DE19542570A1 - Process for the production of granular washing or cleaning agents or components therefor - Google Patents

Abstract

The invention relates to a process for pressing solid, pourables mixtures which is carried out under more gentle conditions than usual in that the holes through which pressing takes place are arranged in two meshing counter-rotating gear-wheel press rolls. If necessary, coarse grain portions can be returned without crushing.

Description

The invention relates to a process for the production of almost spherical bis cylindrical detergent or cleaning agent granules, granules obtained thereafter as well as detergents and cleaning agents containing these granules.

From international patent applications WO-A-91/02047 and WO-A-91/13678 as well as from European patent 486 592 is a process for the production compacted granules of ingredients of washing or cleaning agents known. The granules are made from premixes of at least partially solid ones Ingredients with the addition of water-soluble, water-emulsifiable or water-dispersible plasticizers and / or lubricants, which lead to a homogeneous mass processed and at high pressures between 25 and 200 bar above Hole shapes with opening widths of the predetermined granule dimension strand-shaped be pressed. Conventional granulating devices, for example pellet presses, extruders with one or two shafts, planetary roller extruders and other apparatus can be used. A continuously working two-screw Extruder is preferred. The premix, which is plasticized in the extruder, appears in the form of finer Strands through a perforated nozzle plate. The extrudate is then by means of a rotating knives to almost spherical to cylindrical granules crushed and this still plastic primary granules preferably in a conventional Rounding machine rounded off if necessary with the use of small amounts of dry powder. Additional active ingredients, in particular, can be used to complete the formulation temperature-sensitive recipe components, the possibly dried up granulate added, sprayed on and / or as a separately formed grain under formation of a multigrain mixture.

In this technical embodiment of the prior art, the extrusion through a circular plate provided with nozzle holes. The Perforated nozzles can be arranged vertically or horizontally. The through the hole shapes emerging fine strands from about 0.5 to 5 mm, typically from 0.8 mm to 2.0 mm diameter are in a hot cut from a single or multi-bladed rotating cutter head to almost spherical to cylindrical granules crushed. The knife sheaths of the knock-off device are either 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 consistency that it is below plastically softened under pressure or under the entry of specific work and is extrudable, but at the time of exit from the hole shape, at which none Shear forces affect the system more, the viscosity of the system suddenly so reduced that the extruded strand is cut, namely on Predeterminable dimensions can be cut.

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

It was therefore the task of modifying the method described above in such a way that that pressing the premix under gentler conditions, for example at lower pressures or without cooling without the Cutting ability of the extruded strands after exiting the hole shape get lost.

This object is achieved by a method for producing granular detergents or cleaning agents or components therefor, where a plastifiable and solid, free-flowing premix is pressed by hole molding and these hole shapes in two opposing and interlocking Gear press rolls are arranged.

Such gear press rolls are commercially available. For example, as Granule molding machines, in particular of the G series from Bepex GmbH, Leingarten, Federal Republic of Germany. The granulation by means of a Gear press roll is done in such a way that the feed material from the toothed Rolls are drawn in and pressed through the nozzle bores. As part of this Press rollers use hollow gears with nozzle holes in the tooth base. in the Scraper blades fitted inside the wheel cut off the emerging pellets. The  The compression that can be achieved in addition to shaping is determined by the number of nozzles Nozzle pressure and the ratio of nozzle diameter to nozzle length.

In contrast to the teaching of international patent applications WO-A-91/02047 and WO-A-91/13678 are those from the perforated nozzles of the rotating gear press rolls emerging strands cut by fixed or movable knives.

According to a preferred embodiment of the present method, those in the Press roller according to the invention for hollow granules used for molding granules have nozzle holes in the tooth base.

Usually a pressure of 10 to 200 bar builds up inside the press rolls, preferably 10 to 130 bar, in particular 30 to 60 bar, and that inside the wheel or wiping knives present in the outlet of the press roll produce in this way a granule size of 0.5 to 10 mm, preferably 1 to 5 mm.

Due to the special nature of the premix and the work conditions according to the teaching of international patent applications WO-A-91/02047 and WO-A-91/13678 were able to return any that may have occurred Coarse-grained fractions after grinding or fine fractions only in a relatively small amount Scale, for example up to about 10 wt .-%, based on that to be extruded Premixed. It is a particular advantage of the inventive method that these returns due to the changed Working conditions will also be possible on a much larger scale.

