EP0724620B1 - Process for producing washing or cleaning extrudates with improved redispersibility - Google Patents

Abstract

In order to obtain mechanically stable extrudates by using short-chain C8-C14-alkylsulfates when producing washing granulates by extrusion of a solid premix under high pressure, the short-chain alkylsulfates are used as a granulate produced in a fluidised bed and if required dried at the same time.

Description

The invention relates to a process for the production of washing or cleaning active Extrudates with improved redispersibility, whereby this process is characterized by high process reliability.

From the international patent application WO-A-91/02047 a process for the production of washing or cleaning-active extrudates with high density is known, whereby a homogeneous and solid premix containing a plasticizer and / or lubricant is extruded under pressure and the extrudate after exiting the hole shape can be cut to the predetermined granule size by means of a cutting device. Liquid components can perform the function of a plasticizer and / or lubricant during the extrusion and also function as a binder in the finished extrudates. According to the teaching of German patent application DE-A-42 03 031, relatively short-chain alkyl sulfates having 8 to 16 carbon atoms are used to improve the redispersion behavior. Parts of C ₁₈ alkyl sulfate can also be present in alkyl sulfate mixtures made from natural raw materials. These alkyl sulfates can be introduced into the process in solid or in liquid form, preferably in a 25 to 60% strength by weight aqueous solution. In the case of large-scale extrusion of quantities above 1000 kg / h, however, it has been found that the customary available raw material forms of these alkyl sulfates cause considerable processing problems, in particular if essentially C ₁₂ alkyl sulfate is to be used. The incorporation of commercially available aqueous short-chain alkyl sulfate pastes with concentrations of around 35% by weight introduces excessive amounts of water into the process, so that extrudates with a sticky nature are formed. The use of more concentrated pastes, which can contain up to 65% by weight alkyl sulfate, leads to a lower stickiness of the premix and the resulting extrudates, but these pastes are difficult to handle due to their high viscosity. In addition, it has been shown that the extrudates produced in this way often have a poor mechanical stability and therefore partially disintegrate. It is believed that such highly concentrated alkyl sulfate pastes have insufficient function as binders.

Commercially available solid alkyl sulfates exist, for example, in the form of needles or a fine powder. However, if needles are used in the extrusion process, they will soon clog the perforated plates used. Powder, especially C ₁₂ alkyl sulfate powder, is a dust explosion hazard and irritates the respiratory tract. However, since the development of dust cannot be completely avoided when handling the fine and light powder, the extrusion would have to be carried out in a completely closed apparatus for safety reasons.

Another way of supplying short chain alkyl sulfates in the extrusion premix consists of spray-dried granules, which also still other ingredients, the preferred ingredients of Detergents or cleaning agents are included. These include in particular inorganic components like zeolite, sodium carbonate etc. It has However, it has been shown that with the use of such spray-dried alkyl sulfate Granules no satisfactory extrusion results be achieved. There are non-sticky extrusion strands that can be cut after exiting the hole shapes, but has it has been shown that the extrudates thus produced have a lack of mechanical Have stability and in subsequent processing steps such as rounding, powdering and / or mixing with other granular components of detergents or cleaning agents disintegrated again.

It was therefore the task of a process for the production of mechanical to provide stable extrudates that allow short-chain alkyl sulfates to be brought into the process. Process reliability should also be considered be ensured in the implementation of the extrusion.

The invention accordingly relates to a process for the production high density, active washing or cleaning extrudates, with a solid Premix, which is a plasticizer and / or lubricant as well as short-chain Contains alkyl sulfates in solid form, extruded under pressure and the strand after exiting from a hole shape by means of a Cutting device cut to the predetermined granule dimension be, wherein alkyl sulfates having 8 to 14 carbon atoms alone or in Mixture in the form of a granulated in a fluidized bed and optionally dried granules can be used at the same time.

