WO1995004129A1

WO1995004129A1 - Process for preparing washing or detergent extrudates

Info

Publication number: WO1995004129A1
Application number: PCT/EP1994/002403
Authority: WO
Inventors: Hubert Pawelczyk; Jochen Jacobs; Bernd Larson; Norbert Kühne; Kathrin Schnepp; Wolfgang Seiter; Monika Böcker; Eduard Smulders; Günther VOGT
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1993-07-29
Filing date: 1994-07-21
Publication date: 1995-02-09
Also published as: EP0711338A1; CN1127525A; DE4325500A1; HUT73038A; HU9503968D0

Abstract

The solubility of extruded washing or detergent agents depends to a large extent upon the form of the anionic surfactants when they are added to the premix to be extruded. In order to improve the solubility of the extrudates, the anionic surfactants are added to the premix only in a solid, powdery or granulated preparation form. Such preparation forms have at least partially an anionic surfactant content of at least 50 % by weight.

Description

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

The invention relates to a process for the production of solid detergents or cleaning agents or components of solid detergents or cleaning agents, a premix being used which contains anionic surfactants in a solid preparation form and preferably highly concentrated anionic sides. At the same time, the winding and / or dissolving behavior of the extrudates is improved.

Solid detergent or cleaning agent with a high bulk density, i.e. Agents with a bulk density above 500 g / l have, owing to their compact shape and the resulting smaller surface area, a lower dissolving rate, especially at low temperatures around 15 to 60 ° C., than agents with a comparable composition, but which have a bulk density of, for example, only 300 g / 1. Analogous problems occur when washing in detergents with a high bulk density in washing machines.

From the international patent application WO-A-91/02047 a process for the production of extrudates with high density is known, wherein a solid premix is extruded under pressure and the strand is cut to the predeterminable granulate size after exiting the hole shape by means of a cutting device. The homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work. Preferred plasticizers and / or lubricants are surfactants and / or polymers which are preferably used in liquid, pasty or gel-like preparation form. In particular, nonionic surfactants and aqueous anionic surfactant pastes which are liquid at the processing temperature are preferred. After exiting the hole shape, the system is no longer subjected to shear forces and the viscosity changes in such a way that the extruded strand can be cut to predetermined extrudate dimensions.

In order to improve the dissolving behavior of the extrudates, it was proposed in international patent application WO-A-93/02176 that they act as nonionic surfactants and the ethoxylated alcohols used as plasticizers and / or lubricants in intimate admixture with a structure breaker during the extrusion in order to avoid gel formation prevention when the extrudates dissolve in the wash liquor. It is also known from German patent application DE-A-4203031 that the dissolving behavior of extrudates containing alk (en) yl sulfate, which also tend to yellow, by adding short-chain alkyl sulfates, for example C 1 -C 2 alkyl sulfate, in the premix is improved. In a preferred embodiment, the short-chain alkyl sulfates are introduced into the process in the form of an aqueous solution.

However, it has now been found that, in contrast to the previous teaching of the prior art, the dissolving behavior of extrudates largely depends on the form in which the anionic surfactants are introduced into the premix.

The invention accordingly relates to a process for the production of high density, washable or cleaning-active extrudates, a solid premix being extruded under pressure and the strand being cut out of the hole shape by means of a cutting device to the predetermined granule dimension, the premixed anionic and nonionic surfactants contains and the anionic surfactants are introduced into the premix only via a solid, powdery or granular preparation form. The anionic surfactants are introduced at least in part via a formulation with an anionic surfactant content of at least 50% by weight, based on the formulation.

To explain the actual extrusion process, reference is expressly made to the international patent applications WO-A-91/02047, WO-A-93/02176 and to the older German patent application P 4235646.6. 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 extrusion temperature. Under the shear action of the extruder screws, the premix is pressed under pressure, which is preferably at least 25 bar, at Extremely high throughputs, depending on the apparatus used, but can also be lower, compressed, plasticized, extruded in the form of fine strands through the perforated nozzle plate in the extruder head and finally the extrudate preferably reduced to approximately spherical to cylindrical granules by means of a rotating knives. The hole diameter of the perforated nozzle plate and the length of the strand cut are matched to the selected granule dimension. In this embodiment, granules of an essentially uniformly predeterminable particle size can be produced, the absolute particle sizes in particular being able to be adapted to the intended use. In general, particle diameters 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. In an important embodiment, the length / diameter ratio of the chipped primary granules is in the range from about 1: 1 to about 3: 1. Furthermore, it is preferred to feed the still plastic and moist primary granulate 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. If desired, small amounts of dry powder, for example zeolite powder such as zeolite NaA powder, can also be used in this stage. 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 preferably 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. Optionally, it is also possible to carry out the drying step directly after the extrusion of the crude extrudate and thus before a final shaping, if desired, in a rounding device.

