferably, two or more coatings are applied to one another or one above the other.

Such a coated, optionally multi-coated core-shell aggregate is an agent according to the invention.

The coating can be applied by all conventional methods to the otherwise finished core-shell aggregate, for example by spraying, brushing or dipping. The coating can be applied, for example, as a dispersion, preferably emulsion, solution or melt. It is e.g. possible that the first coating is applied as an emulsion, the subsequent as a melt.

In a preferred embodiment, the coating contains no solid particles, but consists of a liquid system, preferably an emulsion.

In another preferred embodiment, the coating contains particulates, preferably coated by a dispersion.

In the coating e.g. With an emulsion, advantageously, not all of the coating material will remain exclusively on the surface, but advantageously also smaller portions will penetrate somewhat deeper into the core-shell aggregate.

By coating, however, preferably no impregnation is meant, because in the impregnation, the entire particle is permeated with a fluid or impregnated, often with the aid of wetting agents which facilitate the deep penetration of the impregnating agent into the particles by lowering the surface tension. In the coating but essentially only the Surface treated and the particle core remains essentially unchanged and is not changed in its properties substantially.

However, it is of course also possible for the core as such to be impregnated before it is surrounded with the shell, i. ie e.g. impregnated with a solution, dispersion or emulsion of certain active ingredients, preferably to modify the properties of the core. This corresponds to a preferred embodiment.

It is equally possible for the core as such to be coated before it is surrounded with the shell, i. ie e.g. is coated with a solution, dispersion, melt or emulsion of certain active ingredients. This corresponds to a preferred embodiment. For coating the core, materials comprising substances such as nonionic surfactants, cationic surfactants, amphoteric surfactants, silicone oil, triglycerides, terpenes, perfume, glycerol and / or (co) polymer (solutions) are suitable. Furthermore, all those substances come into question, which are disclosed for the coating of the core-shell aggregate elsewhere in this description.

Likewise, it is possible that the uncoated core-shell aggregate as such, before it is finally coated, is previously impregnated, i. e.g. so impregnated with a solution, dispersion or emulsion of certain active ingredients, to modify the properties of the core-shell aggregate. This corresponds to a preferred embodiment.

For impregnating the core or the uncoated core-shell aggregate impregnating agents, preferably silicone-containing impregnating agents can be used, ie mixtures which advantageously contain different polysiloxanes with condensable groups, which advantageously make more or less water repellent. For impregnation, it is preferred to use agents which serve for the hydrophobizing and the core or the uncoated core-shell aggregate.

Preferred hydrophobizing agents, in addition to agents containing silicones, are also agents e.g. Paraffins, waxes, metal soaps (sometimes also with additions of aluminum or zirconium salts), quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, tin-organic compounds and or glutaric dialdehyde.

In principle, of course, a hydrophilization is possible, which corresponds to a preferred embodiment. The hydrophilization takes place with the aid of hydrophilizing agents, which are applied, for example, in the form of aqueous solutions. These are, for example, preparations of ionogenic or nonionic polymers, ethoxylation products and the like. For example, it is possible to hydrophilize the core before it is surrounded by the shell. For impregnation, agents containing lipids are preferably used. Preferred lipids are

(a) lipophilic hydrocarbons (such as triacontane, squalene, or carotenoids, etc.),

(b) lipophilic alcohols (such as wax alcohols, retinol or cholesterol, etc.),

(c) ether lipids

(d) lipophilic carboxylic acids (fatty acids),

(f) lipophilic amides (such as ceramides, etc.),

(g) waxes

(h) lipids with more than 2 hydrolysis products, e.g. Glycolipids, phospholipids, sphingolipids and / or glycerolipids etc. (i) lipids in the form of higher molecular weight conjugates with more than 2 hydrolysis products, e.g. Lipoproteins and / or lipopolysaccharides, etc., (j) phosphorus-free glycolipids, e.g. Glycosphingolipids (such as, preferably, cerebrosides,

Gangliosides, sulphatides) or as e.g. Glycoglycerolipids (preferably glycosyl di- and monoglycerides), etc. (k) carbohydrate-free phospholipids, e.g. Sphingophospholipids (such as, preferably, sphingomyelin) or e.g. Glycerophospholipids (such as preferably lecithins, cephalins, car diolipins, phosphatidylinositols and inositol phosphates, etc.) and / or (I) mixtures of the foregoing.

In a further preferred embodiment, the impregnating agent comprises unsaponifiable lipid, preferably selected from free fatty acids, isoprenoid lipids, in particular steroids, carotenoids, monoterpenes etc. and / or tocopherols.

In another preferred embodiment, the impregnating agent comprises saponifiable lipid, preferably selected from mono-, di-, triacylglycerides, phospholipids (phosphatides), glycolipids, diollipids, waxes and / or sterol esters.

In a further preferred embodiment, the impregnating agent comprises at least one unsaponifiable and one saponifiable lipid.

In another preferred embodiment, the impregnating agent comprises neutral lipid, preferably selected from fatty acids (> C12), mono-, di-, triacylglycerides. Sterols, sterol esters, carotenoids, waxes and / or tocopherols. In another preferred embodiment, the impregnating agent comprises polar lipid, preferably selected from glycerophosphohpides, glyceroglycohpides, sphingophosphohpides and / or sphingoglycolipids

In a further preferred embodiment, the impregnating agent has at least one polar and one nonpolar lipid

It is also possible to carry out a partial hydrophobing in the coating of the core-shell aggregates, that is to make the surface of the particles hydrophobic, by applying hydrophobizing agents as a coating, preferably agents such as silicones, paraffins, waxes, metal soaps (US Pat. partly also with additions of aluminum or zirconium salts), quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, tin-organic compounds and / or glutaric dialdehyde

It is also possible to carry out a partial hydrophilization in the coating of the core-shell aggregates, that is to make the surface of the particles hydrophilic, for example by applying aqueous solutions as a coating to the core-shell aggregate, in particular preparations of ionogenic or ionogenic materials Non-ionogenic polymers, ethoxylation products and the like For example, polyethylene glycol sorbitan fatty acid esters and comparable substances are particularly suitable for the purpose of hydrophilization

The solubility of the shell as such can also be manipulated individually, advantageously via the choice of granulation fluid. For example, the granulation fluid can be rather hydrophobic, with the result that the shell loses more slowly in a watery environment. If the granulation fluid is rather hydrophobic, For example, in the context of this invention, the term "hydrophobically bound" shell is used more simply in the following description. For example, the granulation fluid may be rather hydrophilic, with the result that the shell will dissolve faster in an aqueous environment. If the granulation fluid is rather hydrophilic, then in the context of this invention in the further description of a "hydrophilic bonded" shell the speech

The Granulationsflussigkeit serves as a binder for the Schalenmateπal and serves to Löshchkeitsein- position z B largely lipophilic surfactants, preferably surfactants with

HLB values of 3 to 12, in particular 4 to 10 The term of the HLB value is known to the person skilled in the art. Detailed lists of the HLB values of commercially available surfactants can be found in the relevant literature, for example in Kirk-Othmer As granulation liquid are preferably also single-phase aqueous systems comprising water and optionally salts, alkyl polyglycosides, carbohydrates (saccharides), natural and synthetic polymers (such as cellulose ethers, starch, polyethylene glycol, polyvinyl alcohol) and / or biopolymers. As granulation liquid are preferably single-phase low-water systems, which may contain, for example, swollen polymers and organic solvent. Suitable granulation liquids are preferably monophase anhydrous systems such as melts or systems containing, for example, dihydric / trihydric alcohols. As granulation liquid are preferably multiphase aqueous systems, such as oil / polymer / water emulsions, surfactant / air and / or nonionic surfactant / polymer solution. As granulation liquid are preferably multiphase anhydrous systems such as solids-containing melts and / or polymer / solvent.

By hydrophobing and / or hydrophilization can be realized a variety of coated core-shell aggregates, e.g. such

(a) which have a hydrophobic coating,

(b) which have a hydrophilic coating,

(c) which have a hydrophilic bonded shell,

(d) which have a hydrophobically bound shell,

(e) which have a hydrophobically impregnated core,

(f) which have a hydrophilically impregnated core,

(g) which have a hydrophobically impregnated core-shell aggregate, (h) which have a hydrophilically impregnated core-shell aggregate,

(i) which have a hydrophobically impregnated core and a hydrophobic coating, (j) which have a hydrophobically impregnated core and a hydrophilic coating, (k) which have a hydrophobically impregnated core and a hydrophobically bound shell

(I) which have a hydrophobically impregnated core having a hydrophilic bonded shell (m) having a hydrophilically impregnated core and a hydrophobic coating, (n) having a hydrophilically impregnated core and a hydrophilic coating, (o) having a hydrophilically impregnated core and have a hydrophilic coating, (p) which have a hydrophilically impregnated core and a hydrophobically bonded shell (q) which have a hydrophilically impregnated core and a hydrophobically bonded shell (r) which have a hydrophobically impregnated core-shell aggregate and a hydrophobic coating (s) which have a hydrophobically impregnated core-shell aggregate and a hydrophilic coating,

(t) which have a hydrophobically impregnated core-shell aggregate and a hydrophobically bound shell, (u) which have a hydrophobically impregnated core-shell aggregate and a hydrophilic bonded shell,

(v) which have a hydrophilically impregnated core-shell aggregate and a hydrophobically bound shell,

(w) which have a hydrophilically impregnated core-shell aggregate and a hydrophilic bonded shell,

(x) which have a hydrophobic coating and a hydrophobically bound shell,

(y) which have a hydrophobic coating and a hydrophilic shell,

(z) which have a hydrophilic coating and a hydrophobically bound shell,

(aa) which have a hydrophilic coating and a hydrophilic shell,

(bb) which have a hydrophobically impregnated core, a hydrophobic coating and a hydrophobically bound shell,

(cc) which have a hydrophobically impregnated core, a hydrophobic coating and a hydrophilic bonded shell,

(dd) which have a hydrophobically impregnated core, a hydrophilic coating and a hydrophobically bound shell,

(ee) which have a hydrophilically impregnated core, a hydrophobic coating and a hydrophobically bound shell,

(ff) which have a hydrophilically impregnated core, a hydrophilic coating and a hydrophobically bound shell,

(gg) which have a hydrophilically impregnated core, a hydrophobic coating and a hydrophilic bonded shell,

(hh) which have a hydrophobically impregnated core, a hydrophilic coating and a hydrophilic bonded shell,

(ii) which have a hydrophilically impregnated core, a hydrophilic coating and a hydrophilic bonded shell,

(jj) which have a hydrophobically impregnated core-shell aggregate, a hydrophobic coating and a hydrophobically bound shell,

(kk) which have a hydrophobically impregnated core-shell aggregate, a hydrophobic coating and a hydrophilic bonded shell,

(II) which have a hydrophobically impregnated core-shell aggregate, a hydrophilic coating and a hydrophobically bound shell,

(mm) which have a hydrophilically impregnated core-shell aggregate, a hydrophobic coating and a hydrophobically bound shell,

(nn) which have a hydrophilically impregnated core-shell aggregate, a hydrophilic coating and a hydrophobically bound shell,

(oo) which have a hydrophilically impregnated core-shell aggregate, a hydrophobic coating and a hydrophilic bonded shell, (pp) which have a hydrophobically impregnated core-shell aggregate, a hydrophilic coating and a hydrophilic bonded shell and / or (qq) which have a hydrophilically impregnated core-shell aggregate, a hydrophilic coating and a hydrophilic bonded shell

Of course, not far more diverse combinations are possible here, which are not explicitly listed here for reasons of clarity, but are obvious to the person skilled in the art

This freedom in the design of the coated particles leads to virtually unrivaled possibilities for the use of the coated core-shell aggregates in a particle collective, for example a washing powder, wherein the coated core-shell aggregates can also be the sub-collective of a total collective Loseverzogerung the coated core-shell aggregates is now arbitrarily finely adjustable In addition, the Loseverzogerung on the just described actuators even finer differentiable is indeed on the porosity or density of the core A high porous or less dense Kernmateπal dissolves faster than a less porous or high density Kemmateπal

For the sake of clarity, only two cases are selected from the enormous range of coated particles that can be coated and collectives containing them, although the person skilled in the art is aware of the fact that he has a wide variety of possibilities. A) A particle collective of coated core-shell aggregates (washing powder) can, for example, consist of two types coated core-shell aggregates Type 1 is characterized by the fact that it has a hydrophobically impregnated core, a hydrophobic coating and a hydrophobically bound shell. The core is also less porous or more densely packed. Grade 2 is characterized by: it has a hydrophilically impregnated core, a hydrophilic coating and a hydrophilic bonded shell The core is also porous or slightly compacted

When using such a washing powder, there are now two categories of particles with completely opposite loose behavior, namely a category of particles with very pronounced loose delays (here grade 1) and another category of particles with very pronounced loosely translated (here grade 2) the particles of grade 1 incorporated such active substances which are to be released immediately at the beginning of a washing process, while the particles of grade 2 contain such active substances which are not to be used until late stages of a washing cycle, eg care components or aftertreatment components

As one skilled in the art can readily appreciate, there are many possibilities of variation between these two extremes in order to adapt the loose behavior to the respective needs b) A particle collective of coated core-shell aggregates (washing powder) may consist, for example, of one type of coated core-shell aggregates, which is distinguished by having a hydrophobically impregnated core, a hydrophilic coating and a hydrophobically bound shell is also less porous or more compacted

Such a coated core-shell aggregate was very fast, d h immediately at the beginning of a washing process, release the active substances that covers the coating The active ingredients of the shell were then slowly released The active ingredients of the core were then released again later

As the person skilled in the art immediately recognizes here, the freely adjustable loose behavior is also highly suitable for the production of molded articles, eg tablets. If, for example, to provide an illustrative example, the already mentioned particle collective of coated core-shell aggregates ( Washing powder), which consists of 2 types of coated core-shell aggregates, wherein the variety 1, characterized in that it has a hydrophobically impregnated core, a hydrophobic coating and a hydrophobically bonded shell, wherein the core also less porous or higher is compacted, and wherein the variety 2 is characterized by the fact that it has a hydrophilic impregnated core, a hydrophilic coating and a hydrophilic bonded shell, wherein the core is also porous or slightly compressed, so it can be excellent (washing and Reιnιgungsmιttel -) Making tablets In such a tablet, the particles of grade 2 were added Dissolve contact with water quickly, so that the tablet quickly disintegrates or loses its integrity The tablet disintegrates releasing the contained in the particles of the type 2 active ingredients in the particles of grade 1, which then release their active substances later Also here is one The skilled person immediately apparent variation width given, with which the Auflose- and decay behavior of tablets can almost control arbitrarily

For example, the cores of the coated core-shell aggregates may also contain decomposition accelerators, for example substances which have a high ability to adsorb water (for example starch, cellulose denovates, alginates, dextranes, crosslinked polyvinylpyrrolidone, casein denvates, etc.). and / or in particular gas-evolving substances (for example sodium bicarbonate, citric or tartaric acid, etc.), so that a showering effect or bubbling effect occurs. If the particles of grade 2 contain such disintegration accelerators, the shaped body became even faster decay

Another object of the invention is therefore a Formkorper, preferably tablet containing agents of the invention In a preferred embodiment, a erfindungemäßes, coated core-shell aggregate on a reduced Dusting tendency, wherein it has a dust content (according to the Elutriationsmethode described here)

- of an average of less than 2500 mg / 60g, with bulk densities of the coated core-shell aggregate <500 g / l, or

- From an average of less than 2000 mg / 60g, bulk densities of the coated core-shell aggregate of 501 to 700 g / l, or

- From an average of less than 1500 mg / 60g, bulk densities of the coated core-shell aggregate from 701 to 850 g / l, or

- of an average of less than 700 mg / 60g, with bulk densities of the coated core-shell aggregate of> 851 g / l, depending on the bulk density of the coated core-shell aggregate.

In the elution method used here, 60 g of the coated core-shell aggregate are placed on a glass frit (glass frit from Robu, type: Por 2, pore size 40-100 μm) in a large glass tube (tube height 180 cm, tube diameter 3.3 cm). is placed for 40 minutes at a constant rate of 0.8 m / s air (dehumidified room air with a moisture content of 0.01 g / m ³ corresponding to a dew point of about -60 ° C; temperature of the air T = 20 ° C ± 2 ° C) through the coated core-shell aggregates (air volume: 2.4 m ³ / h, differential pressure: 100 mm WS, regulation with a vacuum pump). The air flow through the coated core-shell aggregates causes them to be whirled up. The resulting dust is carried away by the air stream and collected on a filter (filter Whatman, type: glass fiber microfilter GF / C Circles, pore size 1, 2μm, 150mm diameter). The dust mass can then be determined gravimetrically quantitatively. The dust determination with the elution method is always carried out as a multiple determination, at least as a triple determination, preferably as a quadruple, quintuple or sixfold determination, whereby the mean value from the multiple determinations serves as measured value (dust value). This gives the dust value (synonym: dust content) in mg based on 60 g of the coated core-shell aggregates. The indication that the dust value (dust content) "on average" is smaller than eg 2000 mg / 60 g should indicate that the dust value (dust content) is the result of a multiple determination, ie that the elutriation method was used several times to calculate the dust value ( The elutriation method simulates the formation of dust from granules / agglomerates, such as those encountered during light-duty applications such as transfer, making the elutriation method the method of choice for detecting those stresses and conditions commonly present in the consumer household , For additional details on this well-known method, see, for example, "Enzymes In Detergent," Ed Jan H van Ee, et al, Chpt 15, pgs 310-312 (Marcel Dekker, Ine, New York, NY (1997)), and the references there or the corresponding patent literature

According to a preferred embodiment of the invention, the coated core-shell aggregate has a dust content (according to the elution method described here) of on average less than 2400 mg / 60 g, 2200 mg / 60 g, 2000 mg / 60 g, 1800 mg / 60 g , 1600 mg / 60 g, 1400 mg / 60 g, 1300 mg / 60 g, 1200 mg / 60 g, 1 100 mg / 60 g, 1000 mg / 60 g, 900 mg / 60 g, 800 mg / 60 g, 700 mg / 60 g, 600 mg / 60g, 500mg / 60g, 400mg / 60g, 200mg / 60g or 100mg / 60g, with the benefits increasing in the order of just completed entries, based in each case on coated core-shell aggregates with a stock weight <500 g / l

According to a preferred embodiment of the invention, the coated core-shell aggregate has a dust content (according to the elution method described here) of on average less than 1800 mg / 60 g, 1600 mg / 60 g, 1400 mg / 60 g, 1200 mg / 60 g , 1000mg / 60g, 900mg / 60g, 800mg / 60g, 700mg / 60g, 600mg / 60g, 500mg / 60g, 400mg / 60g, 200mg / 60g or 100mg / 60g, with the benefits being increases in the order of the just made entries, in each case based on coated core-shell aggregates with a total weight of 501 to 700 g / l

According to a preferred embodiment of the invention, the coated core-shell aggregate has a dust content (according to the elution method described here) of on average less than 1400 mg / 60 g, 1200 mg / 60 g, 1000 mg / 60 g, 800 mg / 60 g , 700 mg / 60 g, 600 mg / 60 g, 500 mg / 60 g, 400 mg / 60 g, 200 mg / 60 g or 100 mg / 60 g, with the advantage increasing in the order of the nominations just made, in each case based on coated core Shell aggregates with debris weights from 701 to 850 g / l

According to a preferred embodiment of the invention, the coated core-shell aggregate has a dust content (according to the elution method described here) of on average less than 650 mg / 60 g, 600 mg / 60 g, 500 mg / 60 g, 400 mg / 60 g, 200 mg / 60g or 100 mg / 60g, whereby the advantage in the order of the just made entries increases, in each case based on coated core-shell aggregates with a dry weight> 851 g / l

According to a preferred embodiment of the invention, the coated core-shell aggregates are characterized in that they have a dust content (according to the elution method described here) of on average less than 800 mg / 60 g, preferably a dust value of on average less than 700 mg / 60g, 600mg / 60g, 500mg / 60g, 400mg / 60g, 200mg / 60g or 100mg / 60g, with the benefit increasing in the order of the entries just made. Of course, the coated core-shell aggregates can also advantageously be applied in pouches, bags or sacs. Another object of the invention is a pouch, bag or sack containing the agents according to the invention

Another object of the invention is a detergent or cleaning agent containing inventive compositions, in particular a detergent containing care components

Another object of the invention is a detergent, preferably dishwashing, containing

(A) cleaning component containing, for example, surfactants such as preferably alkanesulfonates, alkyl ether sulfates, alkyl polyglucosides and / or cocoamidopropyl betaine

(b) clear rinse component containing, for example, nonionic surfactants, preferably on a fatty alcohol basis, in particular with additions of lower alcohols as solubilizers and, advantageously, citric acid

(c) Enthartungskomponente containing, for example, phosphonate, polycarboxylate, Natπumglu conat, ethylenediaminetetraacetic acid (EDTA), Nitπlotriessigsaure (NTA) and / or Aluminiumiumsi licaten (zeolites)

(D) Optional other ingredients such as preferably Sιlber- / glass protection component

Another object of the invention is an agglomerate / granules (ie an aggregate), which is a multicomponent system, wherein the substances contained are arranged in at least 3 different phases, preferably in the phases core, shell and coating, wherein in particular the chemical composition of Differentiates phases

But the demonstrated fine-tuning capabilities of the release of active substances go far beyond what has been described so far

According to a further preferred embodiment, the coating is pH-sensitive and / or high-temperature and / or ionic-sensitive or contains pH and / or temperature and / or ionic strength-sensitive materials. According to a further embodiment, the shell is pH and / or temperature and / or ionic strength-sensitive or contains pH and / or temperature and / or ionic strength-sensitive materials. According to a further embodiment, the core is sensitive to pH and / or temperature and / or ionic strength or contains pH and / or Temperature- and / or ion-strength-sensitive materials

In the following, the suitability of the pH and / or temperature and / or ionic strength sensitivity will be explained primarily by the example of the coating. However, it is clear to the person skilled in the art that that it can readily apply the same mechanisms to the preparation of the core and shell. The core may, for example, be a granulate consisting of subparticles held together by a pH and / or temperature and / or ionic strength-sensitive material Thus, the core can thus lose its integrity, that is, decay. The shell can eg with a pH and / or temperature and / or ionic strength-sensitive Granulationsflussigkeit on the core Under adjustable conditions regarding pH and / or temperature and / or ionic strength, the shell can thus lose its integrity and dissolve

It is meant by the term pH Sensιtιvιtat, temperature-sensitive itat and / or ionic strength sensitivity that the coating or the coating forming materials with a change in pH, temperature and / or the ionic strength in the environment, which is exposed to the coating (eg a wash liquor),

(a) undergo a change (increase or decrease) in solubility (preferably in water), and / or

(b) undergo a change (increase or decrease) in diffusion density, and / or

(c) experiencing / experiencing a change (acceleration or deceleration) in the pay kinetics and / or

(d) experience a change (increase or decrease) in mechanical stability

For the temperature sensitivity, in addition to the options (a) to (d) mentioned above, there is the additional option (e) according to which the coating or the materials forming the coating change the state of matter from solid to liquid or if the temperature changes vice versa, ie the materials melt or solidify

In the context of the invention, all those materials whose integrity is a function of the temperature and / or the pH and / or the ionic strength or else those materials which are subject to mechanical stress such as those in the course of a process can serve as the coating material suitable for this purpose Advantageously, the pH Sensιtιvιtat the coating can be used, for example, the coating can be designed so that it dissolves wholly or partially, if the pH drops below a critical mark This can in the example of a Washing process then happen when the alkaline wash water is removed from the machine and fresh water introduced into the machine, preferably in the wake of the washing process. Upon contact with the fresh water, the coating then lose all or part of its integrity and thus makes the core-shell aggregate for the water penetrable The concerned pH at which the coating completely or partially disintegrated, can be set arbitrarily, so that the material example- then its integrity completely or partially loses if the pH z B falls below 9.0, but remains substantially inert, as long as the pH is above 10, 0

The term "inert" is understood according to the invention in the usual sense, ie in such a way that a physical or chemical reaction of the material of the coating with the ambient Miheu essentially not done, but the material of the coating is physically and chemically resistant to this, so that the core-shell aggregate is substantially protected from penetration by the environment, eg the wash liquor

In a particularly preferred embodiment, the coating consists of at least 2 layers, wherein the outermost layer is designed such that it is in, preferably cold, water at pH values below a maximum of 6, preferably below a maximum of 7, in particular below a maximum of 8, is substantially inert, but in, preferably warm, water at pH values above at least 11, preferably above at least 10, in particular above at least 9, their integrity completely or partially loses, and that the innermost layer is designed so that it is in, preferably warm, water at pH values above at least 11, preferably above at least 10, in particular above at least 9, substantially inert, but in, preferably cold water at pH values below a maximum of 6, preferably below of a maximum of 7, in particular below a maximum of 8, their integrity completely or partially loses

This embodiment takes into account the particular requirements at the beginning of the washing process At the beginning, detergents come into contact with, preferably cold, non-alkaline water for a short period of time, and thus encounter conditions similar to those prevailing in the duct. Here, therefore, is an outermost layer advantageous, which is substantially inert to these conditions. The outermost layer is those which directly adjoins the surrounding fluid. Under the outermost layer, one or more layers may follow in the direction of the core-shell aggregate. The last following layer is that in nerste layer This preferably separates the core-shell aggregate from all other layers or the ambient fluid. If the coating consists of only one layer, then the term "outermost" or "innermost" is obsolete. If the coating consists of only one layer, then it is preferably designed so that they are in, preferably warm em, water at pH values above at least 11, preferably above at least 10, in particular above at least 9, is substantially inert, but in, preferably cold, water at pH values below a maximum of 6, preferably below a maximum of 7 , in particular below a maximum of 8, their integrity completely or partially loses In this way you can easily achieve good protection of the core-shell aggregate Since the Einspulvorgang is short-lived and thereby solve the alkaline components of the detergent very quickly, already during the rewinding Ganges alkaline water before, so that is also a coating that is only effective in the sense of the invention from a layer which is pH-sensitive in the just mentioned sense, as it is wetted at most for a few seconds of non-alkaline water.

