EP0486592B1 - Manufacture of compacted granules for washing agents - Google Patents

Abstract

PCT No. PCT/EP90/01247 Sec. 371 Date Apr. 9, 1992 Sec. 102(e) Date Apr. 9, 1992 PCT Filed Jul. 31, 1990 PCT Pub. No. WO91/02047 PCT Pub. Date Feb. 21, 1991.A process for the production of compacted granules for use in a detergent composition by providing a homogeneous, solid, free-flowing premix to which a plasticizer or lubricant is added, and extruding the mixture through a perforated die under a pressure of from about 25 bar to about 200 bar to form strands of the mixture. The perforated die has an opening width corresponding to a predetermined size of the granules. After emerging from the perforated die, the strands are cut to the predetermined size of the granules by means of a cutting unit. The process enables the preparation of detergent compositions containing increased contents of surfactant components.

Description

The invention relates to a process for the production of compacted granules, the granules obtained by using the process and storage-stable and free-flowing detergent concentrates containing them and having a long shelf life.

In the field of solid and free-flowing detergents and cleaning agents for household and commercial use, in particular in the field of powder detergents for textiles, there is currently a trend towards the production of products with increased bulk densities. Newer commercial products of this type have bulk weights in the range of about 700 g / l. This increase in the bulk weights is related to environmental protection requirements for a lower proportion of packaging. In the same direction, efforts are being made to be able to offer washing and cleaning agents in the form of more concentrated mixtures of ingredients. At first, the reduction of fillers in the concentrates seems to be an unnecessary salt load. However, problem solving in this way is not easily possible. The prerequisites for such a modification of the recipe are understandably that, on the one hand, the washing and cleaning performance required by the consumer compared to the products currently on the market is at least maintained, but on the other hand, the storage stability of pourable and free-flowing products is guaranteed. Like through one extensive state of the art is documented, the fulfillment of this requirement profile poses not inconsiderable technological problems.

For example, from German patent application 20 50 560 a process for the production of particulate detergents and cleaning agents ("pasta shape") with bulk weights between 500 and 900 g / l is known, in which a premix of a very specific composition is compressed "under pressure" and then extruded . No information was given regarding the amount of pressure to be applied. In order to prevent the strands from sticking together, they must be cooled by means of an air stream before they are then shredded into pieces of a certain length. The bulk density is inversely proportional to the length of the pieces.

German patent application 21 62 353 describes a process for the production of enzyme granules and detergent granules containing enzymes, which have a bulk density of between 300 and 1,000 g / l. A mechanically pre-machined mass is pressed into a long strand under pressure, which is approximately between 7 and 35 bar. In order to prevent the threads from sticking together to form larger aggregates when they emerge from the extrusion press, they must be "deplastified". This is done either by cooling or by evaporating the moisture, the solvent or the plasticizer (surface hardening). Only then can the thread strands be broken into smaller sections of the desired length.

According to the teaching of German patent application 22 24 300, granulated detergents with bulk weights between 300 and 800 g / l are obtained by extrusion and subsequent rounding of the spaghetti-like extrudates (Marumerizer). All components in the amount present in the end product are carefully mixed together before extrusion. It must be ensured that the components are selected and put together in such a way that they form a tough or plastic mass before extrusion surrender. Variations in the detergent formulations are therefore only possible to a limited extent.

From European patent application 328 880 a process for the production of detergent and cleaning agent extrudates with bulk densities of around 700 to 800 g / l is known, in which a powder premix is initially made into spaghetti-like strands at reduced pressures of 0.1 to 0.5 bar is extruded. Subsequently, the strand is broken into sections, whereupon these are pressed into very special, predetermined shapes. So that the individual end products have the same weight, the division of the spaghetti strand into the sections is monitored by weighing.

On the other hand, European patent application 351 937 describes a process for producing detergent and cleaning agent granules with bulk densities of at least 650 g / l, which in turn is dependent on the formulation. Agents containing 12 to 70% by weight of surfactants must contain at least 15% by weight of water-soluble, crystalline inorganic salts, and the ratio of crystalline salt: surfactant must not be less than 0.4. The agents are dry mixed and granulated in known mixers.

In contrast, European patent application 352 135 describes a process for the production of granular detergents with bulk densities above 650 g / l, which assumes that a solid alkaline material is placed in a mixer or granulator with a cutting device and liquid anionic surfactant in the acid form does not exceed at temperatures 55 ° C is added so slowly that the mixture remains solid throughout the neutralization process. The alkaline material must be used in excess. Only after complete neutralization can a liquid binder, for example water, liquid nonionic surfactant or an aqueous polycarboxylate solution, be added to the mixture. The granulation takes place in known mixers and granulators.

Ultimately, US Pat. No. 3,188,291 discloses the production of soap carriers and detergents in granular form with low bulk densities between approximately 16 and 480 g / l. The mass is extruded at pressures between about 82 and 165 bar. The mass was too viscous for prints beyond this and could no longer be extruded. At pressures below 82 bar, however, the bulk density was too high. This patent thus teaches that when using higher pressures during extrusion, low bulk densities are achieved, while when the pressure is reduced, the bulk density increases.

The object of the invention was to develop a process for the production of compacted granules which are used in detergents and cleaning agents and in particular in textile detergents and detergent concentrates. The granules should be stable in storage and pourable and free-flowing. Furthermore, the object was to provide a method which allows the shape of the individual, compacted granulate to be predetermined.