In a preferred embodiment of the invention, the gear press rolls plasticized premixes supplied, which are 2 to 100 wt .-%, preferably 10 up to 45% by weight and in particular above 10% by weight, for example 15 to 40 % By weight of recycled components. It is not necessary that Grind coarse-grain parts into smaller grains beforehand.

The premix consists at least in part of solid, preferably finely divided, usual ingredients of detergents and cleaning agents, where appropriate liquid components are mixed. The solid ingredients can go through Spray drying tower powders, but also agglomerates and granules, the each selected mixture constituents as pure substances in the finely divided state are mixed together, and mixtures of these.  

Subsequently, the liquid ingredients are optionally added as well selected plasticizers and / or lubricants mixed.

These aids come within the scope of the present invention a polyfunctional Meaning too. In the production of granules, they enable the formation of the primary resulting granules, in which they cause the premix in a high pressure compressed mass is transferred, and if desired subsequent, shaping further processing, in particular from the rounding of the primary granule formed. Furthermore, they contribute to the stabilization of the Granules at, they preserve its predetermined spatial shape, especially when if necessary, mixing with other components, during filling, during transport and storage of the granules and in particular prevent the Formation of unwanted, dusty parts. In practical use of the granular On the other hand, detergents and cleaning agents allow you to quickly do it again Dissolution of the granules as they dissolve the solution, emulsify or Favor dispersion process. Finally, the adjuvants discussed here in particularly important embodiments of the present invention Own action in the washing and cleaning process, especially in interaction with other mixture components.

The plasticizers and / or lubricants used as auxiliaries can Room temperature be solid, flowable, gel-like or pasty, without the use an additional liquid phase is required. Preferred plasticizing and / or Lubricants are based on preparations based on surfactant components and / or Basis of water-soluble or water-emulsifiable or water-dispersible Polymer compounds. Examples of a plasticizer and / or lubricant that without With the use of an additional liquid phase, there are numerous Types of non-ionic agents commonly used in washing and cleaning agents Surfactants.

As plasticizers and / or lubricants that are solid at room temperatures, substances can also be used low melting point (e.g. higher molecular weight polyethylene glycol ether with Molecular masses between 4000 and 20000) can be used.

In a preferred embodiment, however, plasticizers and / or lubricants used, which is produced using limited quantities of auxiliary liquids have been. Organic liquid phases are preferred here, which are water-soluble or water-miscible. For process security reasons, it can  be useful, comparatively high-boiling organic liquids, optionally in a mixture with water. examples for this are higher boiling, optionally polyfunctional alcohols, at room temperature or moderately elevated temperatures flowable polyalkoxylates and the like. Especially however, aqueous preparations of the plasticizers and / or lubricants are preferred.

The surfactants and / or used as plasticizers and / or lubricants Polymer compounds are advantageously used in such a concentrated form in the process introduced that the nature of the plastic, sliding compressible mass can already be set 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, used. Are particularly suitable at least 30% by weight, preferably 40% by weight pastes and gels.

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 fractions 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 manufacture of laundry 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 of water and 4 to 8% by weight of a 55 to 65% C₉ to C₁₃ alkylbenzenesulfonate paste (ABS paste). 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 wt .-% of a 50 to 60 wt .-% aqueous paste of an alkyl polyglycoside (APG) of the general formula RO (G) _x , in which R is a primary straight-chain or methyl branched in the 2-position , 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, and mixtures of ABS pastes and ethoxylated C₈ to C₁₈ fatty alcohols, mixtures of ethoxylated fatty alcohols and water and mixtures of APG: ethoxylated fatty alcohol: water in 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 common in numerous detergents and cleaning agents, because the Polymer compounds, for example, as builders with the ability to Water hardness binding. Examples of these are polymers containing Carboxyl groups, which can 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 from 50% to 10% maleic acid. The The molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on the free acid. Suitable, albeit less preferred, compounds 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 also for Improve the dirt-carrying capacity of the aqueous washing liquor Polymer compounds used. Examples include carboxymethyl cellulose (CMC) and / or methyl cellulose (MC).