To explain the actual extrusion process is explicit to international patent applications WO-A-91/02047, WO-A-93/02176 and to the older German patent application P 42 35 646.6. In a preferred embodiment of the invention is the solid premix preferably continuously a 2-screw extruder with co-rotating or fed against running screw guide, its housing and its extruder pelletizing head to the predetermined extrusion temperature can be heated. Under the shear of the extruder screws the premix is under pressure, which is preferably at least 25 bar, at extremely high throughputs depending on the used But the apparatus can also lie underneath, compressed, plasticized, in shape fine strands are extruded through the perforated nozzle plate in the extruder head and finally, preferably the extrudate using a rotating knife reduced 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 size. In this embodiment one succeeds essentially in the production of granules uniformly predeterminable particle size, the individual being the absolute Particle sizes can be adapted to the intended application. In general, particle diameters up to at most 0.8 cm are preferred. Important embodiments see the production of uniform Granules in the millimeter range, for example in the range of 0.5 to 5 mm and in particular in the range from about 0.8 to 3 mm. The Length / diameter ratio of the chopped off primary granules in an important embodiment in the range from about 1: 1 to about 3: 1. It is further preferred that the still plastic and moist primary granules to supply a further shaping processing step; there edges present on the crude extrudate are rounded off, so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired, small amounts of dry powder, for example zeolite powder, such as zeolite NaA powder, is also used become. This shape can be done in standard rounding machines. Care should be taken to ensure that only small amounts of Fine grain fraction arise. The extrudates are then preferably one Drying step, for example fed to a fluidized bed dryer. The extruded granules, which are peroxy bleaching agents, for example Perborate monohydrate, included, at supply air temperatures between 80 and 150 ° C can be dried without loss of active oxygen. Alternatively, it is also possible to connect the drying step directly to the extrusion of the crude extrudate and thus before a desired one made final shaping in a rounding machine perform. Subsequently, the extrudates with other components of detergents or cleaning agents.

It is generally known that the admixing of relatively short-chain alkyl sulfates to long-chain alkyl sulfates increases the redispersibility of the compositions, in particular at temperatures below 60 ° C. These relatively short-chain alkyl sulfates include those with 8 to 14 carbon atoms, such as C ₈ alkyl sulfate, C ₁₂ alkyl sulfate, mixtures of C ₁₂ -C ₁₈ alkyl sulfate, C ₈ -C ₁₆ alkyl sulfate, the proportion of alkyl sulfates having a carbon chain length above of 14, however, should be a maximum of 10% by weight and in particular a maximum of 5% by weight. The use of essentially C ₁₂ -C ₁₄ alkyl sulfate is particularly preferred, C ₁₂ alkyl sulfate and mixtures of essentially C ₁₂ -C ₁₄ alkyl sulfate being preferred. It has now been found, however, that the disadvantages described above of adding relatively short-chain alkyl sulfates can be avoided if the relatively short-chain alkyl sulfates are added in the form of a particular granulate, which was optionally produced in the fluidized bed with simultaneous drying. Such granules can be produced, for example, according to the teaching of international patent application WO-A-93/04162. Fluidized bed granules containing alkyl sulfate which are preferably used contain 20 to 65% by weight of alkyl sulfate, preferably C ₁₂ -C ₁₄ alkyl sulfate, and 35 to 80% by weight of inorganic constituents. The types of suitable inorganic constituents can also be found in international patent application WO-A-93/04162. However, it is particularly preferred that these fluidized bed granules contain zeolite and / or alkali carbonate such as sodium carbonate and / or potassium carbonate and / or alkali sulfates such as sodium sulfate and / or potassium sulfate as inorganic constituents. In a particularly advantageous embodiment of the invention, fluidized-bed granules containing alkyl sulfate are used which contain 30 to 55% by weight of alkyl sulfate, preferably 40 to 50% by weight of alkyl sulfate and in particular C ₁₂ -C ₁₄ -alkyl sulfate. These advantageous embodiments contain 40 to 60% by weight and preferably 45 to 55% by weight of sodium and / or potassium carbonate, sodium and / or potassium sulfate or mixtures of carbonate and sulfate as inorganic constituents.