After the short moment of Einspülvorgangs is over, therefore alkaline, possibly heated water is present. In this (possibly warm) water at pH values above advantageously at least 11, preferably above at least 10, in particular above at least 9, the outermost coating (in the case of multilayer coating) loses all or part of its integrity. By contrast, the innermost layer would be designed such that it is substantially inert in (possibly warm) water at pH values above advantageously at least 11, preferably above at least 10, in particular above at least 9. The innermost layer advantageously comes naturally only in contact with the wash liquor or water when the outermost layer has lost all or part of its integrity, ie when (possibly warm) alkaline water is present. Under these conditions, the innermost layer is then advantageously substantially inert to the wash liquor and thus sufficiently protects the core from direct contact with the water. In the rinse, the previously completely removed alkaline wash liquor is replaced by fresh non-alkaline water. Under these conditions, ie in, preferably cold, water at pH values below a maximum of 6, preferably below a maximum of 7, in particular below a maximum of 8, advantageously now also the innermost layer loses its integrity completely or partially, so that the core Shell aggregate can be penetrated by the water.

For the sake of clarity, it should be noted that what has just been described relates only to a preferred embodiment of the invention.

Materials which can be used as coating materials, in particular in the sense of such embodiments, are any inorganic and / or organic substances and / or mixtures, but in particular polymers, copolymers, polymeric composites, preferably those which are pH, temperature and / or ionic strength-sensitive are.

As coating materials, preferably in the sense just described, for example, waxes and / or resins are suitable, for. Beeswax, benzoin, carnauba wax, candelilla wax, coumarone-indene resin, copels, shellac, mastic, polyethylene wax oxidates or Sandakar resin. Likewise, paraffins or gelatin, in particular cellulose ethers, are also suitable coating materials.

Particularly preferred as coating materials are polymers and / or copolymers which have film-forming properties and can preferably be used from aqueous dispersion. While organic solvents are also preferred, they can be detrimental to the production of pH-sensitive coatings for many reasons (flammability, toxicity, etc.) its size dispersions are characterized by their ease of handling and the avoidance of all toxicological problems. The decisive factor for the film-forming properties is the glass transition temperature of the film-forming polymer and / or copolymer O- beyond the glass transition temperature, the polymer or copolymer is elastic, meltable and flowable, while it becomes brittle below the glass temperature Only above the glass transition temperature, the polymer can be easily processed, as it is necessary to form a film coating The glass transition temperature can be influenced by the addition of low molecular weight substances with softening properties, the so-called plasticizers in the aqueous dispersion also plasticizers are used as plasticizers are all substances suitable which reduce the glass transition temperature of the used, preferably pH-sensitive polymers and / or copolymers The polymer can s o Particularly preferred plasticizers are citric acid esters (preferably titanium citrate and / or triethyl citrate), phthalic acid esters (preferably dimethyl phthalate, diethyl phthalate and / or dibutyl phthalate), esters of organic polyalcohols (preferably glycerol acetate). , Polyalcohols (preferably glycerol, propylene glycol) and / or polyoxyethylene glycols (preferably polyethylene glycol) The plasticizer deposits between the polymer chains, thereby increasing the mobility, reduces the interactions and avoids abrasion and cracks in the film by reducing the sprouting

It is particularly advantageous if the coating material contains a polyacrylate and / or a derivative thereof and / or a corresponding copolymer based on acrylic acid esters or acrylates and other monomers. Copolymers of acrylamide and acrylic acid and / or derivatives thereof are particularly preferred the coating material of the invention is advantageous

The principle of pH-dependent waterlessness is usually based on protonation or deprotonation of functional groups of the polymer molecules, as a result of which their state of charge changes accordingly. The polymer can now advantageously be such that it is in the charged state stable at a certain pH In the context of the present invention, it is preferred, at least as far as the innermost layer of the coating is concerned, that the polymers used according to the invention, from which the innermost layer of the Coating is at least partially present, have a lower pH at a higher pH Wasserloshchkeit than at lower pH values or even at a higher pH are water insoluble In a preferred embodiment of the invention, it is also advantageous, at least if a coating consisting of a single layer that the polymers which can be used according to the invention and from which the coating can be at least partially At a higher pH, they have lower water solubility than at lower pHs, or are water insoluble even at a higher pH

Conversely, in the context of a preferred embodiment of the present invention, it is advantageous, at least as far as the outermost layer of the coating, that the polymers which can be used according to the invention and from which the outermost layer of the coating can be composed at least partially be at a lower pH have a lower water solubility than at higher pHs or are water insoluble even at a lower pH

Polymers with pH-dependent solubility are known in particular from pharmaceutics Here, for example, acid-insoluble polymers are used to give tablets an enteric coating which is soluble in the intestinal juice. Such acid-insoluble polymers are usually based on derivatives of polyacrylic acid, those in the acidic region in undissociated and thus is insoluble in the alkaline range, but typically neutralized at pH 8, and as polyanion goes into solution. Polymers of similar type, tuned to the particular pH requirements of the machine washing process, are preferred for the outermost layer of the coating Advantageously, if the coating is multilayered, this layer, preferably the outer layer, may advantageously be substantially inert in the neutral to acidic form, but advantageously in the alkaline, ie at pH values above 0.1, preferably above 10, especially above 9, wholly or partially dissolve If the coating is not multilayered, then polymers of this type are rather not advantageous for the design of the coating

According to a preferred embodiment, the multilayer coating, in particular the outermost layer of the coating is such that it consists at least partially of polyacrylic acid and / or derivatives of polyacrylic acid, which at pH values above at least 11, preferably above at least 10, in particular goes above at least 9 as polyanion in solution

Also in the opposite case - soluble in the acidic range, insoluble in the alkaline range - examples are known in the prior art These substances, in which the polymer molecules usually carry amino-substituted functional groups or side chains, are used, for example, for the production of tablet-acid-rich tablet exudates As a rule, at pH values below 5, polymers in which the mobility changes from soluble to insoluble at higher pH values are not known from the pharmaceutical industry, since these pH values have no physiological significance

Particularly preferred substances in the context of the present invention are basic, preferably film-forming, (co) polymers which contain amino groups or aminoalkyl groups. sen. Comonomers may be, for example, conventional acrylates, methacrylates, maleinates or derivatives of these compounds. A particularly suitable aminoalkyl methacrylate copolymer marketed by Rohm and carries the trade name / mark Eudragit ^®.

In a preferred embodiment, the coating contains, at least partially, a substance from the group of amino groups, imino groups and / or polymers containing pyridine groups and / or copolymers, the base exponent of this substance being between 2 and 9, preferably between 2.5 and 8.5 preferably between 3 and 8, even more preferably between 3.5 and 7.5, but in particular between 4 and 6.

The base exponent (pK _B ) is the negative decadic logarithm of the base constants [pK _B = -Ig K _B , with K ₈ = base (dissociation) constant]. These terms are familiar to those skilled in the art.

The base exponent is an equilibrium constant that can change with temperature and / or ionic strength. The stated values refer to a temperature of T = 25 ° C. Relevant pK values can be taken from the literature known in the art. Likewise, the relevant literature provides information on methods for determining the pK values.

In particularly preferred compositions, the coating consists at least partially of a copolymer of basic monomers such as dialkylaminoalkyl (meth) acrylates with acrylic esters. Also agents in which the coating is at least partially made of an ampholytic polymer, preferably a copolymer of basic monomers such as dialkylaminoalkyl (meth) acrylates with substituted or unsubstituted acrylic acids and / or (meth) acrylic acids and / or their esters with aliphatic d-Cβ- Alcohols, constitute a preferred embodiment of the invention.

The amino groups, imino-containing and / or pyridine-containing polymers and / or copolymers contain in a preferred embodiment, alkyl-substituted nitrogen groups, preferably alkyl-substituted amino groups, especially tertiary amino groups containing a branched or unbranched alkyl substituent having up to 22 carbon atoms, preferably 2-20, in particular of 4-18 C atoms, for example 12 C atoms.

The alkyl-substituted nitrogen groups in the (co) polymer contribute to improving the film-forming properties of the (co) polymer.

In addition to the thermodynamic solubility, the dissolution kinetics of the coating may also be important for the application. The dissolution kinetics of the coating materials used according to the invention is advantageously pH-dependent down to the alkaline range, ie For example, the coating materials are much longer stable at a pH of 10 than at a pH of 8.5, although they are thermodynamically soluble at both pHs

In a further embodiment of the present invention, therefore, polymers are used whose water solubility changes between the pH of 7 and the pH of 6 and which are less soluble at higher pH values than those of lower suitable polymers, as already described above basic groups, for example primary, secondary or tertiary amino groups, imino groups, amido groups or phenyl groups, generally those groups which have a quaternizable nitrogen atom. The quaternizable nitrogen atoms are protonated upon lowering the pH, whereby the polymer becomes soluble at higher pH values the molecule is in the uncharged state and is therefore insoluble. Usually, the transition - referred to below as the "switching point" - depends on the pK _B value of the basic groups and also on their density along the polymer chain, in the range of acidic pH values Coating materials therefore preferably comprise Also, a polymer in which the switching point is in a range between pH 6 and 7

In principle, this shift of the switching point of a polymer suitable for the purposes of the present invention succeeds in the following way. Depending on the pK _B value of the functional groups of the polymer, the charge state of the polymer in solution changes very little in the range of higher pH values It is necessary to decisively influence the solubility of the polymer with a slight change in the state of charge of the polymer. The polymer can therefore have precisely such a hydrophilicity that it becomes insoluble in the completely uncharged state but becomes soluble when already slightly charged, for example by protonation

In practice, one skilled in the art will be referred to the general knowledge for coating pharmaceutically used substances such as tablets and coated tablets with non-corrosive coatings. A known class of coating materials which at pH values is less than 6, preferably less than 7 or especially less than 8 , can be used, are copolymers of basic monomers, water-insoluble monomers and, if desired, water-soluble monomers are here as basic monomers, for example, esters of acrylic acid and methacrylic acid and alkylaminoalkyl acrylates or methacrylates in particular dimethylaminoethyl in question further suitable basic monomers are Vinylpyrπdin or Acrylic or Methacrylamiddeπvate substituted with alkylaminoalkyl groups At water-insoluble monomers are esters of acrylic acid or methacrylic acid with alcohols having 1 to 8 carbon atoms, in particular the methyl esters, ethyl esters, butyl esters or 2-hexylet hylester used

As water-soluble monomers it is possible to use substances such as acrylamide, methacrylamide, vinylpyrrolidone or hydroxyethyl acrylates or methacrylates To adjust the hydrophilicity, the following methods can also be used:

• Copolymerization of a monomer with a basic function with a more hydrophilic monomer. The installation ratio of the respective comonomers influences the switching point.

Hydrophilization of the basic group-bearing polymer by a polymer-analogous reaction. The degree of modification influences the switching point.

In addition to simple hydrophilization, it is also possible to introduce basic functions of different pK _B values. Due to the ratio of both groups and the resulting hydrophilicity of the molecule, the switching point can be influenced.

A particularly preferred polymer of this class of substances is an N-oxidized polyvinylpyridine.

Typical coating materials may include, for example, 10 to 60% by weight of the water-insoluble monomers, 20 to 80% by weight of the amino group-bearing monomers, and 0 to 40% by weight of the water-soluble monomers.

According to a particular embodiment, acids such as acrylic or methacrylic acid can be used as water-soluble monomers, furthermore, N-oxides of the aforementioned amino group-carrying monomers can be used, such as vinylpyridine-N-oxide. It is also possible to use quaternized monomers, such as dialkyldiallylammonium salts or quaternization products of the abovementioned amino-containing methacrylic and acrylic esters.

Generally speaking, as the amount of water-insoluble monomers increases, so does the pH at which solution of the polymer enters. The skilled person has the opportunity in this way to set special pH values.

The aforementioned copolymers are preferably prepared by emulsion polymerization, at a pH at which they are not in solution. The polymer dispersions obtained in this way are suitable for coating the core-shell aggregates. In this case, for example, technologies are used, as they are common in drug manufacturing. Thus, especially in slow-running mixing tools, the dispersions and the particles are associated with each other, isolated and dried with thorough mixing.

But it is also possible to work with a dissolved form instead of the dispersions. The pH-dependent soluble polymer can be used not only as a coating but also as a matrix material, binder or disintegrant for the actual core-shell aggregate or shell or core. It is not necessary for the polymer to completely dissolve at the pH conditions characteristic of the polymer for releasing the active ingredient. Rather, it is sufficient if, for example, the permeability of a polymer film changes and, for example, the penetration of water into the formulation and a removal of the dissolved components through the holes or pores formed is made possible. As a result, in a further preferred embodiment of the agents according to the invention, a secondary effect, for example the activation of an effervescent system or the swelling of a water-swellable disintegrants, which are known in particular from pharmacy, for the complete release of the active detergent (s) active, active in washing or active in cleaning (s ) to care.

To more reliably achieve the pH-sensitive coating which is to protect the core-shell aggregate in the early stages of the washing process, it does not dissolve in the earlier stages of the washing process, various methods can be used to reduce losses of active ingredients to avoid.

(a) A sufficient layer thickness of the coating or a sufficiently high molecular weight of the polymer of the coating can be set. The layer thickness is according to the invention preferably in the range of the order of a monomolecular coverage to 50 microns. The molecular weight of the coating of the polymer may, for example, be at least 50 kD, preferably at least 1,000 kD.

A loss of active ingredient can also be avoided by adding a further polymer to the coating material which reduces the solubility of the blend. Examples of such additional polymers are generally those which are less hydrophilic / more hydrophobic than the coating polymer.

(b) As already presented as a preferred embodiment, a multilayer coating comprising at least two different pH-sensitive layers can be built up, the innermost and outermost layers meeting the pH requirements described above.

Following a similar principle, an additional, less readily or less rapidly soluble layer at lower temperature can also be applied. This may be, for example, a paraffin which melts upon reaching a higher temperature (which is passed through in the subsequent step) ("melt coating"), or else a hydrophilic polymer which becomes soluble upon reaching a certain temperature ("polymer coating"). Also very suitable are LCST substances, which will be described later. In another preferred embodiment of the invention, a pH-sensitive coating is coated with a material which in turn is temperature-sensitive. Here, LCST substances are preferably used. LCST substances are substances that have better solubility at low temperatures than at higher temperatures. They are also referred to as lower critical solubility temperature or low lower turbidity or flocculation point substances. Depending on the conditions of use, the lower critical demixing temperature should be between room temperature and the temperature of the heat treatment in the respective washing process, for example between 2O ⁰ C and 120 ⁰ C, preferably between 25 ⁰ C and 100 ⁰ C, in particular between 3O ⁰ C and 50 ° C. The LCST substances are preferably selected from alkylated and / or hydroxyalkylated polysaccharides, cellulose ethers, polyisopropylacrylamide, copolymers of polyisopropylacrylamide and mixtures of one or more of these substances.

Examples of alkylated and / or hydroxyalkylated polysaccharides are hydroxypropylmethylcellulose (HPMC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropylcellulose (HPC), methylcellulose (MC), ethylcellulose (EC), carboxymethylcellulose (CMC) , Carboxymethylmethylcellulose (CMMC), hydroxybutylcellulose (HBC), hydroxybutylmethylcellulose (HBMC), hydroxyethylcellulose (HEC), hydroxyethylcarboxymethylcellulose (HECMC), hydroxyethylethylcellulose (HEEC), hydroxypropylcellulose (HPC), hydroxypropylcarboxymethylcellulose (HPCMC), hydroxyethylmethylcellulose (HEMC ), Methylhydroxyethylcellulose (MHEC), methylhydroxyethylpropylcellulose (MHEPC) and propylcellulose (PC).

Further examples of LCST substances are cellulose ethers and mixtures of cellulose ethers with carboxymethylcellulose (CMC). Other polymers which exhibit a lower critical demixing temperature in water and which are also suitable are polymers of mono- or di-N-substituted acrylamides with acrylates and / or acrylic acids or mixtures of intertwined networks of the abovementioned (co-) polymers. Also suitable are polyethylene oxide or copolymers thereof, such as ethylene oxide-propylene oxide copolymers, graft copolymers of alkylated acrylamides with polyethylene oxide, polymethacrylic acid, polyvinyl alcohol and copolymers thereof, polyvinyl methyl ether, certain proteins such as poly (VATGW), a repeating unit of the natural Protein elastin and certain alginates. Mixtures of these polymers with salts or surfactants can also be used as the LCST substance. By such additives or by the degree of crosslinking of the polymers, the lower critical demixing temperature (LCST) can be modified.

In a further preferred embodiment of the invention, the coating consists of a temperature-sensitive material. The ingredients of the core are at the desired temperature released. The coating material can, for example, at temperatures for example, 5O ⁰ C lose its integrity.

The coating is configured according to a further preferred embodiment of the invention on the core-shell aggregates in a thin as possible, but preferably a complete coating forming thickness. The thickness, as such, is not critical, but is preferably limited by the requirement of working as gently as possible and the potential requirement, e.g. to allow a fast or slow dissolution. At the same time the requirement is taken into account with the lowest possible thicknesses to burden the laundry and the liquor - and thus later the wastewater - with as little water-insoluble materials. Exemplary thicknesses which can be used to advantage are e.g. in the range of 0.005 to 0.5 mm, more preferably in the range of 0.02 to 0.4 mm, which gives, for example, coating weights in the range of, for example, 50 to 500 mg (weight of the pure coating). But there are also all other thicknesses conceivable.

In a preferred embodiment, the coating solution used for coating contains a pH-sensitive, preferably film-forming, polymer and / or copolymer according to the description of the description, a plasticizer and a solvent, which is very particularly preferably water. Furthermore, dyes can be added to the solution to make the core-shell aggregates of this invention distinguishable from the remainder of the detergent.

The (co) polymer is preferably applied to the core-shell aggregates in the form of a preferably aqueous solution or preferably aqueous dispersion. After the solvents have dried, the (co) polymers remain as a coherent, uniform film shell on the cores. From solutions, the film layer is preferably formed via a gel state, whereas in dispersions the film former particles are swollen and coalesce and film during thickening. By evaporation of the dispersant, the particles come into contact with each other. The plasticizer facilitates the diffusion of the polymer beads, which coalesce when touched. The coalescence of the polymer leads to the formation of a continuous film.

When using an aqueous solution or dispersion, the pH of the solution or dispersion can be adjusted to the solubility of the (co) polymer. For example, it may be previously acidified if the (co) polymer is preferably insoluble in the basic.

The coating process can be carried out as a continuous or batch process, ie batchwise. If the highest possible throughputs are to be achieved, with average demands on the completeness of the applied layer, continuous processes are preferred. Batch processes are preferably preferred when very high demands are placed on the coating quality.

Discontinuous apparatus usually consist of a vertical, slightly conical container, which can be adapted by different distributor plates, inserts and internals for different process variants. The conventional fluidized bed coating is usually operated as a top spray, in which the spray liquid is sprayed onto the fluidized bed from above. There are also configurations with nozzles that spray laterally or from below into the fluidized bed. Particles preferably from about 200 microns upwards can be coated.

A preferred method is the Wurster method. Here a centrally arranged riser divides the process space. Inside the tube there is a higher gas velocity, which transports the solid product upwards. In the outer ring, the gas velocity is only slightly above the loosening speed. So the particles are moved vertically in a circle. Through this controlled material flow, a more uniform coating is achieved within a short process times. Due to the high speed inside the tube, the particles do not stick together so easily. Particles preferably down to 50 microns can be coated. Another method uses bottom spray technology. In this technology, one works with a distributor plate, which generates an air flow parallel to the ground surface, so that the material to be coated floats on an air cushion. This leads to significant homogenization of the coating compared to conventional systems.

Continuously operated horizontal fluidized bed apparatuses generally have a rectangular distributor bottom. In the continuous fluidized bed, plug flow occurs. The product passes through several zones separated by temperature and air technology. Thus it is also possible to produce multilayer granules or to carry out different process steps in one apparatus at the same time.

These and similar or other known coating processes, for example agglomeration processes, are each particularly suitable for carrying out a coating of the cores according to the invention.

It should again be pointed out that the pH and / or temperature and / or ionic strength-sensitive materials not only in the coating, but also as a matrix material, binder or disintegrant for the actual core-shell aggregate Core and / or the shell can be used. This corresponds to a preferred embodiment.

As has already been seen, various advantages are associated with the agent according to the invention (coated core-shell aggregate). Thus, for example, the separation of incompatible substances by their division into the 3 phases of the coated core-shell aggregate Advantageously, the granules according to the invention are free-flowing, nearly spherical and therefore aesthetically very appealing The granules are well debris and pourable even after long storage and show no tendency to clumping Even when stored in very large silos, where the granules are exposed to very high pressures due to their own weight, the excellent debris and free-flowing properties are retained and the granules do not clump together. There are no signs of segregation Changes in the average particle size of the granules Advantageously, the granules require neither flow agent nor powdering in order to obtain the excellent powder properties. Advantageously, the granules are dust-free and abrasion-resistant, even at higher mechanical stress, the granules remain Dust-free bonding or caking can not be observed

The core-shell aggregates as such can be produced by conventional agglomeration techniques. These are described in more detail below, for example by build-up agglomeration or by suspension agglomeration. In each case the core is surrounded by particles or particles are attached to the core

For agglomeration, a mixer / granulator can be used. The term mixer / granulator preferably refers to drum and plate mixers and / or fluidized bed granulators, but also to single and twin shaft mixers with fast to slow rotating shafts and Zig-Zag mixers , especially discontinuous machines with low specific energy input The particles in the mixer preferably move over the free fall or by initiating a thrust, launcher or centrifugal force. Freefall mixers are preferably used in the relevant literature known, especially on mechanical process engineering mixer / granulators are accurate In the broadest sense, the term mixer / granulator means any apparatus suitable for mixing / granulating

The suspension agglomeration is a special form of the built-up agglomeration based on a 3-phase mixture consisting of the material to be agglomerated, a suspension liquid and a binding liquid which must not be miscible with each other. The binding fluidity must have the property of better wetting the suspended material than suspension suspension The material to be agglomerated is in suspended form in suspension suspension. Then the binding fluid is introduced, which interacts with the product particles and leads to an increase in grain size, ie an accumulation of the surrounding particles occurs around and around the core separated from the reusable Suspensionsflussigkeit for example by means of a filtering device and, if necessary, dried The agglomerate is the result of solid bridges or bridges of heavily volatile river between the particles thus held together. Solid bridges are formed by crystallization of dissolved substances in the liquid bridge.

