Process for the preparation of granulates / agglomerates for detergent compositions

0001The present invention relates to a process for the preparation of granules or agglomerates for detergents or cleaners. The respective aggregates / agglomerates / granules can be used and used advantageously in the washing or cleaning agent industry.

0002The advantages of a modern industrial society, which among other things manifested in all sorts of technical achievements that make people's lives easier and more beautiful, can, despite all progress, at least temporarily and hypothetically still bring many burdens on people and the environment. Although the singular burdens per se for the system "human" or the system "environment" in most cases do not lead to a system impairment, nevertheless in the worst case with an accumulation of loads, in particular rectified burdens in the individual case system impairments can occur. For this reason, at least the sustainable industry always strives to perfect its products and technologies, that associated risks for humans and the environment are reduced and, ideally, even excluded. At the very least, the aim is to contribute to the perfection of products and technologies.

0003An important example of technical progress is the common use of detergents and cleaners for many decades. Nearly every human being in modern industrial society, or at least those who wash their own textile clothing, are estimated to spend at least 1 to 2 times a week washing and cleaning Cleaning agents in contact.

0004As a result of the at least hypothetical assuming contact with the washing or cleaning agent, it has long been the practiced endeavor of the relevant industry to design their products in such a way that, for example, even particularly sensitive or allergic persons, for example those with predisposition to skin irritation, the products can use carefree.

0005For example, to make the handling of detergents or cleaning agents particularly safe, for example, so-called pouches have been developed. These are offer forms in which the actual washing or cleaning agent, wrapped in films, in such an amount, the so-called disposable portions are present. The consumer can now take such a pouch and place it in the washing drum and is the manual dosing of the detergent or cleaning agent unbound. This ensures that the consumer can not contaminate with the detergent or cleaning agent, for example, in which he pours himself as a result of an unfortunate skill on the hands.

0006A significant disadvantage of such a technology, however, is that the individual dosability is more or less lost when using pouches. The consumer can only think about whether he wants to give 1 or 2 pouches for washing, but a fine adjustment of the dosage is not possible. For this reason, consumers often avoid the use of the pouches to keep the dosing sovereignty.

0007<patcit id="pcit0001" dnum="EP179264A1"><text>EP 179 264 A1</text></patcit> relates to a process for the preparation of a granular detergent component containing (a) alkoxylated nonionic surfactants, (b) inorganic carriers, (c) other organic detergents and (d) adsorptively or hydrate bound water, whereby to obtain the detergent component sprayed aqueous approach using nozzles under a pressure in a drying tower. The procedure described there results in a spray-dried powder.

0008In <patcit id="pcit0002" dnum="US5139693A"><text>US 5,139,693</text></patcit> Spray drying processes or spray drying powders are also described.

0009<patcit id="pcit0003" dnum="EP1186652A1"><text>EP 1 186 652 A1</text></patcit> describes the preparation of pellets wherein a slurry is dried using a countercurrent spray dryer and the resulting powder is then fed along with other ingredients to a continuous kneader and then pelletized. The resulting pellets have no core-shell nature. These pellets are then subjected to a pulverization and granulation process and further treated in other ways.

0010In <patcit id="pcit0004" dnum="WO02078737A1"><text>WO 02/078737 A1</text></patcit> describes how sucrose particles are sprayed with an aqueous protease solution, which further comprises sucrose and corn starch, resulting in coated sucrose particles. These particles are then further sprayed with an aqueous solution of magnesium sulfate and then further sprayed with an aqueous solution comprising titanium dioxide, methyl cellulose and other ingredients. The resulting particles have more than 5% by weight of enzymes.

0011Against this background, therefore, the object of the present invention was to provide a form of supply in the field of detergents which satisfies the consumer need for increased safety comfort in the application.

0012The advantage of the invention lies in the increased safety comfort for the consumer in the application. Powdered detergents and cleaners, like other disperse solid systems, can release dust during handling, such as during storage or filling. In the worst case, dusts released in this way may jeopardize or impair human health, for example by inadvertently inhaling larger quantities of dust. Even with simple Umfüllvorgängen it can namely come to an undesirable dust release. In the context of the present invention, however, the dusting tendency of the washing or cleaning agent is minimized, so that, for example, the danger of inhaling dust tends to zero.

0013In this respect, this invention is of great importance, as it realizes the concept to combat dust even before the emergence. This is the safest way to consistently prevent a human health hazard associated with dust.

0014In the Elutriationsmethode to be used in the invention 60 g of granules / agglomerate on a glass frit (glass frit from Robu, type: Por 2, pore size 40-100μm) placed in a large glass tube (tube height 180 cm, tube diameter 3.3 cm) and 40 minutes at a constant rate of 0.8 m / s air (dehumidified room air with a moisture content of 0.01 g / m³ Corresponding with a dew point of about -60 ° C; Temperature of air T = 20 ° C ± 2 ° C) passed through the granules / agglomerates (amount of air: 2.4 m³/H; Differential pressure: 100 mm WS; Control with a vacuum pump). The air flow through the granules / agglomerates causes them to be whirled up. The resulting dust is carried away by the air stream and collected on a filter (filter Whatman, type: glass fiber microfilter GF / C Circles, pore size 1.2μm: 150mm diameter). The dust mass can then be determined gravimetrically quantitatively. The dust determination with the elution method is always carried out as a multiple determination, at least as a triple determination, preferably as a quadruple, quintuple or sixfold determination, whereby the mean value from the multiple determinations serves as measured value (dust value). This gives the dust value (synonym: dust content) in mg based on 60 g of granules / agglomerate. The indication that the dust value (dust content) "on average" is less than, for example, 2000 mg / 60 g, should indicate that the dust value (dust content) is the result of a multiple determination, so that the Elutriationsmethode was applied several times to get the dust value (dust content). The Elutriationsmethode simulates the dust formation of granules / agglomerates, as it occurs during light use, eg during transfer. The elutriation method is therefore the method of choice to capture those stresses and conditions that are usually present in the consumer budget. as it occurs under light load, for example when decanting. The elutriation method is therefore the method of choice to capture those stresses and conditions that are usually present in the consumer budget. as it occurs under light load, for example when decanting. The elutriation method is therefore the method of choice to capture those stresses and conditions that are usually present in the consumer budget.

