Classifications

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

Definitions

• 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.
• the purchase decision is generally based on very different criteria, but above all on the price of the presented goods and their quality.
• 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.
• 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.
• the object of the present invention was to provide largely aesthetically pleasing granules.
• 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 specializedden 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 ⁇ m, advantageously from 4 to 25 ⁇ m, more preferably from 4 to 15 ⁇ m, in particular from 5 to 10 ⁇ m. This corresponds to a preferred embodiment of the invention.
• 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.
• the three phases differ according to a preferred embodiment in the recipe, i. in their composition.
• 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.
• 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.
• the coating is applied without subsequent post-drying, which corresponds to a preferred embodiment.
• 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.
• 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.
• 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.
• 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.
• nonionic surfactant which is advantageously combined with other components.
• Preferred are e.g. the following combinations: (a) nonionic surfactant, brightener, optional perfume
• nonionic surfactant silicone oil, optionally paraffin (oil), optionally perfume
• nonionic surfactant such as preferably vitamin E, 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.
• 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.
• the coating liquid may also contain larger amounts of water, that is more than preferably 35 wt .-%, based on the total coating liquid.
• 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.
• 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.
• 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 "
• biotechnology produced products such as e.g. Pullulan, Curdlan and / or Xanthan.
• a melt is applied as coating, preferably melting of (co) polymers, waxes, esters and / or fats.
• 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.
• waxing the following may be preferred:
• animal waxes such as preferably beeswax, rumen grease, wool wax, shellac wax and / or spermaceti
• mineral waxes such as preferably ceresin and / or ozokerite
• waxes preferably hard waxes, in particular hydrogenated jojoba waxes, montan ester waxes and / or sasol waxes
• 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
• 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
• the coating preferably comprises esters.
• 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.
• 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.
• the coating contains lipids and / or silicone oil, which corresponds to a preferred embodiment.
• Preferred lipids are
• lipophilic alcohols such as wax alcohols, retinol or cholesterol, etc.
• lipophilic esters such as neutral fats - i. Mono-, Di- u. Triacylglycerols (triglycerides), sterol esters, etc.]
• lipids with more than 2 hydrolysis products such as glycolipids, phospholipids, sphingolipids and / or glycerolipids etc.
• lipids in the form of higher molecular weight conjugates with more than 2 hydrolysis products such as lipoproteins and / or lipopolysaccharides, etc.
• phosphorus-free glycolipids such as glycosphingolipids (such as preferably cerebrosides, gangliosides, sulphatides) or, for example, glycoglycerolipids (as preferably Glykosyldi- and -monogly- ceride), etc.
• 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.)
• sphingophospholipids such as, preferably, sphingomyelin
• glycerophospholipids such as preferably lecithins, cephalins, cariolipins, phosphatidylinositols and inositol phosphates, etc.
• the coating comprises unsaponifiable lipid, preferably selected from free fatty acid, isoprenoid lipids, in particular steroids, carotenoids, monoterpenes etc. and / or tocopherols.
• the coating comprises saponifiable lipid, preferably selected from mono-, di-, triacylglycerides, phospholipids (phosphatides), glycolipids, diollipids, waxes and / or sterol esters.
• saponifiable lipid preferably selected from mono-, di-, triacylglycerides, phospholipids (phosphatides), glycolipids, diollipids, waxes and / or sterol esters.
• the coating comprises at least one unsaponifiable and one saponifiable lipid.
• the coating comprises neutral lipid, preferably selected from fatty acids (> C12), mono-, di-, triacylglycerides, sterols, sterol esters, carotenoids, waxes and / or tocopherols.
• neutral lipid preferably selected from fatty acids (> C12), mono-, di-, triacylglycerides, sterols, sterol esters, carotenoids, waxes and / or tocopherols.
• the coating comprises polar lipid, preferably selected from glycerophospholipids, glyceroglycolipids, sphingophospholipids and / or sphingoglycolipids.
• the coating has at least one polar and one nonpolar lipid.
• 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.
• dispersing agent dispersed continuously
• further (dispersed) preferably as emulsion, aerosol or suspension.
• suspensions ie dispersions of insoluble solid particles with particle sizes down to colloidal dimensions ( ⁇ 10 ⁇ 6 cm) in liquids, plastic masses or solidified melts.
• solvent-containing advantageously aqueous suspensions of pulverulent components, preferably of a few ⁇ m diameter, e.g. aqueous suspensions of pigments.
• Solvent-containing systems preferably contain dispersants, such as in particular
• amphoteric dispersants such as e.g. Soy lecithin etc.
• anionic dispersants e.g. oligomeric or polymeric carboxylic acids, etc.
• Electroneutral dispersants such as e.g. Salts of long-chain polyamines and. Polycarboxylic acids, etc., and / or
• 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.
• 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
• modified natural products e.g. Gum arabic, alginates, casein, gelatin, soy lecithin, tannates and / or ligninsulfonates and / or
• 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,
• 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- bonklachuren, 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.
