WO1996011254A1

WO1996011254A1 - Process for producing extrudates with a washing or cleaning action

Info

Publication number: WO1996011254A1
Application number: PCT/EP1995/003815
Authority: WO
Inventors: Kathrin Schnepp; Wolfgang Seiter; Wieland Schulze; Josef Markiefka; Bernd Larson; Norbert Kühne
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1994-10-06
Filing date: 1995-09-27
Publication date: 1996-04-18
Also published as: DE4435742A1

Abstract

In an extrusion process for producing high-density extrudates with a washing or cleaning action, a uniform, solid and pourable pre-mixture produced with the addition of a plasticiser and/or slip agent is pressed into a strand at high pressures of up to 200 bar and, after leaving the die, the strand is cut by a cutting device to the predetermined grain size, the raw extrudate being taken while still plastic and moist to a further shaping processing stage and then dried. It is possible to reduce the adhesion of the extrudates in the drying stage by adding drying powders as powdering agents either during the drying stage or directly before the raw extrudate is transferred to the drier, but in any event after the completion of any shaping stages in the process.

Description

"Process for the production of washable or cleanly active extrudates"

The invention relates to a method for producing known extrudates which are active in washing and cleaning.

From the international patent application W0-A-91/02047 a process for the production of washable or cleaning-active extrudates with high density is known, wherein a homogeneous, solid and free-flowing premix, which was produced with the addition of a plasticizer and / or lubricant, at high Pressures up to 200 bar are extruded and the extrudate is cut to the pre-determined pellet size using a cutting device after exiting the hole shape. The still plastic, moist raw extrudate can then be fed to a further shaping processing step, for example a rounder, the edges present on the raw extrudate being rounded off, so that ultimately spherical or at least approximately spherical granules / extrudates are obtained. If these crude extrudates are then to be dried, this application suggests using dry powder in this stage of the final shaping of the extrudates, in order to prevent the extrudates from sticking to one another during the subsequent drying. In addition to reducing the bulk density, such bonds also lead to considerable disruptions in the production process and are therefore also to be avoided for safety reasons.

However, it has been shown that the amount of dry powder which has to be used as a powdering agent for the crude extrudates in the fillet is greater than would be necessary to prevent the extrudates from sticking in or before the drying step. These excess quantities either lead to undesirable shifting of the formulation in the end product or have to be removed again, for example by suction and disposal. In addition, it has been shown that higher amounts of dry powder deteriorate the degree of rounding in the final shaping step.

Surprisingly, it has now been found that these disadvantages can be avoided by adding the powdering agent not only or not only during the shaping step, but also afterwards. O 96/11

The invention accordingly relates to a process for the production of extrudates with high density which are active in washing or cleaning, a homogeneous, solid and free-flowing premix which has been produced with the addition of a plasticizer and / or lubricant being extruded at high pressures of up to 200 bar and the strand after exiting the hole shape is cut to the predetermined granule size by means of a cutting device, the still plastic, moist raw extrudate is optionally fed to a further shaping processing step and then dried. In addition, dry powders are added as powdering agents either during the drying step or immediately before the crude extrudate is transferred to the dryer, but in any case after the shaping processing step which may have been carried out.

In particular, finely divided dry powders, which are common ingredients of detergents or cleaning agents, are suitable as powdering agents. Zeolites, in particular zeolites of type A and / or P, silicas, in particular microfine, silanized silica, salts of fatty acids, in particular calcium stearate, finely divided alkyl sulfates, neutral salts, in particular sodium sulfate, or mixtures of these, are preferred, mixtures of zeolite and Silicas or mixtures of zeolite and calcium stearate or mixtures of zeolite, silicas and calcium stearate are particularly preferred.

In a preferred embodiment of the invention, the further shaping processing step after the extrusion is carried out in a rounding device. It is then further preferred that after the completion of the shaping processing step, at least partially dust or fine particles which have accumulated during the shaping processing step are used as the powdering agent.

However, the amount of dust or fine fraction which is used as the powdering agent should advantageously not exceed 5% by weight, in particular 3% by weight, based in each case on the extrudate still to be dried.

The possibility of this use of the dust or fine particles generated in the further shaping processing step is not only concealed by one Advantage that the risk of the extrudates sticking during drying is reduced, but at the same time this increases the process yield and thus also the loss amounts of the premix used, which are normally screened off due to an unfavorable particle size range. It has also proven to be advantageous to use mixtures of dust or fine fractions and conventional powdering agents.