The invention accordingly relates to a first embodiment of the process for the production of compacted granules which are used in detergents and cleaning agents. A homogeneous, solid, free-flowing premix is extruded in the form of a strand with the addition of a plasticizer and / or lubricant via hole shapes with opening widths of the predetermined granule size at high pressures between 25 and 200 bar. The strand is cut to the predetermined pellet dimension immediately after exiting the hole shape by means of a cutting device. The application of the high working pressure causes the premix to be plasticized during the formation of the granulate and ensures the cutting ability of the freshly extruded strands.

The premix consists at least in part of solid, preferably finely divided, conventional ingredients of detergents and cleaning agents, which may contain liquid constituents are mixed. The solid ingredients can be tower powders obtained by spray drying, but also agglomerates, the mixture components selected in each case as pure substances which are mixed with one another in the finely divided state, and mixtures of these.

Subsequently, the liquid ingredients are optionally added and then the plasticizer and / or lubricant selected according to the invention is mixed in.

These aids are of polyfunctional importance in the context of the invention. In the production of granules, they enable the formation of the primary granulate by causing the premix to be converted into a mass which can be pressed under high pressure, and, if desired, subsequent shaping processing, which in particular consists of rounding off the primarily formed granule. Furthermore, they contribute to the stability of the granulate, they maintain its predetermined spatial shape, in particular when mixing with other components, if necessary, during filling, during transport and storage of the granules, and in particular prevent the formation of undesirable dust-like components. Conversely, in practical use of the granular washing and cleaning agent, they enable the granules to dissolve quickly, since they promote the dissolving, emulsifying or dispersing process. Finally, in particularly important embodiments of the invention, the auxiliaries discussed here can have an intrinsic effect in the washing and cleaning process, in particular in interaction with other mixture components.

The plasticizers and / or lubricants used as auxiliaries can be flowable, gel-like or pasty at room temperature without the need to use an additional liquid phase. Preferred plasticizers and / or lubricants are preparations based on surfactant components and / or based on water-soluble or water-emulsifiable or water-dispersible polymer compounds. Examples of a plasticizer and / or lubricant that can be used without the use of an additional liquid phase are numerous types of the nonionic surfactants commonly used in detergents and cleaning agents.

In a preferred embodiment, however, plasticizers and / or lubricants are used which have been produced using limited amounts of auxiliary liquids. Organic liquid phases which are water-soluble or water-miscible are preferably used here. For reasons of process reliability, it may be expedient to use comparatively high-boiling organic liquids, if appropriate in a mixture with water. Examples of these are higher-boiling, optionally polyfunctional alcohols, polyalkoxylates flowable at room temperature or moderately elevated temperatures and the like. In particular, however, aqueous preparations of the plasticizers and / or lubricants are preferred.

The surfactants and / or polymer compounds used as plasticizers and / or lubricants are advantageously introduced into the process in such a concentrated form that the nature of the plastic, slidably compressible mass can be adjusted even with small amounts of these auxiliaries. The pastes are preferably used in amounts not exceeding 12% by weight, in particular in amounts between 0.5 and 10% by weight, and particularly advantageously between 3 to 8% by weight, based on the mixture as a whole. At least 30% by weight, preferably at least 40% by weight pastes and gels are particularly suitable.

In a particularly preferred embodiment, surfactant preparations with a surfactant content of at least 50% by weight, in particular from 50 to 70% by weight, are used. The invention takes advantage of the fact that, in particular, these highly concentrated aqueous surfactant mixtures show a state that is in the form of a paste or gel Lubricant character can be called. In addition, in a further embodiment, in which the primarily formed granules are dried, the surfactant components thus introduced form cover and intermediate layers which act like binders and which are jointly responsible for the grain cohesion. Anionic surfactant salts, in particular sulfates and sulfonates, from the wide range of the compounds proposed here for detergents and cleaning agents, optionally in admixture with customary nonionic compounds, can be of particular importance here. As an example in the production of textile detergents, use a mixture of at least two powder components (tower powder / carrier bead) with or without the addition of sodium perborate (monohydrate and / or tetrahydrate) with the addition of 2 to 5% by weight of water and 4 to 8% by weight. % of a 55- to 65% C₉-C₁₃ alkylbenzenesulfonate paste (ABS paste) called. Equally preferred is the use of 3 to 8% by weight of a 50 to 60% by weight aqueous paste of an alkyl polyglycoside (APG) of the general formula RO (G) _x , in which R is a primary straight-chain or in 2 Position methyl-branched aliphatic radical with 8 to 22, preferably 8 to 18 carbon atoms, G is a symbol which represents a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10. Other preferred plasticizers and / or lubricants based on surfactants are mixtures of ABS and APG pastes, as well as mixtures of ABS pastes and ethoxylated C₈-C₁₈ fatty alcohols, mixtures of ethoxylated fatty alcohols and water and mixtures of APG: ethoxylated fatty alcohol: water in a ratio of 0.5-1: 1-1.5: 1, in which case the APG content is calculated as an active substance and not as a paste.