• AMPS 2-acrylamido-2-methylpropanesulfonic acid
• 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 .
• white auxiliaries such as preferably calcium carbonate, talc 3MgO • 4SiO 2 • H 2 O and / or barium sulfate may be included.
• the pigments may be um
• 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
• 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
• black pigments e.g., aniline black, perylene black, iron oxide pigments, manganese black and / or spinel black
• 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
• 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:
• sulphates such as preferably barite, blanc-fixed and / or calcium sulphates
• silicates such as preferably talc, pyrophyllite, chlorite, hornblende, mica, kaolin wollastonite, slate, precipitated Ca, Al, Ca / Al, Na / Al silicates, feldspars and / or mullite
• 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.
• 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.
• 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
• 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
• the coated tablet would be dissolved after 5 minutes at a value of 500%
• the 3 phases (core / shell / coating) of the agent according to the invention differ in their lot speed
• 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.
• (electron) m ⁇ kroskop ⁇ sche investigations the outer Um ⁇ ßlinien the individual parts are advantageously at least partially still recognizable
• 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%.
• shell 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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, Textilwaschffenbuilder 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.
• 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.
• the core can also be other embodiments
• lamellar plaque and the like or at least approximately lamellar
• the core is designed as such uneven, preferably not spherical or ellipsoidal, but of irregular shape.
• 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
• 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
• 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
• (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.
• 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 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 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
• (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 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
• (c) represent a mixture of cores of very uniform structural composition with nuclei of very inconsistent density. 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
• 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 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.
• active substance contained in them eg surfactant or builder, etc.
• all particles of this collective ⁇ at least one (preferably one and the same) active substance is homogeneously distributed.
• all particles of the collective ⁇ also contain the same amount of the active substance in question. This is the case of a homogeneous individual distribution in a homogeneous collective.
• 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.
• 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 ⁇ 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 ⁇ ) a homogeneous distribution of the relevant active substance (s) through the collective.
• active substance eg surfactant or builder etc.
• all particles of this collective ⁇ at least one (one and the same) active substance is distributed heterogeneously.
• all particles of the collective ⁇ also contain different amounts of the active substance in question. This is the case of a heterogeneous individual distribution in a heterogeneous collective.
• 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.
• 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 ⁇ ) 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 ⁇ ) 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).
• 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 each have a heterogeneous mass distribution as individual objects (ie there is a density gradient in each case) individual nucleus), in which group ⁇ ) formed by the same coated core-shell aggregates is likewise given a heterogeneous mass distribution over the collective (ie, it is present
• the individual particles of this collective ⁇ have a density gradient.
• the particles of the collective ⁇ also have different densities in comparison with each other. This is the case of a heterogeneous individual distribution in a heterogeneous collective.
• the particles of the collective ⁇ have identical densities in comparison with one another. This is the case of a heterogeneous individual distribution in a homogeneous 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.
• 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.
• a coating agent which is preferably solid at room temperature and which contains in particular nonionic surfactant.
• 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.
• the coating contains no solid particles, but consists of a liquid system, preferably an emulsion.
• the coating contains particulates, preferably coated by a dispersion.
• the core as such may 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.
• a solution, dispersion or emulsion of certain active ingredients preferably to modify the properties of the core.
• the core as such is 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.
• a solution, dispersion, melt or emulsion of certain active ingredients i. ie e.g. is coated with a solution, dispersion, melt or emulsion of certain active ingredients.
• materials comprising substances such as nonionic surfactants, cationic surfactants, amphoteric surfactants, silicone oil, triglycerides, terpenes, perfume, glycerol and / or (co) polymer (solutions) are suitable.
• all those substances come into question, which are disclosed for the coating of the core-shell aggregate elsewhere in this description.
• 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.
• a solution, dispersion or emulsion of certain active ingredients to modify the properties of the core-shell aggregate.
• 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.
• agents which serve for the hydrophobizing and the core or the uncoated core-shell aggregate are preferred.
• 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.
• 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.
• 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.
• agents containing lipids are preferably used.
• Preferred lipids are
• lipophilic alcohols such as wax alcohols, retinol or cholesterol, etc.
• lipophilic esters such as neutral fats - i. Mono-, Di- u. Triacylglycerols (triglycerides), sterol esters, etc.]
• lipids with more than 2 hydrolysis products e.g. Glycolipids, phospholipids, sphingolipids and / or glycerolipids etc.
• lipids in the form of higher molecular weight conjugates with more than 2 hydrolysis products e.g. Lipoproteins and / or lipopolysaccharides, etc.
• phosphorus-free glycolipids e.g. Glycosphingolipids (such as, preferably, cerebrosides,
• Gangliosides, sulphatides or as e.g. Glycoglycerolipids (preferably glycosyl di- and monoglycerides), etc.
• 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.