0015For additional details on this well-known method, see eg "<nplcit id="ncit0001" npl-type="b"><text>Enzyme's Detergency ", ed. Jan H. van Ee, et al., Chpt. 15, pgs. 310-312 (Marcel Dekker, Inc., New York, NY (1997</text></nplcit>)), and the references there or the corresponding patent literature.

0016A further advantage of the article according to the invention is an improved stability and improved shelf life of the granules / agglomerates compared to conventional products.

0017The subject of this invention is a process for the construction of granules in a mixer / granulator by presenting a particulate material referred to hereinafter as "particles to be prepared", which is granulated / agglomerated with the addition of granulation aid and further particulate material hereinafter referred to as "particles to be added" being, being<ol id="ol0001" compact="compact" ol-style=""><li>a) the particles to be submitted have a largely uniform particle size,</li><li>b) the particles to be added have a particle diameter d₅₀ having a maximum of one tenth of the particle diameter d₅₀ is to be submitted particles, wherein the particle diameter d₅₀ the particles to be added are preferably in the range from 3 to 50 μm,</li><li>c) the particles to be added are added together with a granulating agent, preferably over a period of at least one minute,</li><li>d) the particles to be added are produced by a milling process,</li></ol>wherein the granules to be presented, the granules to be added and / or the granulating aids comprise ingredients from the range of washing and cleaning agents, the resulting granules containing less than 5% by weight of enzymes, based on the total granules, wherein the built-up granules are sieved and / or sifted after drying to separate the good grain from oversize and fines, the oversize and fines thereafter<ol id="ol0002" compact="compact" ol-style=""><li>a) be subjected to a milling process, so that these particles after grinding a particle diameter d₅₀ having a maximum of one tenth of the particle diameter d₅₀ is to be submitted particles, so that the resulting particles preferably have a particle diameter dso of 3 to 50 microns and then</li><li>b) these particles are fed back to the mixer / granulator as particles to be added.</li></ol>

0018This process allows the production of largely spherical and very low-dust or dust-free and abrasion-resistant granules.

0019According to a preferred embodiment, this process according to the invention is characterized in that the resulting granules have a dust content (according to the elutriation method described here). of on average less than 2500 mg / 60g, preferably on average less than 2000 mg / 60g with bulk densities of the coated core-shell aggregate <500 g / l, or of on average less than 2000 mg / 60g. preferably on average less than 1500 mg / 60 g at bulk densities of the coated core-shell aggregate of 501 to 700 g / l, or of on average less than 1500 mg / 60g, preferably on average less than 1200 mg / 60 g in bulk densities of the coated core-shell aggregate of from 701 to 850 g / l, or of on average less than 700 mg / 60 g, preferably on average less than 600 mg / 60 g at bulk densities of the coated core-shell aggregate of> 851 g / l, depending on the bulk density of the granules.

0020It is particularly advantageous that the specific power of the mixer / granulator less than 8 kW / m³, advantageously less than 5 kW / m³, preferably less than 3 kW / m³, in particular less than 1.5 kW / m³ is, which corresponds to a preferred embodiment of the invention.

0021On the one hand, low energy introduction means an economic advantage over the energy consumption, but in particular a particularly gentle agglomeration without appreciable destruction of already formed granules takes place in this way.

0022By the term mixer / granulator is meant preferably drum and plate mixers and / or fluidized bed granulators, but also single- and two-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 introducing a thrust, throw or centrifugal force. Free-fall mixers are preferably used. From the associated specialist literature, reference is made at this point by way of example to<nplcit id="ncit0002" npl-type="b"><text>Stieß: Mechanical Process Engineering 1, p. 207, Springer 1995</text></nplcit>, referenced. In the broadest sense, the term mixer / granulator means any apparatus suitable for mixing / granulating.

0023As Granulierhilfsmittel preferably granulation or granulation foam can be used. It should be noted at this point that a granulation foam is not granulation liquid. A foam is a complex structure or agglomerate of gas-filled, spherical or polyhedron-shaped cells or bubbles which are bounded by liquid, semi-liquid, highly viscous or solid cell webs, but it is not a liquid. For example, foams usually have a much lower density than liquids and, for example, react quite differently than fluids to compression or mechanical stress. As granulation liquids preferably water or aqueous solutions can be used, but advantageously also other granulation aids than water, For example, liquid nonionic surfactants, polyethylene glycols or other organic solvents. Particularly preferred are aqueous granulation liquids, for example, salts, water glass, 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. It is also possible to melt suitable substances Polyvinyl alcohol and / or biopolymers such as xanthan included. Also possible are water-containing organic solvents with swollen polymers. It is also possible to melt suitable substances Polyvinyl alcohol and / or biopolymers such as xanthan included. Also possible are water-containing organic solvents with swollen polymers. It is also possible to melt suitable substances

0024Advantageously, the granules produced by this process are free-flowing, nearly spherical and therefore aesthetically very attractive. The granules are well pourable and pourable even after long storage and show no tendency to clumping. Advantageously, you do not require any powdering.

0025Due to the very pronounced spherical shape of the particulate particles advantageously the contact area between the individual particles is significantly minimized. This minimization of the contact area between the respective particulate particles is very advantageous because it prevents the particles from intensely contacting each other and thereby interacting by, for example, sticking together. The likelihood of sticking or baking is thus significantly reduced here.

0026It is a further advantage of this invention that the process according to the invention leads only to a negligible extent to granules whose diameters are so small that they fit into the spaces formed by the other particulate particles. The most extensive absence of in relation to the other particles very small granules, which in particular a diameter of less than 0.16 × d₉₀ has, therefore, is advantageous because by incorporation of small granules in the cavities formed an undesirable significant increase in contact surface between the particles would be caused, which would be associated with increased interaction of the individual granules, which, however, is to be avoided.

0027In a preferred embodiment of the method according to the invention, the diameter d₅₀ the particles to be submitted in the range of 0.15 to 5 mm, preferably in the range of 0.2 to 2 mm, in particular in the range of 0.3 to 1 mm.