In particular, highly concentrated, aqueous preparation forms of these Like the surfactant preparations, polymer compounds are characterized by a pronounced lubricating character from the in the inventive method decisive processing aid there. At the same time, these polymer components dry in the inventive formation of the granules to polymer films on on the one hand promote the connection of the grain, on the other hand when added especially aqueous media easily return to the state of the solution or Skip emulsification or dispersion. The use of 3 is particularly preferred up to 8% by weight of a 30 to 50% by weight solution of a polymer, in particular one  Copolymers of acrylic acid and maleic acid in water as plasticizers and / or Lubricant. Mixtures of these polymer solutions and the are also advantageous surfactant, especially anionic plasticizers and / or lubricants.

Practice knows numerous other natural or synthetic polymer types that are here are also used according to the invention as plasticizers and / or lubricants can. Gelatin, starch and starch derivatives, as well, are just examples Called polyvinyl alcohol.

For reasons of sufficient moisture penetration or to dust the To avoid premixing, slightly larger amounts of liquid may be required will. In general, it is advisable to add these additional shares as such Premix and not the surfactant pastes used as lubricants and / or Dilute polymer solutions more. The introduction of such amounts of liquid can be before, during and / or after processing the plasticizer and / or lubricant take place, the addition before processing the plasticizer and / or lubricant is preferred. However, only such limited amounts of liquid phase (s) used that a free-flowing, powdery Structure of the premix even after the addition of the plasticizer and / or lubricant preserved. The content of the respective mixture of free, not as Crystal water or water bound in a comparable form lies in this Processing stage preferably up to 12% by weight, preferably up to 10% by weight and especially in the range of about 4 to 8% by weight. Included in this Amount of water content over the lubricating plasticizer is entered.

If desired, the plasticizer and / or lubricant can also be added other solids are added to the premix. The total mass is briefly mixed, whereby a solid, free-flowing premix is obtained, which for Feeding the gear press roller used according to the invention is suitable.

The granules can then be processed as described in international patent application WO-A- 91/02047 a rounding step are supplied. Here can be usual Rondier devices such as Marumerizer, but also sieve mills, as they are in the trade are also available from Bepex GmbH, for example. Sieve mills of this type have the advantage that coarse-grain fractions that may have occurred can be reduced to a maximum grain limit and the resulting Portions of finer granules are also returned to the premix  can. At the same time, it is also possible to add the granules in this process step to powder yourself with solid substances or with liquid to waxy ones Substances such as nonionic surfactants, foam inhibitors, especially silicone oils and Spray paraffins, as well as fabric softeners or perfume oils.

Following this, the finally shaped granulate is preferably one Drying step, for example a fluidized bed dryer, in which moderately raised supply air temperatures, especially up to a maximum of 80 ° C moderate final product temperatures of, for example, between 55 to 60 ° C, but then not be exceeded. After sufficient drying, the cooling takes place of the product, for example with cold air. Here the content of free water in the Granules are lowered. Preferred residual levels of unbound water are values of 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 less to remove coarse particles formed are classified, for example sieved. Of the Grain content to be set according to the invention is generally above 90%, preferably above 95% of the granulated material. Sometimes it is possible to do this Drying step also directly after pressing the primary granulate and thus before the final shaping, if desired to be carried out in a rounding machine.

At least partially, however, the "internal drying" of the granules is also possible: By using moisture-binding components in the premix in the short processing time the plasticizing effect of the presented Liquid components are exploited: Then the bond takes place at least partially Parts of these liquid parts by drying the ingredients Granules "from the inside out" instead, so that the outer drying can be shortened may or may not apply. Ingredients that are able to form water To bind water of crystallization are, for example, sodium sulfate and / or sodium carbonate anhydrous or water-poor form or also partially from water of crystallization liberated zeolite.

In a further preferred embodiment, the primary and still formed plastic granules before, during and / or after an if necessary made rounding of the other active ingredients are applied. However, sensitive, in particular, can also preferably be used, for example temperature-sensitive ingredients of the dried granules admitted, e.g. B. sprayed and / or as a separately formed grain under  Formation of a multigrain mixture can be added. The invention covers both the area of ready-to-use multi-substance mixtures in the form of uniform Granules as well as partial products that are used to complete the recipe after Mixing with other components of the relevant washing and Cleaning agents are required. Advantageously, more than 60 wt .-% and in particular more than 70 wt .-% of the total mixture after Granules obtained according to the invention with highly compressed and solid Grain structure.