• the impregnating agent comprises unsaponifiable lipid, preferably selected from free fatty acids, isoprenoid lipids, in particular steroids, carotenoids, monoterpenes etc. and / or tocopherols.
• the impregnating agent comprises saponifiable lipid, preferably selected from mono-, di-, triacylglycerides, phospholipids (phosphatides), glycolipids, diollipids, waxes and / or sterol esters.
• the impregnating agent comprises at least one unsaponifiable and one saponifiable lipid.
• the impregnating agent comprises neutral lipid, preferably selected from fatty acids (> C12), mono-, di-, triacylglycerides. Sterols, sterol esters, carotenoids, waxes and / or tocopherols.
• the impregnating agent comprises polar lipid, preferably selected from glycerophosphohpides, glyceroglycohpides, sphingophosphohpides and / or sphingoglycolipids
• the impregnating agent has at least one polar and one nonpolar lipid
• 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
• 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
• aqueous solutions as a coating to the core-shell aggregate
• ionogenic or ionogenic materials Non-ionogenic polymers, ethoxylation products and the like
• 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.
• 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,
• the term "hydrophobically bound" shell is used more simply in the following description.
• 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 Granulationshnetik serves as a binder for the Schalenmate ⁇ al 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
• 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.
• hydrophobing and / or hydrophilization can be realized a variety of coated core-shell aggregates, e.g. such
• a particle collective of coated core-shell aggregates 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
• a particle collective of coated core-shell aggregates 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
• the freely adjustable loose behavior is also highly suitable for the production of molded articles, eg tablets.
• 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
• 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 Re ⁇ n ⁇ gungsm ⁇ ttel -)
• 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 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
• a erfindunstraes, coated core-shell aggregate on a reduced Dusting tendency wherein it has a dust content (according to the Elutriationsmethode described here)
• air volume 2.4 m 3 / h
• differential pressure 100 mm
• 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, 2 ⁇ m, 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 .
• 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
• 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
• 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
• 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
• 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
• 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.
• 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
• Enthartungskomponente containing, for example, phosphonate, polycarboxylate, Nat ⁇ umglu conat, ethylenediaminetetraacetic acid (EDTA), Nit ⁇ lotriessigsaure (NTA) and / or Aluminiumiumsi licaten (zeolites)
• 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
• 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.
• the shell is pH and / or temperature and / or ionic strength-sensitive or contains pH and / or temperature and / or ionic strength-sensitive materials.
• 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
• 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
• the shell can eg with a pH and / or temperature and / or ionic strength-sensitive Granulationstik on the core Under adjustable conditions regarding pH and / or temperature and / or ionic strength, the shell can thus lose its integrity and dissolve
• pH Sens ⁇ t ⁇ v ⁇ tat, 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),
• the pH Sens ⁇ t ⁇ v ⁇ tat 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.
• 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
• 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
• 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.
• an outermost layer advantageous, which is substantially inert to these conditions.
• the outermost layer is those which directly adjoins the surrounding fluid.
• 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.
• 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.
• the outermost coating in the case of multilayer coating
• 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.
• the innermost layer is then advantageously substantially inert to the wash liquor and thus sufficiently protects the core from direct contact with the water.
• the previously completely removed alkaline wash liquor is replaced by fresh non-alkaline water.
• the innermost layer loses its integrity completely or partially, so that the core Shell aggregate can be penetrated by the water.
• Materials which can be used as coating materials 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.
• 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.
• 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
• Polyalcohols preferably glycerol, propylene glycol
• polyoxyethylene glycols preferably polyethylene glycol
• 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
• 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
• 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
• acid-insoluble polymers are used to give tablets an enteric coating which is soluble in the intestinal juice.
• 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.
• 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
• 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
• 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
• 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.
• Comonomers may be, for example, conventional acrylates, methacrylates, maleinates or derivatives of these compounds.
• 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 is an equilibrium constant that can change with temperature and / or ionic strength.
• 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.
• the coating consists at least partially of a copolymer of basic monomers such as dialkylaminoalkyl (meth) acrylates with acrylic esters.
• 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-C ⁇ - 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.
• 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
• 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.
• 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
• this shift of the switching point of a polymer suitable for the purposes of the present invention succeeds in the following way.
• 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
• water-soluble monomers it is possible to use substances such as acrylamide, methacrylamide, vinylpyrrolidone or hydroxyethyl acrylates or methacrylates
• substances such as acrylamide, methacrylamide, vinylpyrrolidone or hydroxyethyl acrylates or methacrylates
• 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.
• 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.
• 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.
• technologies are used, as they are common in drug manufacturing.
• the dispersions and the particles are associated with each other, isolated and dried with thorough mixing.
• 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.
• 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.
• 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.
• additional polymers are generally those which are less hydrophilic / more hydrophobic than the coating polymer.
• 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.
• 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”).
• polymer coating also very suitable are LCST substances, which will be described later.
• a pH-sensitive coating is coated with a material which in turn is temperature-sensitive.