Just like the use of surfactants, the use of polymer compounds in numerous washing and cleaning agents is common today, since the polymer compounds act, for example, as builders with the ability to bind water hardness. Examples of these are polymers containing carboxyl groups, which are also in the salt form, for. B. present as an alkali salt can, like the sodium or potassium salts of homopolymeric or copolymeric polycarboxylates, for example polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those from 50% to 10% maleic acid. The molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on the free acid. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, acrylamide or methacrylamide, ethylene, propylene and styrene, in which the proportion of acid is at least 50%. But polymer compounds are also used to improve the dirt-carrying capacity of an aqueous washing liquor. Examples include carboxymethyl cellulose (CMC) and / or methyl cellulose (MC).

In particular, highly concentrated aqueous preparation forms of these polymer compounds, like the surfactant preparations, are distinguished by a pronounced lubricating character which gives the decisive processing aid in the process according to the invention. At the same time, when the granules are formed according to the invention, these polymer components dry out to polymer films which, on the one hand, promote the cohesion of the granules and, on the other hand, easily change back to the state of solution or emulsification or dispersion when added in aqueous media in particular. It is particularly preferred to use 3 to 8% by weight of a 30 to 50% by weight solution of a polymer, in particular a copolymer of acrylic acid and maleic acid, in water as a plasticizer and / or lubricant. Mixtures of these polymer solutions and the surfactant, in particular anionic surfactant, plasticizers and / or lubricants are also advantageous.

Practice knows numerous other natural or synthetic polymer types, which can also be used here according to the invention as plasticizers and / or lubricants. Just as Examples include gelatin, starch and starch derivatives and polyvinyl alcohol.

For reasons of sufficient moisture penetration or to avoid dusting the premix, slightly larger amounts of liquid may be required. In general, it is advisable to dilute these additional portions as such to the premix and not, for example, the surfactant pastes and / or polymer solutions used as lubricants. Such quantities of liquid can be introduced before, during or after the incorporation of the plasticizer and / or lubricant, the addition prior to the incorporation of the plasticizer and / or lubricant being preferred. However, only such limited amounts of liquid phase (s) are used that, when mixed simply, a free-flowing, powdery structure of the premix is retained even after the addition of the plasticizer and / or lubricant. The content of free water not bound as crystal water or in comparable form in the respective substance mixture in this processing stage is preferably up to 12% by weight, preferably up to 10% by weight and in particular in the range from about 4 to 8% by weight. %. Included in this amount is the amount of water that is entered via the lubricating plasticizer.

If desired, further solids can also be added to the premix after the addition of the plasticizer and / or lubricant. The total mass is briefly mixed in, resulting in a solid, free-flowing premix which is suitable for feeding a homogenization system.

Kneaders of any configuration, for example twin-screw kneaders, can preferably be selected as the homogenizing device. As a rule, it may be expedient in this homogenization step to maintain reliable temperature control of the mixture to be processed, in individual cases the composition of the mixture for the respectively optimal temperature range can be a determining factor. The intensive mixing process can in itself lead to the desired temperature increase. Moderately elevated temperatures of, for example, a maximum of about 60 to 70 ° C. are generally not exceeded. When processing temperature-sensitive substances - for example perborate compounds - compliance with lower temperatures (for example about 40 to 45 ° C.) can be advantageous.

Under the shearing action of the kneading device and the high pressure of 25 to 200 bar, preferably 30 to 200 bar, which is built up therein, the premix is mixed and kneaded so intensively that the previously solid and dry mixture is worked up to the compacted, plasticized and form-compressible mass becomes. At the same time, the cutting ability of the homogenized mixture is ensured.

In a preferred embodiment, the free-flowing premix is preferably fed continuously to a 2-screw kneader (extruder), the housing and the extruder granulation head of which are heated to the predetermined extrusion temperature, for example heated to 40 to 60 ° C. Under the shear action of the extruder screws, the premix is compressed, plasticized at pressures from 50 to 180 bar, in particular at pressures from 80 to 180 bar, extruded in the form of fine strands through the perforated die plate in the extruder head, and finally, preferably by means of a rotating knives, preferably to spherical bis cylindrical granules crushed. The hole diameter in the perforated nozzle plate and the strand cut length are matched to the selected granule size. In this embodiment, the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use. Absolute particle sizes can be, for example, in the range from a few tenths of a millimeter to a few centimeters, for example in the range from about 0.3 mm up to 1 to 2 cm. In general, however, particle diameters of up to at most 0.8 cm will be preferred. Important embodiments of the invention provide for the production of the uniform granule grain with diameters in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm.

In an important embodiment, the length / diameter ratio of the chipped primary granules is in the range from about 1: 1 to about 3: 1.

The steps of homogenization, compression and compression of the premix used in each case require only very short periods of time. Usually, periods in the range of minutes, preferably less than 5 minutes and in particular not more than 3 minutes, are required to get from the premix to the compressed plasticized primary granulate.

In general, it is not necessary, but possibly advantageous depending on the recipe, to cool the mass emerging from the perforated plate in an extruded manner at least on the surface by shock cooling, in particular by blowing cold air into the pelletizing knife area. At the same time, there is a partial removal of surface water from the primary granulate formed. If necessary, the sticking of the still plasticized granules can be reliably prevented in this way.

The granulation in this first homogenizing process step is, however, not restricted to the processing of the plasticized premix via extruder screws and perforated plates of the type described, which are arranged in the extruder head. Also by similar, conventional granulating devices, for example pellet presses, 1- and 2-shaft extruders, planetary roller extruders, plasticized, compressed and homogenized mixtures of substances can be granulated into granular material according to the invention.