According to a particularly important embodiment of the present invention Granulate systems used that are a combination of different granules Represent composition. In this way, the storage-stable union succeeds potentially reactive or at least only partially compatible components. An example for this are common textile detergents, but now in this preparation form Use at least two types of granules mixed together. In a first, for example spherical granule type is the bleach component, in particular perborate or sodium carbonate containing water of crystallization when used a portion of the plasticizers and / or lubricants pelleted, in a separate second Granules are used as a detergent builder if necessary Zeolite, in particular zeolite NaA and / or zeolite P, with the rest of the Detergent ingredients pressed. The storage stability of the mixed product is substantial influencing interaction between peroxy bleach and zeolite - as in Powdery preparations are to be considered - are in this way locked out. With this possibility of using granulate systems differently composed granules can be used in almost any combination Be made use of.

In a further preferred embodiment, the inventive Granules are recycled, d. that is, they can be combined in the first process step with other steps to produce the plasticized premix.

The material densities in the grain and thus also the bulk density of the granules are due to the pressing of the homogenized material through the perforated plates the working pressures significantly determined. By building one sufficiently compacted basic structure of the mass to be pressed and use correspondingly high sealing pressures can e.g. B. with conventional textile detergents Recipes bulk densities well above 700 g / l, preferably above 750 g / l and realize in particular in the range of about 800 to approximately 1000 g / l. So are on  Based on commercial textile detergent formulations, bulk densities in the range of 850 up to 980 g / l with good flowability and a preferably high, uniform, spherical grain structure adjustable. In similar operations are free-flowing Granules 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 has been realized.

As already discussed above, the method according to the invention is characterized by a very low proportion of returned goods. This return share after screening the Granules over a 1.6 mm sieve were in the range of at most 10% by weight. Analogous to conventional detergent preparation, sensitive Recipe components, for example activators for bleach, enzymes, defoamers, especially silicone defoamers, perfume and the like, added to the granules will. Even then, detergent products with bulk densities are still used Obtained range of about 900 g / l.

Today's textile detergents in the form of free-flowing powder and / or Granules usually contain a combination of anionic and non-surfactant detergent components. Generally they do Anionic surfactant components the largest proportion and the nonionic surfactants the smaller proportion Mixture of surfactants. So textile detergent concentrates can contain surfactants for example up to 35% by weight and preferably in the range from about 15 to 25% by weight are produced without gluing and / or product softening are feared, as they are in the marketable, powdery blends such increases in the surfactant content occur occasionally. By combining the Measures to compress the mixtures of substances to high bulk densities and one simultaneous increase of the active washing ingredients, especially the tensides in Their proportion in the detergent mixture makes the target more space-saving and Low-packaging detergent preparations optimally realized without the area free-flowing, storage-stable and fulfilling all other requirements Having to leave detergent preparations.

The preparation of detergents and cleaning agents in the invention Process type of granulation to predetermined particle size brings a variety 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  already processed in the raw mass to be classified and then compressed can be achieved without substantial loss of perborate. So each contains Granules the predetermined amount of granules of peroxy bleach. The use of spray-dried granules with variable admixture are possible. On the other Side are neither spray-dried for the production of the raw materials to be pressed Powder / granules still require pre-formed powder with a bead structure. The stake or the addition of heavy powder of the individual raw materials is not necessary. The Processing of those commonly used in washing and cleaning agents Non-ionic surfactants become problem-free, the pluming that occurs in spray drying Effects, see definition in Römpp chemistry lexicon, 4th edition, volume 5, p. 3488, omitted. The non-ionic surfactants are incorporated into the mixture of substances before Pressing step supplied easily, you can even here as a highly concentrated, aqueous Gel or paste provide valuable procedural help in the manner described.

The possible incorporation of defoamers in liquid form saves a process for separate production of defoamer solid carrier concentrates. This eliminates the admixture of defoamer granules in the preparation of detergents. As The defoamer directly into the plasticizer has proven to be particularly advantageous and / or lubricants.