0028The granules resulting from the process have a comparatively large diameter, in particular, if the particles to be present already have a large diameter, while in particular smaller granules result, if the particles to be present already have a rather small diameter. With regard to the size or the diameter of the resulting granules, it has been found that the process according to the invention is suitable both with regard to granules with particularly large particle diameters, for example with diameters of above 2 to 5 or 10 mm or greater, and also with smaller particulate particles in the range of 0.3 and 2 mm or smaller is advantageous.

0029The particle size distribution is thus freely adjustable, which is an important advantage of the method according to the invention.

0030Depending on the intended use of the particles resulting from the process according to the invention, it may be preferable to obtain rather small particulate particles. Advantageously, then the particles to be submitted are rather small. For example, they may have a particle size in the range of 0.1 to 0.4 mm. Particulate particles of smaller diameters have the advantage that the means consisting of them usually have a high bulk density. This in turn leads advantageously to a significant reduction in the packaging volume. Furthermore, particulate particles having a relatively small particle size are also advantageous if they are to dissolve as quickly as possible, as is often desired, for example, with regard to detergents and / or cleaning agents.

0031However, 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 as a simple dosage of the granules. For example, the user has the opportunity to specifically pick out, assemble and use the granules of defined composition, which may be colored differently.

0032If the particle size distribution of the particles to be submitted is rather narrow, this is advantageous for the purposes of the invention. According to a further preferred embodiment of the invention, therefore, the ratio of d₅₀ to d₉₀ the particles to be submitted at least 0.5, preferably at least 0.6, advantageously at least 0.75 and in particular 0.8, wherein d₅₀ represents the median value. The median value is defined as the particle size below and above which 50% of the particle quantity is located. Accordingly, at d₉₀ 90% of the particle quantity below the value, ie 10% above it. The ratio d₅₀ / d₉₀ approaches the value of 1 for very narrow particle size distributions, or is well below 0.5 for broad distributions.

0033According to a further preferred embodiment of the invention, the granulation aid is a granulation foam. In this connection, express reference is made to the German Offenlegungsschrift<patcit id="pcit0005" dnum="DE10124430A1"><text>DE 101 24 430 A1</text></patcit> Henkel KGaA. In this publication, a granulation process is described in which a flowable component is charged with a gaseous medium and thereby foamed and the resulting foam is subsequently added to a charged in a mixer solid bed. Here, the foam generation takes place under a pressure which is above the pressure in the granulation plant.

0034If the particles of the process according to the invention to be added have a particle diameter d₅₀ to, the maximum of 1/12, preferably a maximum of 1/14, advantageously a maximum of 1/16, more preferably a maximum of 1/18, more preferably a maximum of 1/20, even more advantageously 1/22, in a very advantageous manner a maximum of 1/24 and in particular a maximum of 1/26 of the particle diameter d₅₀ is to be submitted to particles, so again is a preferred embodiment of the invention. The reduction of the particle diameter d₅₀ in the manner described results in that particularly spherical granules / agglomerates are formed. If the particles of the process according to the invention to be added have a particle diameter d₅₀ to, which is in the range 3 to 50 microns, preferably 4 to 30 microns, advantageously 5 to 20 microns, in particular 6 to 12 microns, so is a particularly preferred embodiment of the invention.

0035Advantageously, the reduction of the particle diameter d₅₀ not so far that the particles to be added would be equivalent to a powder. The particles to be added are advantageously not powder. According to general understanding, powder is a kind of flour, ie an accumulation of solid particles with a particle size preferably below 100 nm. It is also advantageous for process-technical reasons, if the particles do not fall below a certain minimum size. According to a preferred embodiment of the invention, therefore, the particles to be added have a particle diameter d₅₀ preferably at least 1/100, advantageously at least 1/80, more preferably at least 1/70, more preferably at least 1/60, even more preferably at least 1/50, most preferably at least 1/40 and in particular at least 1/35 of the particle diameter d₅₀ of the particles to be submitted.

0036If the particles to be present are 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, and the particles to be added more than 50 wt .-%, preferably more than 55 wt .-%, more preferably more than 60 wt .-%, more preferably 65 to 85 wt .-%, in particular 70 to 80 wt. - Make up% of the solids involved in the granulation process, then there is a further preferred embodiment of the invention.

0037According to a very preferred embodiment, the particles to be prepared may also constitute 5 to 25% by weight and the particles to be added 75 to 95% by weight of the solids involved in the granulation process.

0038According to a further preferred embodiment of the invention, the particles to be prepared and the particles to be added are obtained by screening out a starting material, preferably a single starting material, whereby the particles to be added are obtained by grinding the coarse and fine material sieved from this starting material, so that the particle diameter criterion is satisfied according to claim 1, wherein the particle diameter d₅₀ the particles to be added preferably in the range of 3 to 50 microns.

0039According to another preferred embodiment of the invention, the particles to be submitted and a part of the particles to be added are obtained by screening out a powdery or crystalline base material or a granular finished product, preferably a single material, wherein the particles to be added by grinding the sifted out of this material coarse and fine material and optionally other substances are obtained, so that the particle diameter criterion is satisfied according to claim 1, wherein the particle diameter d₅₀ The particles to be added therefore preferably in the range of 3 to 50 microns.

0040Is the granulation process such that the particles to be added and the Granulierhilfsmittel over a period of at least 2, advantageously of at least 3, more advantageously at least 4, more preferably at least 5, are added in a very advantageous at least 6 minutes, wherein preferably an addition period of 50 minutes, advantageously 40 minutes, more advantageously 30 minutes, more preferably 20 minutes, in particular 16 minutes is not exceeded, so is a further preferred embodiment of the invention.

0041Another preferred embodiment is when the granulation process is such that the particles to be added and the granulation aids over a period of a maximum of 5 minutes, advantageously of a maximum of 3 minutes, more advantageously of a maximum of 2 minutes, more preferably of a maximum of 1 minute and in particular of a maximum of 30 seconds are added and granulated.

0042According to a further preferred embodiment of the invention, the granules are dried and / or cooled in a further process step, in a fluidized bed, and advantageously powdered before or after this process step.

0043According to another preferred embodiment of the invention, the particles to be added to a largely uniform particle size, wherein the particle size distribution of these particles is such that the ratio of d₅₀ to d₉₀ the particle to be added is at least 0.5, preferably at least 0.6, in particular at least 0.75, wherein d₅₀ represents the median value.