In a further preferred embodiment, the still plastic, moist primary granulate is first fed to a further shaping processing step. Here, the edges present on the raw granulate are rounded off, so that ultimately spherical or at least approximately spherical granules can be obtained. By using small amounts of dry powder in this stage of the final shaping processing, undesired sticking of the granules to one another before their final drying can be excluded with certainty. Dry powders suitable for detergents and cleaning agents can be pulverulent materials or corresponding inert materials. A particularly useful material in this connection is, for example, zeolite powder such as zeolite NaA powder.

This final shaping of the still moist granulate from the extruder granulation can be carried out batchwise or continuously in standard rounding machines. Corresponding rounding devices with a rotating base plate are suitable, for example, the desired degree of rounding being able to be set by varying the granulate residence time in the rounding device and / or the speed of rotation of the device plate.

Subsequently, the finally shaped granulate is preferably fed to a drying step, for example a fluidized bed dryer, in which, at moderately raised supply air temperatures, in particular up to a maximum of 80 ° C., correspondingly moderate final product temperatures of, for example, between 55 to 60 ° C. are set, but then also not be crossed, be exceeded, be passed. After sufficient drying, the product is cooled with cold air, for example. Here the content of free water in the granulate can be reduced. Preferred residual amounts of unbound water are up to about 1% by weight, preferably in the range from about 0.1 to 0.5% by weight. The resulting very low-dust Product can be classified to remove small coarse particles formed, for example, sieved. The grain proportion to be set according to the invention is generally above 90%, preferably above 95%, of the granulated material. Optionally, it is also possible to carry out this drying step directly after the pressing of the primary granulate and thus before a final shaping, if desired, in a rounding device.

At least in part, however, the "internal drying" of the granules is also possible: by using moisture-binding constituents in the premix, the plasticizing effect of the liquid components present can be exploited in the short processing time; then, by binding at least partial portions of these liquid portions through the mixed-in components, the granules are dried "from the inside out", so that the external drying can be shortened or omitted entirely. Components which are able to bind water in the form of water of crystallization are, for example, sodium sulfate and / or sodium carbonate in anhydrous or low-water form or else a zeolite partially freed from water of crystallization.

In a further preferred embodiment, the primarily formed and still plastic granules can be loaded with further active ingredients before, during and / or after any rounding that may have been carried out. Preferably, however, sensitive, in particular temperature-sensitive, formulation constituents can also be added to the dried granulate, e.g. B. sprayed and / or mixed as a separately formed grain to form a multigrain mixture. The invention, with its granules produced in a novel manner, covers both the area of ready-to-use multi-substance mixtures in the form of uniform granules and also partial products which, in order to complete the formulation, still mix with other constituents of the detergent and cleaning agent concerned need. Advantageously, more than 60% by weight and in particular more than 70% by weight of the total mixture of substances are granules obtained by the process according to the invention with a highly compressed and solid grain structure.

In a particularly important embodiment of the invention, granule systems are used which represent a combination of granules of different compositions. In this way, the storage-stable combination of potentially reactive or at least only partially compatible components is achieved. An example of this are common textile detergents, which, however, now use at least two types of granules in a mixture with one another in the new preparation form. In a first, for example spherical granulate type, the bleaching agent component, in particular perborate and sodium carbonate containing water of crystallization, is pelletized with the use of a proportion of the plasticizers and / or lubricants, in a separate second granulate the zeolite used as detergent builder substance, in particular zeolite NaA, is pressed together with the rest of the detergent components . Interactions between perborate and zeolite which have a substantial influence on the storage stability of the mixed product - as are to be taken into account in powdery formulations - are excluded in this way. This possibility of using granulate systems made up of granules of different compositions can be used in almost any combination.

In a further embodiment, the granules according to the invention can be recycled, i.e. they can be used in the first process step in combination with other substances to produce the plasticized premix.

The material densities in the grain and thus also the bulk density of the granules are largely determined by the working pressures used when the homogenized material is pressed through the perforated plates. By building up a sufficiently compacted basic structure in the mass to be pressed and use correspondingly high pressures z. B. with conventional textile detergent formulations bulk densities well above 700 g / l, preferably above 750 g / l and in particular in the range from about 800 to approximately 1,000 g / l. Bulk weights in the range from 850 to 980 g / l can be set on the basis of commercially available textile detergent formulations, with good free-flowing properties and a preferably homogeneous, spherical grain structure. In similar approaches, free-flowing granules in the dry state with uniform bulk weights of 950 to 980 g / l have been realized with an average particle size of the spherical granules in the range of approximately 1 mm.

The method according to the invention is characterized by a very low proportion of returned goods. The proportion of return material after sieving the granulate through a 1.6 mm sieve was in the range of at most 3%. Analogous to conventional detergent preparation, sensitive formulation components - for example activators for bleaches, enzymes, defoamers, in particular silicone defoamers, perfume and the like - can be added to the granules. Even then, detergent products with bulk weights in the range of about 900 g / l are still obtained.

