WO1997021798A1

WO1997021798A1 - Method of producing granular washing or cleaning agents or components therefor

Info

Publication number: WO1997021798A1
Application number: PCT/EP1996/005409
Authority: WO
Inventors: Manfred Greger; Karl-Martin Faeser
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1995-12-13
Filing date: 1996-12-04
Publication date: 1997-06-19
Also published as: DE19546465A1; EP0871697A1; JP2000501759A

Abstract

The aim is to specify a process for compressing solid pourable initial mixtures which allows operation under less harsh conditions than were hitherto customary. This was achieved by connecting a gear pump upstream of the perforated moulds through which the granules are compressed.

Description

"Process for the production of granular washing or cleaning agents or components therefor"

The invention relates to a process for the production of almost spherical to cylindrical detergent or cleaning agent granules or components therefor, in which a gear pump is used, granules and detergents and cleaning agents thus obtainable.

From international patent applications WO-A-91/02047 and WO-A-91/13678 and from European patent 486 592 a process for the production of compacted granules of ingredients of detergents or cleaning agents is known. The granules are obtained from premixes of at least partially solid ingredients with the addition of water-soluble, water-emulsifiable or water-dispersible plasticizers and / or lubricants, which are processed to a homogeneous mass and at high pressures between 25 and 200 bar via perforated shapes Opening widths of the predetermined granule dimension are pressed in a rope shape. Conventional granulating devices, for example pellet presses, extruders with one or two shafts, planetary roller extruders and other apparatus, can be used as the homogenizing device. A continuously operating twin-screw extruder is preferred. The premix, plasticized in the extruder, emerges in the form of fine strands through a perforated die plate. The extrudate is then comminuted to almost spherical to cylindrical granules by means of a rotating knock-off knife, and these still plastic primary granules are preferably rounded off in a conventional rounding device, possibly with the use of small amounts of dry powder. To complete the formulation, further active ingredients, in particular temperature-sensitive formulation constituents, can be added to the optionally dried-on granules, sprayed on and / or mixed in as a separately formed grain to form a multigrain mixture.

In the technical embodiment, the extrusion is carried out through a circular plate provided with nozzle bores. The hole nozzles can be arranged vertically or horizontally. The fine strands of about 0.5 to 5 mm, typically from 0.8 mm to 2.0 mm in diameter emerging through the hole shapes are converted in a hot cut from a single- or multi-bladed rotating cutter head into almost spherical to cylindrical granules crushed. The knife edges of the knock-off device either lie on the nozzle plate with a low contact pressure or form a gap with the plate which is very small compared to the diameter of the perforated nozzles.

The homogeneous and solid, free-flowing premix must be of such a consistency that it is plastically softened and extrudable under the pressure or under the entry of specific work, but at the time of the exit from the hole shape, at which no shear forces on the system act, the viscosity of the system suddenly decreases so that the extruded strand can be cut and cut to predetermined dimensions.

A disadvantage of this method is that energy losses occur in the form of temperature increases under the high working pressure, so that the extruder housing, including the extruder pelletizing head, normally has to be cooled in order to prevent the viscosity of the premix already during the extrusion sinks so much that an actual extrusion is no longer possible. Excessive temperature increases also lead to the fact that temperature-sensitive ingredients, for example bleaching agents such as perborate or percarbonate, could not be used without cooling the housing.

The object was therefore to modify the process described above in such a way that the premix can be pressed under more gentle conditions, for example also at lower pressures or without cooling, without the cutting ability of the extruded strands being lost after it emerges from the hole shape, or these high pressures can only be built up for a short time. This object is achieved according to the invention by a process for producing granular detergents or cleaning agents or components therefor, a plastifiable and solid, free-flowing premix being pressed by hole molds and a gear pump being connected upstream of these hole molds.