0044According to the invention, the process in which the built-up granules are screened and / or screened after drying, for separating the good grain from oversize and fines, wherein the oversize and the fines are thereafter<ol id="ol0003" compact="compact" ol-style=""><li>a) be subjected to a milling process, so that these particles after grinding a particle diameter d₅₀ which is at most one tenth of the particle diameter dso of the particles to be submitted, the resulting particles preferably having a particle diameter d₅₀ from 3 to 50 microns and then</li><li>b) these particles are fed back to the mixer / granulator as particles to be added.</li></ol>

0045The original process end product consists of good grain, oversize and undersize (fines), although the oversize and undersize fractions are negligible. The term "good grain" refers to the granulated material whose size or diameter is desired. This size range is an individual range, which is oriented to the needs of the user and can be selected according to the respective requirements. The oversize grain is the built-up granulate, which in contrast is too coarse, ie too large. The undersize (fines) is that granulate which in turn is too fine or too small. It is an advantage of the method according to the invention,

0046A method according to the invention, which comprises the steps<ol id="ol0004" compact="compact" ol-style=""><li>a) Aussiebvorgang for the separation of a substantially uniform particulate material in the following to be submitted particles called oversize and fines from a starting material</li><li>b) grinding the separated oversize and the fines, optionally with the addition of further components, to at least one-tenth of the particle diameter of the particle to be submitted or smaller in order to obtain the particles to be added, so that they preferably have a particle diameter d₅₀ from 3 to 50 μm</li><li>c) granulation / agglomeration of the particles to be prepared with the addition of the particles to be added and granulation aids in a mixer / granulator</li><li>d) drying the granules / agglomerates in a fluidized bed</li><li>e) separation of the good grain of oversize and fines by sieving and / or sifting</li><li>f) transferring the oversize and fines to a mill and grinding these particles to a particle diameter d₅₀which is at most one tenth of the particle diameter d₅₀ is to be submitted particles, so that preferably particle diameter d₅₀ be achieved from 3 to 50 microns and then</li><li>g) recycling the milled particles as particles to be added into the mixer / granulator comprises, is a further preferred embodiment of the invention.</li></ol>

0047Of particular importance is the subject of the present invention for the field of particulate detergents and / or cleaning agents.

0048According to a further preferred embodiment of the invention, the granules to be presented, the granules to be added and / or the granulation aids comprise ingredients from the field of detergents and / or cleaning agents.

0049When the granules and / or granules to be added are tower powder products (spray drying products) and / or (raw) products resulting from non-tower technologies (ie products which are not direct spray drying products), preferably resulting from granulation in drum, dish -, mixer and fluidized bed granulators are, or have emerged from these, preferably originate from the same process, then again there is a further preferred embodiment of the invention.

0050The particles to be prepared and / or the particles to be added can preferably also be produced by means of extrusion, particularly preferably using a two-shaft extruder. In this case, the raw materials intended for the respective particulate particles are first mixed and then homogenized and plasticized in the extruder. For example, preformed particles can be obtained by cutting the extruded mass at the extruder head. Extrusion processes suitable according to the invention are known in the art.

0051The preparation of the particles to be submitted and / or the particles to be added, preferably having a defined composition, in the broadest sense quite generally by conventional methods, ie, the particles to be used, for example, as needed by spraying and subsequent dry compaction, by granulation, spray agglomeration or obtained by extrusion.

0052Preferably, the particles to be submitted and / or the particles to be added can be rounded in a method step which precedes the method according to the invention. In particular, the particles to be prepared and / or the particles to be added are rounded with the aid of a so-called spheronizer, a rotary drum, a coating drum or a coating pan.

0053In a preferred embodiment, the particles to be prepared and / or the particles to be added are those which have been prepared by the so-called spray agglomeration method. In the spray agglomeration process, the particles to be used are simultaneously agglomerated in a fluidized bed and dried. The onion-like application of the substances and the movement of the particles give rise to very dense and round particles, which can be processed very advantageously in the method according to the invention.

0054According to a further preferred embodiment of the invention, the granules (constructed as process end products of the process according to the invention) essentially have an average form factor of at least 0.77, preferably of at least 0.79, advantageously of at least 0.81, more preferably of at least zero , 83, more preferably at least 0.85, in particular at least 0.87.

0055"Substantially" means here in particular that at least 80%, preferably at least 90% and more preferably at least 95% of the built-up granules have the aforementioned form factor. The built-up granules are the whole of good grain, oversize and undersize (fines), which proves that oversize and undersize (fines) are negligible.

0056The 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 with the Camsizer® system by Retsch Technology or with the KeSizer® Kemira is feasible, based on the fact that the particles or the bulk material are irradiated with a light source and detects the particles as projection surfaces , digitized and processed by computer technology. The determination of the surface curvature is made by an optical measuring method in which the "shadow" of the parts to be examined is determined and converted into a corresponding form factor. The underlying principle for determining the form factor was, for example,<nplcit id="ncit0003" npl-type="s"><text>Gordon Rittenhouse in "A visual method of estimating two-dimensional sphericity" in the Journal of Sedimentary Petrology, Vol. 13, No. 2, pp. 79-81</text></nplcit> described.

0057The measurement limits of this optical analysis method are 15 μm and 90 mm, respectively. The numerical values ​​for d₅₀ and d₉₀ are also available via the aforementioned measuring method.

0058A further preferred embodiment of the invention is present if the granules constructed as process end product are present in a particle size distribution which is as uniform as possible, ie the ratio of d₅₀ to d₉₀ as high as possible. In a particularly preferred embodiment, the ratio of d₅₀ to d₉₀ at least 0.5, preferably at least 0.6, advantageously at least 0.75, more preferably at least 0.8.

0059A preferred embodiment is a process in which the first process end product resulting from the process is again used as a particle to be prepared in the granulation stage in order to produce a larger and / or rounder granulate.

0060In a further preferred embodiment according to the invention, the granules that are built up are provided with a partial or complete, optionally multi-layered 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, as are suitable inorganic compounds.

0061In a further preferred embodiment of the invention, the method is characterized in that it is carried out at elevated temperatures, at least partially, preferably over all stages, which are in particular in the range of 15 to 75 ° C, but preferably ≥ 20 ° C, advantageously ≥ 25 ° C, in particular in the range 28-40 ° C are. A very suitable temperature range for granulation / agglomeration is 25-35 ° C, for milling operations at 40-50 ° C, achievable by introducing tempered air.