For the use of these alkyl sulfate-containing fluidized bed granules in the Extrusion processes, it is particularly advantageous that the alkyl sulfate-containing Fluid bed granules in their production with a certain Grain spectrum can be produced. Here it turned out to be proved to be advantageous that fluidized bed granules containing alkyl sulfate in the extrusion process are used, which have a maximum grain size of 1 mm. Because even when using the alkyl sulfate-containing Fluidized bed granules can depend on the Composition of the mixture to be extruded still occur that the Perforated plates during extrusion become clogged when the fluidized bed granules significant proportions of particles with a grain size of more have than 2 mm. Guide particles with a maximum grain size of 1 mm not only to the absolutely desired process security, they guarantee also better homogenization in the manufacture of the extrusion Premix.

Other components of the premix are the usual ingredients of Detergents or cleaning agents such as other anionic, nonionic, cationic, amphoteric or zwitterionic surfactants, inorganic and organic Builder substances, alkali carbonates and alkali silicates, bleaching agents, optical brighteners, graying inhibitors and optionally foam inhibitors, Bleach activators, enzymes, fabric softening agents, dyes and Fragrances and neutral salts such as sulfates and chlorides in the form of their Sodium or potassium salts.

Examples of additional anionic surfactants used are those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C ₁₂ -C ₁₈ monoolefins with an end or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.

Also suitable are alkanesulfonates obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfofatty acids (ester sulfonates), for example 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 are 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 ester mixtures, the proportion of the α-sulfonated fatty acid disalts can be up to about 60% by weight, depending on the procedure.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin. The alk (en) yl sulfates additionally preferred here are the sulfuric acid semiesters of the C ₁₆ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from the corresponding oxo alcohols, and those secondary alcohols of this chain length. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. C ₁₆ -C ₁₈ alk (en) yl sulfates are particularly preferred from the point of view of washing technology. The alk (en) yl sulfates and in particular the tallow fatty alkyl sulfates can be introduced into the process in any form. For example, powders, pastes or granular compounds are conceivable, for example those which are likewise obtained according to the teaching of international patent application WO-A-93/04162. Granular compounds which have a high content of alkyl sulfates, in particular a content of above 70% by weight of alkyl sulfates, are preferred.

In a preferred embodiment of the invention, washing or cleaning agents are produced which contain 5 to 30% by weight of C ₈ -C ₁₈ -alk (en) yl sulfates and preferably C ₁₂ -C ₁₈ -alkyl sulfates. A maximum of 50% by weight, based on the total amount of anionic surfactants (without soaps), is used in the form of a C ₁₂ -C ₁₄ -alkyl sulfate granulated in a fluidized bed and optionally dried at the same time.

In a further preferred embodiment of the invention, a washing or cleaning agent is produced which contains 100% by weight of C ₁₂ alkyl sulfate or C ₁₂ -C ₁₄ alkyl sulfate as alk (en) yl sulfate.

Soaps are particularly preferred as further anionic constituents, preferably in amounts of 0.5 to 5% by weight. Saturated ones are suitable Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

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 mono-, Di- or triethanolamine. The anionic are preferably located Surfactants in the form of their sodium or potassium salts, especially in the form of Sodium salts. Preferred washing or cleaning agents contain 5 to 40% by weight of surfactants, which may consist entirely of anionic surfactants and in particular from alk (en) yl sulfates of the type indicated above and in the quantities specified above may exist.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohol with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 5 EO. 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 narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms 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 monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may be suitable. The amount of this nonionic Surfactants are preferably no more than that of the ethoxylated ones Fatty alcohols, especially not more than half of them.

in der R²CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R³ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können. Die bevorzugten Polyhydroxyfettsäureamide stellen Fettsäure-N-alkylglucamide dar.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

in the R ² CO for an aliphatic acyl radical having 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 stands. The polyhydroxy fatty acid amides 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 nonionic Surfactants. Embodiments can be advantageous, which anionic and nonionic surfactants in a weight ratio of 2: 1 up to 1: 2 and in particular around 1: 1 to 1: 1.5.