• 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.
• 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.
• 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).
• HPMC hydroxypropylmethylcellulose
• EHEC hydroxyethy
• LCST substances are cellulose ethers and mixtures of cellulose ethers with carboxymethylcellulose (CMC).
• CMC carboxymethylcellulose
• 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.
• 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.
• VATGW polyvinyl methyl ether
• Mixtures of these polymers with salts or surfactants can also be used as the LCST substance.
• the lower critical demixing temperature (LCST) can be modified.
• 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 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.
• 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.
• 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.
• the pH of the solution or dispersion can be adjusted to the solubility of the (co) polymer.
• 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.
• a preferred method is the Wurster method.
• 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.
• 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.
• the agent according to the invention coated core-shell aggregate
• 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
• the excellent debris and free-flowing properties are retained and the granules do not clump together.
• the granules require neither flow agent nor powdering in order to obtain the excellent powder properties.
• 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
• 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
• 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 Suspensions Wegmaschine 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.
• 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.
• 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 ..
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• the particle diameter d 50 of the particles surrounding the core is greater than 2 ⁇ m.
• the particle diameter d 50 of the particles surrounding the core preferably lies in a range of 3-50 ⁇ m, advantageously 4-25 ⁇ m, more preferably 4-15 ⁇ m, in particular 5-10 ⁇ m.
• 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.
• 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.
• 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.
• 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.
• 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 ,
• 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.
• 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.
• 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.
• 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.
• the lower limit for the bulk density can also be set at a value of preferably 250, 300,
• 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,
• the upper limit is even lower, e.g. at a value of preferably
• 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.
• 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.
• 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. -%.
• 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.
• 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.
• the surfactant content 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 .-%.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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. -%.
• 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.
• 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.
• 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 .-%.
• the core is free of perfume.
• the bleach content of the total agent i.e., coated core-shell aggregate
• the bleach content of the total agent is 5-25% by weight, especially 10-20% by weight.
• the nonionic surfactant content of the entire composition 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.
• the free water content of the entire composition is 0-30% by weight, preferably 0-20% by weight, in particular 0-10% by weight.
• the surfactant content of the entire composition is 0.1-50% by weight, preferably 1-30% by weight, advantageously 5-25% by weight, in particular 10% by weight. 20% by weight
• the skeletal content of the entire agent 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
• the perfume content of the entire composition is 0.1-30% by weight, preferably 1-25% by weight, advantageously 5-22% by weight, in particular 10% by weight. 20% by weight
• the coated core-shell aggregates are buoyant in water, ie do not submerge in water or in a wash liquor, but drive on the water water surface
• the core-shell aggregates 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.
• gases especially air
• 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
• 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
• 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)
• 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 ⁇ m.
• the thermal conductivity is preferably 0.110-0.156 Wm-1 K
• the internal pressure is preferably about 0.2 bar.
• 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.
• 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.
• 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.
• 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.
• 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
• 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.
• the polymeric clay flocculating agent is obtained from monomers selected from ethylene oxide, acrylamide and acrylic acid.
• 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.
• 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.
• the composition according to the invention contains ingredients for cleaning and / or care of dishes, glasses, cutlery and the like.
• 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.
• 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.
• 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.
• 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.
• the coating 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.
• 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.
• 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.
• 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.
• 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.
• the core-shell aggregates according to the invention may contain ingredients for the care and / or after-treatment of textiles.
• 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.
• 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 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
• 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,
• 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.
• 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.
• 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.
• the agent according to the invention contains one or more skin-care and / or skin-protecting and / or skin-healing active substances.
• 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.
• Hydrophobic plant extracts c) Hydrocarbons such as squalene and / or squalanes
• Hydrocarbons such as squalene and / or squalanes
• 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.
• 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.
• 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.
• lipids such as cholesterol, ceramides and / or sucrose esters and others.
• vitamins such as vitamins A and E, vitamin C esters, including vitamin C.
• 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
• 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
• 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.
• powdered plasticizers such as Alkylamidoammoniumlactat and / or clays, such as preferably bentonite, especially in combination with flocculants, such as polyethylene oxide
• 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
• 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.
• skin protection 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 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.
• 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 ,
• 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.
• such strong effectiveness is not sought in the context of the invention, as it would undoubtedly lead to the elimination of harmful germs o. ⁇ ., 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.
• the self-regulatory powers of the skin are sometimes no longer able, even temporarily, to ensure skin health on their own.
• these self-regulating forces are supported, trained and strengthened.
• the detergent according to the invention or the laundry treated with it supports the natural skin flora of humans.
• 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 - Cana ⁇ um luzonicum, Fennel - Foeniculum dulce Spruce needle - Picea abies, Geranium - Pelargonium graveolens, Ho leaf - Cinnamonum camphora, Immortelle ( Helichrysum ang, ginger extra - Zmgiber off, St.