0062In a further preferred embodiment of the invention, the method is characterized in that enzyme-free is used, which means in the context of the invention that the resulting granules / agglomerate contains less than 5 wt .-% of enzymes, based on the total granules / agglomerate. In particular, all enzyme-free work is carried out, so that the resulting granules / agglomerate is also completely enzyme-free, ie 0 wt .-% enzyme, based on the total granules / agglomerate.

0063According to the invention, it is furthermore advantageous to surround the granules with a coating of fine solids, ie to remove them, for example in order to achieve protection. The choice of these fine solids depends on the nature of the granules and their intended use. For example, in the case of granules from the field of detergents and / or cleaning agents, powdering agents are suitable which preferably contain very finely divided zeolite and / or silica, in particular hydrophobic silica.

0064As already mentioned, the process according to the invention is outstandingly suitable for the preparation of corresponding detergents and / or cleaning agents.

0065In this case, the granules 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, complete 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.

0066However, it is also preferred if the granules contain only a certain or several specific detergent and / or detergent ingredients. 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. In such a case, it is preferred if at least two or more granules constructed according to the invention are mixed to form a washing and / or cleaning agent and the resulting fully-fledged washing and / or cleaning agent consists only of these granules constructed according to the invention,

0067In the context of the present invention, the term washing and / or cleaning agent granules is to be understood as meaning both complete washing and / or cleaning agents and also washing and / or cleaning agent components.

0068The washing and / or cleaning agent granules produced in the preparation according to the invention contain constituents which are preferably selected from the group consisting of surfactants, fragrances, dyes, enzymes, enzyme stabilizers, builders, pH adjusters, bleaching agents, bleach activators, soil repellents, optical agents Brightener, grayness inhibitors, disintegration aids, customary ingredients and / or mixtures thereof. Furthermore, all other detergents and / or cleaning agent ingredients known to the person skilled in the art from the prior art may also be present in conventional amounts as constituents of the detergent and / or detergent granules to be produced according to the invention.

0069In the following, some particularly suitable detergent and / or cleaning agent components are explained in greater detail. These ingredients may be included in the detergent and / or detergent granules themselves and / or in appropriate admixtures which may optionally be added to the laundry and / or detergent granules, if required, to provide a full wash and / or detergent receive.

0070As surfactants anion, cation, ampho- and / or nonionic surfactants can be used for the preparation according to the invention of the washing and / or cleaning agent granules.

0071For example, anionic surfactants of the sulfonate and sulfates type can be used. As surfactants of the sulfonate type are preferably C_9-13Alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are known for example from C_12-8Monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained, into consideration. Also suitable are alkanesulfonates which are from C_12-18Alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable. Also suitable are sulfonation of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt .-%. In particular, preferred are α-sulfofatty acid alkyl esters which have an alkyl chain having not more than 4 carbon atoms in the ester group, for example, methyl ester, ethyl ester, propyl ester and butyl ester. With particular advantage, the methyl esters of α-sulfo fatty acids (MES), but also their saponified disalts are used.

0072Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. 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.

0073The alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric acid semiesters of C₁₂-C₁₈Fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C₁₀-C_2OOxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.

0074Suitable 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.

0075As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.

0076The 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. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

0077The anionic surfactants are present in the detergent and / or detergent granules to be produced 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.

0078It is also possible to use alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters. As nonionic surfactants are C₁₂-C₁₈Fatty acid methyl ester with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO preferred. In particular C₁₂-C₁₈Fatty acid methyl esters with 10 to 12 EO can be used as surfactants.

0079Another class of nonionic surfactants which can be used to advantage for the preparation according to the invention of detergent granules and / or detergent granules are the alkylpolyglycosides (APG). Usable Alkypolyglycoside meet the general formula RO (G)_zin which R is a linear or branched, in particular in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit with 5 or 6 C atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.

0080Nonionic 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 suitable for the preparation according to the invention of the detergents and / or detergent granules.

0081Suitable further surfactants for the preparation according to the invention of the washing and / or cleaning agent granules are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is usually a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants not only means dimeric,

0082Gemini surfactants for the preparation according to the invention of detergent granules and / or detergent granules are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis- and trimeralcohol tris-sulfates and ether sulfates. End-capped dimeric and trimeric mixed ethers are characterized in particular by their bi- and multi-functionality. Thus, the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing and / or cleaning processes.

0083The washing and / or cleaning agent granules which can be prepared according to the invention may contain as builder or builder all builders customarily used in detergents and / or cleaning agents, in particular detergents, in particular zeolites, silicates, carbonates, soda, organic cobuilders and also the phosphates. To avoid particulate residues on textiles, it is particularly advantageous to use builders which are completely water-soluble, such as soda or the like.

0084Suitable crystalline, layered sodium silicates have the general formula NaMSi_xO_{2x + 1} H₂O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values ​​for x are 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values ​​2 or 3. In particular, both β- and δ-sodium disilicates are Na₂Si₂O₅ · YH₂O preferred.

0085It is also possible to use amorphous sodium silicates with a Na module₂O: SiO₂ 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. Particularly preferred are amorphous silicates.

0086A useful fine crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. As zeolite P, zeolite MAP^® (Commercial product from Crosfield) particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), by the company CONDEA Augusta SpA under the brand name VEGOBOND AX^® is sold and the formula:         nNa₂O · (1-n) K₂O · Al₂O₃ · (2 - 2.5) SiO₂ · (3.5 - 5.5) H₂O, equivalent.

0087Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

0088According to a preferred embodiment, the content of zeolite granules obtainable according to the invention is up to 60% by weight, advantageously up to 40% by weight and more advantageously up to 30% by weight, although it may be even more advantageous a maximum of 15 wt .-%, preferably at most 12 wt .-%, in particular at most 10 wt .-%, in each case based on the anhydrous active substance, for example 1 to 8 wt .-% or 0 to 5 wt .-% are included. In a particularly preferred embodiment, the granules which can be prepared according to the invention are free of zeolite.