In total, the powdering agents can be used in amounts of up to about 8% by weight. Depending on the recipe, however, in the preferred cases 0.2 to 5% by weight, based on the extrudate to be dried, of powdering agent is sufficient to prevent the extrudates from sticking together in the drying step. Amounts in excess of this are therefore not preferred.

It may be advantageous to add powdering agents both before and during the drying step, it being preferred to use a maximum of 50% by weight, based on the powdering agent, before the drying step.

If it is desired, it is also possible to add powdering agents during the further shaping processing step. It is only essential to the invention that further powdering agents are added in the manner according to the invention after the rounding step.

To explain the actual extrusion process, reference is expressly made to international patent applications WO-A-91/02047, OA-93/02176 and WO-A-94/09111. In a preferred embodiment of the invention, the premix is preferably fed continuously to a 2-screw extruder with a co-rotating or counter-rotating screw guide, the housing and the extruder pelletizing head of which can be heated to the predetermined extruder temperature. Under the shear action of the external screws, the premix is compressed, plasticized, in the form of fine strands by means of pressure, which is preferably at least 25 bar, but at extremely high throughputs depending on the apparatus used Hole die plate extruded in the extruder head and finally reduced the extrudate by means of a rotating knives preferably to approximately spherical to cylindrical granules. The hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granule dimension. In this embodiment, granules of an essentially uniformly predeterminable particle size can be produced, and in particular the absolute particle sizes can be adapted to the intended use. In general, particle diameters of up to at most 0.8 cm are preferred. Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm. The length / diameter ratio of the chipped primary extrudates (crude extrudates) is in an important embodiment in the range from about 1: 1 to about 3: 1. Furthermore, it is preferred to feed the still plastic and moist crude extrudate to a further shaping processing step; edges present on the crude extrudate are rounded off, so that ultimately spherical to approximately spherical extrudate grains can be obtained. This shape can be done in standard rounding machines. Care should be taken to ensure that only small amounts of fine grain are produced in this stage. The extrudates are then fed to a drying step, for example a fluidized bed dryer. The extruded granules, which contain peroxy bleaching agents, for example perborate monohydrate, can be dried at supply air temperatures between 80 and 150 ° C. without loss of active oxygen.

The premix can contain all the usual ingredients of detergents or cleaning agents, such as anionic, nonionic, cationic, amphoteric or zwitterionic surfactants, inorganic and organic builders, alkali carbonates and alkali silicates, bleaches, optical brighteners, graying inhibitors and, if appropriate, foam inhibitors, bleaching enzymes, enzyme activators, Textile calibrating substances, dyes and fragrances and neutral salts such as sulfates and chlorides in the form of their sodium or potassium salts. Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are Cg-Ci3-alkylbenzenesulfonates, olefin sulfonates, dg mixtures of alkene and hydroxyalkalsulfonates and disulfonates, such as are obtained, for example, from Ci2-Ci8 * monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent receives alkaline or acidic hydrolysis of the sulfonation products.

Also suitable are alkanesulfonates which are obtained from Ci2-Ci8-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), e.g. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, or the disalts of the corresponding α-sulfofatty acids. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. The sulfonation products represent a complex mixture which contains mono-, di- and triglyceride sulfonates with an α-position and / or internal sulfonic acid grouping. As by-products, sulfonated fatty acid salts, glyceride sulfates, glycerine sulfates, glycerin and soaps are formed. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol esters, the proportion of the α-sulfonated fatty acid disalts can, depending on the procedure, be up to about 60% by weight.

Suitable sulfate-type surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin. The alk (en) yl sulfates here are the sulfuric acid half-esters of the C 16 -C 16 -alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from the corresponding oxo alcohols, and those secondary alcohols of this chain length prefers. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis and have an analogous degradation behavior like the appropriate compounds based on fettchemis raw materials. Ci6-Cj8-Alk (en) ylsul are particularly preferred from the point of view of washing technology. The alk (en) yl sulfates and, in particular, tallow fatty alkyl sulfates can be introduced into the Ver in any form. Powders, pastes, granular compounds, for example, are also conceivable, for example those which are likewise obtained according to the L of the international patent application WO-A-93/04162. D granular compounds are preferred which have a high content of alkyl sulfates, in particular a content of above 70% by weight of alkyl sulfates. In a preferred embodiment of the invention, detergents or cleaning agents are prepared which contain 5 to% by weight of C8-Ci8-alk (en) yl sulfates and preferably Ci2-Ci8-alk (en) yl sulfate.