Suspension agglomeration takes place, for example, with cyclohexane as the suspension liquid and water as the binding liquid.

The core-shell aggregates can have a plurality of shells and several coatings can be applied to them. According to a preferred embodiment of the invention, therefore, the particles surrounding the core of the core-shell aggregate are applied in multiple layers to the core. According to another preferred embodiment of the invention, the core-shell aggregates are coated several times.

In the context of this application, multi-shelled core-shell aggregates can be obtained if a core-shell aggregate obtained is taken as a "core" for one (or more) further assembly agglomeration The core is then inserted and surrounded with additional particles, new particles are then applied to the original core-shell agglomerate, whereby it is preferred that the shells differ from one another in at least one parameter, for example by physical parameters such as their density, size , and / or by chemical parameters, ie different chemical substances.

In a preferred embodiment, core materials and shell material also differ in at least one physical and / or chemical parameter.

Core-shell aggregates with multiple coatings can be obtained by applying one (or more) further coatings to the finished core-shell aggregate to which a coating has already been applied. So you can, for example apply a first nitrous oxide-containing coating and a subsequent perfume-containing coating, etc ..

According to a further preferred embodiment of the invention, the diameter d _{50 of} the core particles of the agents according to the invention is preferably in the range of 0.05 to 5 mm.

The lower limit of the diameter d _{50 of} the core particles of the agents according to the invention may preferably also be at a value such as in particular 0.06 mm, 0.07 mm, 0.08 mm, 0.09 mm, 0.1 mm, 0.11 mm, 0.12 mm, 0.13 mm, 0.14 mm, 0.15 mm, 0.16 mm, 0.17 mm, 0.18 mm, 0.19 mm, 0.2 mm, 0.21 mm, 0.22 mm, 0.23 mm, 0.24 mm, 0.25 mm, 0.26 mm, 0.27 mm, 0.28 mm, 0.29 mm, 0.30 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm or 1, 0 mm or even between these values, for example, at 0.35 mm, 0.45 mm, etc. lie. Less advantageous, but also possible according to another embodiment, it would also be if the diameter d _{50 of} the core particles of the inventive compositions smaller than 0.05 mm, for example, a value such as preferably 0.01 mm, 0.02 mm, 0.03 mm or 0.04 mm.

The upper limit of the diameter d _{50 of} the core particles of the compositions according to the invention may preferably also be given a value such as in particular 4.8 mm, 4.6 mm, 4.4 mm, 4.2 mm, 4.0 mm, 3.8 mm, 3.6 mm, 3.4 mm, 3.2 mm, 3.0 mm, 2.8 mm, 2.6 mm, 2.4 mm, 2.2 mm, 2.0 mm, 1, 8 mm, 1, 6 mm, 1, 4 mm, 1, 2 mm or 1, 0 mm or even between these values, for example at 4.7 mm, 4.5 mm, etc.

Less advantageous, but it would also be possible according to another embodiment, even if the diameter d _{50 of} the core particles of the inventive compositions greater than 5.0 mm, for example, a value such as in particular 6 mm, 7 mm, 8 mm, 9 mm or 10 mm or values which lie between these values, eg at 5.5 mm, 6.5 mm etc.

According to another preferred embodiment of the invention, the particles surrounding the core of the core-shell aggregate have a particle diameter d ₅₀ which is at most 1/12, preferably at most 1/14, advantageously at most 1/16, in a further advantageous manner at most 1 / 18, more preferably a maximum of 1/20, even more advantageously 1/22, in an extremely advantageous manner, a maximum of 1/24 and in particular a maximum of 1/26 of the particle diameter d _{50 of} the core particles.

It is also possible that the particles surrounding the core of the core-shell aggregate have a particle diameter d ₅₀ with a value of preferably a maximum of 1/28, 1/30, 1/32, 1/34, 1/36, 1 / 40, 1/42, 1/44, 1/50 or 1/60 of the particle diameter d _{50 of} the core particles.

The particles surrounding the core are advantageously not powdered. According to general understanding, powder is a kind of flour, ie an accumulation of solid particles with a particle size preferably below 100 nm. It is also advantageous for process-technical reasons, if the particles do not fall below a certain minimum size. According to a preferred embodiment of the invention, the particles surrounding the core therefore have a particle _diameter d ₅₀ , preferably at least 1/100, advantageously at least 1/80, more preferably at least 1/70, more preferably at least 1/60, in even more preferably, at least 1/50, most preferably at least 1/40 and especially at least 1/35 of the particle diameter d _{50 of} the cores. However, the particle diameter d ₅₀ of the particles surrounding the core can also assume values which lie between the aforementioned, that is, for example, at least 1/90 or at least 1/85 of the particle diameter d _{50 of} the cores. Further such values are for example at least 1/95, 1/75, 1/65, 1/55 or 1/45 of the particle diameter d _{50 of} the cores.

However, it is important that the particle diameter d ₅₀ of the particles surrounding the core is greater than 2 μm.

The particle diameter d ₅₀ of the particles surrounding the core preferably lies in a range of 3-50 μm, advantageously 4-25 μm, more preferably 4-15 μm, in particular 5-10 μm.

According to a further preferred embodiment of the invention, the particles surrounding the core have a largely uniform particle size, wherein advantageously the particle size distribution of the particles surrounding the core is such that the ratio of d ₅₀ to d ₉₀ of the particles surrounding the core is preferably at least 0.5 , more preferably at least 0.6, in particular at least 0.75.

According to a further preferred embodiment of the invention, the core particles of the core-shell aggregate make up less than 50% by weight, preferably less than 45% by weight, advantageously less than 40% by weight, more preferably from 15 to 35% by weight. %, in particular 20 to 30 wt .-%, based on the core-shell aggregate-forming solids.

Importantly, however, the core particles of the core-shell aggregate constitute less than 75% by weight of the solids forming the core-shell aggregates, for example, the core particles of the core-shell aggregate may also contain less than, preferably, 70% by weight. , 65 wt .-% or 60 wt .-% make up.

According to a further preferred embodiment of the invention, the core-shell particles surrounding the core advantageously have more than 50% by weight, preferably more than 55% by weight, more preferably more than 60% by weight even more preferably 65 to 85 wt .-%, in particular 70 to 80 wt .-% of the core-shell aggregates forming solids.

Importantly, however, the particles of the core-shell aggregate surrounding the core account for more than 25% by weight of the solids forming the core-shell aggregates, for example, the core-shell aggregate particles surrounding the core may also more than preferably 30%, 35%, 40% or 45% by weight of the solids forming the core-shell aggregates. According to another preferred embodiment, they make the core surrounding particles of the core-shell aggregate more than preferably 50 wt .-%, 55 wt .-%, 60 wt .-%, 65 wt .-% or 70 wt .-% of the core-shell aggregates forming solids ,

According to a further preferred embodiment of the invention, the core of the core-shell aggregate, the particles surrounding the core and / or the coating of the core-shell aggregates comprise contents and / or auxiliary substances from the field of detergents and / or cleaning agents.

According to a further preferred embodiment of the invention, the agents according to the invention, ie the coated core-shell aggregates, essentially have an average form factor of at least 0.79, preferably of at least 0.81, advantageously of at least 0.83, more preferably of at least 0.85, in particular of at least 0.87.

According to another preferred embodiment of the invention, the compositions according to the invention are present in a substantially uniform particle size distribution, in which the ratio of d ₅₀ to d ₉₀ at least 0.50, preferably at least 0.6, advantageously at least 0.75, in more advantageous Way is at least 0.80.

According to a further preferred embodiment of the invention, core particles of the core-shell aggregate and / or the particles surrounding the core and / or the coating are each formed in one or more parts, i. they can either consist of a single component or of several.

According to another preferred embodiment of the invention, the inventive

Medium, ie the coated core-shell aggregates, bulk densities in the range of 200-1500 g / L.

The lower limit for the bulk density can also be set at a value of preferably 250, 300,

350, 400, 450, 500, 550, 600, 650, 700 or even 750 g / L. It is also possible that the lower limit is even higher, e.g. at 800g / L.

The upper limit for the bulk density may be at a value of preferably 1450, 1400, 1350,

1300, 1250, 1200, 1150, 1100, 1050, 1000, 950, 900, 850, 800 or 750 g / L.

It is also possible that the upper limit is even lower, e.g. at a value of preferably

700, 650, 600, 550 or 500 g / L.

According to a further preferred embodiment of the invention, the surfactant content of the core of the core-shell aggregates 0-99 wt .-%, preferably 1-95 wt .-%, advantageously 5-50 wt .-%, more preferably 10-40 wt .-%, in particular 15-30 wt .-%, based on the entire core. According to another preferred embodiment, the lower limit of the ten but also at a value of preferably 1 wt .-%, 2 wt .-%, 3 wt .-%, 4 wt%, 5 wt .-%, 6 wt .-%, 7 wt .-%, 8 wt .-%, 9 wt .-%, 10 wt .-%, 11 wt .-%, 12 wt .-%, 13 wt .-%, 14 wt .-%, 15 wt .-%, 16 wt % By weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight. %, 25 wt .-%, 26 wt .-%, 27 wt .-%, 28 wt .-%, 29 wt .-% or 30 wt .-% are. The lower limit may in particular even be at even higher values, for example at a value of preferably 35 wt .-%, 40 wt .-%, 45 wt .-%, 50 wt .-%, 55 wt .-% or 60 wt. -%.

However, according to a further preferred embodiment, the upper limit may also be at a value of preferably 70% by weight, 71% by weight, 72% by weight, 73% by weight, 74% by weight, 75% by weight. , 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 Wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt% -%, 93 wt .-%, 94 wt .-% or 95 wt .-% are. In particular, the lower limit may even be at even lower values, e.g. at a value of preferably 65 wt .-%, 60 wt .-%, 55 wt .-%, 50 wt .-%, 45 wt .-%, 40 wt .-%, 35 wt .-%, 30 wt. % or 25% by weight or even only at values such as 20% by weight, 15% by weight or 10% by weight.

According to another preferred embodiment of the invention, the surfactant content of the surrounding particles, based on the mass of the surrounding particles, is 0-99% by weight, preferably 1-95% by weight, advantageously 5-50% by weight, more preferably 10%. 40 wt .-%, in particular 15-30 wt .-%. According to another preferred embodiment, the lower limit of the surfactant content but also at a value of preferably 1 wt .-%, 2 wt .-%, 3 wt .-%, 4 wt .-%, 5 wt .-%, 6 wt. %, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt% , 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, 21 wt.%, 22 wt Wt .-%, 24 wt .-%, 25 wt .-%, 26 wt .-%, 27 wt .-%, 28 wt .-%, 29 wt .-% or 30 wt -% lie. In particular, the lower limit may even be at still higher values, e.g. at a value of preferably 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight or 60% by weight.

However, according to a further preferred embodiment, the upper limit may also be at a value of preferably 70% by weight, 71% by weight, 72% by weight, 73% by weight, 74% by weight, 75% by weight. , 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 Wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt% -%, 93 wt .-%, 94 wt .-% or 95 wt .-% are. In particular, the lower limit may even be at even lower values, e.g. at a value of preferably 65 wt .-%, 60 wt .-%, 55 wt .-%, 50 wt .-%, 45 wt .-%, 40 wt .-%, 35 wt .-%, 30 wt. % or 25% by weight or even only at a value such as preferably 20% by weight, 15% by weight or 10% by weight.

According to a further preferred embodiment of the invention, the builder content of the core of the core-shell aggregates is 0-99% by weight, preferably 1-95% by weight, advantageously Se 5-90 wt .-%. even more advantageously 10-70% by weight, more advantageously 20-60% by weight, based on the total core, in particular 25-50% by weight. According to another preferred embodiment, however, the lower limit of the builder content can also be at a value of preferably 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6 Wt .-%, 7 wt .-%, 8 wt .-%, 9 wt .-%, 10 wt .-%, 11 wt .-%, 12 wt .-%, 13 wt .-%, 14 wt. %, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt% , 23 wt .-%, 24 wt .-%, 25 wt .-%, 26 wt .-%, 27 wt .-%, 28 wt .-%, 29 wt .-% or 30 wt .-% are. The lower limit may in particular even be at even higher values, for example at a value of preferably 35 wt .-%, 40 wt .-%, 45 wt .-%, 50 wt .-%, 55 wt .-% or 60 wt. -%. However, according to a further preferred embodiment, the upper limit may also be at a value of preferably 70% by weight, 71% by weight, 72% by weight, 73% by weight, 74% by weight, 75% by weight. , 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 Wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt% -%, 93 wt .-%, 94 wt .-% or 95 wt .-% are. The lower limit may in particular even be at even lower values, for example at a value of preferably 65 wt .-%, 60 wt .-%, 55 wt .-%, 50 wt .-%, 45 wt .-%, 40 wt. %, 35%, 30% or 25% or even only 20%, 15% or 10% by weight.

According to another preferred embodiment of the invention, the perfume content of the core of the core-shell aggregates is 0-30%, based on the total core, preferably 0.1-20% by weight, advantageously 0.2-10% by weight. , in particular 0.3-5 wt .-%. In a preferred embodiment, however, the core is free of perfume.

According to another preferred embodiment of the invention, the bleach content of the total agent (i.e., coated core-shell aggregate) is 5-25% by weight, especially 10-20% by weight.

According to a further preferred embodiment of the invention, the nonionic surfactant content of the entire composition (ie coated core-shell aggregate) is 0-60% by weight, advantageously 2-15% by weight, in particular 3.5-15% by weight, wherein preferably at least 50 wt .-% of the total nonionic surfactant is contained in the coating of the core-shell aggregate.

According to a further preferred embodiment of the invention, the free water content of the entire composition (ie coated core-shell aggregate) is 0-30% by weight, preferably 0-20% by weight, in particular 0-10% by weight. , According to a further preferred embodiment of the invention, the surfactant content of the entire composition (ie coated core-shell aggregate) is 0.1-50% by weight, preferably 1-30% by weight, advantageously 5-25% by weight, in particular 10% by weight. 20% by weight

According to a further preferred embodiment of the invention, the skeletal content of the entire agent (ie coated core-shell aggregate) is 0.1-50% by weight, preferably 1-40% by weight, advantageously 2-35% by weight, more advantageously Way 5-25% by weight, in particular 10-20% by weight

According to a further preferred embodiment of the invention, the perfume content of the entire composition (ie coated core-shell aggregate) is 0.1-30% by weight, preferably 1-25% by weight, advantageously 5-22% by weight, in particular 10% by weight. 20% by weight

According to a preferred embodiment, the coated core-shell aggregates (in particular those which contain pH, ionic strength and / or temperature-sensitive materials) are buoyant in water, ie do not submerge in water or in a wash liquor, but drive on the water water surface

In order to make the core-shell aggregates floating, it is preferable to adjust their density to values less than 1 g / cm ³ , if necessary. A wide range of possibilities is available. For example, gases, especially air, can be introduced into the core If necessary, the core-shell aggregates per se have a correspondingly low density, so that the additional incorporation of, for example, gases is not necessary, which is likewise preferred

It is likewise preferred to incorporate solids, preferably carrier materials having a density of less than 1 g / cm ³ into the core-shell aggregate, the carriers being substances which are solid at room temperature, preferably builders, carbonates, bicarbonates, sulfates, Phosphates and / or Ohgocarbonsauren solid at room temperature

In order to adjust a density of less than 1 g / cm ³ may preferably hollow microspheres, that is very bulky lightweight fillers, the core-shell units may be incorporated, for example in the core The hollow microspheres are, for example with air, nitrogen or carbon dioxide filled, pass the spherical shells Eg B made of glass (eg Borosihcatglas) or in particular of organic materials, for example of a thermoplastic (eg styrene / acrylate polymer, polyacrylate) You can also with other appropriate materials such as vegetable oils (eg almond oil, density approx 0.91-0.92 g / cm ³ ). The density of the hollow microspheres is preferably <1 g / cm ³ , preferably 0.176-0.9 g / cm ³ or 0.176-0.8 g / cm ³ or 0.176-0 , 7 g / cm ³ or 0.176-0.6 g / cm ³ or 0.176-0.5 g / cm ³ or 0 176-0.4 g / cm ³ The average particle diameter is preferably in the range of 0.4-10 The upper limit of the grain size is preferably 0.4-250 μm. The thermal conductivity is preferably 0.110-0.156 Wm-1 K The internal pressure is preferably about 0.2 bar. At higher shear stress, the hollow spherical shells may burst, in particular the Polyacrylate hollow microspheres are preferably incorporated as an aqueous suspension, for example in the core production, for example by granulation or spray drying, or in the core-shell aggregates preparation, for example by agglomeration.

To set a density of less than 1 g / cm ³ , for example, cork flour can also be incorporated into the core-shell aggregate. Due to its low density of 0.12-0.25 g / cm ^{3 it} is ideally suited for this purpose.

Cork flour is preferably made by crushing and then sieving or sifting cork waste.

According to a preferred embodiment, the composition according to the invention contains ingredients for cleaning, care, conditioning and / or aftertreatment of textiles. Preferred ingredients of fabric care, conditioning and / or post-treatment include the cationic surfactants, preferably esterquats, clays, such as preferably bentonite, especially in combination with flocculants, e.g. Polyethylene oxide, polymeric cationic surfactants, in particular based on silicone, polymers based on polyethylene or powdery fabric softening agents, in particular alkylamidoammonium lactate.

The ingredients for care, conditioning and / or aftertreatment of textiles are preferably contained in the core of the composition according to the invention, preferably contained exclusively in the core.

When the composition according to the invention contains clays, preferably bentonite, which is preferred, it is very advantageous if a polymeric clay flocculating agent is also contained, wherein the clay flocculating agent is a polymer or a copolymer which is preferably derived from monomers selected from ethylene oxide, acrylamide , Acrylic acid, dimethylaminoethyl methacrylate, vinyl alcohol, vinylpyrrolidone, ethyleneimine, and mixtures thereof, more particularly having a weight average molecular weight of 100,000 to 10 million, preferably ranging from 0.005% to 20% by weight to the sound in which means is contained.

Advantageously, the optionally contained, fabric-softening clays are thus more efficiently deposited on the fabric during the washing process. The deposition is increased and runs evenly.

In a preferred embodiment, the polymeric clay flocculating agent is obtained from monomers selected from ethylene oxide, acrylamide and acrylic acid.

In a preferred embodiment, the polymeric clay flocculant has a weight average molecular weight of 150,000 to 5 million, preferably 150,000 to 800,000. In another preferred embodiment, the clay flocculating agent has a weight average molecular weight of 800,000 to 5 million.

In a preferred embodiment, the polymeric clay flocculating agent is present in an amount of from 0.005% to 10%, preferably from 0.005% to 5%, more preferably from 0.005% to 2% by weight. % based on the sound before.

According to a preferred embodiment, the composition according to the invention contains ingredients for cleaning and / or care of dishes, glasses, cutlery and the like.

In a preferred embodiment, the core of the composition according to the invention contains ingredients for care, conditioning and / or aftertreatment of textiles, preferably selected from the group of the auxiliaries, fragrances, pH adjusters, fluorescers, dyes, hydro- tope, silicone oils, anti redeposition agents, optical brighteners , Graying inhibitors, anti-wrinkling agents, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids, repellents and impregnating agents, bleaching agents, acidifiers and / or UV absorbers. In a further preferred embodiment, the agent according to the invention, preferably the core of the agent according to the invention, contains one or more skin-care and / or skin-protecting and / or skin-healing active substances.

In a preferred embodiment, the compositions according to the invention are characterized in that the skin-care and / or skin-protecting and / or skin-healing active ingredients contained in the core are released at least partially onto the fibers of the textile laundry and are released during the washing process, preferably in the rinse cycle remain on this even after completion of the washing process at least partially, this skin-care and / or skin-protecting and / or skin-healing active ingredients are given on contact of the skin with a correspondingly washed textile at least partially from this to the skin and thereby can benefit the skin to the advantage.

Preferably, a suitably prepared coating of the core-shell aggregate in the early stages of the washing process under conditions of a conventional mechanical washing process in Europe may substantially protect the core from direct contact with the liquor, however, the coating which, for example, loses pH, temperature or ionic strength-sensitive, in the late stages of the washing process in which the release of the ingredients from the core (s) into the liquor is desired, preferably under the conditions of the rinse cycle, their integrity in whole or in part. This corresponds to a preferred embodiment. The fact that the core or cores are substantially preserved from direct contact with the liquor by the coating or shell in the early stages of the washing process is intended to mean that the coating or shell remains substantially intact in the early stages of the washing process the core continues to be sufficiently protected from penetration by the water. Sufficient protection is provided when the release of active agent from the core is substantially inhibited or when the release of active compound from the core is slowed down, preferably greatly slowed down, as compared to a free core. Preferably, only in the late stages of the washing process does the coating or shell lose all or part of its integrity, to such an extent that the coating or shell provides substantially no protection or adequate protection against penetration by the water. Penetration through the water is at least possible to the extent that the release of active agent from the nucleus is no longer greatly retarded. Preferably, it is sufficient if the coating has holes or cracks, so that a corresponding penetration of the core with water is well possible.

In a preferred embodiment, the coating is designed so that it is substantially inert in, preferably warm, water at pH values above at least 11, preferably above at least 10, in particular above at least 9. During the actual washing process, the water of the wash liquor is usually heated, for example, common water temperatures are currently in Europe at 40 ⁰ C, rarely lower, or at 60 ° C, rarely higher. The pH of the wash liquor is usually in a pH range above 11. Under these pH conditions, the coating according to a preferred embodiment is substantially inert. Substantially inert here means that the coating is substantially water-insoluble under these conditions and provides the core with sufficient protection against penetration by water, so that release of active substance from the core is prevented or at least slows down with respect to an unencapsulated core.

As already stated, the core-shell aggregates according to the invention may contain ingredients for the care and / or after-treatment of textiles. In a preferred embodiment, the proportion by weight of the ingredient preferably contained in the core for the care and / or aftertreatment of textiles, more than 5 wt .-%, in particular between 20 and 50 wt .-%, based on the core.

In another preferred embodiment, the core-shell aggregate according to the invention, preferably the core, contains retarded fragrance-giving and / or delayed-release biocidal oligomers, polymers and / or copolymers which contain a structural element according to formula (1) at least once

R ¹ O- Si (R ² KR ³⁾ - R _A ⁴ - C (R ⁵ KH) - C (R ⁶⁾ (R ⁷⁾ - Si (1),

I wherein R ² , R ³ are each independently an aliphatic or aromatic, straight-chain or branched, saturated or unsaturated, substituted or unsubstituted hydrocarbon radical which may each contain heteroatoms such as oxygen, nitrogen, sulfur or halogens or others, and wherein R ₃ ^{4 represents} a carbon bridge member which is an aliphatic or aromatic, straight-chain or branched, saturated or unsaturated, substituted or unsubstituted hydrocarbon radical, which may each contain heteroatoms such as oxygen, nitrogen, sulfur or halogens or others, wherein the sequence number a 0 is to 10, and wherein R ⁵ , R ⁶ , R ⁷ are each independently hydrogen or an aliphatic or aromatic, straight-chain or branched, saturated or unsaturated, substituted or unsubstituted carbon hydrogen radical, each heteroatom such as oxygen, S may contain nitrogen, sulfur or halogens or others, and wherein the terminal silicon in the formula (1) independently has any of the remaining three valences of any of the oligomer, polymer or copolymer, and wherein R ¹ O is either a group represented by is a perfume alkoxy group and / or biocide alkoxy group derived from the corresponding perfume and / or biocide alcohol R ¹ OH, or R ¹ O represents a radical derived from an enolisable perfume and / or biocide esters, ketone or aldehyde. Preferably, in the coated core-shell aggregates or in the other detergent at least one on hard and / or soft substrate surfaces, preferably containing at least one cationic charge-bearing compound. These retarded fragrance-giving oligomers, polymers and / or copolymers are able to produce an excellent and very long-lasting odor effect on substrates treated therewith, in particular in conjunction with compounds which accumulate on hard and / or soft substrate surfaces and preferably carry at least one cationic charge.