In a particular embodiment, the invention relates to universal detergents for Textiles that are available in this form of 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 are present and in a particularly important embodiment by a uniform particle shape and size are marked. The preferred particle shape is the spherical shape. Preferred particle sizes here are in the range from 0.5 to 10 mm Ball diameter, especially in the range of about 1 to 5 mm. The Recipe components can be of the type and quantity that are common today correspond to textile detergents containing builders.

General information on the composition of suitable active substance mixtures follows, here, in particular, components of textile detergents customary today are summarized.

Suitable anionic surfactants are, for example, those of the sulfonate and Sulfates. As surfactants of the sulfonate type come alkylbenzenesulfonates (C₉ to C₁₃ alkyl), Olefin sulfonates, i.e. H. Mixtures of alkene and hydroxyalkanesulfonates as well Disulfonates, such as those from C₁₂- to C₁₈ monoolefins with end or  internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products, in Consideration. Also suitable are the alkanesulfonates which consist of C₁₂ to C₁₈ alkanes Sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or are available by addition of bisulfite to olefins, and in particular the esters of α-sulfo fatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of the 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, especially from fatty alcohols, e.g. B. from coconut fatty alcohol, tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or Stearyl alcohol or the C₁₀-C₂₀ oxo alcohols, and those secondary alcohols this chain length. Also the sulfuric acid monoesters with 1 to 6 moles of ethylene oxide ethoxylated alcohols, such as 2-methyl branched C₉-C₁₁ alcohols with the average 3.5 moles of ethylene oxide are suitable. Preferred fatty alkyl sulfates are derived from Coconut oil, palm and palm kernel oil-derived fatty alcohol mixtures that additionally Proportions of unsaturated alcohols, e.g. B. oleyl alcohol, may contain. A Mixtures in which the proportion of the alkyl radicals is 30 are preferably used up to 70% by weight on C₁₂ to 18 to 30% by weight on C₁₄, 5 to 15% by weight on C₁₆, below 3 % By weight on C₁₀ and 0 to 40% by weight on C₁₈ are distributed. Sulphated are also suitable Fatty acid monoglycerides.

Also preferred anionic surfactants are the salts of alkyl sulfosuccinic acid, which too be referred to as sulfosuccinates or as sulfosuccinate and the Monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably Represent fatty alcohols and especially ethoxylated fatty alcohols. Preferred Sulfosuccinates contain C₈ to C₁₈ fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue that differs from derives ethoxylated fatty alcohols, which in themselves are non-ionic surfactants represent. Here again are sulfosuccinates, the fatty alcohol residues of which derive ethoxylated fatty alcohols with a narrow homolog distribution, especially prefers.

Other anionic surfactants include, in particular, soaps, preferably in quantities from 0.5 to 5% by weight. Saturated fatty acid soaps such as that are suitable Salts of lauric acid, myristic acid, palmitic acid or stearic acid, and  especially from natural fatty acids, e.g. B. coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants can be in the form of their sodium, potassium or ammonium salts as well as soluble salts of organic bases, such as mono-, di- or triethanolamine available. The anionic surfactants are preferably in the form of their sodium or Potassium salts. The anionic surfactant content of detergents according to the invention or of 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, are nonionic surfactants 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.

Liquid ethoxylated and / or preferably serve as nonionic surfactants propoxylated alcohols, which differ from primary alcohols with preferably 8 to 18 Derive 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 linear or can contain methyl-branched radicals in the mixture, as is usually the case in Oxo alcohol residues are present. In particular, however, are linear residues from alcohols native origin with 12 to 18 carbon atoms preferred, such as. B. from coconut, Tallow or oleyl alcohol. In particular, C₁₂-C₁₄ alcohols with three moles Ethylene oxide or four moles of ethylene oxide, C₉-C₁₁ alcohol with 7 moles of ethylene oxide, C₁₃-C₁₅- Alcohols with three moles of ethylene oxide, five moles of ethylene oxide, seven moles of ethylene oxide or eight moles of ethylene oxide, C₁₂-C₁₈ 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 C₁₂ bis C₁₄ alcohol with three moles of ethylene oxide and C₁₂ to C₁₈ alcohol with five moles of ethylene oxide used.