• an essential oil selected in particular from the group of Angelica fine - Angelica archangelic
• 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
• 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, Armka ⁇ l Arnica montana, Avocadool Persea ame ⁇ cana, 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.
• a carrier oil in particular selected from the group Algenol Oleum Phaeophyceae, Aloe Vera Oil Alo
• 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 ⁇ -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.
• GLA valuable ⁇ -linolenic acid
• it can increase the care properties or other properties of other oils in particular of all oils explicitly mentioned here.
• 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.
• 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.
• 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.
• active substances include, for example, black cumin oil, Echiumöl, Trichodesmaöl, evening primrose oil and the blackcurrant seed oil.
• almond oil 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.
• 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).
• 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.
• 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,
• moisturizing factors for example those selected from the following group: amino acids, chitosan or chitosan salts / derivatives, ethylene glycol, glucosamine, glycerol, diglycerol, triglycerol
• 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.
• 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.
• the core material of the coated core-shell aggregate comprises one or more ingredients selected from
• Turmeric powders spray drying products containing e.g. Mixtures of thermally stable ingredients of detergents or cleaners
• (C) hydrogencarbonates in particular alkali metal and / or alkaline earth metal hydrogencarbonates
• anionic surfactant compounds including, for example, fatty alcohol sulfates, alkylbenzenesulfonates, alkanesulfonates, alkyl ether sulfates, alkyl sulfates, ⁇ -olefin sulfonates and / or ester sulfonates, in particular methyl ester sulfonates, and / or mixtures thereof),
• 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
• 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.
• 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.
• 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 Ein Hughessch 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.
• the coated core-shell aggregates contained in the detergent are not substantially removed during the washing process in the course of Abpumpvor réellen from the washing machine, but are preferably in the late stages of the washing process, especially in the course of Abpumpvor réellen 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.
• the particles to be prepared have a largely uniform particle size.
• 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.
• 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.
• 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.
• otherwise incompatible active ingredients can be optimally processed into a uniform dosage form.
• the invention enables maximum freedom in the formulation of detergents and cleaning agents while avoiding undesirable incompatibilities through targeted separation of active substances.
• an incrustation inhibitor and a nonionic surfactant can be shelled onto a core of a builder / anionic surfactant mixture.
• a coating e.g. Be included in perfume.
• coated core-shell aggregates having a core of undyed material and a shell of colored material, e.g. are provided with a transparent coating.
• 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.
• the coating to be applied comprises nonionic surfactant.
• 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.
• 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.
• nonionic surfactant which is advantageously combined with other components.
• Preferred are e.g. the following combinations:
• nonionic surfactant silicone oil, optionally paraffin (oil), optionally perfume
• nonionic surfactant such as preferably vitamin E, optional perfume
• 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.
• 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.
• the coating liquid may also contain larger amounts of water, that is more than preferably 35 wt .-%, based on the total coating liquid.
• 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 may even have an even higher water content upper limit, e.g.
• 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.
• waxing the following may be preferred:
• animal waxes such as preferably beeswax, rumen grease, wool wax, shellac wax and / or spermaceti
• mineral waxes such as preferably ceresin and / or ozokerite
• waxes preferably hard waxes, in particular hydrogenated jojoba waxes, montan ester waxes and / or sasol waxes
• 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
• 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.
• 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.
• 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.
• the higher molecular weight solid polyethylene glycols also called polyethylene oxides, are also preferred.
• the coating contains lipids, which corresponds to a preferred embodiment.
• Preferred lipids are
• lipophilic alcohols such as wax alcohols, retinol or cholesterol, etc.
• lipophilic esters such as neutral fats - i. Mono-, Di- u. Triacylglycerols (triglycerides), sterol esters, etc.]
• lipids with more than 2 hydrolysis products e.g. Glycolipids, phospholipids, sphingolipids and / or glycerolipids etc.
• lipids in the form of higher molecular weight conjugates with more than 2 hydrolysis products e.g. Lipoproteins and / or lipopolysaccharides, etc.
• 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.)
• Sphingophospholipids such as, preferably, sphingomyelin
• Glycerophospholipids such as preferably lecithins, cephalins, car diolipins, phosphatidylinositols and inositol phosphates, etc.
• the coating has unsaponifiable lipid, preferably selected from free fatty acids, isoprenoid lipids, in particular steroids, carotenoids, monoterpenes etc. and / or tocopherols.
• the coating comprises saponifiable lipid, preferably selected from mono-, di-, triacylglycerides, phospholipids (phosphatides), glycolipids, diollipids, waxes and / or sterol esters.
• saponifiable lipid preferably selected from mono-, di-, triacylglycerides, phospholipids (phosphatides), glycolipids, diollipids, waxes and / or sterol esters.
• the coating comprises at least one unsaponifiable and one saponifiable lipid.
• the coating comprises neutral lipid, preferably selected from fatty acids (> C12), mono-, di-, triacylglycerides, sterols, sterol esters, carotenoids, waxes and / or tocopherols.