For the purposes of the present invention, the term "fragrance" is understood to mean all those fragrances or substances or mixtures thereof which are perceived by humans as odor and trigger a sensation of smell in humans, preferably a pleasant sensation of smell Scents or fragrances which have free hydroxyl groups, regardless of how the molecule is further structured.In analogy to this, fragrance esters, ketones, aldehydes designate such fragrances, which according to free esters, keto or aldehyde This implies that certain molecules, such as, for example, salicylic acid esters in the sense of this invention, can function both as a fragrance-alcohol and as a fragrance ester, for example. -Ketone understood all compounds containing the corresponding alcohol, aldehyde, Es ter- or keto functionality in the sense just mentioned, and are able to inhibit germ growth at least. Biocides are compounds which inhibit germ growth or at least kill, depending on the individual case, a broad spectrum of organisms, for example of viruses, bacteria, fungi, insects. The dates perfume-alkoxy group or biocide-alkoxy group are explained in the foregoing, these are the corresponding anions of the relevant perfume alcohols or biocide alcohols, which result by abstraction of a hydrogen atom. It has already been described that, in a preferred embodiment, the agent according to the invention contains one or more skin-care and / or skin-protecting and / or skin-healing active substances. Furthermore, it has been found that in a preferred embodiment, the skin-care and / or skin-protecting and / or skin-healing active ingredients preferably present in the core are released during the washing process, preferably in the rinse, at least partially on the fibers of the textile laundry and on this after completion of the washing process remain at least partially, said skin-care and / or skin-protecting and / or skin-healing active ingredients are given at least partially of this skin contact with the skin with a correspondingly washed textile, which is beneficial to the skin.

Skin-care active substances are all those active substances which give the skin a sensory and / or cosmetic advantage. Skin-care active substances are preferably selected from the following substances: a) waxes such as, for example, carnauba, spermaceti, beeswax, lanolin and / or derivatives thereof and others. b) Hydrophobic plant extracts c) Hydrocarbons such as squalene and / or squalanes d) Higher fatty acids, preferably those having at least 12 carbon atoms, for example lauric acid, stearic acid, behenic acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, isostearic acid and / or polyunsaturated fatty acids and other. e) Higher fatty alcohols, preferably those having at least 12 carbon atoms, for example, lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, cholesterol and / or 2-hexadecanol and others. f) esters, preferably such as cetyl octanoate, lauryl lactate, myristyl lactate, cetyl lactate, isopropyl myristate, myristyl myristate, isopropyl palmitate, isopropyl adipate, butyl stearate, decyl oleate, cholesterol isostearate, glycerol monostearate, glycerol distearate, glycerol tristearate, alkyl lactates, alkyl citrates and / or alkyl tartrates and others. g) lipids such as cholesterol, ceramides and / or sucrose esters and others. h) vitamins such as vitamins A and E, vitamin C esters, including vitamin C.

Alkyl esters and others, i) sunscreens j) phospholipids k) derivatives of alpha-hydroxy acids I) fragrances m) Germicides for cosmetic use, both synthetic and, for example, sahcylic acid and / or other as well as natural, such as neemol and / or other n) silicones, as well as mixtures of any of the abovementioned components

In a preferred embodiment, the core-shell aggregates contain skin-care and / or skin-protecting and / or skin-healing active substances as well as textile-softening quaternary ammonium compounds, preferably esterquats

Instead of the fabric softening quaternary ammonium compounds or in combination with these, other fabric softeners, such as powdered plasticizers such as Alkylamidoammoniumlactat and / or clays, such as preferably bentonite, especially in combination with flocculants, such as polyethylene oxide, can be used The use of Alkylamidoammoniumlactat is Skin-protecting and / or skin-healing active substances are active substances which confer on the skin an advantage which goes beyond a mere sensory and / or cosmetic advantage

The term skin healing or skin-healing attribute in the context of this invention is most easily defined by the condition of healthy human skin. Healthy human skin is characterized by providing sufficient protection against microorganisms, germs and pathogens through its intact acid mantle their buffer capacity and alkalinity-neutralizing ability are sufficient to ward off harmful influences of surrounding fluids, that there is a high degree of freedom from redness, and that there is freedom from skin damage such as cuts, abrasions, burns, irritation, inflammation, and allergies, as well as being cracked Furthermore, healthy skin is characterized by the fact that it takes on a depot function for fat, water and blood and an important role in the metabolism Is the skin unable to take over the above functions or shows obvious damage or leaves the skin Skin-healing in the context of the present invention is now all that helps the skin to return to its original state. It is also the skin-healing that stimulates, trains, supports, and supports the self-regulating powers of the skin and calls, so that it is able to fulfill its functions, in that it returns to the natural state of equilibrium Further understood by the term skin healing in the context of this invention, all the influences that lead to obvious skin diseases such as eczema, Rashes, redness, itching, swelling, blistering, oozing, crusts in various forms are at least alleviated, if not cured

The term "skin protection", on the other hand, refers to everything that is necessary to maintain the normal performance of the skin in terms of its functions under specific stress situations and goes beyond its own protective mechanisms. This concept also differs significantly from skincare because skincare is achieved only one cosmetic benefits in terms of sensory needs z. Softness or gloss under normal conditions. The skin protection, however, supports the skin with additional agents that help the skin, for example, even in adverse conditions, to fulfill their multifaceted functions. Such adverse conditions can z. As friction, cold, heat, UV radiation, aggressive ambient fluids, contact with skin-irritating materials. In a preferred embodiment, at least one of the skin-healing and / or skin-protecting active ingredients contained in the coated core-shell aggregates is antiseptic or contains at least one antiseptic substance, wherein the antiseptic substance is preferably an oil, in particular an essential oil ,

In the context of this invention, the attribute of antiseptic efficacy means an effect that is beneficial to the self-regulating forces of human skin. This efficacy is not in its expression with that of classical germicidal or germicidal agents such. Phenols, halogens, alcohols with which e.g. Skin and Mucous membranes Wounds or even medical instruments treated to achieve asepsis (germ-free) compare. The classical antiseptic includes antimicrobial measures at the point of origin or at the portal of entry of a possible infection or at the site of infection on the body surface. However, such strong effectiveness is not sought in the context of the invention, as it would undoubtedly lead to the elimination of harmful germs o. Ä., But it would also affect the natural skin flora of humans.

The particular advantage of the antiseptic active substances which can be used according to the invention results from a synergistic interaction of these substances with the general functional mechanisms of human skin, since these mildly antiseptic substances reduce, for example, germs, including harmful germs, but not completely, that is to sterility , destroy. So there are enough germs on the skin that are sufficient to train and strengthen the self-regulating powers of human skin. The interaction of the self-regulating forces of the skin with the antiseptic capacity of the active ingredients in the middle of the skin supports the general functioning of the skin. This is of great advantage, especially with regard to already irritated and / or otherwise damaged skin. In already irritated and / or sensitized and / or otherwise damaged or even particularly sensitive skin, the self-regulatory powers of the skin are sometimes no longer able, even temporarily, to ensure skin health on their own. In synergistic interaction with the agents according to the invention and their use according to the invention, these self-regulating forces are supported, trained and strengthened. In this way, the detergent according to the invention or the laundry treated with it supports the natural skin flora of humans. In order not to impair the natural skin flora of humans, it is advantageous to exclude (largely) those substances that are strongly disinfecting or antiseptic effective, such as glutaraldehyde, but at the same time hold a high allergy potential and are irritating to the skin and mucous membranes

Unexpectedly, coated core-shell aggregates of such an embodiment are particularly useful for their purpose when the antiseptic agent is an oil, preferably an essential oil

This antiseptic oil is preferably an essential oil selected in particular from the group of Angelica fine - Angelica archangelica, Anis - Pimpinella anisum, Benzoin siam - Styrax tokinensis, Cabreuva - Myrocarpus fastigiatus, Cajeput - Melaleuca leucadendron, Cistrose - Cistrus ladaniferus, Copaiba balm - Copaifera reticulata, Costuswurzel - Saussurea discolor, Edeltann needle - Abies alba, Elemi - Canaπum luzonicum, Fennel - Foeniculum dulce Spruce needle - Picea abies, Geranium - Pelargonium graveolens, Ho leaf - Cinnamonum camphora, Immortelle ( Helichrysum ang, ginger extra - Zmgiber off, St. John's wort - Hypericum perforatum, jojoba, chamomile German - Matπcaria recutita, chamomile blue fine - Matπcaria chamomilla, chamomile rom - Anthemis nobilis, chamomile wild- Ormensis multicaulis, carrot - Daucus carota, mountain pine - Pinus mugho, Lavandin - Lavendula hybnda, Litsea cubeba - (May Chang), Manuka - Leptospermum sc opaπum, Melissa - Melissa officinahs, Sea pine - Pinus pinaster ,, Myrrh - Commiphora molmol, Myrtle - Myrtus communis, Neem - Azaurachta, Niaouli - (MQV) Melaleuca quin viπdiflora, Palmarosa - Cymbopogom martini, Patchouh - Pogostemon patschuh, Peru balsam - Myroxylon balsamum var pereirae, Raventsara aromatica, rosewood - Aniba pink odora, sage - Salvia officinahs Horsetail - Equisetaceae, yarrow extra - Achillea millefoha, plantain lanceolate - Plantago lanceolata, Styrax - Liquidambar onentalis, Tagetes (marigold) Tagetes patula, tea tree - Melaleuca alternifolia, Tolu Balsam - Myroxylon Balsamum L, Virginia Cedar - Juniperus virginiana, Frankincense (Olibanum) - Boswelha carten, Silver Fir - Abies alba

Another advantage of the aforementioned essential oils lies in their particular multifunctional seam, which, in addition to the described mild antiseptic activity, results from a large number of other desirable organoleptic properties attributable to these oils. In most cases, these oils have a mucolytic effect In addition, a desirable feeling of warmth can be established. Deodorizing, pain-relieving, circulation-promoting, calming effects could be observed in connection with the use according to the invention of these designated oils and be recognized as particularly advantageous organoleptic properties of these oils are usually not influenced by the main components, but by the minor or trace constituents, which can often go into the hundreds and sometimes interact synergistically Another advantage in terms of The result of these oils is their harmonic odor and fragrance, which in many cases leads to positive feelings in people

In this way, for example, supports a corresponding detergent or washed with this wash not only the natural skin flora of humans, but helps the human body to additional benefits just described type Against this background, especially the tea tree oil of great advantage for the subject invention In addition to its considerable germicidal , Antiseptic, fungicidal, antiviral, wound healing, anti-inflammatory, scarring effect, it has excellent Hautverträghchkeit on and offers a wide range of other applications, for example, with regard to the supporting treatment of Erkältungskrankheiten or diseases of the rheumatic type, gout, muscle pain

In a preferred embodiment, the skin-protecting active substances contained in the coated core-shell aggregates are a skin-protecting oil. The skin-protecting substance is advantageously a skin-protecting oil, for example a carrier oil, in particular selected from the group Algenol Oleum Phaeophyceae, Aloe Vera Oil Aloe vera brasihana, Apnkosenkernol Prunus armeniaca, Armkaόl Arnica montana, Avocadool Persea ameπcana, Borage officinalis, Calendulaol Calendula officinahs, Camelhaol Camellia oleifera, Distemper oil Carthamus tinctonus, Peanut oil Arachis hypogaea, Hemp oil Cannabis sativa, hazelnut oil Corylus avellana /, hypericum perforatum St. John's wort, jojoba oil Simondsia chinensis, carrotsol Daucus carota, coconut oil Cocos nucifera, turmeric curcumin Curcubita pepo, kukui- nussol Aleuπtes moluccana, macadamia nutol Macadamia ternifoha, almond oil Prunus dulcis, olive oil Olea europaea, peach kernel Prunus persica, R apsöl Brassica oleifera, Ricinus communis castor oil, Nigella sativa black sorrel, Sesamium sesamium indicum, sunflower oil HeIi- anthus annus, grape seed oil Vitis vinifera, Walnussol Juglans regia, wheat germ Tπticum sativum, of which the borage oil, hemp oil and almond oil are especially beneficial

All the oils listed above are natural emollients, ie agents that soften and soften the body tissue and reduce the roughness of the skin. These oils therefore have a skin-conditioning effect. On the other hand, these oils have further specific effects which synergistically interact with the skin and skin whose self-governing powers entail and provide protection even in adverse conditions

A particularly preferred oil in the sense of this invention is, for example, hemp oil hemp oil, which has a high proportion of essential fatty acids and additionally contains up to 6% by weight of valuable γ-linolenic acid (GLA), additionally has anti-inflammatory, mild analgesic, healing properties, nourishing, improving skin structure, preventing signs of aging It improves renewal tion processes in the tissue and has a high regenerative effect on injured tissue. In addition, it can increase the care properties or other properties of other oils in particular of all oils explicitly mentioned here. Since essential fatty acids are significantly involved in the maintenance of the barrier function of the skin, because they help to regulate and normalize the transepidermal water loss through the skin, the hemp oil for the purposes of this invention as a result of its high GLA content to play a special role, as In case of disturbed transepidermal water loss, topical treatment with GLA leads to the greatest reduction in transepidermal water loss. Furthermore, hemp oil has further positive effects on the human organism in terms of arteriosclerosis, rheumatoid arthritis, diabetic neuropathy to heart problems. Another preferred oil for the purposes of this invention is the borage oil.

Due to its high GLA content (up to 25% by weight) it has comparable properties and advantages to hemp oil.

In a preferred embodiment, the agents according to the invention contain skin-healing active substances which have a minimum content of 0.1% by weight of GLA, preferably of 0.3% by weight, more preferably of 0.5% by weight, based on the respective active substance. These include, for example, black cumin oil, Echiumöl, Trichodesmaöl, evening primrose oil and the blackcurrant seed oil.

Another preferred oil is almond oil. It is characterized by the fact that it can enhance the effect of other oils, which is why it is advantageously used in combination with other oils.

According to another embodiment of the invention, it is advantageous to combine different oils in the core-shell aggregates, i. H. So to combine the antiseptic effective with the skin-protecting or even to combine the antiseptic and the skin-protecting one another.

In a preferred embodiment, the agents according to the invention contain at least 1% by weight, preferably at least 5% by weight, more preferably at least 10% by weight, most preferably at least 15% by weight of one or more skin-protecting and / or skin-healing active substances or oils or essential oils, it being even more advantageous if even at least 20 wt .-%, especially even more than 25 wt .-%, even better than 30 wt .-% of one or more skin-protecting and / or skin-healing active substances or oils or essential oils are contained, in each case based on the entire agent (ie coated core-shell aggregate). In a preferred embodiment, the coated core-shell aggregates additionally contain urea and / or lactic acid and / or citric acid and / or salts thereof.

Urea promotes skin health by providing anti-microbial, water-binding, anti-itching, dandruff-releasing, skin-smoothing, and inhibiting excessive cell growth. Furthermore, it can serve the skin as a moisturizing factor, i. H. it can help the skin to retain moisture.

Lactic acid and / or citric acid and / or their salts serve u. a. to support or renew the natural acid mantle or hydrolipid film of the skin. The hydrolipidic film of the skin is attacked or destroyed by alkaline influences, resulting in a loss of the barrier function of the skin, so that microorganisms or pollutants can more easily penetrate the skin. The preferably contained lactic and / or citric acid in the inventive compositions can be z. B. Remove residual alkali from clothing and adjust the pH of the textiles to a pH range around 5. The additional lactic acid, which is already part of the epidermis, has an additional stabilizing effect on the acidic pH of the skin (pH approx. 5.2) and serves as a moisturizing factor, since it can improve the water binding ability of the skin. Furthermore, the lactic acid smoothes the skin and supports the detachment of dander. In addition to the special moisturizing factors mentioned, in a preferred embodiment the compositions according to the invention may contain further moisturizing factors, for example those selected from the following group: amino acids, chitosan or chitosan salts / derivatives, ethylene glycol, glucosamine, glycerol, diglycerol, triglycerol, uric acid, honey and hardened honey, creatinine, cleavage products of collagen, lactitol, polyols and polyol derivatives (for example, butylene glycol, erythritol, propylene glycol, 1, 2,6-hexane triol, polyethylene glycols such as PEG-4, PEG-6, PEG-7, PEG-8, PEG- 9, PEG-10, PEG-12, PEG-14, PEG-16, PEG-18, PEG-20), pyrrolidone carboxylic acid, sugars and sugar derivatives (for example, fructose, glucose, maltose, maltitol, mannitol, inositol, sorbitol, sorbitylsilanediol Acidosis, trehalose, xylose, XyNt, glucuronic acid and salts thereof), ethoxylated sorbitol (sorbeth-6, sorbeth-20, sorbeth-30, sorbeth-40), hardened starch hydrolysates and mixtures of hydrogenated W egg protein and PEG-20 acetate copolymer, especially panthenol.

In a preferred embodiment, the skin-protecting and / or skin-healing and / or skin-care active ingredients preferably contained in the coated core-shell aggregates are reversibly fixed to a polymeric carrier, preferably a silicic acid ester, so that a delayed release of the skin-protecting and / or skin-healing Active substances is possible. The skin-healing and / or skin-protecting and / or skin-care active ingredients are thus z. B. reversibly fixed by adsorption on a polymeric carrier, optionally with the participation of surfactants, so that a delayed release of the healing active ingredients is possible. This is particularly advantageous, since in this way an even longer-lasting effect can be achieved, which is particularly beneficial for consumers with particularly irritated skin of skin. is zen. The fact that the healing and / or protective and / or nourishing substances continuously over a longer period z. B. delivered in relatively low dosage to the skin, it is possible to intervene in a very gentle manner in the particularly sensitive balance of self-regulatory strong irritated skin supportive. The effect of the active ingredients is so mild that, in spite of their effectiveness, it does not overwhelm the already highly irritated skin.

Particularly preferred polymeric carriers belong to the class of silicic acid esters. However, it can also be any conceivable other carrier, with the only provisos that they allow delayed release of active ingredient and as such have no negative or irritating effect on the skin, if used for the purposes of this invention.

According to a preferred embodiment of the invention, the core material of the coated core-shell aggregate comprises one or more ingredients selected from

(a) Turmeric powders (spray drying products) containing e.g. Mixtures of thermally stable ingredients of detergents or cleaners

(b) carbonates, such as preferably soda,

(C) hydrogencarbonates, in particular alkali metal and / or alkaline earth metal hydrogencarbonates

(d) sulfates, especially alkali and / or alkaline earth sulfates

(e) anionic surfactant compounds (including, for example, fatty alcohol sulfates, alkylbenzenesulfonates, alkanesulfonates, alkyl ether sulfates, alkyl sulfates, α-olefin sulfonates and / or ester sulfonates, in particular methyl ester sulfonates, and / or mixtures thereof),

(f) bleach activators, in particular N, N, N ', N'-tetraacetylethylenediamine,

(C) citrates, preferably alkali and / or alkaline earth citrates, in particular Na, K and / or Mg citrates

(h) builder (compounds), preferably zeolite (compounds) and / or polycarboxylate (compounds)

The use of coated core-shell aggregates comprising at least one skin-protecting and / or skin-healing active substance for producing a medically active detergent for finishing textiles for the supportive treatment of irritated and / or sensitized and / or diseased human skin and for the prophylactic treatment of healthy skin provides preferred embodiment of the invention.

The use of at least one skin-protecting and / or skin-healing active substance for the production of a medically effective additive in the form of coated core-shell aggregates for detergents for finishing textiles for the supportive treatment of irritated and / or sensitized and / or diseased human skin as well as for the prophylactic treatment of healthy skin constitutes a preferred embodiment of the invention. The invention also relates to the use of a detergent according to the invention, which comprises coated core-shell aggregates, in a laundry process or a machine wash washing process.

According to a preferred embodiment, such a washing process is characterized in that the coated core-shell aggregates are substantially not removed from the washing machine during the washing process in the course of pumping operations and preferably precipitate on the laundry during the washing process in the course of pumping operations.

Thus, it could be advantageously observed when using a detergent according to the invention with certain buoyant coated core-shell aggregates in a conventional machine laundry process that the means of the invention, if one interrupts the washing program after the main wash, and immediately before the rinse cycle and the laundry in the Wash drum visually inspected, deposited on the laundry well visible. At such an observation time, the washing liquor contaminated as a result of the cleaning process is largely pumped out of the machine and the laundry is dripping wet in the washing drum or washing chamber. Although the particular coated core-shell aggregates are theoretically pumpable with the wash liquor since they fit, for example, in size through the many small apertures of a wash basket, the particular coated core-shell aggregates will remain within the inventive use of this preferred embodiment essential in the washing drum, preferably as a precipitate on the laundry. It could further be observed that, following this visual inspection of the laundry, the washing machine closes again, and the rinse continues, the particular coated core-shell aggregates dissolve in the rinse liquor after completion of the rinse cycle and before the start of the spin cycle to have. If you open the washing machine immediately after completion of the rinse cycle and before the start of the spin cycle and visually inspected the dripping wet laundry, in this particular embodiment, none of these coated core-shell aggregates are more visible on the laundry.

The invention also relates to a washing process in a commercial washing machine, wherein one brings a detergent according to the invention, which contains coated core-shell aggregates, in the washing machine and brings it there with water and the laundry in contact, preferably in that the detergent in the Einspülkammer introduces the commercial washing machine and rinsed with water in the washing chamber or washing drum, and a conventional washing program, wherein preferably the coating of the contained coated core-shell aggregates during the washing of the detergent and during the Vorwaschganges and during the early stages of the main wash retains its integrity in whole or in part, advantageously in the late stages of Hauptwaschganges and / or In the rinse, however, loses its integrity.

In a preferred embodiment of the method, the coated core-shell aggregates contained in the detergent are not substantially removed during the washing process in the course of Abpumpvorgängen from the washing machine, but are preferably in the late stages of the washing process, especially in the course of Abpumpvorgängen on the Wash down.

Another object of the present invention is a process for the construction of core-shell aggregates, wherein in a mixer / granulator by presenting a particulate material ("particles to be prepared"), which with the addition of granulation and other particulate material ("Particles to be added") granulated / agglomerated, core-shell aggregates produced, wherein the particles to be added have a particle diameter d ₅₀ which is at most one tenth of the particle diameter d _{50 of} the particles to be submitted, but greater than 2 microns, with the proviso in that at least one further coating is applied to the core-shell aggregate from the outside, for example by spraying.

According to a preferred embodiment, the particles to be prepared have a largely uniform particle size. According to another preferred embodiment, the core particles constitute less than 75% by weight and the particles to be added constitute more than 25% by weight of the solids forming the core-shell aggregate.

It has been found that under these conditions it is possible that the particles to be added advantageously do not accumulate on themselves with spontaneous nucleation, but rather on the preformed agglomerates. In contrast, a conventional granulation / agglomeration process normally proceeds in two phases. In the first phase granulation germs are formed from the material to be agglomerated. Only then follows the build-up phase of the granules / agglomerates. The first phase, which relates to granulation nucleation, has been omitted in the process according to the invention.

The inventive method has a variety of applications. For use in the washing and cleaning agent sector, for example, agglomerates with a density gradient varying from the center point can be produced, in which the amount of active substance released both over the diameter and over a diameter-dependent porosity can be influenced. Furthermore, according to the method of the invention, washing and cleaning agent forms can be prepared in which two or more different active ingredients are combined, which are released one after the other. For example, a certain active substance in an outer shell already during the flushing process in the washing machine, another active in an inner shell, or in the core, are released only in the main wash, a perfume, which is in the coating, exudes its fragrance of From the beginning.

According to the method of the invention, otherwise incompatible active ingredients can be optimally processed into a uniform dosage form. In this case, the invention enables maximum freedom in the formulation of detergents and cleaning agents while avoiding undesirable incompatibilities through targeted separation of active substances.

In the field of detergent products z. For example, an incrustation inhibitor and a nonionic surfactant can be shelled onto a core of a builder / anionic surfactant mixture. In the coating, e.g. Be included in perfume.

For example, coated core-shell aggregates having a core of undyed material and a shell of colored material, e.g. are provided with a transparent coating.

Another advantage is that coated core-shell aggregates can be prepared by the process of the present invention, offering a variety of possibilities for timing activation release, e.g. in the sense of a controlled-release mechanism.

The particles to be prepared in the process according to the invention may themselves be primary agglomerates containing particulate solid. These can be produced by any agglomeration process. They may be spray-dried products or extrudates, etc.

The core-shell aggregates which can be prepared by the process according to the invention can, in turn, serve as cores (particles to be prepared) for the agglomeration of further identical or different solids. In this way, core-shell aggregates having two or more shells around a core can be obtained. These are still coated afterwards, as it corresponds to the invention.