0089Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates. The granules according to the invention are preferably not only zeolite but also low in phosphate. Thus, the phosphate content is advantageously at most 15 wt .-%, preferably at most 12 wt .-%, in particular at most 10 wt .-%, for example 1 to 8 wt .-% or 0 to 5 wt .-%. Very particular preference is given to granules which are both free of zeolite and of phosphate.

0090As organic cobuilders, the detergent and / or cleaning agent granules according to the invention may contain, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and also phosphonates. These classes of substances are described below.

0091Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning 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, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological 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.

0092The acids themselves can also be used. In addition to their builder action, the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents and / or cleaning agents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

0093Other suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

0094The molecular weights stated for polymeric polycarboxylates are weight-average molar masses M for the purposes of this document_w the respective acid form, which were determined in principle by gel permeation chromatography (GPC), using a UV detector was used. The measurement was carried out against an external standard of polyacrylic acid, which provides realistic molecular weight values ​​on account of its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

0095Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

0096Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, 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.

0097Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,

0098Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

0099Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.

0100Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

0101Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, 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 common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.

0102The 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 ring to the carboxylic acid function. A to C₆ The saccharide oxidized product may be particularly advantageous.

0103A preferred dextrin is in the British patent application <patcit id="pcit0006" dnum="GB9419091A"><text>94 19 091</text></patcit> described. 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 ring to the carboxylic acid function. Such oxidized dextrins and methods of their preparation are known. A product oxidized at C6 of the saccharide ring may be particularly advantageous.

0104Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat<patcit id="pcit0007" dnum="US4524009A"><text>US 4,524,009</text></patcit>. <patcit id="pcit0008" dnum="US4639325A"><text>US 4,639,325</text></patcit> to be discribed.

0105Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such co-builders are known.

0106Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the washing and / or cleaning agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned for producing the granules.

0107In addition, all compounds capable of forming complexes with alkaline earth ions can be used as co-builders.

0108Further suitable builder substances for preparing the detergent granules according to the invention are oxidation products of carboxyl-containing polyglucosans and / or their water-soluble salts. Also suitable are oxidized oligosaccharides.

0109Further builder substances which are suitable for the preparation according to the invention of the detergent granules and / or detergent granules are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

0110In order to reduce the pH of detergents and / or cleaning agents, in particular detergents, the granules which can be prepared according to the invention can also have acid salts or slightly alkaline salts. Preferred acidifying components here are bisulfates and / or bicarbonates or organic polycarboxylic acids which can also be used simultaneously as builders. Particularly preferred is the use of citric acid.

0111The laundry and / or cleaning agent granules which can be prepared according to the invention can also comprise bleaching agents. Among those serving as bleach, in water H₂O₂ Sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance in delivering compounds. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H.₂O₂ supplying peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

0112It is also possible to use bleaching agents from the group of organic bleaching agents for the preparation of the washing and / or cleaning agent granules. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.

0113Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkyleroxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimido peroxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-Decyldiperoxybutane-1,4-diacid, N, N-tere-phthaloyl-di (6-aminopercapronic) can be used to prepare the granules of the invention.

0114Chlorine or bromine-releasing substances can also be used as bleaching agents in the detergent and / or detergent granules which can be prepared according to the invention. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribrornisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium hydantoin compounds, such as 1 3-dichloro-5,5-dimethylhydantoin are also suitable.

0115The content of bleaching agents is preferably from 0 to 25% by weight and in particular from 1 to 20% by weight, based on the total composition of the laundry detergent and / or detergent granules obtainable according to the invention.

0116In order to achieve an improved bleaching effect when washing or cleaning at temperatures of 60 ° C and below, bleach activators may be included.

0117As bleach activators for the preparation of the detergent granules according to the invention, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates,

0118In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be used for the preparation according to the invention of the detergent granules and / or detergent granules. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline 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 can also be used as bleach catalysts.

0119Suitable bleach activators for the preparation according to the invention of the detergent granules and also the enol esters and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl, tetraacetylxylose and octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example, N-benzoyl caprolactam. The known hydrophilic substituted acylacetals and acyl lactams are likewise preferably used for the preparation of the detergent and / or detergent granules according to the invention. Combinations of conventional bleach activators can also be used to prepare the detergent and / or detergent granules according to the invention.

0120In particular when used in automatic washing processes, it may be advantageous to add to the washing and / or cleaning agent granules customary foam inhibitors. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C18-C24 fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide.

0121Suitable enzymes for the preparation according to the invention of the detergent and / or cleaning agent granules are, in particular, those from the classes of the hydrolases, such as proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of said enzymes. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains.

0122For bleaching and oxidoreductases can be used. Particularly suitable for the preparation of detergents and / or detergent granules are those obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Coprinus Cinereus and Humicola insolens and from their genetically modified variants enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are obtained. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or. Mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases. Oxireductases are also suitable.

0123For the preparation according to the invention of the washing and / or cleaning agent granules, in addition to the abovementioned enzymes, cellulases may additionally be considered. Cellulases and other glycosyl hydrolases can contribute to color retention and increase the softness of the fabric by removing pilling and microfibrils. Cellulases used are preferably cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures of these. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

0124The proportion of the enzymes or enzyme mixtures may be, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-%, based on the detergent and / or Reinigungsmittelgranulatzusammensetzung.

0125In addition to phosphonates, the washing and / or cleaning agent granules which can be prepared according to the invention can also contain further enzyme stabilizers. For example, the washing and / or cleaning agent granules may contain sodium formate. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. In addition to calcium salts, magnesium salts also serve as stabilizers. However, it is particularly advantageous to use boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H.₃BO₃), the metaboric acid (HBO₂) and pyroboric acid (tetraboric acid H₂B₄O₇).

0126The washing and / or cleaning agent granules may also contain grayness inhibitors. Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.