The degrees of ethoxylation given represent statistical mean values for a special product can be an integer or a fractional number. Preferred Alcohol ethoxylates have a narrow homolog distribution (narrow range Ethoxylates, NRE). In particular, alcohol ethoxylates are preferred which are average Have 2 to 8 ethylene oxide groups.  

In addition, alkyl polyglycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary, straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, C-atoms branched methyl and G denotes Is 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

in the R₂ - CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R₃ for Hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. Preferably as Polyhydroxy fatty acid amides fatty acid-N-alkyl glucamides used in the R₃ for Hydrogen or an alkyl group, R₂ - CO for the acyl radical of a saturated or unsaturated fatty acid and [Z] stands for a glucose residue.

Among those which serve as bleaching agents and which supply hydrogen peroxide in water Compounds have sodium perborate tetrahydrate, sodium perborate monohydrate and the sodium percarbonate is of particular importance. Other bleaches that can be used are for example peroxypyrophosphates, citrate perhydrates and hydrogen peroxide delivering peracidic salts or peracids, such as perbenzoates, peroxophthalates, Diperazelaic acid or diperdodecanedioic acid. The bleach content of the agent is preferably 5 to 25 wt .-% and in particular 10 to 20 wt .-%, wherein perborate monohydrate or percarbonate are advantageously used.

To improve when washing at a temperature of 60 ° C and below To achieve bleaching effects, bleach activators can be incorporated into the preparations will. Examples include N- forming organic peracids with hydrogen peroxide. Acyl or O-acyl compounds, preferably N, N'-tetraacylated diamines, furthermore  Carboxylic anhydrides and esters of polyols such as glucose pentaacetate. The salary of the bleach-containing agents on bleach activators are in the usual range, preferably between 1 and 10% by weight and 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, they are also not or not completely water soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule of Interest, especially when combined with water soluble, nonionic or anionic surfactants are used.

Weakly acidic, neutral are suitable as organic or inorganic builders or alkaline reacting soluble and / or insoluble components, the calcium ions failures or complex ties. Suitable and especially ecological harmless substances, such as finely crystalline, synthetic water-containing zeolites from Type NaA, which has a calcium binding capacity in the range of 100-200 mg CaO / g (according to the details of DE 24 12 837), and / or zeolite P find a preferred one Use. Their average particle size is usually in the range of 1-10 Micrometer (measurement method: Coulter Counter; volume distribution). Her salary is in general 0-40, preferably 10-30 wt .-%, based on the anhydrous Substance. Zeolite NaA falls during its production as a water-containing slurry (masterbatch) to one of the usual methods of manufacturing textile detergents Drying, in particular spray drying. Your water content is preferably between 19 and 22% by weight. They have practically no larger particles than 30 µm and preferably consist of at least 80% particles of one size smaller than 10 µm. Zeolite A and Zeolite P are particularly suitable, as well Zeolite X and mixtures of A and X and / or P. Quantities and Weight ratios that meet the builders are within the scope of the present Invention - unless otherwise stated - on anhydrous active substance based.

Suitable substitutes or partial substitutes for phosphates and zeolite are crystalline, layered silicates of the general formula NaMSi _x O _{2x + 1} · yH₂O, where M is sodium or hydrogen, x is a number from 1.9-4 and y is a number from 0-20 is. Layered silicates of this type are described, for example, in European patent application 0164514. In particular, both β- and δ- sodium disilicates Na₂Si₂O₅ · yH₂O are preferred. Further builder substances are amorphous silicates with secondary washing power, for example those according to DE-P 44 00 024.3, DE-P 44 19 745.4 and DE-P 44 46 363.4. According to the invention, it will also be possible to use zeolite and / or the crystalline sheet 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 washing power 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 to the premix in the form of the undried masterbatch or a material which has only partially dried and thus only has a limited water content.