In a preferred embodiment of the invention, the nonionic Surfactants and especially ethoxylated fatty alcohols in combination used with ingredients that improve the solubility of the extrudates. Such components are used, for example, in the international Patent application WO-A-93/02176 and the older international patent application WO-A-93/15180. Among the preferred ones 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 EO and Tallow fatty alcohol with 40 EO, but also fatty alcohols with 14 EO, for example as well as polyethylene glycols with a molecular weight between 200 and 2000.

Phosphates and in particular zeolites are suitable as builder substances. The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. However, zeolite NaX, 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 may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ 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 NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to Is 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

Preferred washing or cleaning agents contain 20 to 60% by weight of inorganic Builder substances of the type specified above.

Useful organic builder substances are preferred, for example polycarboxylic acids used in the form of their sodium salts, such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, Aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. Their salary is in the washing or Detergents preferably 0 to 20 wt .-%.

Suitable polymeric polycarboxylates are, for example, the sodium salts 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 acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain. Their relative molecular mass, 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 can be used either as a powder or as an aqueous solution, 20 up to 55% by weight aqueous solutions are preferred. Particularly preferred are also biodegradable terpolymers, for example those that are considered Monomeric salts of acrylic acid and maleic acid as well as vinyl alcohol or Vinyl alcohol derivatives (P 43 00 772.4) or as the monomers salts of Acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives (DE 42 21 381) included. The content of the agents in (co) polymeric polycarboxylates is preferably 0.5 to 10% by weight and in particular 2 to 8% by weight.

Other suitable builder substances are polyacetals, which by reaction of dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and have at least 3 hydroxyl groups, for example as in European Patent application EP-A-0 280 223 can be obtained. Preferred polyacetals are derived from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from polyol carboxylic 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 of these; In particular, alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used. The sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight. The sodium silicate content of the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.

In one embodiment of the invention, it is preferred to use the alkali silicates at least partially in the form of an aqueous solution, for example in the form of a 10 to 45 wt .-% aqueous water glass solution, in the To bring proceedings.

According to the teaching of the older German patent application P 43 19 578.4 Alkali carbonates also by sulfur-free, 2 to 11 carbon atoms and optionally having a further carboxyl and / or amino group Amino acids and / or their salts are replaced. Within the scope of this invention it is preferred that a partial to complete exchange the alkali carbonates are made by glycine or glycinate.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, 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 these are N-acyl or O-acyl compounds which form organic peracids with H ₂ O ₂ , preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239. The bleach activators contain bleach activators in the usual 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-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).

A reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, for example 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 which contain a high proportion of C ₁₈ -C ₂₄ 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 various foam inhibitors are also used with advantages, for example those made of silicones, 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 come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. Are particularly well suited Strains of bacteria or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably become proteases of the subtilisin type and in particular proteases that are obtained from Bacillus lentus. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or Protease and cellulase or from cellulase and lipase or from protease, Amylase and lipase or protease, lipase and cellulase, but especially Mixtures of cellulase of particular interest. Peroxidases too or oxidases have been found to be suitable in some cases. The enzymes can be adsorbed on carrier substances and / or in coating substances embedded to protect them against premature decomposition. The amount the enzymes, enzyme mixtures or enzyme granules can for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

The salts of polyphosphonic acids, in particular 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylene triamine pentamethylene phosphonate, are suitable as stabilizers, in particular for per compounds and enzymes. 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 (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous.

Graying inhibitors have the task of removing the fiber Keep dirt suspended in the fleet and prevent 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 Starch or the cellulose or salts of acidic sulfuric acid esters Cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Furthermore, soluble ones Use starch preparations and other starch products than those mentioned above, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, cellulose ethers such as carboxymethyl cellulose are preferred (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as Methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition.