0127In addition, dirt-repellent substances which have a positive influence on the oil and grease washability of textiles (so-called soil repellents) can also be used for the preparation of the detergent tablets and / or detergent granules. This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component. The preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ethers,

0128These substances, which are also called "whiteners", can be used to produce the detergent and / or cleaning agent granules. Optical brighteners are organic dyes that convert part of the invisible UV radiation of sunlight into longer-wavelength blue light. The emission of this blue light complements the "gap" in the light reflected from the textile so that a fabric treated with optical brightener appears whiter and brighter to the eye. Since the mechanism of action of brighteners requires their application to the fibers, a distinction is made depending on the "fibers to be dyed", for example, brighteners for cotton, polyamide or polyester fibers. The commercially available brighteners which are suitable for the preparation of the washing and / or cleaning agent granules essentially comprise five structural groups, namely the stilbene, diphenylstilbene, coumarin-quinoline, diphenylpyrazoline and the group of the combination of benzoxazole or benzimidazole with conjugated systems. An overview of common brighteners is, for example, in<nplcit id="ncit0004" npl-type="b"><text>G. Jakobi, A. Löhr "Detergents and Textile Washing", VCH Verlag, Weinheim, 1987, pages 94 to 100</text></nplcit>, to find. Suitable salts are, for example, salts of 4,4'-bis [(4-anilino-6-morpholino-s-triazin-2-yl) amino] stilbene-2,2'-disulphonic acid or compounds of similar construction which are used in place of the morpholino Group a Diethanolaminogruppe, a methylamino group, an anilino group or a 2-Methoxyethylaminogruppe carry. Furthermore, brighteners of the substituted diphenylstyrene type may be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or (4-chlorostyryl) -4 '- (2-sulfostyryl). It is also possible to use mixtures of the abovementioned brighteners.

0129Fragrances can be added to the detergent and / or detergent granules to be produced according to the invention in order to improve the aesthetic impression of the resulting granules and to provide the consumer with a sensory "typical and unmistakable" washing and / or cleaning agent in addition to the cleaning performance and the color impression. As perfume oils or fragrances, individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate, Styrallyl propionate 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, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, α-isomethylionone and Methylcedrylketon to the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, mixtures of different fragrances are preferably used for the preparation of the detergent and / or detergent granules according to the invention, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures, such as those available from plant sources, eg pine, Citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, orange blossom oil, neroliol, orange peel oil and sandalwood oil.

0130In order to facilitate the disintegration of the detergent and / or cleaning agent granules according to the invention in solid form, for example in tablet form, it is possible to incorporate disintegration aids, so-called tablet disintegrants, in them in order to shorten the disintegration times. By tablet disintegrants or disintegrants are meant auxiliaries which ensure the rapid disintegration of tablets into water or gastric juice and for the release of the drugs in resorbable form.

0131These substances, which are also referred to as explosives due to their effect, increase their volume when water enters, on the one hand increases the intrinsic volume (swelling), on the other hand, via the release of gases, a pressure can be generated, which can disintegrate the tablet into smaller particles. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

0132Conventional washing and / or cleaning agent granules advantageously contain 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-% of one or more disintegration aids, each based on the washing and / or detergent granules.

0133As preferred disintegrating agents which are suitable for the preparation of the detergent and / or cleaning agent granules according to the invention, disintegrating agents based on cellulose are used in the context of the present invention. Pure cellulose has the formal gross composition (C₆H₁₀O₅)_n and formally represents a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, more preferably below 20% by weight, based on the cellulose-based disintegration agent. It is particularly preferred to use pure cellulose as the cellulose-based disintegrating agent for the preparation of the washing and / or cleaning agent granules according to the invention, which is free of cellulose derivatives. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, more preferably below 20% by weight, based on the cellulose-based disintegration agent. It is particularly preferred to use pure cellulose as the cellulose-based disintegrating agent for the preparation of the washing and / or cleaning agent granules according to the invention, which is free of cellulose derivatives. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, more preferably below 20% by weight, based on the cellulose-based disintegration agent. It is particularly preferred to use pure cellulose as the cellulose-based disintegrating agent for the preparation of the washing and / or cleaning agent granules according to the invention, which is free of cellulose derivatives. more preferably below 20% by weight, based on the cellulose-based disintegrant. It is particularly preferred to use pure cellulose as the cellulose-based disintegrating agent for the preparation of the washing and / or cleaning agent granules according to the invention, which is free of cellulose derivatives. more preferably below 20% by weight, based on the cellulose-based disintegrant. It is particularly preferred to use pure cellulose as the cellulose-based disintegrating agent for the preparation of the washing and / or cleaning agent granules according to the invention, which is free of cellulose derivatives.

0134As a further cellulose-based disintegrating agent for the preparation of the washing and / or cleaning agent granules according to the invention, microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulosic mass) of the celluloses, leaving the crystalline regions (about 70%) intact ,

0135In order to further improve the aesthetic impression of the detergent and / or cleaning agent granules preparable according to the invention, the washing and / or cleaning agent granules can be dyed with suitable dyes, with the brightener phase (s) preferably containing the total amount of dye (s). contains / contain. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of detergents and / or cleaning agents and to light and no pronounced substantivity to textile fibers so as not to stain them.

0136Preferred for the production of detergents and / or cleaning agents according to the invention are 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 to be advantageous to use colorants for the preparation of the detergent and / or cleaning agent granules according to the invention, which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe. 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 thereof with suitable blue dyes. Further dyes are Pigmosol^® 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^® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acid Blue 183), Pigment Blue 15 (CI 74160), Supranol^® Blue GLW (CAS 12219-32-8, CI Acidblue 221), Nylosan^® Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan^® Blue (CI Acid Blue 182, CAS 12219-26-0).

0137When 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 detergent and / or detergent granules varies. In the case of readily water-soluble colorants, for example the abovementioned Basacid^® Green or the same Sandolan mentioned above^® Blue, typically will have colorant concentrations in the range of several tens^-2 until 10^-3 % By weight, based in each case on the total detergent and / or detergent granules. In the case of the particularly preferred, but less readily water-soluble pigment dyes, for example, the above-mentioned pigmosol due to their brilliance^®Dyes, the appropriate concentration of the colorant in detergents and / or cleaning agents, on the other hand, is typically about 10^-3 until 10^-4 % By weight, based on the total washing and / or cleaning agent.

0138The following examples serve to illustrate the invention and are not to be considered as limiting.