Gear pumps of this type are commercially available. For example, they can be purchased from Witte GmbH, Federal Republic of Germany. The gear pumps used in the production process of granular detergents or cleaning agents according to the invention are generically a rotating displacement pump Depending on the viscosity of the material to be carried through, a throughput of 0.1 to 300 m ³ per hour, but preferably 1 to 20 m ³ per hour, can usually be achieved. The temperature in the gear pump can also be varied over wide ranges, for example from 0 ° C. to about 300 ° C, but it is preferably operated at usual operating temperatures of 30 to 70 ° C. The pre-mix to be compressed, plasticized, solid and free-flowing can either be drawn in directly or, for example, pre-plastified in an extruder upstream of the gear pump

Since the premix does not remain in the gear pump and does not experience any mechanical energy input, but a plasticized premix is still required for the pressing, the plastification of the premix (material supply) must take place before the supply to the gear wheels. This plasticizing can be carried out using customary and known methods, for example in mixers, extruders, stuffing screws or devices made from mixers and kneaders

According to a preferred embodiment of the present method, a pressure of 6 to 200 bar, preferably 30 to 120 bar, builds up within the gearwheels. According to the invention, the residence time of the premix to be pressed is only 1/10 to 1/3 of the time in the range of the aforementioned high pressure and the aforementioned temperature before the perforated plate, as is required according to the teaching of EP 486 592 In this way, the knock-off device, in particular a doctor blade, at the outlet of the gear pump produces a granulate size of 0.5 to 10 mm, preferably 1 to 5 mm.

The premix consists at least in part of solid, preferably finely divided, customary ingredients of detergents and cleaning agents, to which liquid constituents may have been added. 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 added, if appropriate, and the plasticizer and / or lubricant selected according to the invention is then mixed in.

These aids are of polyfunctional importance in the context of the present invention. In the production of granules, they enable the formation of the primary granulate granule by causing the premix to be converted into a mass pressed under high pressure and, if desired, subsequent subsequent shaping processing, which in particular results from the rounding off of the primary mär formed granules. Furthermore, they contribute to the stabilization of the granules, 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 detergent and cleaning agent, they enable the granules to dissolve quickly, since they promote the dissolving, emulsifying or dispersing process. Finally, the auxiliaries discussed here, in particularly important embodiments of the present invention, 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 solid, 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 on the basis of water-soluble or water-emulsifiable or water-dispersible polymer compounds. Examples of a plasticizer and / or lubricant which can be used without the use of an additional Liquid phase can be used, numerous types of the non-ionic surfactants commonly used in detergents and cleaning agents.

Substances with a low melting point (e.g. higher molecular weight polyethylene glycol ethers with molecular weights between 4,000 and 20,000) can be used as plasticizers and / or lubricants which are solid at room temperature.

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 preferred 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 which flow 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, smoothly compressible mass can be adjusted even in 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 with particular advantage between 3 and 8% by weight, based on the total mixture set. At least 30% by weight, preferably 40% by weight pastes and gels are particularly suitable.

According to a particularly preferred embodiment of the present invention, surfactant preparations with a surfactant content of at least 50% by weight, in particular from 50 to 70% by weight, are used. The present invention takes advantage of the fact that, in particular, these highly concentrated, aqueous surfactant mixtures show a state that can be described as a pasty or gel-like preparation form with a lubricant character. 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 compounds proposed here for detergents and cleaners, optionally in admixture with customary, nonionic compounds, can be of particular importance. As an example in the manufacture of textile detergents, use a mixture of at least two solid components (spray-dried granulate / fatty alkyl sulfate compound) with or without the addition of sodium perborate (monohydrate and / or tetrahydrate) with the addition of 2 to 5% by weight. Water and 4 to 8 wt .-% of a 55 to 65% C ₉ to C ₁₃ alkyl benzene sulfonate paste (ABS paste) called. Instead of the aforementioned combination of a spray-dried granulate and a fatty alkyl sulfate compound with further components, a corresponding carrier bead can also be used instead of the fatty alkyl sulfate compound as described in European patent 0486592 B1. 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 means methyl-branched, aliphatic radical having 8 to 22, preferably 8 to 18 carbon atoms, G is a symbol, which stands for a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10. Further preferred plasticizers and / or lubricants based on surfactants are mixtures of ABS and APG pastes, as well as mixtures of ABS pastes and ethoxylated C ₈ to C ₁₈ fatty alcohols, mixtures of ethoxylated fatty alcohols and water and mixtures of APG: ethoxylated Fatty alcohol: water in the ratio of (0.5 - 1): 1: (1, 5 - 1), the content of APG in this case being calculated as an active substance and not as a paste.