The agents can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed connections that instead the morpholino group is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present be, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

The finished washing or cleaning agents can consist of Extrudate be built up, which have the above-mentioned ingredients. In a further embodiment of the invention, the extrudates but prepared with other ingredients of washing or cleaning agents. This may look like the detergent or cleaning agent a mixture of several different granules can be obtained, of which the extrudates according to the invention form the main component. So be preferably 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, mixtures of 2 or 3 enzymes can be particularly advantageous, and perfume added afterwards. The extrudates can also be made before Mixing of enzymes and the other components with other fine particles Dry powders are processed. Examples include zeolite, Silicas and salts of fatty acids, for example calcium stearate, Bleach activator or mixtures of zeolite with one of the others mentioned Powder. 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, if necessary silanized silica as well as paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide, at least partially not extruded, but later with the extrudate is mixed. It is also possible that the surface of the extrudate according to the invention e.g. first with zeolite or a zeolite-containing one Mix and then coated with a foam inhibitor becomes. Such measures will further improve the induction behavior which enables extrudates. The bulk density of the invention extrudates produced is preferably between 600 and 1200 g / l, bulk densities between 700 and 1000 g / l and in particular between 750 and 950 g / l are particularly preferred.

Examples

ABS

C₉-C₁₃-Alkylbenzolsulfonat-Natriumsalz, eingebracht über ein sprühgetrocknetes Granulat, welches außer Alkylbenzolsulfonat noch Zeolith, Seife, gegebenenfalls Sokalan CP 5^(R), Wasserglas und gegebenenfalls Alkylsulfat enthielt

FASTP/ TASTP

C₁₂-Alkylsulfat bzw. Talgfettalkoholsulfat, eingebracht über ein sprühgetrocknetes Granulat, welches außer Alkylsulfat noch Zeolith, Seife, gegebenenfalls Sokalan CP 5^(R) und Alkylbenzolsulfonat und Wasserglas enthielt

FAS47/ TAS47

C₁₂-Fettalkoholsulfat bzw. Talgfettalkoholsulfat, berechnet als 100% Aktivsubstanz, eingesetzt als 47 Gew.-%iges Granulat, das als Träger 50 Gew.-% Natriumcarbonat, sonstige Salze und weniger als 1 Gew.-% nichtchemisch gebundenes Wasser enthielt, hergestellt durch Granulierung und gleichzeitige Trocknung in der Wirbelschicht gemäß der Lehre der internationalen Patentanmeldung WO-A-93/04162; Korngröße maximal 1,0 mm

Nadeln

C₁₂-Alkylsulfat, berechnet als 100% Aktivsubstanz, eingebracht als 87 Gew.-%iges handelsübliches Produkt (Rest Salze wie Sulfat und Wasser)

Paste35

C₁₂-Alkylsulfatpaste, berechnet als 100% Aktivsubstanz, eingebracht als 35 Gew.-% wäßrige Paste (2 Gew.-% Salze)

Paste50

C₁₂-Alkylsulfatpaste, berechnet als 100% Aktivsubstanz, eingebracht als 50 Gew.-% wäßrige Paste (2 Gew.-% Salze)

FA5EO

C₁₂-C₁₈-Fettalkohol mit 5 Ethylenoxidgruppen (EO)

TA5EO

Talgfettalkohol mit 5 E0

Seife

gesättigte C₁₂-C₁₈-Fettsäureseife

Zeolith

Zeolith A, berechnet als wasserfreie Aktivsubstanz

Soda

Natriumcarbonat

Sil2,0

Natriumsilikat mit einem Gewichtsverhältnis Na₂O:SiO₂ von 1:2,0

Citrat

Natriumcitrat-Dihydrat

PVP

Polyvinylpyrrolidon, relative durchschnittliche Molekülmasse 40 000

CP5

Sokalan CP5^(R), Copolymeres der Salze der Acrylsäure und der Maleinsäure

SIK

granularer Schauminhibitor auf Basis von Silikonöl

A premix of the compositions given in the examples was prepared in a continuously operating mixer equipped with a cutter head chopper and extruded in accordance with the teaching of international patent application WO-A-91/02047. The finished extrudate was dried, but not worked up any further. The compositions of the finished extrudates can be found in the following table. The abbreviations mentioned mean:

SECTION

C ₉ -C ₁₃ alkylbenzenesulfonate sodium salt, introduced via spray-dried granules which, in addition to alkylbenzenesulfonate, also contained zeolite, soap, optionally Sokalan CP 5 ^(R) , water glass and optionally alkyl sulfate