<u>Examples</u>

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

0139To obtain a core material zeolite-containing Turpululver was screened with alkylbenzenesulfonate as an anionic surfactant to a particle size between 0.6 and 1.4 mm (d50 = 0.77 mm) on a biplane sieve. Oversize and undersize grains have been milled together with sodium carbonate, sodium sulfate, TAED and foam inhibitor concentrate to a mean particle size d 50 of 9 μm with an eddy current mill. Core material and the milled mixture were placed in a batch Lödige mixer. Mixture was via the plowshare mixer elements at a Froude number of 6.5. With addition of the granulation liquid, the fine particles were adhered to the core material. As granulation liquid, an aqueous 25% Sokalan solution (maleic acid acrylic acid copolymer sodium salt (30:70)) has been used. The actual agglomeration took only about 10 to 40 seconds. The water of the polymer solution has subsequently been removed again in a fluidized bed. The dried material was then screened to 0.6 to 1.4 mm (d 50 = 1.02 mm, d 90 = 1.32 mm, Shape factor = form factor = Q3 = 0.87). Upper and lower grain were ground down to about 10 μm by means of a mill and returned to the granulator. The good grain came into a gentle mixer and was there coated with a mixture of Nioterisid / Brightener / Perfume. Upper and lower grain were ground down to about 10 μm by means of a mill and returned to the granulator. The good grain came into a gentle mixer and was there coated with a mixture of Nioterisid / Brightener / Perfume. Upper and lower grain were ground down to about 10 μm by means of a mill and returned to the granulator. The good grain came into a gentle mixer and was there coated with a mixture of Nioterisid / Brightener / Perfume.

0140Thus, a coated core-shell aggregate resulted.

0141The 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.

0142The advantages compared to marketable products were: The coated core-shell aggregates can not segregate as nearly all constituents are in each grain. The coated core-shell aggregates are dust-free in the area of ​​the invention and resistant to abrasion. 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.

B) A starting granulate was prepared in a standard spray-drying process.

0143This starting granulate consisted of:<tables id="tabl0001" num="0001"><table frame="bottom"><tgroup cols="2" colsep="0"><colspec colnum="1" colname="col1" colwidth="113mm" /><colspec colnum="2" colname="col2" colwidth="27mm" /><tbody><row rowsep="0"><entry>Sodium aluminum silicate</entry><entry align="right">45.74% by weight</entry></row><row rowsep="0"><entry>Tallow fatty alcohol ethoxylated (5 ethoxy units)</entry><entry align="right">1.24% by weight</entry></row><row rowsep="0"><entry>Edenor® ST 1</entry><entry align="right">1.37% by weight</entry></row><row rowsep="0"><entry>Alkylbenzenesulfonic acid sodium salt</entry><entry align="right">24.70% by weight</entry></row><row rowsep="0"><entry>Soda calcined</entry><entry align="right">3.92% by weight</entry></row><row rowsep="0"><entry>Sokalan® CP 5</entry><entry align="right">8.30% by weight</entry></row><row rowsep="0"><entry>Turpinal® 4 NL</entry><entry align="right">1.66% by weight</entry></row><row rowsep="0"><entry>caustic soda</entry><entry align="right">0.47% by weight</entry></row><row rowsep="0"><entry>Salts (from raw materials)</entry><entry align="right">0.72% by weight</entry></row><row><entry>water</entry><entry align="right">11.88% by weight</entry></row><row rowsep="0"><entry>wherein Edenor® ST 1 = palmitic acid-stearic acid mixture (ex Cognis)</entry><entry align="right" /></row><row rowsep="0"><entry>Sokalan® CP 5 = maleic acid acrylic acid copolymer sodium salt (ex BASF)</entry><entry align="right" /></row><row><entry>Turpinal® 4 NL = hydroxyethane-1,1-diphosphonic acid tetra-sodium salt</entry><entry align="right" /></row></tbody></tgroup></table></tables>

0144This starting granules were each processed by sieving to obtain substantially uniform particulate materials (hereinafter referred to as "particles to be prepared") from which fines and oversize were separated. A total of 3 different particles to be submitted A, B, C were produced, namely:<ul><li>Submitted particles A: Fine particles less than 0.1 mm and oversize larger than 0.4 mm were separated here.</li><li>Submitted particles B: Fines less than 0.4 mm and oversize larger than 0.8 mm were separated here.</li><li>Submitted particles C: Fines smaller than 0.6 mm and oversize larger than 1.0 mm were separated here.</li></ul>

0145On the basis of these particles A, B, C, granules / agglomerates were generated independently of each other.

0146The separated fines and the oversize were each by milling to about one-twelfth of the particle diameter d₅₀ the particles to be submitted milled. The material thus ground in each case is referred to below as "particles to be added".

0147Subsequently, the particles to be submitted A, B, C were added with the addition of each associated milled particles and a granulation {25 wt .-% aqueous solution of Sokalan® CP 45 (= acrylic acid-maleic acid copolymer sodium salt ex BASF)} granulated / agglomerated in a mixer / agglomerator. The ground particles to be added and the granulation liquid were added over a period of 10 minutes. The specific power of the mixer / granulator was 1.4 kW / m³,

0148The amount of each granulating liquid added was 9 parts by weight with respect to an amount of 100 parts by weight of particles (sum of the particles to be charged and added).

0149After drying each of the resulting, built-up granules / agglomerates A, B, C in a fluidized bed, these were removed by sieving oversize and fines, namely:<ul><li>built-up granules / agglomerate A: here fines less than 0.1 mm and oversize greater than 0.6 mm were separated.</li><li>built-up granules / agglomerate B: fines smaller than 0.4 mm and oversize larger than 1.0 mm were separated here.</li><li>built-up granules / agglomerate C: fines less than 0.6 mm and oversize larger than 1.2 mm were separated here.</li></ul>

0150The resulting built-up granules / agglomerates each had a form factor of 0.87 for A, 0.85 for B, and 0.83 for C. The ratio d₅₀/ d₉₀ was from 0.75 to 0.82.

0151The bulk density was for<ul><li>built-up granules / agglomerate A at 510 g / L,</li><li>built-up granules / agglomerate B at 500 g / L,</li><li>built-up granules / agglomerate C at 530 g / L.</li></ul>

0152It has been found that the storage stability of the respective resulting, built-up granules A, B, C is significantly better compared to the starting granules. Even after storage over a period of 6 weeks, the resulting, built-up granules were still very readily pourable and flowable and did not stick or have no caking, were dust-free in the range according to the invention and were abrasion-resistant.