Just like the use of surfactants, the use of polymer compounds in numerous detergents and cleaning agents is common today, since the polymer compounds act, for example, as builders with the ability to bind the water hardness. Examples of these are polymers containing carboxyl groups, which may be present in the salt form, for example as an alkali salt, such as 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 made 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, methyl esters, acrylamide and 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 the 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 processes according to the invention. At the same time, these polymer components dry in the inventive Formation of the granulate to polymer films, which on the one hand promote the connection of the grain, on the other hand easily change back to the state of the solution or emulsification or dispersion when aqueous media are added. It is particularly preferred to use from 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. Gelatin, starch and starch derivatives as well as polyvinyl alcohol may only be mentioned here as examples.

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 amounts of liquid can be introduced before, during and / or after the processing of the plasticizer and / or lubricant, the addition before processing 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 the respective substance mixture in free water which is not bound as crystal water or in a comparable form is preferably up to 12% by weight, preferably up to 10% by weight and in particular in the range from about 4 to in this processing stage 8% by weight. Included in this amount is the amount of water that is entered via the plasticizing aids with a lubricating character. 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, a solid, free-flowing premix being obtained which is suitable for feeding the gear pump used according to the invention.

The granules can then be fed to a rounding step as in international patent application WO-A-91/02047. Usual rounding devices such as Marumerizer, but also sieve mills, as are commercially available from Bepex GmbH, for example, can be used here. Sieve mills of this type have the advantage that any coarse-grained fractions that may have occurred are reduced to a maximum grain size limit and the fractions of finer granules that are produced in this way can likewise be returned to the premix. At the same time, it is also possible in this process step to powder the granules in a conventional manner with solid substances or to spray them with liquid to wax-like substances such as nonionic surfactants, foam inhibitors, in particular silicone oils and paraffins, and textile softeners or perfume oils.

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

At least partially, however, the "internal drying" of the granules is also possible: by using moisture-binding components in the premix, the plasticizing effect of the liquid components presented can be exploited in the short processing time: Then at least partial components are found by binding of these liquid components due to the mixed-in constituents, the granules are dried "from the inside", so that the external drying can be shortened or omitted entirely. Constituents 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 applied before, during and / or after any rounding off of the further active ingredients. 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 encompasses both the area of ready-to-use multi-substance mixtures in the form of uniform granulate bodies and also partial products which, in order to complete the recipe, require mixing of further constituents of the particular detergent and cleaning agent concerned. Advantageously, more than 60% by weight and in particular more than 70% by weight of the total mixture are granules obtained by the process according to the invention with a highly compressed and solid grain structure.

According to a particularly important embodiment of the present 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 succeeds. An example of this are conventional textile detergents, which, however, now use at least two types of granules in a mixture with one another in this preparation form. In a first, for example spherical type of granulate, the bleaching agent component, in particular perborate or 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, if used as detergent builder, in particular zeolite NaA and / or zeolite P, pressed with the rest of the detergent components. The storage stability of the mixed product, which has a substantially influencing interaction between peroxy bleaching agent and zeolite - as must be taken into account in powdery preparations - is excluded in this way. With this possibility of using granulate systems of differently composed granules, use can be made in almost any combination.

In a further preferred embodiment, the granules according to the invention can be recycled, ie. that is, they can be used in the first process step in combination with other steps to produce the plasticized premix.

The material densities in the grain and thus also the bulk density of the granules are decisively determined by the working pressures used in pressing the homogenized material through the perforated plates. By building up a sufficiently compacted basic structure of the mass to be pressed and using correspondingly high sealing 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 densities in the range from 850 to 980 g / l can be adjusted on the basis of commercially available textile detergent formulations with good free-flowing properties and a preferably high, uniform, spherical grain structure. In similar applications, free-flowing granules are in the dry state with uniform bulk densities of 950 to 980 g / l an average particle size of the spherical granules in the range of, for example, about 1 mm.

As already discussed above, the method according to the invention is characterized by a very low proportion of returned goods. This portion of the return material after sieving the granules through a 1.6 mm sieve was in each case in the range of at most 7% by weight. Analogous to conventional detergent preparation, sensitive formulation constituents, for example activators for bleaching agents, enzymes, defoamers, in particular Silicone defoamers, perfume and the like are added to the granules. Even then, detergent products with bulk densities in the range of about 900 g / l are still obtained.