FASTP / TASTP

C ₁₂ alkyl sulfate or tallow fatty alcohol sulfate, introduced via spray-dried granules which, in addition to alkyl sulfate, also contained zeolite, soap, optionally Sokalan CP 5 ^(R) and alkylbenzenesulfonate and water glass

FAS47 / TAS47

C ₁₂ fatty alcohol sulfate or tallow fatty alcohol sulfate, calculated as 100% active substance, used as 47% by weight granules which contained 50% by weight sodium carbonate, other salts and less than 1% by weight non-chemically bound water as a carrier by granulation and simultaneous drying in the fluidized bed in accordance with the teaching of international patent application WO-A-93/04162; Grain size maximum 1.0 mm

Needles

C ₁₂ alkyl sulfate, calculated as 100% active substance, introduced as an 87% by weight commercial product (remainder salts such as sulfate and water)

Paste35

C ₁₂ alkyl sulfate paste, calculated as 100% active substance, introduced as 35% by weight aqueous paste (2% by weight salts)

Paste50

C ₁₂ alkyl sulfate paste, calculated as 100% active substance, introduced as 50% by weight aqueous paste (2% by weight salts)

FA5EO

C ₁₂ -C ₁₈ fatty alcohol with 5 ethylene oxide groups (EO)

TA5EO

Tallow fatty alcohol with 5 E0

Soap

saturated C ₁₂ -C ₁₈ fatty acid soap

Zeolite

Zeolite A, calculated as an anhydrous active substance

soda

sodium

Sil2.0

Sodium silicate with a Na ₂ O: SiO ₂ weight ratio of 1: 2.0

Citrate

Sodium citrate dihydrate

PVP

Polyvinyl pyrrolidone, relative average molecular weight 40,000

CP5

Sokalan CP5 ^(R) , copolymer of the salts of acrylic acid and maleic acid

SIK

granular foam inhibitor based on silicone oil

In addition to the nonionic surfactants, a 35% by weight aqueous sodium silicate solution (1: 2.0) was used as plasticizer and / or lubricant in the premixes for M1 and M2, and a 30% by weight aqueous Sokalan CPS ^{( R)} solution, a 30% by weight aqueous Sokalan CP 5 ^(R) solution in the premixes to Comparative Examples V1 to V3 and a 35% by weight aqueous C ₁₂ alkyl sulfate paste in the premixes to Comparative Examples V4 and V5 uses a 50% by weight aqueous C ₁₂ alkyl sulfate paste. In comparative examples V4 and V5, CP5 was introduced over the spray-dried granulate. Compositions from M1 to M3 and V1 to V5 (in% by weight) M1 M2 M3 V1 V2 V3 V4 V5 SECTION 6.7 6.5 7.0 5.0 6.5 7.0 7.0 7.0 FASTP - - - 3.0 3.5 - - - TASTP - - - - 1.0 - 1.0 0.8 FAS47 3.3 3.5 3.5 - - - - - Needles - - - - - 4.0 - - Paste35 - - - - - - 3.85 - Paste50 - - - - - - - 4.0 TAS 47 - - - 2.5 - - - - FA5EO 9.0 11.0 9.0 11.0 11.0 11.0 11.0 9.0 TA5EO 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Soap 1.5 1.9 1.9 1.0 2.0 1.0 1.0 1.0 SIK 4.0 2.0 4.0 4.0 4.0 4.0 4.0 4.0 Zeolite 37.0 35.0 36.0 37.0 39.0 37.0 40.0 40.0 soda 6.0 7.0 5.5 5.5 2.0 6.0 2.0 2.0 Citrate 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 Sil2.0 2.2 2.2 2.2 3.0 2.0 2.3 2.0 2.0 CP5 3.5 3.5 3.5 2.0 1.5 2.0 2.0 2.0 PVP 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Water and sulfate rest rest rest rest rest rest rest rest

Comparative Example 1:

The extrusion had to be stopped for safety reasons. because the perforated plates clogged.