• the coating comprises polar lipid, preferably selected from glycerophospholipids, glyceroglycolipids, sphingophospholipids and / or sphingoglycolipids.
• the coating has at least one polar and one nonpolar lipid.
• 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.
• suspensions ie dispersions of insoluble solid particles with particle sizes down to colloidal dimensions ( ⁇ 10 ⁇ 6 cm) in liquids, plastic masses or solidified melts.
• solvent-containing advantageously aqueous suspensions of pulverulent components, preferably of a few ⁇ m diameter, e.g. aqueous suspensions of pigments.
• Solvent-containing systems preferably contain dispersants, such as in particular
• amphoteric dispersants such as e.g. Soy lecithin etc.
• anionic dispersants e.g. oligomeric or polymeric carboxylic acids, etc.
• Electroneutral dispersants such as e.g. Salts of long-chain polyamines and. Polycarboxylic acids, etc., and / or
• Aqueous systems preferably contain dispersants, such as in particular
• inorganic dispersants here preferably so-called Pickering dispersants, ie fine-grained, insoluble inorganic compounds such as CaCO 3 or Ca 3 (PO 4 ) 2 ,
• polyphosphates such as preferably salts of the pyro, meta 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,
• 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.
• AMPS 2-acrylamido-2-methylpropanesulfonic acid
• acrylamide or acrylonitrile maleic anhydride with ethylene or other 1-alkenes
• Polyaldehydo-carboxylic acids such as preferably co- or terpolymers of acrylic acid
• 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
• white auxiliaries such as preferably calcium carbonate, talc 3MgO ⁇ 4SiO 2 • H 2 O and / or barium sulfate may be included.
• the pigments may be um
• 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
• 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
• black pigments e.g., aniline black, perylene black, iron oxide pigments, manganese black and / or spinel black
• 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
• 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 coating materials:
• sulphates such as preferably barite, blanc-fixed and / or calcium sulphates
• silicates such as preferably talc, pyrophyllite, chlorite, hornblende, mica, kaolin
• 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
• oxides in particular aluminum hydroxide and / or magnesium hydroxide
• 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.
• 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.
• foams usually have a much lower density than liquids and, for example, react quite differently than fluids to compression or mechanical stress.
• 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.
• 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.
• 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.
• 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).
• 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.
• 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.
• 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.
• 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.
• the solid in an outer shell has a smaller particle size than the solid in the underlying shell.
• 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.
• 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.
• a polymeric binder is added to the binding fluid and / or to the particles to be agglomerated.
• 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, copoly
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• the particles to be submitted are rather small.
• 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.
• 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.
• 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.
• 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.
• the user has the opportunity to specifically pick out, assemble and use the granules of defined composition, which may be colored differently.
• 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.
• 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.
• 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.
• 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 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.
• (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.
• 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.
• granulation auxiliaries are used which at least partially comprise valuable substances and / or auxiliaries from the field of textile detergents.
• 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.
• 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.
• 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.
• 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.
• 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.
• the particle diameter d 50 of the particles to be added is greater than 2 ⁇ m.
• 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.
• 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.
• 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.
• 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.
• 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.
• eddy current mills preferably multi-stage eddy current mills can be used with great advantage. These are among the stick mills.
• 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 Vorzerklein ceremoniesswerkmaschinemaschineen and then passes into the grinding gap.
• the ground material which has been fluidized in the air flow is crushed by impact on the comminution tools of the rotor and stator.
• 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.
• 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.
• the particles to be submitted and the particles to be added differ in at least one component of their composition.
• 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.
• 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.
• 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 .
• 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.
• 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.
• 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.
• 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.
• 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.
• a solution, dispersion or emulsion of certain active ingredients to modify the properties of the core-shell aggregate.
• 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.
• 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 ,
• 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 ,
• 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.
• agents containing lipids are preferably used.
• Preferred lipids are
• lipophilic alcohols such as wax alcohols, retinol or cholesterol, etc.
• lipophilic esters such as neutral fats - i. Mono-, Di- u. Triacylglycerols (triglycerides), sterol esters, etc.]
• lipids with more than 2 hydrolysis products such as glycolipids, phospholipids, sphingolipids and / or glycerolipids, etc.
• lipids in the form of higher molecular weight conjugates with more than 2 hydrolysis products such as lipoproteins and / or lipopolysaccharides etc.
• Phosphorus-free glycolipids such as glycosphingolipids (such as preferably cerebrosides, gangliosides, sulphatides) or, for example, glycoglycerolipids (preferably glycosyldi- and monoglycerides), etc.
• 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.
• sphingophospholipids such as sphingolymphins
• glycerophospholipids such as preferably lecithins, cephalins, cardiolipins, phosphatidylinositols and inositol phosphates etc.
• the impregnating agent comprises unsaponifiable lipid, preferably selected from free fatty acids, isoprenoid lipids, in particular steroids, carotenoids, monoterpenes etc. and / or tocopherols.