The textile detergents which are customary on the market today in the form of free-flowing powders and / or granules generally contain a combination of anionic-surfactant and non-surfactant active detergent components. In general, the anionic surfactant components make up the larger proportion and the nonionic surfactants make up the smaller proportion of the surfactant mixture. The total surfactant content for powdery, free-flowing household detergents is about 12 to a maximum of 15% by weight, based on the total detergent. This also applies to the detergents with increased bulk density that are currently on the market. In contrast, the invention allows the use of the described method for the production of detergent concentrates, in particular corresponding concentrates, which are essentially non-sticky, free-flowing and free-flowing, storage-stable for textile detergents with a significantly increased content of detergent surfactants. Textile detergent concentrates with surfactant contents of up to about 35% by weight and preferably in the range from about 15 to 25% by weight can be produced without the fear of sticking and / or product softening, as would be the case with such an increase in the powdery mixtures available on the market of the surfactant content occur. By combining the measures of compression of the substance mixtures to high bulk densities and a simultaneous increase in the detergent active ingredients, especially the surfactants in their proportion in the detergent mixture, the goal of space-saving and low-packaging detergent preparations is optimally achieved without leaving the field of free-flowing, stable storage detergent preparations and fulfilling all other requirements to have to.

The preparation of detergents and cleaning agents in the process type of granulation according to the invention to a predeterminable particle size brings a number of advantages:

It has been shown that in the process according to the invention, the bleach, in particular sodium perborate in the form of the monohydrate and / or the tetrahydrate, can already be processed in the raw material to be plasticized and then pressed, without substantial losses of perborate occurring. Each granulate thus contains the predetermined percentage of perborate. Spray-dried powders with variable admixtures can be used. On the other hand, neither spray-dried powders nor pre-formed powders with a bead structure are required to produce the raw materials to be pressed. The use or addition of heavy powder of the individual raw materials is not necessary. The processing of the nonionic surfactants usually used in detergents and cleaning agents becomes problem-free, and the pluming problems that usually occur in spray drying are eliminated. The nonionic surfactants are easily added by incorporation into the mixture before extrusion, they can even be used here highly concentrated aqueous gel or paste provide valuable process help in the manner described.

The production of detergents with an increased proportion of arbitrarily selected surfactants or surfactant mixtures is possible, which was not previously possible using the spray drying process. The possible incorporation of defoamers in liquid form saves a process for the separate production of defoamer solid carrier concentrates. This eliminates the need to add defoamer granules to the detergent preparation. It has proven to be particularly advantageous to mix the defoamer directly into the plasticizer and / or lubricant.

In a particular embodiment, the invention relates to universal detergents for textiles which are present in the new form of the free-flowing granules with bulk densities above 750 g / l, in particular above 800 g / l, for example in the range from 850 to 950 g / l and in a particularly important one Embodiment are characterized by a uniform particle shape and size. The preferred particle shape is spherical. Preferred particle sizes here are in the range from about 0.5 to 5 mm ball diameter, in particular in the range from about 0.8 to 2 mm. The type and quantity of the recipe components can correspond to that of today's textile detergents containing builders. The following is general information on the composition of suitable active substance mixtures, the components of textile detergents which are common today, in particular, being summarized here.

Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are alkylbenzenesulfonates (C₉-C₁₅-alkyl), olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C₁₂-C₁₈ monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent or acid hydrolysis of the Receives sulfonation products. Also suitable are dialcan sulfonates which are obtainable from C₁₂-C₁₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and in particular the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Suitable sulfate type surfactants are the sulfuric acid monoesters of primary alcohols of natural and synthetic origin, i.e. H. from fatty alcohols, e.g. B. coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C₁₀-C₂₀ oxo alcohols, and those secondary alcohols of this chain length. The sulfuric acid monoesters of alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl branched C₉-C₁₁ alcohols with an average of 3.5 moles of ethylene oxide, are suitable. Sulfated fatty acid monoglycerides are also suitable.

Furthermore, for. B. soaps from natural or synthetic, preferably saturated fatty acids. Are particularly suitable from natural fatty acids such. B. coconut, palm kernel or tallow fatty acid derived soap mixtures. Preferred are those which are composed of 50 to 100% of saturated C₁₂-C₁₈ fatty acid soaps and 0 to 50% of oleic acid soap.

The anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The content of anionic surfactants or anionic surfactant mixtures in detergents according to the invention is preferably 5 to 40, in particular 8 to 30,% by weight.

Addition products of 1 to 40, preferably 2 to 20 moles of ethylene oxide with 1 mole of an aliphatic compound having essentially 10 to 20 carbon atoms from the are nonionic surfactants Group of alcohols, carboxylic acids, fatty amines, carboxamides or alkanesulfonamides can be used. The addition products of 8 to 20 moles of ethylene oxide with primary alcohols, such as, for. B. on coconut or tallow fatty alcohols, on oleyl alcohol, on oxo alcohols, or on secondary alcohols with 8 to 18, preferably 12 to 18 carbon atoms.

In addition to the water-soluble nonionics, non-fully or not completely water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble, nonionic or anionic surfactants.

In addition, alkyl glycosides of the general formula RO- (G) _x can also be used as nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18 C atoms, methyl-branched in the 2-position, G is a symbol is a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10.