According to the invention, the anionic surfactants used are only introduced into the premix via a solid preparation. These solid preparation forms can be in powder form, but can also be made of neten and / or granulated compounds with more or less high proportions of anionic surfactants. In a preferred embodiment of the invention, the anionic surfactants are preferably at least 30% by weight and in particular at least 50% by weight, in each case based on the total amount of anionic surfactant, as a solid, powdery or granular formulation an anionic surfactant content of at least 50% by weight, preferably from 60 to 100% by weight and in particular from 70 to 95% by weight, in each case based on the solid preparation, introduced into the process. It is possible that all of the anionic surfactants are contained in a solid preparation form or are distributed over several solid preparation forms. For example, it is possible for a spray-dried granulate which contains one or more anionic surfactants in amounts of, for example, up to 45% by weight, and a granulate obtained by granulation or a powder with preferably at least 75% by weight of anionic surfactant in the Premix can be used. In a particularly preferred embodiment of the invention, however, only preparation forms are used which each contain at least 75% by weight and preferably at least 80% by weight of one or more anionic surfactants. The content of the anionic surfactants in the premix is preferably 5 to 30% by weight, but can also go well beyond this. Lower proportions of anionic surfactants are less preferred for technical reasons.

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, i.e. Mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from Ci2-Ci8 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent 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-sulfofatty acids (ester sulfonates), for example the -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 sul- gated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as 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 become. The sulfonation products are a complex mixture which contains mono-, di- and triglyceride sulfonates with oc and / or sulfonic acid groups in the interior. 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 are the sulfuric acid half-esters of the Ci2-Ci8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the Cιo-C2θ-oxo alcohols, and those secondary alcohols this chain length preferred. 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. Ci6-Ci8-alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use Ci6-Ci8-alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and with relatively low detergents temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize. In a preferred embodiment of the invention, the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of (2-Ci4-fatty alkyl sulfates or Ci2-Ci8-fatty alkyl sulfates with Ci6-Ci8-fatty alkyl sulfates and in particular Ci2-Ci6- In a preferred embodiment of the invention, alk (en) yl sulfates are used in the premix for reasons of washing technology used, the proportion of short-chain alkyl sulfates such as Cχ2-alkyl sulfate or even shorter-chain alkyl sulfates, based on the sum of the total alk (en) yl sulfates used, not more than 30% by weight. In a further preferred embodiment of the invention, however, not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C to C22 are used. Mixtures of saturated, predominantly consisting of (45 existing sulfated fatty alcohols and unsaturated, predominantly consisting of Ci8 sulfated fatty alcohols are preferred, for example those derived from solid or liquid fatty alcohol mixtures of the HD-Ocenol ( ^R ) type (commercial product of the applicant) Weight ratios of alkyl sulfates to alkenyl sulfates of 10: 1 to 1: 2 and in particular of about 5: 1 to 1: 1 are preferred.

The sulfuric acid monoesters of the straight-chain or branched C7-C2i alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol of ethylene oxide (E0) or Ci2-Ci8 -Fatty alcohols with 2 to 4 E0 are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain CQ to Ciβ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, viewed in isolation, are nonionic surfactants (for a description, see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. However, preferred anionic surfactants are alkylbenzenesulfonates and / or alk (en) - ylsulfates, especially fatty alkyl sulfates. In a further preferred embodiment of the invention, 8 to 25% by weight of alkylbenzenesulfonates and / or alk (en) ylsulfates are used in the premix. It is particularly advantageous if alkylbenzenesulfonates are used as the sole anionic surfactants in the form of a highly concentrated powder, for example as a powder with an active substance content of above 85% by weight, for example around 90% by weight. In a further advantageous embodiment of the invention, however, alkylbenzenesulfonate and alk (en) ylsulfonate, in particular fatty alkyl sulfate, in a weight ratio of 0.5: 1 to 1.5: 1, preferably up to 1.2: 1 and used in particular by 1: 1 in the premix. However, premixes free from alkylbenzenesulfonate are also preferred. In all cases in which alk (en) yl sulfates are introduced into the premix as the sole anionic surfactant or as one anionic surfactant, there are solid preparation forms with alk (en) yl sulfate contents of at least 75% by weight and in total particularly preferred of at least 80% by weight, which can be produced, for example, by means of a process according to international patent application WO-A-93/04162 or the older German patent application DE 4232874 by granulation with, if appropriate, simultaneous drying, in particular in a fluidized bed .

The anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanola in. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

In addition to the anionic surfactants, other ingredients of the premix include soaps, preferably in amounts of 0.5 to 4% by weight. Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. In particular, such mixtures are preferred which are 50 to 100% by weight saturated C12-C24- Fatty acid soaps and 0 to 50 wt .-% are composed of oleic acid soap.

The nonionic surfactants used are preferably alkoxylated, advantageously liquid ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 30 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably in 2 Position can be methyl-branched, or can 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 C atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Cn alcohol 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 Ci2-Ci4 alcohol with 3 EO and Ci2-Ci8 ~ alcohol with 5 EO. The degrees of ethoxylation given represent statistical mean values which can be an integer or a fraction for a special product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). Other preferred nonionic surfactants are, in particular, tallow fatty alcohols with 11 EO, 14 EO or 25 EO. It has been shown that these nonionic surfactants can also be granulated or spray-dried together with anionic surfactants and thus lead to improved application properties of the finished extrudates. According to the teaching of international application WO-A-93/02176, in addition to the alkoxylated alcohols mentioned, alkoxylated alcohols with up to 80 EO, preferably tallow fatty alcohol with 30 or 40 E0, or polyethylene glycols, preferably with a relative molecular weight between 200 and 600, can be used in a mixture with other nonionic surfactants. Within the scope of this invention, however, the teaching disclosed in the earlier national application P 4319666.7 of incorporating alkoxylated alcohols with a maximum of 40 E0 in the form of a solid preparation into the premix is preferred and particularly preferred if the premix is granular preparation forms with high contents contains alk (en) yl sulfates. 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 monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4. The alkyl glycosides can be present in the premix in amounts of, for example, 1 to 5% by weight.

Another class of nonionic surfactants that can be used, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 Carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP-A-58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533. 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 which can replace alkyl glycosides or can be used in combination with them are polyhydroxy fatty acid amides of the formula (I),

R3

I.

R -C0-N- [Z] (I)

in R2C0 for an aliphatic acyl residue with 6 to 22 carbon atoms, R-3 for hydrogen, an alkyl or hydroxyalkyl residue with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydro xyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. 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.

Non-ionic surfactants are preferably used in the premix in amounts of 0.5 to 25% by weight. Amounts of 2 to 20% by weight and preferably 5 to 15% by weight of nonionic surfactants are advantageous, with 50 to 100% by weight, based on the nonionic surfactants, of ethoxylated alcohols.

In a preferred embodiment of the invention, premixes are used which contain 15 to 25% by weight alkylbenzenesulfonates as sole anionic surfactants, preferably in the form of an 85 to 95% by weight powder, and 0.5 to 5 % By weight nonionic surfactants, preferably ethoxylated fatty alcohols and / or alkyl glycosides, in particular ethoxylated fatty alcohols or mixtures of ethoxylated fatty alcohols and alkyl glycosides.

In a further preferred embodiment of the invention, premixes are used which contain 10 to 20% by weight of anionic surfactants, preferably alkylbenzenesulfonates and alk (en) yl sulfates in a weight ratio of 0.8: 1 to 1.2: 1, and Contain 0.5 to 5 wt .-% nonionic surfactants as above.