• the impregnating agent comprises saponifiable lipid, preferably selected from mono-, di-, triacylglycerides, phospholipids (phosphatides), glycolipids, diollipids, waxes and / or sterol esters.
• the impregnating agent comprises at least one unsaponifiable and one saponifiable lipid.
• the impregnating agent comprises neutral lipid, preferably selected from fatty acids (> C12), mono-, di-, triacylglycerides, sterols, sterol esters, carotenoids, waxes and / or tocopherols.
• neutral lipid preferably selected from fatty acids (> C12), mono-, di-, triacylglycerides, sterols, sterol esters, carotenoids, waxes and / or tocopherols.
• the impregnating agent comprises polar lipid, preferably selected from glycerophospholipids, glyceroglycolipids, sphingophospholipids and / or sphingoglycolipids.
• the impregnating agent has at least one polar and one nonpolar lipid.
• the coating of the core-shell aggregates can 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
• water repellents 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
• the coating of the core-shell aggregates can 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
• aqueous solutions as a coating to the core-shell aggregate
• ionogenic or mungionogenic polymers ethoxylation products and the like
• polyethylene glycol sorbitan fatty acid esters and comparable substances are particularly suitable for hydrophilization
• the detachment of the shell as such can be manipulated individually, advantageously via the choice of granulation fluid.
• 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,
• the term "hydrophobically bound" shell is used in a simplified manner.
• 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
• 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
• 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.).
• gas-evolving substances for example sodium bicarbonate, citric or tartaric acid, etc.
• 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.
• the shell is pH- and / or temperature-sensitive and / or ionic-strong-sensitive or contains pH-sensitive and / or high-temperature and / or ionic-strong-sensitive materials.
• the core is pH and / or temperature and / or ionic strength-sensitive or contains pH and / or temperature and / or ionic strength-sensitive materials
• the pH and / or temperature and / or high-ion-intensity-sensitive materials not only in the coating, but also as Matrixmate ⁇ al, 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
• 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
• the granules are sieved, preferably after drying, sieved and / or sifted to separate the Gutkorns of U- berkorn and Feman too, 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
• a plurality of powders 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 is advantageous in accordance with a further preferred embodiment.
• a comminuting device I 1 preferably fed to a mill and there adjusted to the required particle size of the "to be added particles".
• the former 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.
• the resulting agglomerates are then preferably passed into a fluidized bed dryer where it is dried / cooled.
• 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.
• the undersize and oversize (corresponding to agglomerate grain) resulting from this rejection 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.
• 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.
• such a coated core-shell aggregate may already be an independent washing or cleaning or care agent.
• the coated core-shell aggregate can also be a washing or cleaning or care additive.
• 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.
• the further particles with which the coated core-shell aggregates are mixed are also coated particles.
• 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.
• 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.
• 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.
• 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.
• the raw materials intended for the respective particulate particles are first mixed and then homogenized and plasticized in the extruder.
• preformed particles can be obtained by cutting the extruded mass at the extruder head.
• 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.
• 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.
• 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.
• the particles to be prepared and / or the particles to be added are those which, after the so-called spray agglomeration driving were made.
• 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.
• 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 measurement limits of this optical analysis method are 15 ⁇ m and 90 mm, respectively.
• the numerical values for d 50 and d 90 are also available via the aforementioned measuring method.
• the built-up, coated granules 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.
• 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.
• the coated granules with a coating of fine solids, ie to remove them, for example in order to achieve protection.
• fine solids ie to remove them, for example in order to achieve protection.
• powdering agents are suitable which preferably contain very finely divided zeolite and / or silica, in particular hydrophobic silica.
• 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.
• 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.
• 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.
• detergents and cleaners such as commercial detergents and / or cleaning agents
• 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)
• 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
• 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 -Monoolef ⁇ nen with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration
• alkanesulfonates which are prepared from C 12 -i ⁇ - Alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
• esters of .alpha.-sulfo fatty acids for example the .alpha.-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
• esters of unsaturated fatty acids for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt .-%.
• ⁇ -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.
• MES ⁇ -Suifofett Textren
• 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 Schwefelklareschester 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.
• 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.
• 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.
• C 12 -C 18 fatty acid methyl esters with 10 to 12 EO can be used as surfactants.
• APG alkylpolyglycosides
• 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
• 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.
• gemini surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is 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 are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis- and trimer alcohol t ⁇ s-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
• 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, Gerüstscher 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 ⁇ - and ⁇ -Nat ⁇ umdisilikate Na 2 Si 2 O 5 yH 2 O are preferred
• compositions according to the invention may also comprise optional cationic surfactant, advantageously in the core, in particular exclusively in the core.