Weakly acidic, neutral or alkaline-reacting soluble and / or insoluble components which are able to precipitate or bind complex ions are suitable as organic and inorganic builders. Suitable and, in particular, ecologically harmless builder substances, such as finely crystalline, synthetic water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in DE 24 12 837) find a preferred use. Their average particle size is usually in the range from 1 to 10 »m (measurement method: Coulter Counter, volume distribution). Their content is generally 0 to 40, preferably 10 to 30% by weight, based on the anhydrous substance. Zeolite NaA is produced in the form of a water-containing slurry (masterbatch), which is subjected to drying, in particular spray drying, using the processes customary today for the production of textile detergents.

According to the invention, it will be possible to add the zeolite or at least zeolite fractions to the premix in the form of the undried masterbatch or a material which has only partially dried and is therefore only limited in its water content.

Other builder components which can be used in particular together with the zeolites are (co) polymeric polycarboxylates, such as polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those from 50% to 10% maleic acid. The molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, in which the proportion of acid is at least 50%. Also useful are polyacetal carboxylic acids, as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, and polymeric acids which are obtained by polymerizing acrolein and subsequent disproportionation using alkalis and are composed of acrylic acid units and vinyl alcohol units or acrolein units.

Usable organic builders are, for example, the polycarboxylic acid preferably used in the form of their sodium salts, such as citric acid and nitrilotriacetate (NTA), provided that such use is not objectionable for ecological reasons.

In cases where a phosphate content is tolerated, phosphates can also be used, in particular pentasodium triphosphate, optionally also pyrophosphates and orthophosphates, which act primarily as precipitants for lime salts. The phosphate content, based on pentasodium triphosphate, is below 30% by weight. However, agents without a phosphate content are preferably used.

Suitable inorganic, non-complexing salts are the bicarbonates, carbonates, borates or silicates of the alkalis, which are also referred to as "washing alkalis"; Of the alkali silicates, especially the sodium silicates with a Na₂O: SiO₂ ratio of 1: 1 to 1: 3.5 can be used.

The other detergent ingredients include graying inhibitors (dirt carriers), foam inhibitors, bleaching agents and bleach activators, optical brighteners, enzymes, fabric softening agents, dyes and fragrances as well as neutral salts.

Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying. For this purpose, water-soluble colloids of mostly organic nature are suitable, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. Carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof are preferably used.

The foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a reduction can also be achieved by adding non-surfactant-like organic substances. A reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, e.g. B. of sulfates and / or sulfonates with nonionics and / or with soaps. Soap rises the foam-suppressing effect with the degree of saturation and the C number of the fatty acid residue. Soaps of natural and synthetic origin are suitable as foam-inhibiting soaps, which have a high proportion of C₁ eignen-C₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Bisacylamides derived from C₁₂-C₂₀ alkylamines and C₂-C₆ dicarboxylic acids are also useful. Mixtures of different foam inhibitors are also advantageously used, e.g. B. from silicone and paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance or are admixed with the plasticizer and / or lubricant.

Of the compounds used as bleaching agents which supply H₂O₂ in water, sodium perborate tetrahydrate (NaBO₂. H₂O₂. 3 H₂O) and sodium perborate monohydrate (NaBO₂. H₂O₂) are of particular importance. Other usable bleaching agents are, for example, peroxy carbonate (Na₂CO₃. 1.5 H₂O₂), peroxypyrophosphates, citrate perhydrates and H₂O₂-delivering peracidic salts or peracids, such as perbenzoates, peroxaphthalates, diperazelaic acid or diperdodecanedioic acid.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples include N-acyl or O-acyl compounds which form organic peracids with H₂O₂, preferably N, N'-tetraacylated diamines, such as N, N, N ', N'-tetraacetylethylenediamine, furthermore carboxylic acid anhydrides and esters of polyols, such as Glucose pentaacetate.

The detergents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.

Are suitable for. B. salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or Compounds of the same structure which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group. Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present; e.g. B. the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

Enzymes from the class of proteases, lipases and amylases or their mixtures are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.

The salts of polyphosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and aminotrimethylenephosphonic acid (ATP) or diethylenetriamine-pentamethylenephosphonic acid (DTPMP or DETPMP) come into consideration as stabilizers, in particular for per-compounds and enzymes.

Examples Examples 1 to 5

To produce textile detergents in the form of the free-flowing granules according to the invention, two mixture components previously obtained separately were mixed and worked up in the mixing ratios shown in Table 1.

The first mixture component was a spray-dried powder (tower powder) based on the following main components:
Surfactant mixture I 17.5% by weight
calcined soda 35% by weight
Zeolite NaA, anhydrous substance 22% by weight
Acrylic acid copolymer (Sokalan CP5 ^(R) ) 10% by weight
Water, bound 8.2% by weight
Water, free 1.8% by weight
the rest of the usual detergent additives

Surfactant mixture I consisted of sodium dodecylbenzenesulfonate (ABS) and tallow fatty alcohol reacted with 5 ethylene oxide groups (EO) in a ratio of 11.5: 1.

The second mixture component was a carrier bead containing non-surfactant, which was composed of the following main components:
C₁₂-C₁₈ fatty alcohol with 5 EO 22% by weight
Zeolite NaA, anhydrous substance 55% by weight
Acrylic acid copolymer (Sokalan CP5 ^(R) ) 3% by weight
Water, bound 14.5% by weight
Water, free 1.3% by weight
the rest sodium sulfate and other usual auxiliary substances

In the procedure described in detail below, the two constituents of the mixture were comminuted and mixed, then the amount of water required and that in Table 1 were in each case specified amount of 55% aqueous paste of ABS pumped in. Finally, in Examples 1 to 3 sodium perborate monohydrate was added and mixed briefly.