The textile detergents which are customary in the market today in the form of free-flowing powders and / or granules generally contain a combination of anionic surfactant and nonionic surfactant detergent components. In general, the anionic surfactant components make up the largest proportion and the nonionic surfactants make up the smaller proportion of the surfactant mixture. Textile detergent concentrates with surfactant contents, for example, of up to 35% by weight and preferably in the range of about 15 to 25% by weight can be produced without the fear of sticking and / or product softening, as is the case in the commercially available powdery formulations Mixtures occur with such increases in the surfactant content. By combining the measures of compression of the substance mixtures to high bulk densities and a simultaneous increase in the detergent 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 the area of free-flowing, storage-stable and all other requirements having to leave fulfilling detergent preparations.

The preparation of detergents and cleaning agents in the process type of granulation according to the invention to the predetermined particle size brings a number of advantages: It has been shown that in the process according to the invention the bleaching agent, in particular sodium perborate in the form of the monohydrate and / or the tetrahydrate, can already be processed in the raw material to be classified and then pressed without substantial losses of perborate occurring . Each granulate thus contains the predetermined proportion of granules of peroxy bleach. The use of spray-dried powders / granules with variable admixture is possible. On the other hand, neither spray-dried powders / granules 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 commonly used in detergents and cleaning agents is no problem, and the pluming effects that occur in spray drying, see definition in Römpp Chemielexikon, 4th edition, volume 5, p. 3488, are eliminated. The nonionic surfactants are added without problems by incorporation into the mixture of substances before the pressing step; they can even provide valuable process help in the manner described here as a highly concentrated, aqueous gel or paste.

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 this 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 one particularly important 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 0.5 to 10 mm ball diameter, in particular in the range from approximately 1 to 5 mm. The type and quantity of the formulation components can correspond to that of today's textile detergents containing builder substances.

The following is general information on the composition of suitable active substance mixtures, with components of textile detergents customary today being summarized here.

Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are alkylbenzene sulfonates (C ₉ to C ₁₃ alkyl), olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates of the type obtained, for example, from C ₁₂ to C ₁₈ monoolefins with terminal or internal ones Double bond obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are the alkanesulfonates which are obtainable from C ₁₂ to C ₁₈ 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), for . B. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural or synthetic origin, in particular from fatty alcohols, e.g. B. from coconut oil alcohol, tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ - C ₂ o-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 Cg-C- * •, alcohols with an average of 3.5 moles of ethylene oxide, are also suitable. Preferred fatty alkyl sulfates are derived from fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil, which additionally contain proportions of unsaturated alcohols, e.g. B. oleyl alcohol, may contain. Mixtures in which the proportion of the alkyl radicals is 30 to 70% by weight on C ₁₂ to 18 to 30% by weight on C _14> 5 to 15% by weight find a preferred use. are distributed on C ₁₆ , less than 3% by weight on C ₁₀ and 0 to 40% by weight on C _18. Sulfated fatty acid monoglycides are also suitable

Likewise preferred anionic surfactants are the salts of alkyl sulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ - C ₁₈ -fatty alcohol residues or mixtures of these, in particular preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are non-ionic surfactants. In turn, sulfosuccinates whose fatty alcohol residues differ from ethoxylated fatty alcohols derive narrowed homogeneous distribution, particularly preferred

Other suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.5 to 5% by weight. Saturated fatty acid soaps, such as the salts of lauric acid, mypinsic acid, palmitic acid or stearic acid, and in particular from natural fat, are suitable ¬ acidic, eg coconut, palm kernel or tallow fatty acids, derived soap mixtures