According to a preferred embodiment of the invention, the coating to be applied comprises nonionic surfactant. According to a preferred embodiment, the coating applied is a liquid, preferably water-free, in particular anhydrous liquid, advantageously selected from nonionic surfactant, brightener, silicone oil, paraffin (oil), perfume, vitamin E and / or natural oils. Such a liquid advantageously does not remain liquid on the surface of the core-shell aggregate, but draws on, so that the surface of the core-shell aggregate is advantageously not wet or sticky.

Very preferred here is nonionic surfactant, which is advantageously combined with other components. Preferred are e.g. the following combinations:

(a) nonionic surfactant, brightener, optional perfume

(c) silicone oil, whitener, optional perfume, optional nonionic surfactant

(e) nonionic surfactant, natural oils, optional perfume

(f) nonionic surfactant, vitamin (derivative), natural oils, optional perfume.

Low-water means in this context that the coating liquid used contains less than 35 wt .-% water, based on the total coating liquid. In preferred embodiments, this upper limit of water content may also be at lower levels, e.g. at a value of preferably 30% by weight, 25% by weight, 20% by weight, 15% by weight, 10% by weight or 5% by weight or between these values, e.g. at a value of preferably 9, 8, 7 or 6 wt .-% based on the total coating liquid.

An anhydrous coating liquid contains a maximum of 4 wt .-%, advantageously at most 3 wt .-%, more preferably at most 2 wt .-%, preferably at most 1 wt .-% or in particular no water based on the total coating liquid.

However, according to another preferred embodiment, the coating liquid may also contain larger amounts of water, that is more than preferably 35 wt .-%, based on the total coating liquid. In preferred embodiments, this minimum water content limit may also be at higher levels, e.g. at a value of preferably 40%, 45%, 50%, 55%, 60% or 65% or between these values, e.g. at a value such as 41, 42, 43 or 44% by weight. based on the entire coating liquid. A highly water-rich liquid, according to a preferred embodiment, may even have an even higher water content upper limit, e.g. with a value of preferably 70 wt .-%, 75 wt .-%, 80 wt .-%, 85 wt .-%, 90 wt .-% or 95 wt .-% water based on the total coating liquid.

According to another preferred embodiment, a melt is applied as coating, preferably melting of (co) polymers, waxes, esters and / or fats. A sol- The melt advantageously remains on the surface of the core-shell aggregate no melt, but after being drawn and cooled down advantageously solid, so that the surface of the core-shell aggregate is advantageously not sticky.

The coating to be applied may contain waxes. For waxing, the following may be preferred:

(c) mineral waxes such as preferably ceresin and / or ozokerite

(F) microwaxes, so preferably higher melting ingredients of petroleum, which in particular consist of a mixture of saturated hydrocarbons (isoalkanes) and advantageously still contain alkyl-substituted cycloparaffins and alkyl-substituted or naphthene-substituted aromatics, advantageously petrolatum, micrographic micro waxes and Hartmikrowachse

The coating to be applied may contain esters. For esters, the esters of long chain fatty acids are advantageously preferred, especially having at least 22 carbon atoms, e.g. Behenic acid, tetracosanoic acid, cerotic acid and / or triacontanoic acid, etc. The coating to be applied may contain fats. By fats is preferably meant the solid or semi-solid products, which consist essentially of mixed glycerol esters of higher fatty acids.

The coating to be applied may contain (co) polymers. Polyethylene glycols, polyacrylic acids, polyacrylamides, polyvinylpyrrolidones, polyvinyl acetates and polyvinyl alcohols are particularly preferred in the (co) polymers.

Polyethylene glycols having molecular weights of about 200-5000000 g / mol, corresponding polymerization degrees Pn of about 5 to> 100,000 are preferred. Liquid products with molecular weights <approx. 25,000 g / mol can also be used as a coating material.

In general, it is very preferred if the coating contains lipids, which corresponds to a preferred embodiment. Preferred lipids are

(b) lipophilic alcohols (such as wax alcohols, retinol or cholesterol, etc.),

(c) ether lipids

(d) lipophilic carboxylic acids (fatty acids),

(f) lipophilic amides (such as ceramides, etc.),

(g) waxes

(h) lipids with more than 2 hydrolysis products, e.g. Glycolipids, phospholipids, sphingolipids and / or glycerolipids etc. (i) lipids in the form of higher molecular weight conjugates with more than 2 hydrolysis products, e.g. Lipoproteins and / or lipopolysaccharides, etc., (j) phosphorus-free glycolipids, e.g. Glycosphingolipids (such as, preferably, cerebrosides, gan gliosides, sulfatides) or as described e.g. Glycoglycerolipids (such as preferably glycosyl di- and monoglycerides), etc. (k) carbohydrate-free phospholipids, e.g. Sphingophospholipids (such as, preferably, sphingomyelin) or e.g. Glycerophospholipids (such as preferably lecithins, cephalins, car diolipins, phosphatidylinositols and inositol phosphates, etc.) (I) Mixtures of the abovementioned.

In a further preferred embodiment, the coating has unsaponifiable lipid, preferably selected from free fatty acids, isoprenoid lipids, in particular steroids, carotenoids, monoterpenes etc. and / or tocopherols.

In a further preferred embodiment, the coating comprises at least one unsaponifiable and one saponifiable lipid. In another preferred embodiment, the coating comprises neutral lipid, preferably selected from fatty acids (> C12), mono-, di-, triacylglycerides, sterols, sterol esters, carotenoids, waxes and / or tocopherols.

According to a preferred embodiment, the coating is applied as a dispersion, thus advantageously as a system of several phases, one of which is dispersed continuously (dispersion medium) and at least one further (dispersed) (dispersed phase), preferably as emulsion, aerosol or suspension.

Most preferred are suspensions, ie dispersions of insoluble solid particles with particle sizes down to colloidal dimensions (<10 ^{~ 6} cm) in liquids, plastic masses or solidified melts.

(a) oligomeric titanates and / or silanes,

(b) amphoteric dispersants such as e.g. Soy lecithin etc.

(c) anionic dispersants, e.g. oligomeric or polymeric carboxylic acids, etc.,

(d) cationic dispersants, e.g. Polyamines etc.,

Aqueous systems preferably contain dispersants, such as in particular

(a) inorganic dispersants, here preferably so-called Pickering dispersants, ie fine-grained, insoluble inorganic compounds such as CaCO ₃ or Ca ₃ (PO ₄ ) ₂ ,

(b) polyphosphates, such as preferably salts of the pyro, meta or. Polyphosphoric acid of the general formula M _{n + 2} P _n O _{3n + 1} or. Mn [H ₂ P _n O _{3n + 1} ] with M = Na +, K +, NH ⁴⁺ ; n = 2-10 oligophosphates, eg pentasodium triphosphate Na ₅ P ₃ O ₁₀ , n> 10 polyphosphates

(C) modified natural substances, such as gum arabic, alginates, casein, gelatin, soybean lecithin, tannates and / or lignosulfonates and / or (d) synthetic polymers, for example predominantly water-soluble Na ⁺ or NH ⁴ ⁺ salts of anionic synthetic polymers with carboxylate, sulfate or sulfonate groups, homopolymers, such as preferably polyacrylic acid, polymethacrylic acid,

(e) Copolymers, such as preferably acrylic acid or methacrylic acid with vinyl (ethene), allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), acrylamide or acrylonitrile, maleic anhydride with ethylene or other 1-alkenes, methyl vinyl ether or styrene , Polyaldehydo-carboxylic acids, such as preferably co- or terpolymers of acrylic acid, acrylamide, acrylonitrile, in the presence and incorporation of long-chain, branched or linear mercaptans as regulators, naphthalenesulfonate-formaldehyde condensation products.

In a further preferred embodiment, the coating comprises pigments, advantageously in the nanoscale range or in the micrometer range, preferably white pigments, in particular selected from titanium dioxide pigments, in particular anatase pigments and / or rutile pigments, zinc sulfide pigments, zinc oxide (zinc white) , antimony trioxide (antimony white), basic lead carbonate (white lead) 2PbCO ₃ Pb ^• (OH) _2, lithopone ZnS + BaSO. ₄ Preferably, white auxiliaries, such as preferably calcium carbonate, talc 3MgO ^■ 4SiO ₂ ^• H ₂ O and / or barium sulfate may be included.

In another preferred embodiment, the pigments may be um

The coating may preferably also comprise the following coating materials:

(c) silicates, such as preferably talc, pyrophyllite, chlorite, hornblende, mica, kaolin

(d) wollastonite, slate meal, precipitated Ca, Al, Ca / Al, Na / Al silicates, feldspars and / or mullite (E) silicas, such as quartz, quartz, cristobalite, kieselguhr, Neuburg Siliceous Earth, precipitated silica, fumed silica, glass flour, pumice, pearlite, Ca-metasilicates and / or fibers from melting of glass, basalts, slags

(f) oxides, in particular aluminum hydroxide and / or magnesium hydroxide

(g) organic fibers, such as in particular textile fibers, cellulose fibers, polyethylene fibers, polypropylene fibers, polyamide fibers, polyacrylonitrile fibers and / or polyester fibers, preferably with lengths in the nanometer or micrometer range and / or

(h) flours, e.g. Starch flours.

It should be pointed out explicitly that the statements made above on the coated core-shell aggregate, the core, the coating and the shell, their ingredients, materials, for their impregnation, etc., also for preferred embodiments of the method according to the invention apply. It should also be noted that the description made in the description of the method according to the invention also apply to preferred embodiments of the coated core-shell aggregates.

For the production of the core-shell aggregates, as already mentioned, in principle all agglomeration processes are suitable. For this purpose, all common types of mixers such as cone mixers, Zigzag mixers, horizontal or vertical mixers or drum mixers, possibly with a chopper, are suitable.

As Granulierhilfsmittel preferably granulation or granulation foam can be used. It should be noted at this point that a granulation foam is not granulation liquid. A foam is a complex structure or agglomerate of gas-filled, spherical or polyhedron-shaped cells or bubbles, which are bounded by liquid, semi-liquid, highly viscous or solid cell webs, but it is not a liquid. For example, foams usually have a much lower density than liquids and, for example, react quite differently than fluids to compression or mechanical stress. As granulation liquids preferably water or aqueous solutions can be used, but advantageously also other granulation aids than water, for example liquid nonionic surfactants, polyethylene glycols or other organic solvents. Particular preference is given to aqueous granulation liquids which are, for example, salts, waterglass, alkyl polyglycosides, carbohydrates, natural polymers, synthetic polymers, eg. As cellulose ethers, starch, polyethylene glycol, polyvinyl alcohol and / or biopolymers such as xanthan gum. Also possible are water-containing organic solvents with swollen polymers. Melting of suitable substances is also possible. Alternatively, as already outlined above, the process according to the invention can be carried out in the form of suspension agglomeration. The process involves the aggregation of the particulate solids, that is, the occupancy of the core ("particles to be prepared") with surrounding particles in the liquid phase, cores (particles to be prepared), particles to be added, and optionally further auxiliaries are distributed in a suspension liquid.

The suspension liquid must be selected in a suspension agglomeration so that both the cores and the particulate solid therein are substantially insoluble. In this suspension, the binding liquid is introduced. Binding fluid and suspension fluid must be selected so that they are substantially immiscible with each other. The binding liquid can be introduced, for example, directly via a nozzle or in the form of an emulsion of binding and suspension liquid.

The binding liquid must be selected in a suspension agglomeration so that it wets the particles better than the suspension liquid. Under the action of the binding liquid, the particles interact and agglomerate in the form of a shell around the cores (particles to be prepared).

To carry out the suspension agglomeration z. As a stirred tank or a continuously operated cylinder stirrer suitable. The separation of the agglomerates formed from the suspension liquid can take place by means of any device suitable for this purpose, for example a filtration device. The agglomerates can then be dried.

To produce the core-shell aggregates, for example, it is also possible to use material-identical solids of different particle size. This is e.g. interesting in cases where a uniform release characteristic of active ingredients over the entire washing and cleaning process is desired. For example, it is possible to combine a porous core of larger particle size solids (core to be coated) and a higher density shell of smaller particle size solids, or vice versa. The porous core would compensate for the decreasing surface upon dissolution of the agglomerate, thereby ensuring that the rate of release does not decrease significantly.

In general, as far as the dishes are concerned, it is preferred that in cases of multi-shell, the solid in an outer shell has a smaller particle size than the solid in the underlying shell.

In particular, in the case of suspension agglomeration, preferably in the event that the solid to be agglomerated in the binder liquid is only very slightly soluble or completely insoluble, For example, a binding-liquid-soluble substance may be added to the binding fluid and / or the particles to be agglomerated, resulting in proper material bridges between the particles after drying of the core-shell aggregate. This is of course also possible with a normal agglomeration.

For this, e.g. organic and inorganic salts such as sodium chloride, potassium chloride, potassium nitrate, sodium nitrate or sodium acetate, organic acids solid at room temperature such as ascorbic acid, lactic acid, citric acid, adipic acid, sugars, e.g. Monosaccharides, such as glucose, fructose, di- or oligosaccharides, such as sucrose or lactose or urea best suited.

In preferred embodiments, in particular in the case of suspension agglomeration, a polymeric binder is added to the binding fluid and / or to the particles to be agglomerated. Examples of suitable polymeric binders are polyethylene glycols, polypropylene glycols and mixed polymers thereof, polyvinyl lactams, in particular polyvinylpyrrolidone (PVP), copolymers of vinyl lactams, such as N-vinylpyrrolidone, N-vinylpiperidone and N-vinyl-epsiloncaprolactam, N-vinylpyrrolidone with (meth) acrylic acid, (meth) acrylic esters, vinyl esters, in particular vinyl acetate, copolymers of vinyl acetate and crotonic acid, partially saponified polyvinyl acetate, polyvinyl alcohol, polyhydroxyalkyl acrylates, polyhydroxyalkyl (meth) acrylates, polyacrylates and poly (meth) acrylates, copolymers of methyl (meth) acrylate and acrylic acid, cellulose esters, cellulose ethers, in particular methylcellulose and ethylcellulose, hydroxyalkylcelluloses, in particular hydroxypropylcellulose, hydroxyalkylalkylcelluloses, in particular hydroxypropyl-ethylcellulose, cellulose phthalates, in particular cellulose acetate phthalate and hydroxypropylmethylcellulose phthalate, and mannans, especially galacto mannans. Also useful are biodegradable polymers such as polyhydroxyalkanoates, e.g. Polyhydroxybutyric acid, polylactic acid, polyamino acids, e.g. Polylysine, polyasparagine, polydioxanes and polypeptides. The polymeric binders used may be hydrophilic or hydrophobic, depending on the nature of the solid to be agglomerated. The binders may be soluble or dispersed or dispersible in the respective binding fluid.

According to another preferred embodiment of the method according to the invention, a multicomponent carrier grain is used as the core material, preferably by extrusion of the multicomponent mixture under the action of elevated pressures - preferably pressures of up to 200 bar and in particular in the range of 15 to 150 bar - with subsequent granulation and preferably rounding the particular strand-like extrudate, or by adherent compression of finely divided multi-component mixture by agglomeration / granulation - optionally with the concomitant use of a water-soluble binder - to suitable grain sizes of preferably at least 0.05 mm, advantageously at least 0.1 mm and in particular equal to / greater than 0.5 mm has been produced. According to a further preferred embodiment of the method according to the invention, the particles to be added are added over a period of at least one minute.

An advantage of the method according to the invention is that the actual agglomeration / granulation process to build up the core-shell aggregate is completed in a significantly shorter time than is usual in conventional agglomeration / granulation. With the method according to the invention, for example, it takes only 10-40 seconds to obtain agglomerates / granules of the same size as those obtained in a conventional granulation after about 5 minutes. This reduction of the effective granulation time is therefore also resource-conserving in terms of the energy aspect. A further advantage of the method according to the invention is that the entire agglomeration / granulation process for the construction of the core-shell aggregate is accompanied by a significantly reduced amount of granulation auxiliary agent compared to what is required in conventional agglomeration / granulation.

According to another preferred embodiment of the method according to the invention, the diameter d _{50 of} the particles to be submitted is in the range of 0.05 to 5 mm.

The lower limit of the diameter d _{50 of} the particles to be prepared may also preferably be at a value of 0.06 mm, 0.07 mm, 0.08 mm, 0.09 mm, 0.1 mm, 0.11 mm, 0.12 mm, 0.13 mm, 0.14 mm, 0.15 mm, 0.16 mm, 0.17 mm, 0.18 mm, 0.19 mm, 0.2 mm, 0.21 mm, 0.22 mm, 0.23 mm, 0.24 mm, 0.25 mm, 0.26 mm, 0.27 mm, 0.28 mm, 0.29 mm, 0.30 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm or 1, 0 mm or even between these values, for example, at 0.35 mm, 0.45 mm, etc. lie.

According to another embodiment, it would also be possible if the diameter d _{50 of} the particles to be submitted has smaller values than 0.05 mm, for example 0.01 mm.

The upper limit of the diameter d _{50 of} the particles to be prepared may also preferably be 4.8 mm, 4.6 mm, 4.4 mm, 4.2 mm, 4.0 mm, 3.8 mm, 3.6 mm, 3.4 mm, 3.2 mm, 3.0 mm, 2.8 mm, 2.6 mm, 2.4 mm, 2.2 mm, 2.0 mm, 1.8 mm, 1.6 mm, 1.4 mm, 1, 2 mm or 1.0 mm, or even between these values, eg at 4.7 mm, 4.5 mm etc.

According to another embodiment, it would also be possible if the upper limit of the diameter d _{50 of} the particles to be submitted is greater than 5.0 mm, for example 6 mm, 7 mm, 8 mm, 9 mm or 10 mm, or between these values is eg at 5.5 mm, 6.5 mm etc. With regard to the size or the diameter of the resulting granules, it has been found that the inventive method both with respect to granules with particularly large particle diameters, for example with diameters of above 2 to 5 or 10 mm or larger, as well as smaller particulate particles in the range of 0.3 and 2 mm or smaller is advantageous. Due to the largely spherical shape of the granules and the uniform particle size distribution, the resulting advantages are essentially independent of the diameter of the particulate particles, since the contact area between the individual particulate particles is very low, so that undesired interactions and interactions between the individual particles are minimized ,

The particle size distribution is thus freely adjustable, which is an important advantage of the method according to the invention.

Depending on the intended use of the particles resulting from the process according to the invention, it may be preferable to obtain rather small particulate particles. Advantageously, then the particles to be submitted are rather small. For example, they may have a particle size in the range of 0.1 to 0.4 mm. Particulate particles of smaller diameters have the advantage that the means consisting of them usually have a high bulk density. This in turn leads advantageously to a significant reduction in the packaging volume. Furthermore, particulate particles having a relatively small particle size are also advantageous if they are to dissolve as quickly as possible, as is often desired, for example with regard to detergents and / or cleaning agents. Accordingly, rather small particulate particles according to the invention advantageously combine high bulk densities on the one hand and, if appropriate, good dispersibility and solubility - for example in the flushing phase of a washing powder in conventional household washing machines.

However, the inventive concept also offers advantages in terms of very large granules with a particle size of, for example, up to 5 mm in diameter or up to 10 mm in diameter or even beyond, such. B. a simple dosage of the granules. For example, the user has the opportunity to specifically pick out, assemble and use the granules of defined composition, which may be colored differently.

According to a further preferred embodiment of the method according to the invention, the particle size distribution of the particles to be prepared is such that the ratio of d ₅₀ to d _{90 of} the particles to be prepared is substantially at least 0.5, preferably at least 0.6, advantageously at least 0.75 and in particular at least 0.8 is.

d ₅₀ represents the median value. The median value is defined as the particle size below and above which in each case 50% of the particle quantity lie. According to lie at d ₉₀ 90% of the Particle quantity below the value, ie 10% above. The ratio d ₅ o / d ₉ o approaches the value of 1 for very narrow particle size distributions, or is well below 0.5 for broad distributions.

According to another preferred embodiment of the method according to the invention, the granulation aid is a granulation foam.

A granulation foam is obtained when a flowable component is charged with a gaseous medium and thus foamed. A granulation foam is, for example, a surfactant foam which has been obtained by foaming a flowable, surfactant-containing component with a gaseous medium and can be used as a granulation aid. The granulation foam preferably has mean pore sizes below 10 mm, preferably below 5 mm and in particular below 2 mm. By using a granulation foam instead of conventional granulating liquids even more homogeneous liquid distributions can be achieved in the granulation / agglomeration process. The particles to be agglomerated / granulated can be wetted even better and, overall, even less granulating liquid can be required to form the agglomerates / granules. Furthermore, an even more homogeneous particle size distribution of the resulting agglomerates / granules is achieved. Possible dust and fines are bound even more effectively.

If the foam generation takes place under a pressure which is above the pressure in the granulation plant, then a particularly advantageous embodiment is present.

According to a further preferred embodiment of the process according to the invention, granulated / agglomerated by (co-) use of an organic and / or inorganic binder which is also soluble in cold water and / or dispersible at room temperature. Preferably, cold water is understood to mean that having a temperature of less than 30 ° C., preferably less than 25 ° C., advantageously less than 20 ° C., in particular less than 18 ° C.

According to another preferred embodiment of the process according to the invention, (co) use preferably film-forming organic components having softening and / or melting points not below 45 ° C, preferably of at least 60 ° C and in particular of at least 75 ° C, are also present with excipients, such as dispersants and / or solubilizers, granulated / agglomerated.

According to a further preferred embodiment of the process according to the invention, water-soluble and / or water-dispersible oligomer and / or polymer compounds of synthetic, semi-synthetic and / or natural origin are granulated / agglomerated by (co) use. According to a further preferred embodiment of the process according to the invention, granulation auxiliaries are used which at least partially comprise valuable substances and / or auxiliaries from the field of textile detergents.

According to a further preferred embodiment of the method _according to the invention, the particles to be added have a particle _diameter d ₅₀ which is at most 1/12, preferably at most 1/14, advantageously at most 1/16, more preferably at most 1/18, more preferably at most 1 / 20, more preferably a maximum of 1/22, in a very advantageous manner a maximum of 1/24 and in particular a maximum of 1/26 of the particle diameter d _{50 of} the particles to be submitted. The reduction of the particle diameter d ₅₀ in the manner described results in the formation of particularly spherical granules / agglomerates.

It is also possible that the particles to be added have a particle diameter d ₅₀ having a value of preferably at most 1/28, 1/30, 1/32, 1/34, 1/36, 1/40, 1/42, 1 / 44, 1/50 or 1/60 of the particle diameter d _{50 of} the particles to be submitted.

Advantageously, the reduction of the particle diameter d ₅₀ does not go so far that the particles to be added would be equivalent to a powder. The particles to be added are advantageously not powder. According to general understanding, powder is a kind of flour, ie an accumulation of solid particles with a particle size preferably below 100 nm. It is also advantageous for process-technical reasons, if the particles do not fall below a certain minimum size. According to a preferred embodiment of the invention therefore have to be added, the particles have a particle diameter d _so, of preferably at least 1/100, advantageously at least 1/80, in a further advantageous manner at least 1/70, more advantageously more advantageously at least 1/60, in yet Way is at least 1/50, in an extremely advantageous manner at least 1/40 and in particular at least 1/35 of the particle diameter d _{50 of} the particles to be submitted.

The particle diameter d _{50 of} the particles to be added may, however, also assume values which lie between the abovementioned, that is, for example, at least 1/90 or at least 1/85 of the particle diameter d _{50 of} the particles to be submitted. Further such values are for example at least 1/95, 1/75, 1/65, 1/55 or 1/45 of the particle diameter d _{50 of} the particles to be submitted.

However, it is important that the particle diameter d _{50 of} the particles to be added is greater than 2 μm. According to another preferred embodiment of the process according to the invention, the particles to be prepared make up less than 50% by weight, preferably less than 45% by weight, advantageously less than 40% by weight, more preferably from 15 to 35% by weight, in particular From 20 to 30% by weight.

It is important, however, that the particles to be prepared make up less than 75% by weight of the solids involved in the granulation process; for example, the particles to be prepared may also be less than 70% by weight, 65% by weight or 60% by weight.

According to another preferred embodiment of the process according to the invention, the particles to be added make up more than 50% by weight, preferably more than 55% by weight, more preferably more than 60% by weight, more preferably from 65 to 85% by weight. %, in particular 70 to 80 wt .-% of the solids involved in the granulation process.