The free-flowing material thus obtained was fed to the homogenizing compression and plasticization. The mass formed was extruded in the form of a strand, chopped into cylindrical granulate particles, rounded off and dried.

The following details apply:

Premix production

The tower powder (TP) and the carrier bead (TB) were placed in a batch mixer (20 liters) equipped with a cutter head shredder and 0.5 min. mixed. With the mixer and cutter head chopper running, the required amount of water and then the entire ABS paste was pumped in via a slot nozzle (2.5 min.). Finally, if necessary, the entire amount of Na perborate monohydrate was added and 1 min. mixed. The resulting premix was free-flowing and could be used to feed the continuous kneader-extruder system.

Kneader extruder / granulation

The premix obtained was fed continuously to a 2-screw kneader (extruder), the housing of which, including the extruder pelletizing head, was heated to about 45 to 50 ° C. Under the shear of the extruder screws, the premix was plasticized and then extruded through the extruder head perforated die plate into fine strands (1.0 and 1.2 mm in diameter), which were chopped into cylindrical granules (length / diameter Ratio about 1, hot tee).

Rounding

The warm and moist granules obtained from the extruder granulation were rounded off batchwise or continuously in a commercially available rounding machine of the Marumerizer type with the addition of zeolite NaA powder as a powdering agent.

The desired degree of rounding was set by varying the granulate dwell time in the rounding device and the speed of rotation of the device disc.

Granulate drying

The moist granules from the rounding device were dried in a discontinuously operating fluidized bed dryer at a supply air temperature of 75 to 80 ° C. to a product temperature of 55 to 60 ° C. for 15 minutes. After the product had been cooled to 30 ° C. with cold air, a free-flowing product was obtained.

Granulate screening

The very low-dust product was sieved through a sieve with a mesh size of 1.6 mm. The proportion of return material above 1.6 mm was in the range of maximum 3% in all cases. The sieved gut grain was used as the basis for the blending of detergent end products.

Example 6

According to the procedure from Examples 1 to 5, a tower powder (ABS 9%, calcined soda 25%, zeolite NaA (anhydrous substance) 38%, acrylic acid copolymer 8%, water 15%, the rest of the usual detergent components) was used in an amount of 88 , 5 wt .-% with 2.5 wt .-% water, 5 wt .-% nonionic surfactant based on C₁₂-C₁₈ fatty alcohol · 5 EO and 4 wt .-% 55% ABS Na paste and worked up.

Free-flowing granules with a bulk density of 950 g / l were obtained.

Example 7

When processing a mixture of active ingredients from tower powder and carrier bead analogously to Examples 1 to 5 and using a 40% solution of the acrylic acid copolymer (commercial product Sokalan CP 5 ^(R) ) in an amount of 4.5% by weight as plasticizer and with the additional addition of water of 6% by weight, free-flowing and nevertheless readily water-soluble granules in spherical form were obtained.

Example 8

The following mixture components were used in the sense of the teaching of Examples 1 to 5:

Free-flowing tower powder based on the following main components: 22% by weight of surfactant mixture I, 2.5% by weight of sodium soap based on sebum, 15% by weight of calcined soda, 7% by weight of water glass, 26.5% by weight % Zeolite NaA (anhydrous substance), 7.5% by weight acrylic copolymer, 12% by weight water, the rest of the usual co-formulants.

Carrier bead based on the following main components: 22% by weight C₁₂-C₁₈ fatty alcohol · 5 EO, tallow-based Na soap 2% by weight, Zeolite NaA (anhydrous substance) 55% by weight, acrylic acid copolymer 3% by weight, water 15% by weight.

The comminuted and mixed material according to the working instructions from Examples 1 to 5 was mixed with approximately 11% by weight (based on the total mixture) of 60% ABS paste and homogenized. The resulting material was plasticized by kneading and pressed to give shape. Free-flowing granules in the form of spheres with bulk densities in the range from 900 to 950 g / l were obtained which were stable in storage (storage time: 1 year).

Example 9

A phosphate-free and pH-neutral tower powder with the following composition
Surfactant mixture I 16% by weight
Soap 2.8% by weight
Zeolite 16.0% by weight
Sokalan CP 5 ^(R) 3.2% by weight
Na₂SO₄ 58% by weight
The rest of the usual small components
was intensively mixed with 5% by weight ABS paste (40%) and then first plasticized in an extruder and then extruded through a perforated disk with 1.2 mm nozzle bores. The temperature was controlled by tempering the jacket in such a way that product temperatures of 45 to 50 ° C. were established. The compressed mass strands emerging from the nozzle plate were cut off by rotating knives and cylindrical particles with a length / diameter ratio of approx. 1 were obtained. The still warm particles were rounded in a Marumerizer with the addition of 2% by weight of zeolite NaA powder and dried in a fluidized bed dryer as described above. After drying, products with bulk densities between 850 - 920 g / l were obtained - the respective bulk density was dependent on the extent of the rounding.

The preparation with 3% by weight of small detergent components which are customary in practice (perfume, enzyme, if appropriate sprinkles of paint) did not lead to any significant change in the bulk densities.