Useful organic builders are, for example, polycarboxylates 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 for ecological reasons objectionable, as well as mixtures of these and (co) polymers Polycarboxylic acids and polycarboxylates, such as the sodium salts of polyacrylic acids or Polymethacrylic acids, for example those with a molecular weight of 800 to 150,000 (based on acid) and in particular those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid are preferred, additionally included. Copolymers of acrylic acid have proven particularly suitable proven with maleic acid, the 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% Contain maleic acid. Their relative molecular mass, based on free acids, is in generally 5,000 to 200,000, preferably 10,000 to 120,000 and especially 50,000 up to 100,000. Also particularly preferred are biodegradable terpolymers, for example those which according to DE-A-43 00 772 as monomers salts of Acrylic acid and maleic acid and vinyl alcohols or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of acrylic acid and 2- Contain alkylallylsulfonic acid as well as sugar derivatives. Other preferred copolymers are those described in German patent applications DE-A-43 03 320 and P 44 17 734.8 and as monomers preferably acrolein and Have acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

In cases where a phosphate content is tolerated, phosphate can also are also used, in particular pentasodium triphosphate, if appropriate also Pyrophosphates like Orthophosphate, which are primarily used as precipitants for Lime salts work. The phosphate content is based on pentasodium triphosphate  below 30% by weight. However, agents without a phosphate content are preferred here used.

Suitable inorganic, non-complexing salts are - also as washing alkalis designated - bicarbonates, carbonates, borates or silicates of alkalis; of the Alkali silicates are primarily sodium silicates with a Na₂O: SiO₂ ratio of 1: 1 up to 1: 3.5 usable (see above).

The other detergent ingredients include graying inhibitors (Dirt carrier), foam inhibitors, optical brighteners, enzymes, fabric softening agents Fabrics, colors and fragrances as well as neutral salts.

Graying inhibitors have the task of removing the dirt detached from the fiber to keep the fleet suspended and thus prevent graying. For this are water-soluble colloids mostly of an organic nature, 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 Strength. Water-soluble polyamides containing acid groups are also for this Suitable purpose. Soluble starch preparations and others other than that can also be used Use the above starch products, e.g. B. degraded starch, aldehyde starches etc. Polyvinyl pyrrolidone is also useful. However, are preferred Carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and their mixtures and polyvinylpyrrolidone, for example in amounts from 0.1 to 5 % By weight, based on the composition.

The foaming power of the surfactants can be achieved by combining suitable types of surfactants increase or decrease; a reduction cannot be made by additions either achieve surfactant-like substances. A reduced foaming power that Working in machines is often achieved through a combination different types of surfactants, e.g. B. of sulfates and / or sulfonates with nonionic Surfactants and / or with soaps. With soaps, the foam-suppressing effect increases with Degree of saturation and the C number of the fatty acid salt. As a foam-inhibiting soap Soaps of natural or synthetic origin that are high are suitable Have proportion of C₁₈-C₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes  and their mixtures with silanized silica. Also from C₁₂ to C₂₀ alkylamines and C₂- to C₆-dicarboxylic acids derived bisacylamides are useful. With advantage also mixtures of different foam inhibitors used, e.g. B. from Silicones, paraffins or waxes. The foam inhibitors are preferably limited to one granular, water-soluble or dispersible carrier substance bound or are added to the plasticizer and / or lubricant.

In addition, the agents can contain enzyme stabilizers. For example, 0.5 up to 1% by weight sodium formate can be used. It is also possible to use Proteases with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme, are stabilized. It is particularly advantageous however, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H₃BO₃), the Metaboric acid (HBO₂) and pyrobic acid (tetraboric acid H₂B₄O₇).

The detergents can be derivatives of diaminostilbenedisulfonic acid as optical brighteners or their alkali 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, which instead the morpholino group is a diethanolamino group, a methylamino group, a Wear anilino group or a 2-methoxyamino group. Furthermore, brighteners of the Type of the substituted 4,4'-distyryl-diphenyl be present; for example the Compounds 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned Brighteners can be used.

Enzymes come from the class of proteases, lipases, cutinases, Cellulases and amylases or their mixtures in question. Are particularly well suited from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis or Streptomyces griseus enzymatic substances obtained. Preferably be Proteases of the Sulbtilis type and in particular proteases derived from Bacillus Lentus are obtained, advantageously used in a mixture with other enzymes. The enzymes can be adsorbed on carriers and / or embedded in coating substances to them protect against premature decomposition. Their share can be about 0.2 to 2% by weight be.

The salts of. Can be used as stabilizers, in particular for per-compounds or enzymes Polyphosphonic acids, hydroxyethane-1,1-diphosphonic acid (HEDP) and  Ethylenediaminetetramethylenephosphonic acid (EDTMP) or diethylenetriamine Pentamethylenephosphonic acid (DTPMP or DETPMP) come into consideration.