It is important, however, that the particles of the core-shell aggregate to be added make up more than 25% by weight of the solids involved in the granulation process; for example, the particles to be added may also contain more than 30% by weight, 35% by weight, 40% by weight .-% or 45 wt .-% of the solids involved in the granulation process.

According to a further preferred embodiment of the method according to the invention, the particles to be submitted and the particles to be added are obtained by screening out granular heaps, preferably a single granular heap, wherein at least parts of the particles to be added can advantageously be obtained by grinding the coarse and fine material removed from the granular heap if the criteria required for the particle size are met.

In the context of this invention, in particular the so-called eddy current mills, preferably multi-stage eddy current mills can be used with great advantage. These are among the stick mills.

In an eddy current mill, the material to be ground generally passes from the inlet box to the cover plate of a rotor, is detected during the acceleration to the outside of Vorzerkleinerungswerkzeugen and then passes into the grinding gap. Here, in general, the ground material which has been fluidized in the air flow is crushed by impact on the comminution tools of the rotor and stator. Furthermore, extreme air turbulences generally occur in the work spaces of the rotor, which causes additional comminution processes in the form of mutual particle collisions and friction / shearing stresses. In an eddy-current mill, preferably a multistage eddy-current mill, the particles can be easily comminuted to the desired fineness. The fineness can be set in a very wide range via the parameters grinding gap, air flow rate and rotor speed.

It is very advantageous if the particles to be submitted and the particles to be added differ in at least one component of their composition.

According to another preferred embodiment of the method according to the invention, the granulation process is such that the particles to be added and the granulation aids over a period of at least 2, advantageously of at least 3, more advantageously of at least 4, more preferably of at least 5, in a highly advantageous manner of at least 6 minutes, wherein preferably an addition period of 50 minutes, advantageously 40 minutes, more advantageously 30 minutes, more preferably 20 minutes, especially 16 minutes, is not exceeded.

According to a further preferred embodiment of the process according to the invention, the granules, ie the coated core-shell aggregate, are dried and / or cooled in a further process step, preferably in a fluidized bed, and advantageously powdered before or after this process step.

According to another preferred embodiment of the method according to the invention, the specific power of the mixer / granulator is less than 5 kW / m ³ , preferably less than 3 kW / m ³ , in particular less than 1, 5 kW / m ³ .

On the one hand, low energy introduction means an economic advantage over the energy consumption, but in particular a particularly gentle agglomeration without appreciable destruction of already formed granules takes place in this way.

According to a further preferred embodiment of the method according to the invention, the particles to be added have a largely uniform particle size, wherein advantageously the particle size distribution of the particles to be added is such that the ratio of d.sub.50 to d.sub.50 of the particles to be added is preferably at least 0.5, more preferably at least 0.6 , in particular at least 0.75.

According to a preferred embodiment, the core as such, before being surrounded by the shell, coated or coated, ie, for example, coated or coated with a solution, dispersion, emulsion or melt certain active ingredients. This corresponds to a preferred embodiment. According to a preferred embodiment, the core is impregnated as such before it is surrounded with the shell, ie, for example impregnated with a solution, dispersion, melt or emulsion of certain active substances, preferably to modify the properties of the core. This corresponds to a preferred embodiment.

According to a preferred embodiment, the uncoated core-shell aggregate as such, before it is finally coated, is previously impregnated, i. e.g. so impregnated with a solution, dispersion or emulsion of certain active ingredients, to modify the properties of the core-shell aggregate. This corresponds to a preferred embodiment. For impregnating the core or the uncoated core-shell aggregate impregnating agents, preferably silicone-containing impregnating agents can be used, ie mixtures which advantageously contain different polysiloxanes with condensable groups, which advantageously make more or less water repellent. For impregnation, it is preferred to use agents which serve for the hydrophobizing and the core or the uncoated core-shell aggregate.

Preferred hydrophobizing agents include, in addition to agents, the silicones also agents which are e.g. Paraffins, waxes, metal soaps (sometimes also with additions of aluminum or zirconium salts), quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, tin organic compounds and / or glutaraldehyde ,

In principle, of course, a hydrophilization is possible, which corresponds to a preferred embodiment. The hydrophilization is carried out with the aid of hydrophilizing agents, e.g. be applied in the form of aqueous solutions. It is e.g. to formulations of ionic or nonionic polymers, ethoxylation products and the like. It is e.g. it is possible to hydrophilize the core before it is surrounded by the shell.

For impregnation, agents containing lipids are preferably used. Preferred lipids are

(b) lipophilic alcohols (such as wax alcohols, retinol or cholesterol, etc.),

(c) ether lipids

(d) lipophilic carboxylic acids (fatty acids),

(f) lipophilic amides (such as ceramides, etc.),

(g) waxes (h) lipids with more than 2 hydrolysis products, such as glycolipids, phospholipids, sphingolipids and / or glycerolipids, etc. (i) lipids in the form of higher molecular weight conjugates with more than 2 hydrolysis products, such as lipoproteins and / or lipopolysaccharides etc., G) Phosphorus-free glycolipids, such as glycosphingolipids (such as preferably cerebrosides, gangliosides, sulphatides) or, for example, glycoglycerolipids (preferably glycosyldi- and monoglycerides), etc. (k) carbohydrate-free phospholipids, such as, for example, sphingophospholipids (such as sphingolymphins) or, for example, glycerophospholipids (such as preferably lecithins, cephalins, cardiolipins, phosphatidylinositols and inositol phosphates etc.) and / or (I) mixtures of the abovementioned.

In another preferred embodiment, the impregnating agent comprises neutral lipid, preferably selected from fatty acids (> C12), mono-, di-, triacylglycerides, sterols, sterol esters, carotenoids, waxes and / or tocopherols.

In another preferred embodiment, the impregnating agent comprises polar lipid, preferably selected from glycerophospholipids, glyceroglycolipids, sphingophospholipids and / or sphingoglycolipids.

In a further preferred embodiment, the impregnating agent has at least one polar and one nonpolar lipid.

It is also possible in the coating of the core-shell aggregates to perform a partial hydrophobization, that is to make the surface of the particles hydrophobic by applying water repellents as a coating, preferably agents such as silicones, paraffins, waxes, metal soaps (partly with additions of aluminum or zirconium salts), quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified Melamine resins, chromium complex salts, tin organic compounds and / or glutardialdehyde

It is also possible in the coating of the core-shell aggregates to carry out a partial hydrophilization, that is to make the surface of the particles hydrophilic, for example by applying aqueous solutions as a coating to the core-shell aggregate, in particular preparations of ionogenic or mungionogenic polymers, ethoxylation products and the like For example, polyethylene glycol sorbitan fatty acid esters and comparable substances are particularly suitable for hydrophilization

Also, the detachment of the shell as such can be manipulated individually, advantageously via the choice of granulation fluid. For example, the granulation fluid may be more hydrophobic, with the result that the shell loses more slowly in an aqueous environment. If the granulation fluid is rather hydrophobic, In the context of this invention, in the further description, the term "hydrophobically bound" shell is used in a simplified manner. For example, the granulation fluid can be rather hydrophilic, with the result that the shell dissolves more quickly in a moist environment. If the granulation fluid is rather hydrophilic, then in the context of this invention in the further description of a "hydrophilic bonded" shell the speech

For example, the cores of the coated core-shell aggregates may also contain decomposition accelerators, for example substances which have a high ability to adsorb water (for example starch, cellulose derivatives, alginates, dextrans, cross-linked polyvinylpyrrolidone, casein derivatives, etc.). and / or in particular gas-evolving substances (for example sodium bicarbonate, citric or tartaric acid, etc.), so that a showering effect or effervescent effect occurs

According to a further preferred embodiment, the coating is sensitive to pH and / or temperature and / or ionic strength or contains pH and / or high-temperature and / or ionic-strong-sensitive materials. According to a further embodiment, the shell is pH- and / or or temperature-sensitive and / or ionic-strong-sensitive or contains pH-sensitive and / or high-temperature and / or ionic-strong-sensitive materials. According to a further embodiment, the core is pH and / or temperature and / or ionic strength-sensitive or contains pH and / or temperature and / or ionic strength-sensitive materials

It should be pointed out once again that the pH and / or temperature and / or high-ion-intensity-sensitive materials not only in the coating, but also as Matrixmateπal, binding or disintegrating agent for the actual core-shell aggregate, the Core and / or the shell can be used This corresponds to a preferred embodiment According to a preferred embodiment, the coated core-shell aggregates are floatable in water, ie do not submerge in water or in a wash liquor, but float on the water surface

In order to make the core-shell aggregates floating, it is preferable to adjust their density to values less than 1 g / cm ³ , if necessary

According to another preferred embodiment of the erfmdungsgemaßen process the granules are sieved, preferably after drying, sieved and / or sifted to separate the Gutkorns of U- berkorn and Femanteilen, the Uberkom and the fines are then subjected to a grinding process a), so that these particles after grinding a particle diameter d ₅₀ have, the more than one tenth of the particle diameter d amounts to the submitted particles _50, and then b) these particles as to be added particles back to the mixer / granulator are fed to the product particles is coated inventively

The product may consist of good grain, overcorn and undersize (fines), although the Uberkorn- and Unterkomanteile are advantageously negligible The term of the Gutkorns referred to that built up granules whose size or diameter is desired This large area is an individual area that is Based on the needs of the user and can be selected according to the respective requirements The Uberkorn is that built-up granules, which in contrast is too coarse, ie too large The undersize (fines) is that granules, which in turn to fine or too small It is an advantage of the process according to the invention that oversize and undersize grains already occupy only a negligible proportion in the process product

According to a preferred embodiment of the inventive method, a plurality of powders (corresponding to granular debris I) are taken and separated according to their grain size, preferably with the help of sieves or other technical aids which meet the same tick, in order in this way from the granular heap I. the particles of particles to be used (cores) to be used in the process according to the invention are to be separated out (corresponds to good particle I) (note The desired particle size of the good grain I is an individual which is oriented to the needs of the users. The particle size then depends on this particle size the particle to be added)

The undersize and oversize grain (corresponding to defective grain I) obtained in this rejection process, preferably a sieving process, is advantageous in accordance with a further preferred embodiment. legally not discarded, but in particular a comminuting device I ₁ preferably fed to a mill and there adjusted to the required particle size of the "to be added particles". After passing through the crushing means I, the former outsize I thus exactly the desired particle size to which the "to be added particles "must have according to the invention and can be used according to the granulation / agglomeration according to the invention.

Advantageously, however, it is not only the named defective grain I that passes through a comminuting device. Advantageously, another or several other powders (corresponding to granular debris II) are also taken and likewise passed through a comminution device, preferably the same comminution device I, which corresponds to a preferred embodiment.

The comminuted material which can be removed from the comminution devices, preferably the comminution device I, which now has the particle size according to the invention for the "particles to be added" and preferably originates from defective grain I and granular pile II, is then mixed with the particles to be prepared (good grain I) in the mixer / Granulator agglomerated / Granulated with the addition of granulation, which corresponds to a preferred embodiment.

The resulting agglomerates are then preferably passed into a fluidized bed dryer where it is dried / cooled. According to a preferred embodiment, the agglomerates are then separated according to their grain size, preferably by means of sieves or else by other technical aids which fulfill the same purpose.

In this way, from the agglomerates, those with the desired particle size, the so-called agglomerate Gutkorn, discarded. (Note: The desired particle size of the agglomerate good grain is an individual, which is oriented to the needs of the user.)

The undersize and oversize (corresponding to agglomerate grain) resulting from this rejection process, preferably a sieving process, is advantageously not discarded, but in particular fed to a comminuting device, preferably a mill. This mill may preferably be a further comminuting device (corresponding to comminuting device II), but it is also advantageously possible for it to be the same comminuting device (corresponding to comminuting device I) that was previously used. When passing through this comminution device, the agglomerate false grain is adjusted to the particle size which the "particles to be added" according to the invention must have, ie that the agglomerate, which is agglomerate false grain, is comminuted again to subject it to agglomeration again Shape of the "particles to be added". The agglomerate good grain (core-shell aggregate) is finally taken and according to the invention provided with at least one coating containing, for example, nonionic surfactant, brightener and / or perfume. The result is a coated core-shell aggregate. According to the invention, such a coated core-shell aggregate may already be an independent washing or cleaning or care agent. According to the invention, however, such a coated core-shell aggregate can also be a washing or cleaning or care additive. According to the invention, the coated core-shell aggregate can be mixed with further particles. These further particles preferably have an approximately identical shape and / or approximately the same particle size as the coated core-shell aggregates. Advantageously, the further particles with which the coated core-shell aggregates are mixed are also coated particles. In a particular way, it is preferred, for example, to produce the coated core-shell aggregates by the process according to the invention and to mix them with at least two further, different, preferably coated particle types, namely in particular with enzyme-containing particles and in particular with bleach, preferably percarbonate-containing particles ,

In a preferred embodiment, the method according to the invention comprises the following steps: a) sieving process for separating a particulate material with largely uniform particle size (particles to be prepared) of oversize and fines from at least one granular heap I b) crushing, preferably grinding, the granulated heap I. Separated oversize and the fines to at least one tenth of the particle diameter d _{50 of} the particles to be submitted or smaller to obtain "particles to be added" c) Optional: crushing, preferably grinding at least one granular heap Il to at least one tenth of the particle diameter d _{50 of} the particles to be submitted or smaller in order to obtain "particles to be added", preferably in the same comminution device as in step b) d) granulation / agglomeration of the particles to be prepared (from step a)) with the addition of the particles to be added (from step b) and optionally c) e) Optional: Drying and / or Cooling of Granules / Agglomerates in a Fluidized Bed f) Separation of the Good Grain from Oversize and Fines by Screening and / or Screening g) Transfer of Oversize and Fines (out Step f)) in a comminution device, preferably mill and crushing, preferably grinding these particles to a particle diameter d ₅₀ , which is at most one tenth of the particle diameter d _{50 of} the particles to be submitted, and then h) recycling of the milled particles (from step g) as particles to be added into the mixer / granulator, i) Gutkombeschichtung.

This method can be carried out on the basis of a single particle material mixture and on the basis of different particle materials for particles to be prepared and added.

According to another preferred embodiment of the process according to the invention, the particles to be prepared, the particles to be added and / or the granulation aids comprise ingredients from the field of detergents and / or cleaning agents.

According to another preferred embodiment of the process according to the invention, the particles to be prepared and / or the particles to be added are tower powder products and / or (raw) products of non-tower technologies, preferably resulting from granulation in drum, plate, mixer and fluidized bed granulators or have emerged from these.

The particles to be prepared and / or the particles to be added can preferably also be produced by means of extrusion, particularly preferably using a two-shaft extruder. In this case, the raw materials intended for the respective particulate particles are first mixed and then homogenized and plasticized in the extruder. For example, preformed particles can be obtained by cutting the extruded mass at the extruder head. Extrusion processes suitable according to the invention are known in the art and are described in the relevant patent and technical literature.

The preparation of the particles to be submitted and / or the particles to be added, preferably with a defined composition, can in the broadest sense be carried out quite generally according to methods known per se, ie. H. The particles to be used can be obtained, for example, as needed by spraying and subsequent dry compaction, by granulation, spray agglomeration or by extrusion.

Preferably, the particles to be submitted and / or the particles to be added can be rounded in a method step which precedes the method according to the invention. In particular, the particles to be prepared and / or the particles to be added are rounded with the aid of a so-called spheronizer, a rotary drum, a coating drum or a coating pan.

In a preferred embodiment, the particles to be prepared and / or the particles to be added are those which, after the so-called spray agglomeration driving were made. In the spray agglomeration process, the particles to be used are simultaneously agglomerated in a fluidized bed and dried. The onion-like application of the substances and the movement of the particles give rise to very dense and round particles, which can be processed very advantageously in the method according to the invention.

According to another preferred embodiment of the method according to the invention, the coated granules (constructed as final product) essentially have an average form factor of at least 0.79, preferably of at least 0.81, advantageously of at least 0.83, more preferably of at least zero , 85, in particular of at least 0.87. "Substantially" here means in particular that at least 80%, preferably at least 90% and in an advantageous manner at least 95% of the built-up granules have the aforementioned form factor The granules formed are preferably the entirety of good grain, oversize grain and The form factor (shape factor) in the sense of the present invention can be precisely determined by modern particle-measuring techniques with digital image processing in a typical particle shape analysis, as for example can be carried out with the Camsizer® system from Retsch Technology or also with the KeSizer® from Kemira, based on the fact that the particles or the bulk material are irradiated with a light source and the particles are detected as projection surfaces, digitized and processed by computer technology Determination of the surface The curvature is effected by an optical measuring method in which the "shadow cast" of the parts to be examined is determined and converted into a corresponding shape factor. The underlying principle for determining the shape factor has been described, for example, by Gordon Rittenhouse in "A Visual Method of Estimating Two-dimensional Sphericity" in the Journal of Sedimentary Petrology, Vol. 13, No. 2, pp. 79-81.

The measurement limits of this optical analysis method are 15 μm and 90 mm, respectively. The numerical values for d ₅₀ and d ₉₀ are also available via the aforementioned measuring method.

According to a further preferred embodiment of the process according to the invention, the built-up, coated granules (final process product) are present essentially in a particle size distribution which is as uniform as possible, in which the ratio of d ₅₀ to d _{90 is} at least 0.50, preferably at least 0.6, advantageously at least 0 , 75, in a further advantageous manner is at least 0.80.

In a further preferred embodiment according to the invention, the built-up, coated granules are provided with a further coating of an at least partially water-soluble polymer material for additional stabilization. Inorganic compounds are also suitable. Suitable polymers are well known in the art, including suitable inorganic compounds. This coating is applied after the coating.

According to the invention, it is furthermore advantageous to surround the coated granules with a coating of fine solids, ie to remove them, for example in order to achieve protection. The choice of these fine solids depends on the nature of the granules and their intended use. For example, in the case of granules from the field of detergents and / or cleaners, powdering agents are suitable which preferably contain very finely divided zeolite and / or silica, in particular hydrophobic silica.

In this case, the granules according to the invention may preferably contain all the ingredients required or commonly used for a washing and / or cleaning process, so that such granules are in themselves an independent, fully functional and functional washing and / or cleaning agent. An inventively constructed detergent and / or detergent granules is therefore preferably a complete washing and / or cleaning agent.

However, it is also preferred if the granulate according to the invention contains only one particular or several particular detergent and / or cleaning agent constituents. Such a granulate constructed in accordance with the invention would then not be an independent, complete and functional washing and / or cleaning agent, but rather a detergent and / or detergent component. Such a granulate would then be mixed with the other customary components which are necessary for the formation of a complete washing and / or cleaning agent. It is preferred in such a case if at least two or more granules constructed according to the invention are mixed to form a washing and / or cleaning agent and the resulting fully-fledged washing and / or cleaning agent consists only of these granules constructed according to the invention, the different granules preferably having different colors exhibit.

In the context of the present invention, the term coated core-shell aggregates also encompasses washing and / or cleaning agent granules, i. to understand both full-strength detergents and / or detergents as well as detergent and / or detergent components.

Another object of the present invention is the use of the inventive method for transferring powdery and / or fine-grained multi-component mixtures from the field of detergents and cleaners, such as commercial detergents and / or cleaning agents, provided with a coating core-shell aggregates. In this way, the refinement of conventional detergents to high-quality dosage forms with controlled release of active ingredient, sustained release effect and optically unique quality succeeds

Although neither the inventive method nor erfindungsgernäße agent is basically limited to the field of detergents and cleaning agents, however, such means and / or method particularly preferred embodiments of the invention Therefore, in the following closer to possible ingredients according to the invention to be produced washing and / or Cleaning agent granules, so besch- coated detergent and / or detergent granules (coated core-shell aggregates), received

The constituents contained in the detergent and / or detergent granules (coated core-shell aggregates) to be produced according to the invention are preferably selected from the group comprising surfactants, fragrances, dyes, scaffolds, pH adjusters, bleaches, bleach activators, soil repellents Furthermore, all other detergents and / or cleaning agent ingredients known to the person skilled in the art from the prior art can also be used in the customary amounts of constituents of the wash to be produced according to the invention, not explicitly mentioned here - And / or detergent granules (coated core-shell aggregates)

Some of the washing and / or cleaning agent constituents which are particularly suitable according to the invention are described in more detail below. These constituents can be present in the washing and / or cleaning agent granules (coated core-shell aggregates) themselves and / or in corresponding admixtures which are added to the detergent compositions If appropriate, it is also possible to add washing and / or cleaning agent granules (coated core-shell aggregates) if this is necessary in order to obtain a complete washing and / or cleaning agent

Surfactants which can be used for the preparation according to the invention of the washing and cleaning agent granules (coated core-shell aggregates) are anion, cation, amphos and / or nonionic surfactants

For example, anionic surfactants of the sulfonate-sulfates type can be used. Sulfonate-type surfactants are preferably used

Benzenesulfonates, Olefinsulfonate, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from C ₁₂ i ₈ -Monoolefιnen with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration Also suitable are alkanesulfonates which are prepared from C ₁₂ -iβ- Alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise suitable are the esters of .alpha.-sulfo fatty acids (ester sulfonates), for example the .alpha.-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. Also suitable are sulfonation of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt .-%. In particular, preferred are α-sulfofatty acid alkyl esters which have an alkyl chain having not more than 4 carbon atoms in the ester group, for example, methyl ester, ethyl ester, propyl ester and butyl ester. With particular advantage, the methyl esters of α-Suifofettsäuren (MES), but also their saponified Disalze be used.

Further suitable anionic surfactants are su lfierte fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as in the preparation by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol Glycerol can be obtained. 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.

Alk (en) yl sulfates are the alkali and especially the sodium salts of Schwefelsäurehalbester the C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C ₁₀ -C ₂ o Oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of the aforementioned chain length, which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis, which have an analogous decomposition behavior to the adequate compounds based on oleochemical raw materials.

Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides). Particularly preferred are the sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate.

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases such as mono-, di- or tri-ethanolamine, available. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The anionic surfactants may be present in the detergent and / or detergent granules (coated core-shell aggregates) to be prepared according to the invention preferably in amounts of from 1 to 30% by weight and in particular in amounts of from 5 to 25% by weight.

It is also possible to use alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese Patent Application JP 58/217598. Preferred nonionic surfactants are C ₁₂ -C ₁₈ fatty acid methyl esters having an average of from 3 to 15 EO, in particular having an average of from 5 to 12 EO. In particular, C ₁₂ -C ₁₈ fatty acid methyl esters with 10 to 12 EO can be used as surfactants.

Another class of nonionic surfactants which can be advantageously used for the production according to the invention of detergent granules and / or detergent granules (coated core-shell aggregates) are the alkylpolyglycosides (APG). Usable Alkypolyglycoside meet the general formula RO (G) _Z , in which R is a linear or branched, in particular 2-methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The glycosidation degree z is between 1, 0 and 4.0, preferably between 1, 0 and 2.0 and in particular between 1, 1 and 1, 4.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl N, N-dimethylamine oxide and N-tallowalkyl N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be used for the inventive preparation of the detergent granules (coated core-shell aggregates ) be suitable.