Example 10

A mixture of 12.5% by weight ABS and 7.5% by weight C₁₂-C₁₈ fatty alcohol · 5 EO, 25% by weight soda, 40% by weight zeolite (anhydrous substance) and 12% by weight % bound water and several small components were prepared in a mixer and then sprayed with 5% by weight of a 55% ABS paste, based on the sum of the mixture and ABS paste.

The plasticization with compression and compression of the compacted mass was carried out in a pellet press. The procedure was as follows:

The premix prepared as described above was introduced into the annular space of the pellet press via a screw conveyor. The press consisted of a rotating wooden roller into which radial holes were made, distributed over the entire circumference. A press roll was arranged eccentrically in this ring die. In this experiment, a ring die with a diameter of approx. 80 mm and approx. 500 holes was used. The bore diameter was 1.5 mm.

A continuous feeding of the product was achieved through the screw dosing. The product was compacted in the gap between the roller and the die. When the pressure defined by the extrudability of the mass was reached, the product was pressed through the radial channels of the die and the entire strand was pushed out by the appropriate length. The strand was cut to a length of 1.5 mm by a knife attached to the outside of the die. The cylindrical granules produced in this way were rounded off in a further process step.

This was done by rolling off in a rounding machine. Depending on the dwell time (between 15 and 120 seconds) in this rounding machine, either rounded corners or spherical granules were obtained.

In a further test, the strength of the granules could be improved by adding 3% by weight of zeolite NaA in the rounding step.

Subsequent drying in a fluidized bed dryer removed the water required for the granulation.

Abrasion-resistant and very free-flowing granules with a bulk density of the dry products of 950 g / l were obtained.

Claims (11)

1. A process for the production of compacted granules for use in detergents, in which a homogeneous premix, to which a plasticizer and/or lubricant is added, is extruded through perforated dies under high pressures of 25 to 200 bar to form strands, the perforated dies having opening widths corresponding to the predetermined size of the granules, characterized in that a homogeneous, solid, free-flowing premix is extruded into a strand under high pressures of 25 to 200 bar and the strand, after emerging from the perforated die, is cut to the predetermined size of the granules by means of a cutting unit.
2. A process as claimed in claim 1, characterized in that the pressure is between 30 and 200 bar and, more particularly, between 50 and 180 bar while the uniform granules have a diameter of 0.5 to 5 mm and, more particularly, 0.8 to 3 mm.
3. A process as claimed in claim 1 or 2, characterized in that flowable, gel-form or paste-like preparations based on anionic or nonionic surfactants, water-soluble or water-emulsifiable or dispersible polymer compounds or mixtures thereof are used as the plasticizer and/or lubricant, highly concentrated aqueous pastes or solutions being preferred.
4. A process as claimed in claim 3, characterized in that aqueous surfactant pastes are used in quantities of 0.5 to 10% by weight as the plasticizer and/or lubricant.
5. A process as claimed in any of claims 1 to 4, characterized in that the premix obtained with addition of the plasticizer and/or lubricant contains up to 10% by weight and, more particularly, between 4 and 8% by weight free water, i.e. water which is not bound as water of crystallization or in comparable form.
6. A process as claimed in any of claims 1 to 5, characterized in that standard granulators, for example pelletizing presses, single-screw and twin-screw extruders, planetary roll extruders, are suitable for use as the homogenizing unit, a continuous twin-screw extruder of which the housing and granulation head are heated to the predetermined extrusion temperature being preferred.
7. A process as claimed in claim 6, characterized in that, under the shearing effect of the extruder screws, the free-flowing premix is compacted at 50 to 180 bar, plasticized, extruded in the form of fine strands through the multiple-bore die, of which the bore diameter is adapted to the size selected for the granules, in the extruder head and the extrudate is size-reduced by means of a rotating chopping blade to spherical or cylindrical granules with a length-to-diameter ratio of about 1:1 to 3:1 which, while still moist and plastic, are rounded in a commercially available rounding unit using small quantities of drying powder, preferably zeolite NaA.
8. A process as claimed in any of claims 1 to 7, characterized in that, through the use of moisture-binding constituents, preferably sodium sulfate, sodium carbonate and/or zeolite in anhydrous or substantially anhydrous form, in the premix, the granules are at least partly internally dried by at least partial binding of the liquid components present, so that external drying, which is preferably carried out in a fluidized-bed dryer at moderately elevated air entry temperatures of up to at most 80°C and correspondingly moderate final product temperatures of 55 to 60°C, can be shortened or even eliminated altogether.
9. A process as claimed in any of claims 1 to 8, characterized in that the granules initially formed are treated while still plastic with other active substances before, during and/or after rounding, if any, temperature-sensitive constituents of the formulation in particular being added to or sprayed onto the dried granules and/or being mixed therewith in the form of separately prepared granules to form a multiple-granule mixture.
10. Granules obtained by the process claimed in any of claims 1 to 9, characterized in that they have an apparent density above 700 g/l, preferably in the range from 750 to 1,000 g/l and, more preferably, in the range from 850 to 980 g/l and are present as a ready-to-use multi-component mixture in the form of uniform granules or as a combination of granules differing in composition or as a partial product which has to be mixed with other standard detergent constituents to complete the formulation.
11. Detergents containing the granules claimed in claim 10, characterized in that they have an increased content of surfactants of up to 35% by weight and preferably between 15 and 25% by weight.