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

Addition products of 1-40, preferably 2-20 moles of ethylene oxide to one mole of an aliphatic compound having essentially 10-20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxamides and alkanesulfonamides can be used as nonionic surfactants The preferred nonionic surfactants are liquid ethoxylated and / or propoxylated alcohols derived from primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of alkylene oxide, in which the alcohol residue can be linear or methyl-branched in the 2-position, or can contain linear or methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, linear residues of alcohols of native origin with 12 to 18 carbon atoms are preferred, such as. B. from Ko¬ kos-, tallow or oleyl alcohol. In particular, C ₁₂ -C ₁₄ alcohols with three moles of ethylene oxide or four moles of ethylene oxide, C ₉ -C _{ι r} alcohol with 7 moles of ethylene oxide, C ₁₃ -C ₁₅ alcohols with three moles of ethylene oxide, five moles of ethylene oxide, seven moles of ethylene oxide or Eight moles of ethylene oxide, C ₁₂ -C ₁₈ alcohols with three moles of ethylene oxide, five moles of ethylene oxide or seven moles of ethylene oxide or mixtures thereof, such as mixtures of C ₁₂ to C ₁₄ alcohol with three moles of ethylene oxide and C ₁₂ to C ₁₈ -Alcohol used with five moles of ethylene oxide.

The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NRE). In particular, alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.

In addition, alkylpolyglycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R is a primary, straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms branched in the 2-position means and G is the symbol which stands for a glucose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides or oligoglycosides, is any number between 1 and 10. Other suitable surfactants are polyhydroxy fatty acid amides of the general formula

R ₃

R ₂ - CO - N - [Z],

in the R ₂ - CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ₃ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides used are preferably fatty acid N-alkylglucamides in which R _{3 is} hydrogen or an alkyl group, R ₂ - CO is the acyl radical of a saturated or unsaturated fatty acid and [Z] is a glucose radical.

Among the compounds which serve as bleaching agents and which are hydrogen peroxide in water, sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate are of importance. Further bleaching agents that can be used are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids providing hydrogen peroxide, such as perbenzoates, peroxophthalates, diperazelaic acid or dimerododecanedioic acid. The bleach content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate or percarbonate advantageously being used.

In order to achieve an improved bleaching effect when washing at a temperature of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples of these are N-acyl or O-acyl compounds which form organic peracids with hydrogen peroxide, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. The bleaching agent content of bleach activators is in the usual range, preferably between 1 and 10% by weight and in particular in particular between 2 and 8% by weight. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine, 1,4-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine, also carboxylic anhydrides and esters of polyols, such as Glucose pentaacetate.

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

Weakly acidic, neutral or alkaline-reacting soluble and / or insoluble components which precipitate or bind calcium ions in a complex manner are suitable as organic or inorganic builders. Suitable and, in particular, ecologically harmless substances, such as finely crystalline, synthetic water-containing zeolites of the NaA type and / or zeolite P, 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) a preferred use. Their average particle size is usually in the range from 1 to 10 micrometers (measurement method: Coulter Counter; volume distribution). Their content is generally 0-40, preferably 10-30% 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. Their water content is preferably between 19 and 22% by weight. They have practically no particles larger than 30 micrometers and preferably consist of at least 80% particles smaller than 10 micrometers. Zeolite A and zeolite P are particularly suitable, as are zeolite X and mixtures of A and X and / or P. Quantities and weight ratios that affect the builders are based on the anhydrous active substance in the context of the present invention, unless stated otherwise . Suitable substitutes or partial substitutes for phosphates and zeolite are crystalline, layered silicates of the general formula NaMSi _x θ2 _{X +} ι ^• VH2O, where M is sodium or hydrogen, x is a number from 1.9 to 4, y is a number from 0 to 20 is. Such layer silicates are described, for example, in European patent application 0164514. In particular, both β- and δ-sodium disilicates Na2Si2θ ₅ ^• yH ₂ O are preferred. Other builder substances are amorphous silicates with secondary washing power, for example those according to DE-P44 00 024.3, DE-P44 19 745.4 and DE-P44 46 363.4. According to the invention, it will also be possible to use zeolite and / or the crystalline layered silicate and / or the amorphous silicate as mixtures, the mixing ratio being arbitrary. However, zeolite is preferably used either alone or with a zeolite to crystalline layered silicate or amorphous silicate weight ratio with secondary washability of 10: 1 to 1: 3 and in particular 3: 1 to 1: 1. According to the invention, it is further possible to add the zeolite or at least zeolite fractions in the form of the undried masterbatch or only partially dried and thus only water-depleted material to the premix.