Other suitable surfactants for the preparation according to the invention of the washing and / or cleaning agent granules (coated core-shell aggregates) are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants. Gemini surfactants for the preparation according to the invention of washing and / or cleaning agent granules (coated core-shell aggregates) are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis- and trimer alcohol tπs-sulfates and ether sulfates. Final-group-closed dimeric and linear mixed ethers are distinguished in particular by their Bi- and Multifunktionahtat from So said end-capped surfactants have good wetting properties and are low in foaming, so they are particularly suitable for use in machine washing and / or cleaning process The inventively produced washing and / or cleaning granules (coated core) Shell aggregates) may contain as Geruststoff or Builder all commonly used in detergents and / or cleaning agents, especially in detergents, Gerüststoffe used, in particular zeolites, silicates, carbonates, soda, organic cobuilders and the phosphates To avoid particulate In the case of textiles, it is particularly advantageous to use builders which are completely water-soluble, such as soda or the like

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are Preferred crystalline sheet silicates of the formula given are those in which M is sodium and x has the values 2 or 3. In particular, both β- and δ-Natπumdisilikate Na ₂ Si ₂ O ₅ yH ₂ O are preferred

Preferably, the compositions according to the invention may also comprise optional cationic surfactant, advantageously in the core, in particular exclusively in the core. In a preferred embodiment, the cationic surfactant is a quaternary ammonium compound, preferably an alkylated quaternary ammonium compound

This is according to a preferred embodiment, a quaternary ammonium compound according to the following formula,

R ¹ (R ² ) (R ³ ) (R ⁴ ) N ⁺ X ^" , where

R ¹ , R ² and R ^{3 are} independently selected from C ₁ -C ₄ -AlkYl. ₁

Benzyl and - (C ₂ H ₄ O) _x H, where x is 2 to 5, and wherein R ^{4 is} C ₈ -C ₂₂ alkyl, and where X ^'is an anion, preferably a halide, methosulfate , Methophosphat- or phosphate ion and mixtures thereof

According to a further preferred embodiment, the cationic surfactant is a quaternary ammonium compound of the following formula

R ⁵ R ⁶ _n R ⁷ ₃ .nN ⁺ X- wherein R ^{5 is} a C ₆ -C ₂₄ alkyl or alkenyl wherein each R ^{6 is} independently a - (C _n H ₂ nO) _x R ⁸ group, where n is 1 to 4 and x is 1 to 14 and wherein R ^{8 is} a methyl ethyl or preferably a hydrogen, and wherein each R ^{7 is} independently a C ₁ -C ₁₂ alkyl or alkenyl group, with m is 1 to 3, and wherein X- is an anion, preferably a halide, methosulfate, methophosphate or phosphate ion as well as mixtures of these particular R ^{6 is} a -CH ₂ CH ₂ OH group, in particular R ⁷ is independently a Ci-C ₄ alkyl, with m is 1 or 2 and in particular R ^{5 is} a linear C ₆ -C ₁₄ alkyl group

In a preferred embodiment, the cationic surfactant may be a C ₈ -C ₁₆ -alkyl-dι (hydroxyethyl) methylammonium compound, preferably a C ₁₂ -C ₁₄ -alkyldi- (hydroxyethyl) methyl ammonium compound, and / or a C ₈ -C ₁₆ -alkyl (hydroxyethyl) -dimethylammonium compound, preferably C ₁₂ -C ₁₄ -alkyl (hydroxyethyl) -dimethylammonium compound, in particular the respective halides, methosulfates, methophosphates or phosphates and mixtures thereof

However, it is also possible to use other cationic surfactants, but advantageously alkylated quaternary ammonium compounds, preferably having two hydrophobic groups, which are linked in particular via ester or amido groups to a quaternized di- or triethanolamine or an analogous compound

Such compounds may be advantageously selected from the following formula

X

Here, R ^{9 is} an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds, R ¹⁰ is H, OH or in particular 0 (CO) R ¹² , R ¹¹ is independently of R ^{10 is} H, OH or 0 (CO) R ¹³ , where R ¹² and R ¹³ independently of one another each represent an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds, a, b and c can each independently of one another have the value 1, 2 or 3, X ^" is a suitable anion, preferably a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof, and / or the following formula

wherein R ¹⁴ , R ¹⁵ and R ¹⁶ independently represent a C ₁ ^ -AlkVl-, alkenyl or hydroxyalkyl group, R ¹⁷ and R ¹⁸ each independently selected a C ₈ _ ₂₈ alkyl group with 0, 1, 2 or 3 represents double bonds and u is a number between 0 and 5, X ^" is a suitable anion, preferably a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof.

Preferred representatives of this type are N-methyl-N (2-hydroxyethyl) -N, N- (ditalgacyloxyethyl) ammonium methosulphate or N-methyl-N (2-hydroxyethyl) -N, N- (dipalmitoylethyl) ammonium methosulphate ,

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8, and in particular from 1: 2 to 1: 2.6. Particular preference is given to amorphous silicates.

A useful fine crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. As zeolite P zeolite MAP ^® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is marketed by CONDEA Augusta SpA under the trade name AX VEGOBOND ^® and the formula: Na ₂ O. (1-1I) K ₂ O Al ₂ O ₃ (2 - 2.5), SiO ₂ (3.5 - 5.5) H ₂ O corresponds.

Suitable zeolites preferably have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain from 18 to 22% by weight, in particular from 20 to 22% by weight, of bound water.

The content of the granules of zeolite according to the invention can be up to 60 wt .-%, advantageously up to 40 wt .-% and in a further advantageous manner up to 30 wt .-% according to a preferred embodiment, and it may be even more advantageous if at most 15% by weight, preferably at most 12% by weight, in particular not more than 10% by weight, based in each case on the anhydrous active substance, for example 1 to 8% by weight or 0 to 5% by weight. In a particularly preferred embodiment, the granules which can be prepared according to the invention are free of zeolite.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular Preferably, the granules according to the invention are not only zeohth- but also low in phosphate Thus, the phosphate content is advantageously at most 15% by weight, preferably at most 12% by weight, especially at most 10% by weight, for example 1 to 8% by weight or 0 to 5% by weight Very particularly preferred are granules which are both free from zeolite and from phosphate

As organic cobuilders, the inventive detergent and / or detergent granules (coated core-shell aggregates) may contain in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates These classes of substances are described below

Useful organic framework substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, Aminocarboxylic acids, Nitπlotπessigsaure (NTA), if such use is not objectionable for environmental reasons, and mixtures of 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 thereof

The acids themselves can also be used. In addition to their builder effect, the acids also typically have the property of an acid component and thus also serve for setting a lower and milder pH of detergents and / or cleaning agents. Citric acid, succinic acid, glutaric acid are particularly suitable To name adipic acid, gluconic acid and any mixtures of these

Other suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC) using a UV detector. The measurement was carried out against an external polyacrylic acid Standard, which provides realistic molecular weight values owing to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data in which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrenesulfonic acids are generally much higher than those specified in this document molecular weights Suitable polymers are, in particular, polyacrylates which preferably have a molecular mass of from 2000 to 20 000 g / mol. Because of their superior solubility, this group may in turn comprise the short-chain polyacrylates, the molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, have, be preferred

Also suitable are copolymeric polycarboxylates, 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 particularly suitable Their relative molecular mass, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those containing as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or the monomers of the salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives

Further preferred copolymers are those which have as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursor substances Particularly preferred are polyaspartic acids or their salts and derivatives which have not only co-builder properties but also a bleach-stabilizing effect

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are prepared from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as Gluconic acid and / or glucoheptonic acid

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, the hydrolysis products have average molecular weights in the range from 400 to 500000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a customary measure of the reducing action of a polysaccharide in comparison to dextrose, which has a DE of 100, is usable both Maltodextnne with a DE between 3 and 20 and dry glucose syrups having a DE of between 20 and 37, and so-called yellow dextrins and white dextrins having higher molecular weights in the range of 2,000 to 30,000 g / mol

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide to the carboxylic acid function. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous

Oxydisuccinates and other derivatives of disuccinates, preferably Ethylendiamm disucci--nat, further suitable co-builders are Here, Ethylendιamιn-N, N ^{'-dιsuccιnat} (EDDS) is preferably in the form of its sodium or magnesium salts thereof are furthermore preferred in this context, and Glyceπndisuccinate Glyceπntrisuccinate

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups

A further class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkanes, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt. wherein the Dinatnumsalz neutral and the tetrasodium salt alkaline (pH 9) are reacted as aminoalkane phosphonates are preferably ethylenediaminetetramethylene (EDTMP), Diethylentπaminpentamethylenphos- phonate (DTPMP) and their higher homologs in question They are preferably in the form of neutral sodium salts, eg B as the hexasodium salt the EDTMP or as Hepta- and Octa-Natnumsalz the DTPMP, used as a builder is preferably from the class of phosphonates HEDP used The Aminoalkanphosphonate also have a pronounced Schwermetallbindevermogen Accordingly, it may, especially if the washing and / or Reinigungsmitmit also contain bleach, it is preferable to use its aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the abovementioned phosphonates for the preparation of the granules

In addition, all compounds capable of forming complexes with alkaline earths can be used as co-builders

Further suitable builder substances for the preparation of the washing and / or cleaning agent granules according to the invention (coated core-shell aggregates) are oxidation products of carboxyl-containing polyglucosans and / or their water-soluble salts Also suitable are oxidized oligosaccharides

Further builders suitable for the preparation according to the invention of the detergent granules (coated core-shell aggregates) are polyacetals which are prepared by reacting dialdehydes with polyolcarboxylic acids having 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are selected from dialdehydes, such as Glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from Polycarbonsauren such as gluconate and / or glucoheptonic acid

In order to reduce the pH of detergents and / or cleaning agents, in particular detergents, the granules which can be prepared according to the invention may also have acid salts or slightly alkaline salts. Preferred as the acid component are bisulfates and / or bicarbonates or organic polycarboxylic acids, which are also known as Builder substances can be used. Particularly preferred is the use of citric acid

The washing and / or cleaning agent granules (coated core-shell aggregates) which can be prepared according to the invention can also contain bleaches. Among the compounds which serve as bleaches and deliver H ₂ O ₂ in water, the sodium hydrogenated tetrahydrate and sodium borate monohydrate are of particular importance. Further useful bleaching agents are, for example Natπumpercarbonat, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelic acid, Phthaloiminopersauer or Diperdodecandisaure

It is also possible to use bleaching agents from the group of organic bleaching agents for the preparation of the washing and / or cleaning agent granules (coated core-shell aggregates). Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Further typical organic bleaching agents are the peroxyacids, where Examples especially the alkyl peroxyacids and the aryl peroxyacids may be mentioned

Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkyl peroxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylic acid, peroxystearic acid, ε-phthalimido peroxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamιdoperadipic acid and N-nonenylamethylenopyrimnate, and (c) peroxydicarboxylic acids, such as 1,12-dimercarboxylic acid, 1,9-dipoxyazelaic acid, dipocycacybetic acid, diperoxybrassylic acid, the diperoxy-phthalic acids, 2-Decyldιperoxybutan-1, 4-diacid, N, N-tere-phthaloyl-dι (6-aminopercapronone) can be used for the preparation of the granules of the invention Chlorine or bromine-releasing substances can also be used as bleaching agents in the detergent and / or detergent granules prepared according to the invention. Heterocyclic N-bromo- and N-chloramides, for example, are used as suitable chlorine or bromine-releasing materials Trichlorocyanocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloro-cyanuric acid (DICA) and / or salts thereof with cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethyl-danthoin, are also suitable

The content of bleaching agents may preferably be from 0 to 25% by weight and in particular from 1 to 20% by weight, based on the total composition of the washing and / or reminiscent granules prepared according to the invention (coated core-shell aggregate).

In order to achieve an improved bleaching effect during washing or cleaning at temperatures of 60 ^° C. and below, bleach activators may be present

As bleach activators for the preparation according to the invention of the laundry and / or remover granules (coated core-shell aggregates), it is possible to use compounds containing perhydrolysis compounds of aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and Suitable are substances which carry O- and / or N-acyl groups of said carbon atom number and / or optionally substituted benzoyl groups. Preferred are polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated Tπazinderivate, in particular 1, 5-Dιacetyl-2,4-dιoxohexahydro-1, 3,5-trιazιn (DADHT), acylated Glycolunle, in particular tetraacetylglycoluril (TAGU), N-Acylιmιde, in particular N-Nonanoylsuccιnιmιd (NOSI), acylated phenolsulfonates, in particular n- Nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially Tnacetin, ethylene glycol diacetate and 2,5-Dι-acetoxy-2,5-diphohydrofuran

In addition to the conventional bleach activators or in their place so-called bleach catalysts can also be used for the inventive production of detergent and / or cleaning granules (coated core-shell aggregates) These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe , Co, Ru or Mo salt complexes or carbonyl complexes Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and co-, Fe, Cu and Ru ammine complexes are useful as bleach catalysts

Suitable bleach activators for the preparation according to the invention of the washing and / or cleaning agent granules (coated core-shell aggregates) are also enol esters and acetylated sorbitol and mannitol, acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose as well as acetylated, if appropriate N - alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl caprolactam. Hydrophilically substituted acylacetals and acyl lactams are likewise preferably used for the preparation of the washing and / or cleaning agent granules according to the invention (coated core-shell aggregates).

In particular, when used in machine washing process, it may be advantageous to the washing and / or detergent granules (coated core-shell aggregates) are added conventional foam inhibitors. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C18-C24 fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally signed silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with signed silica or bistearylethylenediamide.

According to a preferred embodiment of the invention, the coated core-shell aggregates according to the invention are free of enzymes, which means for the purposes of the invention that they are less than 30 wt .-%, preferably less than 25 wt .-%, advantageously less than 20 Wt .-%, more preferably less than 15 wt .-%, more preferably less than 10 wt .-%, in turn, more advantageously, less than 5 wt .-% of enzymes contained, based on the total coated core-shell aggregate. In particular, however, they are completely enzyme-free, ie contain 0 wt .-% of enzyme based on the total coated core-shell aggregate.

According to another preferred embodiment of the invention, the core and / or the shell and / or the coating of the coated core-shell aggregate according to the invention, free of enzymes, which means in the context of the invention that in each case the core and / or the shell and or the coating is less than 30% by weight, preferably less than 25% by weight, advantageously less than 20% by weight, more preferably less than 15% by weight, even more advantageously less than 10 Wt .-%, in turn advantageously less than 5 wt .-%, in particular 0 wt .-% of enzymes contained, based on the respective phase of the coated core-shell aggregate. However, it is very preferred if both the core and the shell and also the coating are free of enzymes in the just mentioned sense, in particular they each contain 0 wt .-% of enzyme based on the entire coated core-shell aggregate.

However, it is most preferred if at least the shell of the coated core-shell aggregate according to the invention is free of enzymes, which means in the context of the invention that the shell less than 30 wt .-%, preferably less than 25 wt. %, advantageously less than 20% by weight, more preferably less than 15% by weight, even more advantageously less than 10% by weight, again in a further advantageous manner less than 5% by weight, in - contains particular 0 wt .-% of enzymes, based on the total coated core-shell aggregate.

However, if enzymes should be present, which corresponds to another preferred embodiment, as enzymes for the preparation according to the invention of the washing and / or cleaning agent granules (coated core-shell aggregates), in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, A-mylases, Glykosylhydrolasen and mixtures of said enzymes in question. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains.

According to a further preferred embodiment, the coated core-shell aggregate is enzyme-containing, wherein according to a preferred embodiment, advantageously 2 phases of the coated core-shell aggregate according to the invention, namely preferably shell and coating, are completely free of enzymes, whereas advantageously the third Phase, preferably the core, contains enzyme, in particular in amounts greater than 1 wt .-%, but less than 80 wt .-%, preferably less than 70 wt .-%, advantageously less than 60 wt .-%, in a further advantageous manner less than 50% by weight, more preferably less than 40% by weight, again more advantageously less than 30% by weight, more preferably less than 20% by weight, even more advantageously less as 10 wt .-%, based on the total mass of the core.

According to the aforementioned embodiment, a further subject of the invention is the use of the erfindungemäßen, coated core-shell aggregates as enzyme granules, which preferably have an enzyme-free shell and / or an enzyme-free coating.

For bleaching oxidoreductases may preferably be used. Particularly suitable for the preparation of detergents and / or cleaning granules (coated core-shell aggregates) are those enzymes which consist of bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Coprinus cinereus and Humicola insolens and their genetically modified variants recovered enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are obtained. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic acting Enzymes are the known cutinases Peroxidases or oxidases have proven to be suitable in some cases to the appro designated amylases pay in particular alpha-amylases, iso-amylases, pullulanases and pectmas Oxireduktasen are also suitable

Cellulases and other glycosyl hydrolases can be obtained by removing pilling and myofibrils for color retention and to increase the softness of the skin Contributing to Textile Cellulases used are preferably cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures of these. Since different types of cellulases differ in their CMCase and avicelase activities, targeted mixtures of the cellulases can be used The proportion of enzymes or Enzymemiscriungen can, if the coated core-Sxchale- aggregates are not completely enzyme-free, which is preferred, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt -%, based on the total coated e core-shell aggregate amount

In addition to optionally phosphonates, the washing and / or cleaning agent granules prepared according to the invention (coated core-shell aggregates) may contain further enzyme stabilizers. For example, the washing and / or cleaning agent granules (coated core-shell aggregates) may contain sodium formate Proteases which are stabilized with soluble calcium salts and a calcium content of preferably approximately 1, 2 Gew. -%, related to the enzyme Beside calcium salts also magnesium salts serve as stabilizers. However particularly advantageous is the employment of boron connections, for example from boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyroboric acid (tetraboric acid H ₂ B ₄ O ₇ )

The coated core-shell aggregates can also contain grayness inhibitors. The function of antigloss inhibitors is to keep the dirt detached from the fiber suspended in the liquor and thus prevent the re-emergence of the soil. Water-soluble colloids of mostly organic nature are suitable, for example the water-soluble ones Salts of polymeric carboxylic acids, glue, gelatin, salts of ethercarboxylic acids or ether sulphonic acids or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also water-soluble polyamides containing acidic groups are suitable for this purpose Furthermore, soluble starch preparations and others can be prepared Also, polyvinylpyrrolidone is useful. However, preferred are cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyet hylcellulose, methylhydroxypropylcellulose loosely, methylcarboxymethylcellulose and mixtures thereof, as well as polyvinylpyrrolidone in the coated core-shell aggregates according to the invention

In addition, dirt-repellent substances can be used to produce the coated core-shell aggregates, which positively influence the oil and grease leaching properties of textiles (so-called soil repellents). This effect becomes particularly clear when a textile that has previously been soiled is soiled The preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl Groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether, and the polymers known from the prior art of phthalic acid and / or terephthalic acid or their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these

These substances, also known as "white toners", can be used to produce the coated core-shell aggregates. Optical brighteners are organic dyes that convert part of the invisible UV radiation of sunlight into long-wave blue light. The emission of this blue light complements the "gap" in the light reflected from the textile, so that treated with optical brightener textile the eye appears whiter and brighter Since the mechanism of action of brighteners requires their mounting on the fibers, one differentiates depending on "fibers to be dyed", for example, brightener for cotton, polyamide The commercially available brighteners suitable for producing the coated core-shell aggregates essentially comprise five structural groups, namely the stilbene, diphenylstilbene, cumene-quinoline, diphenylpyrazoline and the group of the combination of benzoxazole or benzimidazole with a conjugated system s is an overview of common brighteners suitable are easy to find in the literature for example einschlagigen salts of 4,4 ^'-Bιs [(4- anιlιno-6-morpholιno-s-trιazιn-2-yl) amιno] -stιlben-2 , 2 -disulfonic acid or similarly structured compounds which carry a diethanolamino group, a methylamino group, an anilmo group or a 2-methoxyethylamino group in place of the morpholino group. Further, brighteners of the substituted diphenylstyrene type may be present, for example the alkali metal salts of 4,4 '- Bιs (2-sulfostyryl) -dιphenyls, 4,4'-Bιs (4-chloro-3-sulfostyryl) -dιphenyls, or 4- (4-chlorostyryl) -4' - (2-sulfostyryl) -diphenyls also mixtures the vorgenan ned brightener can be used fragrances can be added to the inventively produced coated core-shell aggregates to improve the aesthetic impression of the resulting granules and the consumer in addition to the Remigungsleistung un d the color impression a sensory "typi To provide discreet and unmistakable "detergents and / or cleansing agents. Perfume oils or fragrances may be selected from individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, oc-lsomethylionon and Methylcedrylketon , the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes such as limonene and pinene. However, mixtures of different fragrances are preferably used for the production of the coated core-shell aggregates according to the invention, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures, such as those obtainable from vegetable sources, for example pine, citrus, jasmine, patchuly, rose or ylang-ylang oil. Muskateller, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil are also suitable. In order to facilitate the disintegration of the coated core-shell aggregates which can be prepared according to the invention, for example in tablet form, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these in order to shorten the disintegration times. According to the general understanding, tablet disintegrants or disintegrants are understood as meaning excipients which ensure rapid disintegration of tablets in water and release of the active substances.

These substances, which are also referred to as explosives due to their action, increase their volume upon ingress of water, whereby on the one hand the intrinsic volume increases (swelling), on the other hand a pressure can be generated via the release of gases which causes the tablet to disintegrate into smaller particles. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Conventional coated core-shell aggregates may advantageously contain from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, of one or more disintegration aids, in each case based on the wash and / or Detergent granules, included.

As preferred disintegrating agents which are suitable for the production of the coated core-shell aggregates according to the invention, cellulose-based disintegrating agents are used in the context of the present invention. Pure cellulose has the formal gross composition (C ₆ H ₁₀ Os) _n and is formally a β-1,4-polyacetal of cellobiose, which Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulosic disintegrating agents which can be used in the context of the present invention are cellulose derivatives which are polymer-analogous reactions Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted, but also celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom For example, alkali celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers and aminocelluloses fall into the group of cellulose derivatives. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents on cellulose The content of these mixtures of cellulose derivatives is preferably less than 50% by weight, more preferably less than 20% by weight, based on the cellulose-based disintegration agent. Cellulose-based disintegration agent is particularly preferably pure cellulose for the production of the novel compounds Microcrystalline cellulose can be used as another cellulose-based disintegrant for the production of the coated core-shell aggregates according to the invention. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only the cellulosic Amorphous areas (about 30% of the total Cellu-Iosemasse) of the celluloses attack and completely dissolve, the crystalline areas (about 70%) but leave unscathed

In order to further improve the aesthetic impression of the coated core-shell aggregates which can be prepared according to the invention, the coated core-shell aggregates can be colored with suitable dyes, the brightener-containing phase (s) preferably containing the total amount of dye (s). Contains / contain Preferred dyes whose selection the expert does not cause any difficulty, have a high storage stability and immaturity compared to the other ingredients of detergents and / or cleaning agents and against light and no pronounced substantivity to textile fibers, so as not to stain them

Preference for the preparation of the compositions according to the invention is given to all colorants which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proved advantageous to use colorants for producing the coated core-shell aggregates according to the invention, which are dissolved in water Suitable examples are anionic colorants, such as anionic nitroso dyes. A possible colorant is, for example, naphthol green (Color Index (CI) Part 1 Acid Green 1, Part 2 10020), which is available as a commercial product, for example as basacid ^® Green 970 from BASF, Ludwigshafen, and mixtures gene this with suitable blue dyes. Further suitable colorants Pigmosol come ^® Blue 6900 (CI 74160), Pigmosol ^® Green 8730 (CI 74260), Basonyl ^® Red 545 FL (CI 45170), Sandolan® ^® rhodamine EB400 (CI 45100), Basacid® ^® Yellow 094 (CI 47005) Sicovit ^® Patentblau 85 e 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), pigment Blue 15 (Cl 74160), Supranol Blue ^® GLW (CAS 12219-32-8, Cl Acidblue 221 ), Nylosan Yellow ^® N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan Blue ^® (Cl Acid Blue 182, CAS 12219-26-0) is used. When choosing the colorant, it must be taken into account that the colorants do not have too high an affinity for the textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the coated core-shell aggregates varies. For highly soluble dyes, for example, the above-mentioned Basacid ^® Green or the above-mentioned Sandolan ^® Blue are typically colorant Kon-concentrations in the range of some 10 ^'2 to 10 ^"3 wt .-%, each based on the total detergent -. and / or cleaning agent granules, chosen at due to their brilliance, particularly preferred, but are less readily water-soluble pigment dyes, for example the Pigmosol ^® ATTO-dyes mentioned above, on the other hand is the appropriate concentration of the colorant in detergents and / or cleaning agents typically a few 10 ^'3 to 10 ^' ⁴ wt .-%, based on the total detergent and / or cleaning agent.

The following example serves to illustrate the invention and is not to be considered as limiting.

example

Preparation of a Coated Core / Shell Aggregate of Detergent and Detergent Ingredients

To obtain a core material, zeolite-containing tower powder with alkylbenzenesulfonate as anionic surfactant was sieved to a particle size between 0.6 and 1.4 mm (d ₅₀ = 0.77 mm) over a biplane sieve. Oversize and undersize grains have been milled together with sodium carbonate, sodium sulfate, TAED and foam inhibitor concentrate to a mean particle size d ₅₀ of 9 μm with an eddy current mill. Core material and the milled mixture were placed in a batch Lödige mixer. Mixture was via the plowshare mixer elements at a Froude number of 6.5. With addition of the granulation liquid, the fine particles were adhered to the core material. As granulation liquid, an aqueous 25% Sokalan solution (maleic acid acrylic acid copolymer sodium salt (30:70)) has been used. The actual agglomeration took only about 10 to 40 seconds. The water of the polymer solution has subsequently been removed again in a fluidized bed. The dried material was then screened to 0.6-1.4 mm (d ₅₀ = 1.02 mm, d ₉₀ = 1.32 mm, Shape factor = form factor = Q 3 = 0.87). Upper and lower grain were ground down to about 10 μm by means of a mill and returned to the granulator. The good grain arrived in a gentle mixer and was there coated with a mixture of nonionic surfactant / brightener / perfume. Thus, a coated core-shell aggregate resulted.