Comparative example 2:

The extrudate was mechanically unstable and already partially disintegrated directly after cutting and partly during processing (e.g. in Fillet).

Comparative Example 3:

The extrusion had to be stopped for safety reasons. because the perforated plates clogged.

Comparative Example 4:

The use of 11 parts by weight of a 35% by weight C ₁₂ alkyl sulfate paste already led to a premix which was no longer free-flowing and which already tended to cake in the premixing route of the extrusion. The extrudate strands obtained were sticky and could not be cut immediately after exiting the hole shape. The use of smaller amounts of this paste led to extrudable premixes, but the extrudates were sticky.

Comparative Example 5:

The use of 8 parts by weight of an approximately 50% by weight C ₁₂ alkyl sulfate paste did result in an extrudable premix, but the extrudates obtained were mechanically unstable and about 30 to 50% by weight either already fell apart directly after cutting or preparation (for example in the fillet). The bulk density of the extrudates was 732 g / l.

Example 1 :

The mechanically stable and non-sticky extrudate had after drying a bulk density of 762 g / l.

Example 2 :

The mechanically stable and non-sticky extrudate had after drying a bulk density of 781 g / l.

Example 3 :

The mechanically stable and non-sticky extrudate had after drying a bulk density of 765 g / l.

Claims (9)

1. A process for the production of high-density washing- or cleaning-active extrudates in which a solid compound containing a plasticizer and/or lubricant and short-chain alkyl sulfates in solid form is extruded under pressure to form strands and, after leaving the multiple-bore extrusion die, the strands are cut by means of a cutting unit to granules of predetermined size, characterized in that alkyl sulfates containing 8 to 14 carbon atoms are used on their own or in admixture in the form of granules granulated and optionally dried in a fluidized bed.
2. A process as claimed in claim 1, characterized in that C₈ alkyl sulfate, C₁₂ alkyl sulfate, mixtures of C_12-18 alkyl sulfate, C_8-16 alkyl sulfate, the percentage content of alkyl sulfates with a carbon chain length above 14 being at most 10% by weight and, more particularly, at most 5% by weight, and alkyl sulfate essentially containing 12 to 14 carbon atoms are used as the short-chain alkyl sulfate, C₁₂ alkyl sulfate and mixtures of alkyl sulfate essentially containing 12 to 14 carbon atoms being preferred.
3. A process as claimed in claim 1 or 2, characterized in that the alkyl-sulfate-containing fluidized bed granules used contain 20 to 65% by weight of alkyl sulfate and 35 to 80% by weight of inorganic constituents, preferably zeolite and/or alkali metal carbonate and/or alkali metal sulfate.
4. A process as claimed in any of claims 1 to 3, characterized in that the alkyl-sulfate-containing fluidized bed granules used contain 30 to 55% by weight of alkyl sulfate and preferably 40 to 50% by weight of alkyl sulfate.
5. A process as claimed in any of claims 1 to 4, characterized in that the alkyl-sulfate-containing fluidized bed granules used contain 40 to 60% by weight and preferably 45 to 55% by weight of sodium and/or potassium carbonate, sodium and/or potassium sulfate or mixtures of carbonate and sulfate.
6. A process as claimed in any of claims 1 to 5, characterized in that alkyl-sulfate-containing fluidized granules with a maximum particle size of 1 mm are used.
7. A process as claimed in any of claims 1 to 6, characterized in that a detergent or cleaning formulation containing C_8-18 alk(en)yl sulfates, preferably C_12-18 alkyl sulfate, in quantities of 5 to 30% by weight is produced, at most 50% by weight - based on the total quantity of anionic surfactants (without soaps) - being used in the form of a C_12-14 alkyl sulfate granulated and optionally dried in a fluidized bed.
8. A process as claimed in any of claims 1 to 7, characterized in that a detergent or cleaning formulation containing up to 100% by weight of C₁₂ alkyl sulfate or C_12-14 alkyl sulfate is used as the alk(en)yl sulfate.
9. A process as claimed in any of claims 1 to 8, characterized in that the extrudates produced are processed with other ingredients of detergents or cleaning formulations.