Usable organic builders are, for example, polycarboxylates, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, aminocarboxylic acid, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons. and mixtures of these and (co) -polymeric polycarboxylic acids and polycarboxylates, such as the sodium salts of polyacrylic acids or polymethacrylic acids, for example those with a relative molecular weight of 800 to 150,000 (based on acid) and in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid are preferred, additionally contained. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000, and in particular more 5000 to 100000. Also particularly preferred are biodegradable terpolymers, for example those which, according to DE-A-43 00 772, as salts of acrylic acid and maleic acid as well as vinyl alcohols or vinyl alcohol derivatives or according to DE-C- 42 21 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives. Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and P 44 17 734.8 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

In cases where a phosphate content is tolerated, phosphate can also be used, in particular pentasodium triphosphate, possibly also pyrophosphates such as 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 here.

Suitable inorganic, non-complexing salts are the bicarbonates, also known as washing alkalis, carbonates, borates or silicates of the alkalis. Of the alkali silicates, especially the sodium silicates with a ratio Na2θ: Siθ2 such as 1: 1 to 1: 3.5 usable (see above).

The other detergent ingredients include graying inhibitors (dirt carriers), foam inhibitors, optical brighteners, enzymes, fabric softening agents, colorants 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. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch and cellulose, ether sulfonic acids or salts of acidic sulfuric acid esters of cellulose or starch. Also water soluble, Acid-containing polyamides are suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starches, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose are preferred and their mixtures and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition

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 substances. A reduced foaming power, which is desirable when working in machines, can be achieved in many cases by combining different tenants sidtypes, for example sulfates and / or sulfonates with nonionic tensides and / or with soaps. In the case of soaps, the foam-dampening effect increases with the degree of saturation and the C number of the fatty acid salt. Soaps of natural or synthetic origin are therefore suitable as foam-inhibiting soaps, a high proportion of C ιβ "C ₂₄ -Fettsauren have Suitable non-active foam inhibitors are beispiels¬, organopolysiloxanes and mixtures thereof with microfine, if appropriate silanized silica and also paraffins, waxes, waxes Mikrokristallin¬ and mixtures thereof with silanized silica also of C | 2-bιs C2o-alkylamines and C2-bis Ce.Dicarboxylic acids derived bisacylamides can be used. Mixtures of different foam inhibitors are also advantageously used, for example those made of silicones, paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance or who ¬ added to the plasticizers and / or lubricants

In addition, the agents can contain enzyme stabilizers. For example, 0.5 to 1% by weight of sodium formate can be used. It is also possible to use proteases containing soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme , are stabilized but the use is particularly advantageous boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ 0 ₇ ).

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

For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triacin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure are suitable, which instead of the morpholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyamino group. Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present; for example the compounds 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

Enzymes from the class of proteases, lipases, cutinases, cellulases and amylases or their mixtures are possible. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subiii, Bacillus licheniformis or Streptomyces griseus are particularly suitable. Proteases of the subtilis type and in particular proteases which are obtained from Bacillus lentus are preferably used in a mixture with other enzymes. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. Their proportion can be about 0.2 to 2% by weight.

The salts of polyphosphonic acids, hydroxyethane-1,1-diphosphonic acid (HEDP) and ethylenediaminetetramethylenephosphonic acid (EDTMP) or diethylenetriamine-pentamethylenephosphonic acid (DTPMP or DETPMP) are suitable as stabilizers, in particular for per-compounds or enzymes.

According to a further preferred embodiment, the present invention also relates to granules which, according to the have been obtained, which are characterized in that they have a bulk density of above 700 g / l, preferably 750 to 1,000 g / l and in particular 850 to 980 g / l, and as a ready-to-use multi-substance mixture in the form of uniform granules or as a combination of granules of different compositions or as a partial product which, in order to complete the recipe, still requires mixing with other constituents of conventional washing and cleaning agents

Finally, the present invention relates to detergents and cleaners containing granules of the aforementioned type, which are characterized in that they contain a surfactant content of up to 40% by weight, preferably 15 to 25% by weight

example

To produce textile detergents in the form of the storage-stable, free-flowing granules according to the invention, first a plastifiable, solid, free-flowing premix was obtained by reacting 61.6% by weight of a spray-dried granulate, 5% by weight of an alkyl sulfate compound, 20.7 % By weight sodium perborate monohydrate, 3.5% by weight C ₁₂ -C ₁₈ fatty alcohol with 7 EO, 1.7% by weight polyethylene glycol (PEG 400), 1.8% by weight