Soaps, in particular in quantities of 0.5 to 5% by weight, are particularly suitable as further anionic components. Suitable fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, P mitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap genes.

The anionic surfactants and soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mon di- or triethanola in. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of sodium salts. Preferred detergents or cleaning agents contain 5 40% by weight of surfactants, which may optionally consist entirely of anionic surfactants and in particular of alk (en) yl sulfates of the type specified above and in the amounts specified above.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably up to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (E0) per alcohol, in which the alcohol radical can be linear or preferably methyl-branched or linear and can contain methyl-branched Re in the mixture, as is usually the case in oxo alcohols O 96/11254 PCI7EP95 / 0

available. However, alcohol ethoxyates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Cn-Alkonol with 7 EO, Ci3-Ci5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-Ci8- Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-Ci4 alcohol rr 3 EO and Ci2-Ci8 alcohol with 5 EO. The ethoxylation stated: ide represent statistical averages, which can be a whole for a special Prouukt or a broken Zah ^'. Preferred alcohol ethoxylates have a narrow homolc distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula R0 (G) _x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18, C. -Atoms means and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycos and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid of the formula (I),

R3

I.

R2-C0-N- [Z] (I) l in R ² C0 for an aliphatic acyl radical with 6 to 22 carbon atoms, R * - * 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 ides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The preferred polyhydroxy fatty acid amides are fatty acid N-alkylglucamides.

Preferred washing or cleaning agents contain 2 to 25% by weight of non-ionic surfactants. In this case, embodiments can be advantageous which contain anionic and nonionic surfactants in a weight ratio of 2: 1 to 1: 2 and in particular around 1: 1 to 1: 1.5.

In a preferred embodiment of the invention, the nonionic surfactants and in particular ethoxylated fatty alcohols are used in combination with constituents which improve the solubility of the extrudates. Such components are described, for example, in international patent applications WO-A-93/02176 and WO-A-93/15180. The preferred ingredients include, in particular, fatty alcohols with 20 to 80 moles of ethylene oxide per mole of fatty alcohol, for example tallow fatty alcohol with 30 E0 and tallow alcohol with 40 E0, but also fatty alcohols with for example 14 E0 and polyethylene glycols with a relative molecular weight between 200 and 2000 .

Phosphates and in particular zeolites are suitable as builder substances. The fine-crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. However, zeolite X or P and mixtures of A, X and / or P are also suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production. In the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite ethoxylated Ci2-Ci8 fatty alcohols with 2 to 5 ethylene oxide groups, Ci2-Ci4 ~ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the formula Na Si θ2χ ₊ ι * yH2θ, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline sheet silicates are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and Üf sodium disilicate Na2Si2θ5 * yH2θ are preferred.

In addition to the crystalline layered sodium silicates, it is also possible to use known amorphous sodium silicates, in particular those with secondary washing power.

Washing or cleaning agents which are preferably produced contain 15 to 60% by weight, in particular at least 20% by weight, of inorganic builder substances of the type specified above.

Is Useful organic builders are, for example, preferably in the form of their sodium salts polycarboxylic acids used, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such a ^r domestic set for ecological reasons not objectionable , as well as mixed: n from these. Preferred salts are the salts of the polycarboxylic acids wit tronic acid, adipic acid, succinic acid, glutaric acid, tartaric acid, zuc acids and mixtures of these. Their content in the washing / cleaning agents is preferably 0 to 20% by weight. The polycarboxylic acids, in particular citric acid, can also be used in highly toxic agents. AO

Suitable polymeric polycarboxylates are, for example, the sodium salt of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which have 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable contain. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, 2 to 55% by weight. % aqueous solutions are preferred. Also particularly preferred are biodegradable terpolymers or quadropolymers, for example those which, according to DE-A-4300772, are salts of acrylic acid and de-maleic acid as monomers and vinyl alcohol or vinyl alcohol derivatives or DE-C-4221 381 are monomers of acrylic acid salts and the 2-A1 contain kylallylsulfonic acid as well as sugar derivatives. The content of (co) polymeric polycarboxylates in the middle is preferably 2 to 8% by weight.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures thereof; In particular, alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na2θ: Siθ2 of 1: to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used. The content of sodium carbonate in the agent is preferably up to 20% by weight, advantageously between 5 and 15% by weight. The content of sodium silicate in the compositions is generally up to 15% by weight and preferably between 2 and 10% by weight. Η

In one embodiment of the invention, it is preferred to introduce the alkali silicates into the process at least partially in the form of an aqueous solution, for example in the form of a 10 to 45% by weight aqueous water glass solution.