• the cationic surfactant is a quaternary ammonium compound, preferably an alkylated quaternary ammonium compound
• 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
• the cationic surfactant is a quaternary ammonium compound of the following formula
• R 5 is a C 6 -C 24 alkyl or alkenyl
• 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
• each R 7 is independently a C 1 -C 12 alkyl or alkenyl group, with m is 1 to 3
• 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
• 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
• the cationic surfactant may be a C 8 -C 16 -alkyl-d ⁇ (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
• 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
• 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
• 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
• 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 ,
• 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.
• zeolite P zeolite MAP ® commercial product from Crosfield
• zeolite X and mixtures of A, X and / or P are particularly preferred.
• 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 ⁇ m (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.
• the granules which can be prepared according to the invention are free of zeolite.
• the granules according to the invention are not only zeohth- but also low in phosphate
• 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
• the inventive detergent and / or detergent granules 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, Nit ⁇ lot ⁇ essigsaure (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.
• 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
• 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
• 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.
• 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
• 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
• 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
• copolymers are those which have as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate
• 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
• 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
• 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.
• 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
• Ethylend ⁇ am ⁇ n-N, N '-d ⁇ succ ⁇ nat (EDDS) is preferably in the form of its sodium or magnesium salts thereof are furthermore preferred in this context
• 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.
• HEDP 1-hydroxyethane-1,1-diphosphonate
• the Dinatnumsalz neutral and the tetrasodium salt alkaline (pH 9) are reacted as aminoalkane phosphonates are preferably ethylenediaminetetramethylene (EDTMP), Diethylent ⁇ aminpentamethylenphos- 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 makesmit 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 granule
• oxidation products of carboxyl-containing polyglucosans and / or their water-soluble salts are also suitable.
• 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
• 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.
• bleaches include 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 Nat ⁇ umpercarbonat, peroxypyrophosphates, citrate perhydrates and H 2 O 2 supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelic acid, Phthaloiminopersauer or Diperdodecandisaure
• 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- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylic acid, peroxystearic acid, ⁇ -phthalimido peroxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylam ⁇ doperadipic 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-Decyld ⁇ peroxybutan-1
• Heterocyclic N-bromo- and N-chloramides 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.
• Trichlorocyanocyanuric acid tribromoisocyanuric acid
• DICA dichloro-cyanuric acid
• 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 pronounced granules prepared according to the invention (coated core-shell aggregate).
• bleach activators may be present
• bleach activators for the preparation according to the invention of the laundry and / or remover granules (coated core-shell aggregates)
• 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.
• polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated T ⁇ azinderivate, in particular 1, 5-D ⁇ acetyl-2,4-d ⁇ oxohexahydro-1, 3,5-tr ⁇ az ⁇ n (DADHT), acylated Glycolunle, in particular tetraacetylglycoluril (TAGU), N-Acyl ⁇ m ⁇ de, in particular N-Nonanoylsucc ⁇ n ⁇ m ⁇ d (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-D ⁇ -acetoxy-2,5-diphohydr
• 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
• 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 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).
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• a further subject of the invention is the use of the erfindunplien, coated core-shell aggregates as enzyme granules, which preferably have an enzyme-free shell and / or an enzyme-free coating.
• 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.
• Bacillus subtilis Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Coprinus cinereus and Humicola insolens and their genetically modified variants recovered enzymatic agents.
• subtilisin-type proteases and in particular proteases derived from Bacillus lentus are obtained.
• 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.
• 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.
• 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
• the washing and / or cleaning agent granules prepared according to the invention may contain further enzyme stabilizers.
• 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.
• 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.
• water-soluble polyamides containing acidic groups are suitable for this purpose
• soluble starch preparations and others can be prepared Also, polyvinylpyrrolidone is useful.
• 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
• 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
• 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 '-B ⁇ s [(4- an ⁇ l ⁇ no-6-
• brighteners of the substituted diphenylstyrene type may be present, for example the alkali metal salts of 4,4 '- B ⁇ s (2-sulfostyryl) -d ⁇ phenyls, 4,4'-B ⁇ s (4-chloro-3-sulfostyryl) -d ⁇ phenyls, 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 Remists antique 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.
• fragrance 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.
• 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.
• tablet disintegrants are understood as meaning excipients which ensure rapid disintegration of tablets in water and release of the active substances.
• Swelling 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.
• 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 ⁇ -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
• 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
• the coated core-shell aggregates can be colored with suitable dyes, the brightener-containing phase (s) preferably containing the total amount of dye (s).
• suitable dyes the brightener-containing phase (s) preferably containing the total amount of dye (s).
• 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.
• 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.
• the colorant 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.
• 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.
• 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 ⁇ m 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.
• 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 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.

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• 2005
  • 2005-07-29 DE DE200510036346 patent/DE102005036346A1/de not_active Ceased
• 2006
  • 2006-06-24 WO PCT/EP2006/006112 patent/WO2007014601A1/de active Application Filing
  • 2006-06-24 JP JP2008523152A patent/JP2009503156A/ja active Pending

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