% Soda (anhydrous) and 5.6% by weight of a 30% aqueous polycar

® boxylat solution (Sokalan CP5) mixed and worked up. Composition of the spray-dried granules:

27.4% by weight of a surfactant mixture of sodium dodecylbenzenesulfonate (ABS) and of tallow fatty alcohol reacted with 5 ethylene oxide groups (EO) in a ratio of 24: 1;

9.4% by weight of a calcined soda,

39.4% by weight of zeolite NaA as an anhydrous substance,

4% by weight of an acrylic acid copolymer (Sokalan "CP5 from BASF AG),

9.9% by weight of bound water,

- 3.6% by weight of free water and

- on 100 wt .-% sodium sulfate and salts from raw materials

In the premix production, the powder components were placed in a batch mixer of 130 l, which was equipped with a cutter head comminutor, and then with the mixer running, the premixed nonionic surfactant / PEG 400 mixture and then the carboxylate solution were added and the mixture was mixed for 30 seconds .

The premix obtained was free-flowing and could be fed to feed the granulating system according to the invention, the hole shapes of which were preceded by an extruder with a gear pump connected to it. Within the scope of the exemplary embodiment, an extruder from Lei¬stritz, Federal Republic of Germany, with the designation LSM 30.34 GL, was used. In the connecting piece between the extruder and the gear pump there was a perforated disk with a diameter of 3 mm for pre-plasticizing the premix.

The following granulation conditions had to be observed for pressing the plastifiable, solid and free-flowing premix by hole shapes:

The gear pump according to the invention used in the granulation was a model available from Witte GmbH, Federal Republic of Germany, under the name VAH 2.78 M, with a typical throughput of 4 kg per hour for a typical hole Nozzle diameter of 1.5 mm is carried out, product outlet and discharge temperatures of 60 ° C. being used. It was not necessary to cool the apparatus. The subsequent batch rounding was carried out optimally within a batch time of 1 min at a rotor peripheral speed of 8 m / s in the presence of 3.2% by weight of zeolite NaA powder. After sieving through a 1.6 mm sieve, a granulate with a granular bulk density of about 800 g / l was obtained in a granulate yield of 93%.

Claims

claims

1. Process for the production of granular detergents or cleaning agents or components therefor by pressing a plastifiable, solid, free-flowing premix by hole molds, characterized in that a gear pump is connected upstream of these hole molds.

2. The method according to claim 1, characterized in that the strands emerging from the perforated nozzles of the gear pump are cut by knock-off devices, in particular rotating knives.

3. The method according to claim 1 or 2, characterized in that the pressure in the gear pump is between 6 and 200 bar, in particular 30 to 120 bar and the press nozzle produces a granulate of 0.5 to 10 mm, preferably 1 to 5 mm .

4. The method according to any one of claims 1 to 3, characterized gekennzeich¬ net that the gear pump is operated with a throughput of 0.1 to 300 m ³ / h, preferably 1 to 20 m ³ / h.

5. The method according to any one of claims 1 to 4, characterized gekennzeich¬ net that the premix to be compressed in the pump inlet temperatures from 20 to 80 ° C, preferably 30 to 60 ° C and in the outlet 40 to 100 ° C, preferably 45 up to 75 ° C.

6. The method according to any one of claims 1 to 5, characterized gekennzeich¬ net that the premix in the gear pumps upstream mixers, extruders or devices from mixers and kneaders is plasticized.

7 The method according to one of claims 1 to 6, characterized in that a rounding step is followed

8. Granules obtained according to one of claims 1 to 7, characterized ge indicates that it has a bulk density of above 700 g / l, preferably 750 to 1000 g / l and in particular 850 to 980 g / l and as ready-to-use Multicomponent mixture in the form of uniform granules or as a combination of granules of different compositions or as a partial product which, in order to complete the recipe, still requires mixing with other constituents of conventional washing and cleaning agents.

9 washing and cleaning agents containing granules according to claim 8, characterized in that they contain a surfactant content of up to 40% by weight, preferably between 15 and 25% by weight