According to the teaching of German patent application DE 43 19 578, alkali metal carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and optionally an additional carboxyl and / or amino group and amino acids and / or their salts. Within the scope of this invention, it is possible for the alkali metal carbonates to be partially or completely replaced by glycine or glycinate.

Of the compounds which serve as bleaching agents and supply H2O2 in water, the sodium perborate tetrahydrate and the sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids providing H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples of this are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Other known bleach activators are cetylated mixtures of sorbitol and mannitol, as are described, for example, in European patent application EP-A-0525239. The content of lead activators in the bleach-containing compositions is in the customary range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight. Particularly preferred bleach activators are N, N, N '.N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dicxo-hexahydro-1,5,5-triazine (DADHT) and acetylated sorbitoi-mannitol mixtures (S0RMAN). Λl

A reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, e.g. of sulfates and / or sulfonates with nonionic surfactants and / or with soaps. In the case of soaps, the foam-suppressing effect increases with the degree of saturation and the C number of the fatty acid residue. Soaps of natural or synthetic origin that contain a high proportion of Ci8-C24 fatty acids are therefore suitable as foam-inhibiting soaps. Suitable non-surfactant-like 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 or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, e.g. those made of silicone, paraffins or waxes. The foam inhibitors, in particular silicone or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

Enzymes from the class of proteases, lipases, aylases, Ce11ulases or mixtures thereof are possible. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniform and Strepto yces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest. Peroxides or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in Hü11 substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

The salts of polyphosphonic acids, in particular l-hydroxyethane-l, l-diphos-, come as stabilizers, in particular for per-compounds and enzymes. Phonic acid (HEDP) and Diethylerr iaminpentamethylenphosphonat into consideration. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. 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), metaboric acid (HBO2) and pyrobic acid (tetraboric acid H2B4O7), is particularly advantageous.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed onto the fiber. For this purpose, water-soluble colloids of mostly organic nature are suitable, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid ester cellulose or starch. Also contain water-soluble, acidic groups. de Polyamides are suitable for this purpose. Furthermore, soluble starch preparations and starch products other than those mentioned above can be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, preference is given to cellulose ethers, such as carboxyethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrole, for example in amounts of 0.1 to 5% by weight, based on the Means used.

As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which contain an replace the morpholino group with a diethanola ino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, the type of the substituted diphenylstyryls can be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro- _J- sulfostyryl) diphenyl , or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. AI,

In a preferred embodiment of the invention, premixes are used which contain 10 to 30% by weight and in particular 15 to 25% by weight of anionic and nonionic surfactants, 20 to 40% by weight of zeolite, 2 to 15% by weight of sodium carbonate, 0 to 10% by weight sodium citrate, 1 to 5% by weight polymeric polycarboxylates and 0 to 20% by weight peroxy bleaching agent.

The finished washing or cleaning agents can be built up uniformly from extrudates which have the above-mentioned ingredients. In a further embodiment of the invention, however, the extrudates are prepared with further ingredients of washing or cleaning agents. This can be such that the washing or cleaning agents are obtained from a mixture of several different granules, of which the extrudates according to the invention form the main component. Bleach activators, for example N, N'-tetraacylated diamines such as N, N, N ', N'-tetraacetylethylenediamine, enzyme granules containing enzymes, in particular protease and / or lipase and / or cellulase and / or amylase, are preferred, blends consisting of 2 or 3 enzymes can be particularly advantageous, and perfume added afterwards.