According to a further preferred embodiment are therefore the subject of present invention also granules obtained according to the aforementioned type which are characterized in that they have a bulk density 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 Combination of granules of different composition or as a partial product, that to complete the recipe, the mixing with other ingredients usual detergents and cleaning agents.

Finally, the present invention relates to washing and cleaning agents, containing granules of the aforementioned type, which are characterized in that they a surfactant content of up to 35% by weight, preferably 15 to 25% by weight contain.

example

For the production of textile detergents in the form of the storage-stable, free-flowing granules first became plasticizable, solid, free-flowing Premix by reaction of 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 of C₁₂-C₁₈ fatty alcohol with 7 EO, 1.7% by weight of polyethylene glycol (PEG 400) 1.8 % By weight of soda (anhydrous) and 5.6% of a 30% aqueous polycarboxylate solution (Sokalan® CP5) mixed and worked up. Composition of the spray-dried Granules:

• - 27.4 wt .-% of a surfactant mixture of sodium dodecylbenzenesulfonate (ABS) and from 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

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

In the premix production process, a 130 l batch mixer was used was equipped with a cutter head shredder, presented the solid components and then, while the mixer is running, the premixed nonionic surfactant / PEG 400- Mixture and then added the carboxylate solution and 30 seconds mixed.

The premix obtained was free-flowing and could be used to feed the Granulation plant according to the invention, a gear press roller, are supplied.

For pressing the plasticizable, solid and free-flowing premix The following granulation conditions had to be observed:

The gear press roller according to the invention used in the granulation was one from Bepex GmbH, Federal Republic of Germany, under the designation Granule molding machine GCS 200/40 available model, typically a Throughput of 0.2 m³ per hour with a typical hole nozzle diameter of 1.5 mm was carried out, with product outlet or discharge temperatures of 58 ° C.  were used. It was not necessary to cool the apparatus. The best of it subsequent batch rounding was carried out within a batch time of 1 min a circumferential rotor speed of 8 m / s in the presence of 3.2% by weight of zeolite NaA powder performed. After sieving through a 1.6 mm sieve one obtained from this in a granulate yield of 90%, a granulate with a granulate bulk density of about 820 g / l.

The coarse grain could be returned without grinding.

Claims (10)

1. A process for the production of granular detergents or cleaning agents or components therefor by pressing a plastifiable and solid, free-flowing premix by hole molds, characterized in that these hole molds are arranged in two counter-rotating and intermeshing gear press rolls. 2. The method according to claim 1, characterized in that from the perforated nozzles of the rotating gear press rolls emerging strands by fixed or movable knives can be cut. 3. The method according to claim 1 or 2, characterized in that the pressure in the Press roll 10 to 200 bar, preferably between 10 and 130 bar, in particular 30 is up to 60 bar and the press nozzle has a granule size of 0.5 to 10 mm, preferably 1 to 5 mm. 4. The method according to any one of the preceding claims, characterized in that the press roll has a pelletizing head with interchangeable nozzle inserts. 5. The method according to any one of claims 1 to 4, characterized in that the Premixed in the gear press rollers upstream mixers homogenized becomes. 6. The method according to any one of claims 1 to 5, characterized in that the Gear press rolls plasticized premixes are fed, which to 2 to 100% by weight, preferably 10 to 45% by weight and in particular above Contain 10% by weight, for example 15 to 40% by weight of recycled portions. 7. The method according to any one of claims 1 to 6, characterized in that the Coarse particles are not ground before they are returned. 8. The method according to any one of claims 1 to 7, characterized in that a Rounding step is followed, with conventional rounding devices, for example Marumerizer or sieve mills can be used.   9. Granules obtained according to one of the preceding claims, characterized characterized in that it has a bulk density of above 700 g / l, preferably 750 up to 1000 g / l and in particular 850 to 980 g / l and as ready-to-use Multi-substance mixture in the form of uniform granules or as a combination of Granules of different compositions or as a sub-product that is used for Completion of the recipe and mixing with other ingredients usual detergents and cleaning agents. 10. washing and cleaning agent containing granules according to claim 9, characterized characterized in that they have a surfactant content of up to 40% by weight, preferably contain between 15 and 25 wt .-%.