The coated core-shell aggregate was then mixed with coated enzyme-containing particles (uniform particle size d ₅₀ of about 0.9 mm) and coated percarbonate-containing particles (uniform particle size d ₅₀ of about 1.0 mm) to form a detergent.

The advantages compared to marketable products were:

The coated core-shell aggregates can not segregate as nearly all constituents are in each grain. The coated core-shell aggregates are dust-free and abrasion-resistant. The particles are nearly spherical with correspondingly high form factors. The particle size distributions are relatively narrow. The visual appearance of a single coated core-shell aggregate as well as aggregates in the collective are excellent. The coated core-shell aggregates have excellent powder properties in terms of flowability and storage stability.

Claims

Patentannsprüche

1. core-shell aggregate for washing or cleaning agent, which consists of a core and the core surrounding particles, characterized in that the particles surrounding the core have a particle diameter d ₅₀ which is at most one tenth of the particle diameter d _{50 of} the core particles but greater than 2 microns, with the proviso that on the core-shell aggregate from the outside at least one further coating is applied.

2. Aggregate according to claim 1, characterized in that the core particles less than 75 wt .-% and the particles to be added make up more than 25 wt .-% of the core-shell aggregate forming solids

3. Unit according to one of the preceding claims, characterized in that the coating comprises lipids and / or silicone oil.

4. Unit according to one of the preceding claims, characterized in that the coating comprises nonionic surfactant.

5. Unit according to one of the preceding claims, characterized in that the coating comprises pigments.

6. Unit according to one of the preceding claims, characterized in that the 3 phases (core / shell / coating) of the coated core-shell aggregate differ in their Lo- speed in water.

7. Unit according to one of the preceding claims, characterized in that it contains effervescent components.

8. Unit according to one of the preceding claims, characterized in that it is impregnated.

9. Aggregate according to one of the preceding claims, characterized in that it contains pH and / or temperature and / or ionic strength-sensitive materials.

10. Unit according to one of the preceding claims, characterized in that it is buoyant in water.

11. Unit according to one of the preceding claims, characterized in that it contains ingredients for cleaning, care, conditioning and / or treatment of textiles, wherein the ingredients for care, conditioning and / or treatment of textiles preferably in the core, in particular exclusively in the core , are included.

12. Unit according to one of the preceding claims, characterized in that it contains ingredients for cleaning and / or care of dishes, glasses, cutlery and the like.

13. Aggregate according to one of the preceding claims, characterized in that it contains, preferably in the core, one or more skin-care and / or skin-protecting and / or skin-healing active ingredients.

14. Unit according to one of the preceding claims, characterized in that the diameter d _{50 of} the core particles in the range of 0.05 to 5 mm.

15. Unit according to one of the preceding claims, characterized in that the particles surrounding the core have a particle diameter d ₅₀ which is at most 1/12 of the particle diameter d _{50 of} the core particles.

16. Aggregate according to one of the preceding claims, characterized in that the core particles less than 50 wt .-%, preferably less than 45 wt .-%, advantageously less than 40 wt .-%, more preferably 15 to 35 parts by weight. %, in particular 20 to 30 wt .-% of the core-shell aggregates forming solids.

17. Aggregate according to one of the preceding claims, characterized in that the particles surrounding the core more than 50 wt .-%, preferably more than 55 wt .-%, more preferably more than 60 wt .-%, in an even more advantageous manner 65 to 85 wt .-%, in particular 70 to 80 wt .-% make up of the core-shell aggregates forming solids.

18. Aggregate according to one of the preceding claims, characterized in that the particles surrounding the core have a largely uniform particle size, wherein advantageously the particle size distribution of the particles surrounding the core is such that the ratio of d ₅₀ to d ₉₀ of the particles surrounding the core preferably at least 0.5, more preferably at least 0.6, in particular at least 0.75.

19. Unit according to one of the preceding claims, characterized in that the core, the particles surrounding the core and / or the coating of the core-shell aggregates comprise ingredients from the field of detergents and / or cleaning agents.

20. An aggregate according to one of the preceding claims, characterized in that the core particles and / or the particles surrounding the core tower powder products and / or (raw) products of non-tower technologies, preferably resulting from the granulation in drum, plate , Mixer and fluidized bed granulators, are or have emerged from these.

21. Aggregate according to one of the preceding claims, characterized in that it has an average form factor of at least 0.79, preferably of at least 0.81, advantageously of at least 0.83, in a further advantageous manner of at least 0.85, in particular substantially of at least 0.87.

22. Aggregates according to one of the preceding claims, characterized in that they are present in a substantially uniform particle size distribution, in which the ratio from d ₅₀ to d _{90 is} at least 0.50, preferably at least 0.6, advantageously at least 0.75, more preferably at least 0.80.

23. Aggregate according to one of the preceding claims, characterized in that the core particles and / or the particles surrounding the core are each formed one and / or multi-component.

24. Unit according to one of the preceding claims, characterized in that the core of the core-shell aggregate compression methods such as wet granulation, preferably at the same time compressing entry of mechanical energy, melt agglomeration, spray drying, spray agglomeration in particular rotating fluidized bed, roll compaction, but especially by extrusion and related compaction methods - if necessary, each with included molding to the individual core - has been produced.

25. Unit according to one of the preceding claims, characterized in that the core of the core-shell aggregate of a plurality of smaller particles, in particular with the concomitant use of a, preferably soluble in cold water, binder is constructed.

26. Aggregate according to one of the preceding claims, characterized in that the core of the core-shell aggregate is predominantly formed by water-soluble and / or ultrafine water-insoluble inorganic and / or organic components of conventional detergents and cleaners - for example Textilwaschmittelbuilder and / or cobuilder, alkalizing agents, temperature-stable bleaching agents based on hydrogen peroxide, such as perborate compounds, but also preferably in minor amounts, ingredients of organic origin, for example at least largely gel-free soluble surfactant compounds, in particular corresponding anionic surfactants and / or nonionic surfactants, co-builders, Brightener and the like, may be part (s) of the core.

27. Aggregate according to one of the preceding claims, characterized in that the particles surrounding the core are coated in multiple layers on the core.

28. Unit according to one of the preceding claims, characterized in that core-shell aggregates are coated several times.

29. Aggregates according to one of the preceding claims, characterized in that they

(a) a hydrophobic coating,

(b) a hydrophilic coating,

(c) a hydrophilic bonded shell,

(d) a hydrophobically bound shell,

(e) a hydrophobically impregnated core, (f) a hydrophilically impregnated core,

(g) a hydrophobically impregnated core-shell aggregate, (h) a hydrophilically impregnated core-shell aggregate,

(i) a hydrophobically impregnated core and a hydrophobic coating, (j) a hydrophobically impregnated core and a hydrophilic coating, (k) a hydrophobically impregnated core and a hydrophobically bonded shell (I) a hydrophobically impregnated core a hydrophilic bonded shell (m) a hydrophilically impregnated core and a hydrophobic coating, (n) a hydrophilically impregnated core and a hydrophilic coating, (o) a hydrophilically impregnated core and a hydrophilic coating, (p) a hydrophilically impregnated core, and a hydrophobically bonded shell (q) a hydrophilic one impregnated core and a hydrophobically bonded shell (r) a hydrophobically impregnated core-shell aggregate and a hydrophobic coating, (s) a hydrophobically impregnated core-shell aggregate and a hydrophilic coating, (t) a hydrophobically impregnated core-shell aggregate and a hydrophobically bonded shell,

(u) a hydrophobically impregnated core-shell aggregate and a hydrophilic-bonded shell, (v) a hydrophilically impregnated core-shell aggregate and a hydrophobically bound shell, (w) a hydrophilically impregnated core-shell aggregate and a hydrophilic bonded shell (x) a hydrophobic coating and a hydrophobically bound shell, (y) a hydrophobic coating and a hydrophilic bonded shell, (z) a hydrophilic coating and a hydrophobically bound shell, (aa) a hydrophilic coating and a hydrophilic bonded shell, ( bb) a hydrophobically impregnated core, a hydrophobic coating and a hydrophobically bonded shell, (cc) a hydrophobically impregnated core, a hydrophobic coating and a hydrophilic bonded shell, (dd) a hydrophobically impregnated core, a hydrophilic coating and a hydrophobically bound shell, (ee) a hydrophilically impregnated core, a hydrophobic coating and a hydrophobically bound shell, (ff) a hy hydrophilically impregnated core, a hydrophilic coating and a hydrophobically bonded shell, (gg) a hydrophilically impregnated core, a hydrophobic coating and a hydrophilic bonded shell, (hh) a hydrophobically impregnated core, a hydrophilic coating and a hydrophilic bonded shell, (ii) a hydrophilically impregnated core, a hydrophilic coating and a hydrophilic bonded shell, (jj) a hydrophobically impregnated core-shell aggregate, a hydrophobic coating and a hydrophobically bound shell, (kk) a hydrophobically impregnated core-shell aggregate, a hydrophobic coating and a hydrophilic bonded shell, (II) a hydrophobically impregnated core-shell aggregate, a hydrophilic coating and a hydrophobically bound shell, (mm) a hydrophilically impregnated core-shell aggregate, a hydrophobic coating and a hydrophobically bound shell , (nn) a hydrophilically impregnated core-shell aggregate, a hydrophilic coating and a hydrophobically bound shell, (oo) a hydrophilically impregnated core-shell aggregate, a hydrophobic coating and a hydrophilic bonded shell, (pp) a hydrophobically impregnated core Shell aggregate, a hydrophilic coating and a hydrophilic bound shell and / or (qq) a hydrophilic impregnating Have core-shell aggregate, a hydrophilic coating and a hydrophilic bonded shell.

30. agglomerate / granules, which is a multi-substance system, wherein the substances contained are arranged in at least 3 different phases, preferably in the phases core, shell and coating, wherein in particular the chemical composition of the phases is different.

31. Aggregate according to one of the preceding claims, characterized in that the ingredients contained in the core are released delayed.

32. Aggregate according to one of the preceding claims, characterized in that it is enzyme-free.

33. Aggregate according to one of claims 1-31, characterized in that it enzyme-containing, preferably 2 phases of the coated core-shell aggregate, namely in particular shell and coating are completely free of enzymes, whereas advantageously the third phase, preferably the Core, contains enzyme.

34. Use of an aggregate according to claim 33 as enzyme granules, which preferably has an enzyme-free shell and / or an enzyme-free coating.

35. Use of an aggregate according to one of the preceding claims as a washing or cleaning agent or as a component of a washing or cleaning agent.

36. Shaped body, preferably tablet, containing aggregates according to one of the preceding claims.

37. Pouch, bag or sack, containing aggregates according to one of the preceding claims.

38. Detergents or cleaning compositions containing aggregates according to one of the preceding claims.

39. Detergent according to the preceding claim containing care components.

40. Detergent, preferably dishwashing detergent, according to claim 38, containing

(b) Rinse aid component containing, for example, nonionic surfactants, preferably on a fatty alcohol basis, in particular with additions of lower alcohols as solubilizers and advantageously of citric acid

(c) Softening component comprising, for example, phosphonate, polycarboxylate, sodium gluconate, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and / or aluminum silicate (zeolite).

(d) Optional: other ingredients such as preferably silver / glass protection component

41. Collectively coated core-shell aggregates according to one of claims 1-33, characterized in that

(b) the majority, preferably at least 75%, in particular the total number, of the cores of the coated core-shell aggregates is uneven, or

(C) mixtures of substantially uniformly and non-uniformly formed cores are present, preferably in the ratio of 200: 1 to 1: 200.

42. Collectively coated core-shell aggregates according to one of claims 1-33, characterized in that

(a) the cores have in the majority, preferably at least 75%, in particular the total number of cores, a more uniform grain size, or

(b) the cores have in the majority, preferably at least 75%, in particular the total number of cores, a rather non-uniform grain size, or

(C) a mixture of cores of very uniform grain size is present with cores of very non-uniform grain size, preferably in the ratio of 200: 1 to 1: 200.

43. Collectively coated core-shell aggregates according to one of claims 1 to 33, characterized in that

(a) the cores have in the majority, preferably at least 75%, in particular the total number of cores, a more uniform density, or (b) the cores have in the majority, preferably at least 75%, in particular the total number of cores, a rather different density, or

(c) a mixture of cores of very uniform density with nuclei of very non-uniform density, preferably in the ratio of 200: 1 to 1: 200.

44. Collectively coated core-shell aggregates according to any one of claims 1-33, characterized in that

(a) the cores in the majority, preferably at least 75%, in particular the total number of cores, have a more uniform structural configuration, i. e.g. either granules, extrudates or agglomerates, etc., or

(b) the cores in the majority, preferably at least 75%, in particular the total number of cores, have a rather different structural configuration, i. both as extrudates, agglomerates, single grains, etc., or

(c) there is a mixture of cores of very uniform structural construction with cores of very non-uniform density, preferably in the ratio of 200: 1 to 1: 200.

45. Collectively coated core-shell aggregates according to one of claims 1-33, characterized in that

(a) the cores have in the majority, preferably at least 75%, in particular the total number of cores, a more uniform chemical composition in relation to the collective, or;

(b) the cores have in the majority, preferably at least 75%, in particular the total number of cores, a rather non-uniform chemical composition, relative to the collective, or

(C) a mixture of cores of very uniform chemical composition with cores of very non-uniform chemical composition, based on the collective, is present, preferably in the ratio of 200: 1 to 1: 200.

46. Collectively coated core-shell aggregates according to any one of claims 1-33, characterized in that the cores of the collective as individual objects in each case a homogeneous distribution of at least one (preferably one and the same) contained in them active substance (eg surfactant or builder, etc .), wherein formed in the core coated by the same core-shell aggregates group α) is also a homogeneous distribution of the relevant active substances (s) on the collective, or ß) a heterogeneous distribution of (the) relevant active substances (s) is given through the collective.

47. Collectively coated core-shell aggregates according to any one of claims 1-33, characterized in that the cores of the collective as individual objects each have a heterogeneous distribution of at least one (preferably one and the same) contained in them active substance (eg surfactant or builder, etc .) (ie have a concentration gradient of the active material on a particle), wherein formed in the core coated by the same shell-shell aggregates χ) also a heterogeneous distribution of the relevant active substances (s) on the

Is given collectively, or δ) a homogeneous distribution of the relevant active substance (s) is given by the collective.

48. Collectively coated core-shell aggregates according to any one of claims 1-33, characterized in that the cores of the collective as individual objects each having a homogeneous mass distribution (ie there is no density gradient in the individual core before), wherein in the coated by the same Core-shell aggregates formed collective ε) is also given a homogeneous mass distribution over the collective (ie there is no density gradient over the collective as a whole, so that all the collective forming particles have the same density), or φ) a heterogeneous mass distribution is given over the collective (ie there is a density gradient over the collective as a whole, so that therefore the particles forming the collective do not have the same densities).

49. Collectively coated core-shell aggregates according to any one of claims 1-33, characterized in that the cores of the collective as individual objects each having a heterogeneous mass distribution (ie, there is a density gradient in the individual core before), wherein in by the same collective core-shell aggregates γ) is also given a heterogeneous mass distribution over the collective (ie there is a density gradient across the collective as a whole, so that the particles forming the collective do not all have the same density), or η) a homogeneous mass distribution over the collective is given (ie there is no density gradient over the collective as a whole, so that therefore the particles forming the collective have the same densities).

50. A process for the construction of core-shell aggregates, characterized in that in a mixer / granulator by presenting a particulate material ("particles to be prepared"), which with the addition of granulation and other particulate material ("particles to be added") granulated / agglomerated, produces core-shell aggregates, wherein the particles to be added have a particle diameter d ₅₀ , the maximum times one tenth of the particle diameter d _{50 of} the particles to be submitted, but is greater than 2 microns, wherein on the core-shell aggregate from the outside at least one further coating is applied.

51. The method according to the preceding claim, characterized in that the particles to be submitted have a largely uniform particle size.

52. The method according to claim 1, characterized in that the core particles constitute less than 75% by weight and the particles to be added make up more than 25% by weight of the solids forming the core-shell aggregate.

53. Method according to the preceding claim, characterized in that the coating comprises lipids.

54. The method according to any one of the preceding claims, characterized in that the coating comprises nonionic surfactant.

55. The method according to any one of the preceding claims, characterized in that the coating comprises pigments.

56. The method according to any one of the preceding claims, characterized in that the particles to be submitted and / or the particles to be added are impregnated.

57. The method according to any one of the preceding claims, characterized in that the constructed core-shell aggregate is impregnated prior to coating.

58. The method according to any one of the preceding claims, characterized in that the coated core-shell aggregate is provided with concomitant use of pH and / or temperature and / or ionic strength-sensitive materials.

59. The method according to any one of the preceding claims, characterized in that the coated core-shell aggregate is provided with the concomitant use of ingredients for the care, conditioning and / or treatment of textiles.

60. The method according to any one of the preceding claims, characterized in that under the (co-) use of a soluble and / or dispersible even in cold water at room temperature solid organic and / or inorganic binder granulated / agglomerated.

61. The method according to any one of the preceding claims that under (co) use preferably film-forming organic components having softening and / or melting points not below 45 ° C, preferably of at least 60 ° C and in particular of at least 75 ° C, are present also with excipients, such as dispersants and / or solubilizers, granulated / - agglomerated.

62. Method according to claim 1, characterized in that water-soluble and / or water-dispersible oligomer and / or polymer compounds of synthetic, semisynthetic and / or natural origin are granulated / agglomerated by (co) use.

63. The method according to any one of the preceding claims, characterized in that granulation aids are used which are at least partially value and / or auxiliaries from the field of laundry detergents.

64. The method according to any one of the preceding claims, characterized in that one uses as a core material, a multicomponent Trägerkom, by extrusion of the multicomponent mixture under the action of elevated pressures - preferably pressures up to 200 bar and in particular in the range of 15 to 150 bar - with subsequent granulation and preferably rounding of the particular strand-shaped extrudate, or by adherent compression of the finely divided multi-component mixture by agglomeration / granulation - optionally with the concomitant use of a water-soluble binder - to suitable grain sizes of at least 0.5 mm, preferably of at least 0.6 mm and in particular equal to or greater than 0.8 mm has been produced.

65. The method according to any one of the preceding claims, characterized in that the particles to be added are added over a period of at least one minute

66. The method according to any one of the preceding claims, characterized in that the diameter d _{50 of} the particles to be submitted in the range of 0.055 to 5 mm.

67. The method according to any one of the preceding claims, characterized in that the particle size distribution of the particles to be submitted is such that the ratio of d ₅₀ to d _{90 of} the particles to be submitted substantially at least 0.5, preferably at least 0.6, advantageously at least 0, 75 and in particular at least 0.8.

68. The method according to any one of the preceding claims, characterized in that it is the granulation a granulation foam.

69. The method according to any one of the preceding claims, characterized in that the particles to be added have a particle diameter d ₅₀ , the maximum of 1/12, preferably a maximum of 1/14, advantageously a maximum of 1/16, more preferably a maximum of 1/18, in more preferably, a maximum of 1/20, more preferably a maximum of 1/22, in a very advantageous manner, a maximum of 1/24 and in particular a maximum of 1/26 of the particle diameter d _{50 of} the particles to be submitted.

70. The method according to any one of the preceding claims, characterized in that the particles to be submitted less than 50 wt .-%, preferably less than 45 wt .-%, advantageously less than 40% by weight, more preferably 15 to 35% by weight, in particular 20 to 30% by weight, of the solids involved in the granulation process.

71. The method according to any one of the preceding claims, characterized in that the particles to be added more than 50 wt .-%, preferably more than 55 wt .-%, more preferably more than 60 wt .-%, more preferably 65 bis Make up 85 wt .-%, in particular 70 to 80 wt .-% of the solids involved in the granulation process.

72. The method according to any one of the preceding claims, characterized in that the particles to be submitted and the particles to be added by sieving of base material (s), preferably a single base material, are obtained, wherein the particles to be added by grinding the sifted from the base material coarse and fine be obtained, so that the criteria required for the particle size are met.

73. The method according to any one of the preceding claims, characterized in that the granulation process is such that the particles to be added and the Granulierhilfsmittel over a period of at least 2, advantageously of at least 3, more advantageously of at least 4, more preferably at least 5, be added in an extremely advantageous manner of at least 6 minutes, wherein preferably an addition period of 50 minutes, advantageously 40 minutes, more advantageously 30 minutes, more preferably 20 minutes, in particular 16 minutes is not exceeded.

74. The method according to any one of the preceding claims, characterized in that the granules in a further process step, preferably in a fluidized bed, dried and / or cooled, and advantageously before or after this process step is powdered.

75. The method according to any one of the preceding claims, characterized in that the specific power of the mixer / granulator is less than 5 kW / m ³ , preferably less than 3 kW / m ³ , in particular less than 1, 5 kW / m ³ .

76. The method according to any one of the preceding claims, characterized in that the particles to be added have a largely uniform particle size, advantageously the particle size distribution of the particles to be added is such that the ratio of d ₅₀ to dgo of the particles to be added preferably at least 0.5, still more preferably at least 0.6, in particular at least 0.75.

77. The method according to any one of the preceding claims, characterized in that the built-up granules, preferably after drying, sieved and / or sifted to separate the good grain of oversize and fines, wherein the oversize and the fine fractions thereafter a) are subjected to a milling process, so that these particles after grinding have a particle diameter d ₅₀ which is at most one tenth of the particle diameter d _{50 of} the particles to be submitted, and then b) these particles are fed back to the mixer / granulator as particles to be added.

78. The method according to any one of the preceding claims, characterized by the following steps: a) Aussiebvorgang for separating a particulate material with largely uniform particle size (particles to be submitted) of oversize and fines from at least one granular debris I b) crushing, preferably grinding of the granular Aggregate I separated from oversized grain and the fines to at least one tenth of the particle diameter d _{50 of} the particles to be submitted or smaller to obtain "particles to be added" c) Optional: crushing, preferably grinding at least one granular heap Il to at least one tenth of the particle diameter d ₅₀ of particles to be prepared or smaller in order to obtain "particles to be added", preferably in the same comminuting device as in step b) d) granulation / agglomeration of the particles to be prepared (from step a)) with addition of the particles to be added (from step b) and optionally c )) and Granu auxiliaries in a mixer / granulator e) Optional: Drying and / or cooling of the granules / agglomerates in a fluidized bed f) Separation of the oversize and fine particles by sieving and / or sifting g) Transfer of oversize and fines (from step f) in a comminution device, preferably mill and crushing, preferably grinding these particles to a particle diameter d ₅₀ , which is at most one tenth of the particle diameter d _{50 of} the particles to be submitted, and then h) recycling the milled particles (from step g) as particles to be added the mixer / granulator, i) good grain coating.

79. The method according to any one of the preceding claims, characterized in that the granules to be submitted, the granules to be added and / or the granulating aids comprise ingredients from the field of detergents and / or cleaning agents.

80. The method according to any one of the preceding claims, characterized in that the granules to be submitted and / or the granules to be added tower powder products and / or (raw) - products of non-tower technologies, preferably resulting from the granulation in drum, plate , Mixer and fluidized bed granulators, are or have emerged from these.

81. The method according to any one of the preceding claims, characterized in that the (as a process end product) constructed, coated granules substantially a mean molding factor of at least 0.79, preferably of at least 0.81, advantageously of at least 0.83, more preferably of at least 0.85, in particular of at least 0.87.

82. The method according to any one of the preceding claims, characterized in that the built up granules (process end product) are present in a substantially uniform particle size distribution, in which the ratio of d ₅₀ to d ₉₀ at least 0.50, preferably at least 0.6, advantageously at least 0.75, more preferably at least 0.80.

83. Application of the method according to any one of the preceding claims for the transfer of pulverulent and / or fine-grained multi-component mixtures from the field of detergents and cleaners in provided with a coating core-shell aggregates.