The extrudates can also be prepared with further finely divided dry powders before enzymes and the other ingredients are added. Examples include zeolite, silicas and salts of fatty acids, for example calcium stearate, bleach activator or mixtures of zeolite with one of the other powders mentioned. It has also been shown that the foaming behavior for detergents can be positively influenced if the foam inhibitor, for example organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide, at least in part is not extruded, but is subsequently mixed with the extrudate. It is also possible that the surface of the extrudate according to the invention is first covered, for example, with zeolite or a zeolite-containing mixture and then with a foam inhibitor. Such measures make it possible to further improve the flushing behavior of the extrudates. The bulk density of the extrudates produced according to the invention is preferably between 600 and 1200 g / 1, bulk densities between 700 and 1000 g / 1 and in particular between 750 and 950 g / 1 being particularly preferred.

BeispieleQ examples

In a continuously operating mixer equipped with a cutter head chopper, a premix was prepared which was 7 parts by weight of alkylbenzenesulfonate and 6.5 parts by weight of C12-Ci8-alkyl sulfate. 2 parts by weight of Ci2-Ci8 fatty acid soap, 9 parts by weight of

with 5 ethylene oxide groups, 37 parts by weight of zeolite, based on anhydrous active substance, 7.5 parts by weight of sodium citrate, 5.4 parts by weight of copolymeric salt of acrylic acid and maleic acid, 7 parts by weight .-% parts of sodium carbonate, 2 parts by weight of sodium sulfate, 0.4 parts by weight of salts from solutions and 11.2 parts by weight of water. This premix was extruded, rounded and dried in accordance with the teaching of international patent application WO91 / 02047. As in the table for Examples 1 to 7 (in contrast to Comparative Examples VI to V4), dust or fine fractions from the rounder and / or finely divided zeolite powder were conveyed directly to the fluidized bed dryer or in the dryer Given raw extrudate. In experiments 2 to 4, zeolite powder was also added in the fillet.

Table: Powdering raw extrudate before and in the dryer

Example powdering agent in parts by weight place product evaluation

VI Zeolite 3.6 rounder 0.0 glued in front of dryer 0.0 in dryer

V2 zeolite 4.3 rounder glued 0.0 before dryer 0.0 in dryer

V3 Zeolite 5.0 rounder glued 0.0 before dryer 0.0 in dryer

V4 Zeolite 5.5 Rounder does not stick 0.0 before dryer 0.0 in dryer

1 zeolite 3.6 rounder 0.0 before dryer does not stick dust 1.5 in the dryer

2 Zeolite 3.6 Rounded zeolite 0.7 before dryer does not stick 0.0 in the dryer

3 zeolite 3.6 rounder 0.0 before dryer does not stick zeolite 0.7 in the dryer

4 Zeolite 3.6 Rounding Zeolite 1.7 before dryer does not stick 0.0 in the dryer

5 Zeolite 3.6 rounder 0.0 before dryer does not stick Zeolite 1.4 in the dryer

6 Zeolite 3.6 Rounding Zeolite 2.5 before dryer does not stick 0.0 in the dryer

7 Zeolite 3.6 Rounder 0.0 before dryer does not stick dust 2.5 in the dryer

Claims

claims

1. Process for the production of washable or cleaning-active extrudates with a high density, a homogeneous, solid and free-flowing pre-mixture, which was produced with the addition of a plasticizer and / or lubricant, being extruded at high pressures of up to 200 bar and the extrudate following Exit from the hole shape by means of a cutting device tailored to the predetermined granulate dimension, the still plastic, moist raw extrudate, if necessary, is fed to a further shaping processing step and then dried, characterized in that the addition of dry powders as powdering agents either during the drying step or directly before the transfer of the crude extrudate into the dryer, but in any case after the completion of the shaping processing step which may have been carried out.

2. The method according to claim 1, characterized in that dry powder from the group of zeolites, silicas, salts of fatty acids, alkyl sulfates or mixtures of these are used as the powdering agent.

3. The method according to claim 1 or 2, characterized in that dust or fine particles, which are obtained during the further for - gebeπden processing step, are used as the powder.

4. The method according to claim 3, characterized in that the dust or fine fractions are used in amounts which do not exceed 5% by weight, based on the extrudate still to be dried.

5. The method according to any one of claims 1 to 4, characterized in that powdering agents are used in amounts of 0.2 to 5 wt .-%, based on the extrudate to be dried.

6. The method according to any one of claims 1 to 5, characterized in that powdering agents are added both before and during the drying step.

7. The method according to claim 6, characterized in that a maximum of 50 wt .-% of the total powder used are used before the drying step.