In particularly preferred embodiments of the invention, premixes are used which contain 5 to 15% by weight of anionic surfactants, preferably mixtures of alkylbenzenesulfonates and alk (en) ylsulfates in a weight ratio of 0.5: 1.2, in particular of 0.5: 1 to a maximum of 1: 1, and 10 to 20% by weight nonionic surfactants, preferably ethoxylated fatty alcohols or mixtures of ethoxylated fatty alcohols and other nonionic surfactants, the content of ethoxylated fatty alcohols based on the total amount of nonionic surfactants, is at least 50% by weight, in particular is at least 60% by weight, or premixes are used which, as the sole anionic surfactant, are 5 to 15% by weight, preferably contain at least 8% by weight alk (en) yl sulfates and 5 to 15% by weight, preferably at least 8% by weight nonionic surfactants as stated above. The alk (en) yl sulfates are preferably always used in the form of highly concentrated granules with contents between 80 and 95% by weight alk (en) yl sulfate, while the alkylbenzenesulfonates in cases in which they are not the sole anionic surfactant can also be used in the form of, for example, spray-dried granules with contents below 45% by weight of alkylbenzenesulfonate, based on these spray-dried granules.

Other ingredients of the premix are, for example, inorganic and organic builder substances, alkali carbonates and alkali silicates, optical brighteners, bleaching agents, optical brighteners, graying inhibitors and, if appropriate, foam inhibitors, bleach activators, enzymes, textile-softening substances, colorants and fragrances and neutral salts such as sulfate salts Chlorides in the form of their sodium or potassium salts.

Suitable inorganic buder substances are, for example, zeolites, phosphates and layered silicates.

The fine crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. However, zeolite NaX and mixtures of NaA and NaX 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, of ethoxylated C 12 -C 18 fatty alcohols with 2 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, in particular 20 to 22% by weight of bound water.

Suitable substitutes or partial substitutes for the zeolite are layer silicates of natural and synthetic origin. Such layer sil kate are known for example from the patent applications DE-B-23 34899, EP-A-0 026 529 and DE-A-35 26 405. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here.

In addition, small amounts of iron can be built into the crystal lattice of the layered silicates. Furthermore, due to their ion-exchanging properties, the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na ⁺ and Ca ⁺⁺ . The amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing. Layered silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x θ2χ ₊ 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-0164514. Preferred crystalline layered silicates are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and ft-sodium disilicate Na2Si2θ5 * H2θ are preferred.

The content of these inorganic builder substances in the premixes is preferably between 15 to 60% by weight, phosphate contents preferably being less than 15% by weight and particularly preferred premixes being free of phosphate-containing builder substances.

Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitric acid (NTA), provided that such use is not objectionable for ecological reasons , and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as Ci tronic acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Suitable polymeric polycarboxylates are, for example, the sodium salts 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 contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. Biodegradable terpolymers are also particularly preferred, for example those which, as monomers, contain salts of acrylic acid and maleic acid and vinyl alcohol or Contain vinyl alcohol derivatives or the salts of acrylic acid and 2-alkylallylsulfonic acid as monomers and sugar derivatives. The (co) polymeric or terpolymeric polycarboxylates can be used either as a powder, as a spray-dried or granulated compound or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred. The content of the premixes of (co) polymeric or terpoly eren polycarboxylates is preferably up to a maximum of 8 wt .-% and in particular between 0 and 5 wt .-%.

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 their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable ingredients of the premixes 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 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5. The content of sodium carbonate in the premixes is preferably up to 20% by weight, advantageously between 2 and 15% by weight. The sodium silicate content of the premixes 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 incorporate 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 the older German patent application P 4319578.4, alkali metal carbonates can also be replaced by sulfur-free amino acids and / or salts thereof having 2 to 11 carbon atoms and optionally a further carboxyl and / or amino group. In the context of this invention, it is preferred that the alkali metal carbonates be partially or completely replaced by glycine or glycinate.

Among the compounds which serve as bleaching agents and supply H2O2 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 peracid salts or peracids providing H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. The bleaching agent content of the premixes is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate.

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 0-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. The content of bleach activators in the pre-primers or in the finished agents of bleach activators is 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 NNN'.N'-tetraacetyl-ethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine. In addition, the agents can also contain components which have a positive influence on the oil and fat washability from textiles. This effect is particularly evident when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or known from the prior art. of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, are preferably used.

Suitable foam inhibitors are, for example, soaps of natural or synthetic origin which have a high proportion of Ci8-C24 fatty acids. 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, eg 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.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces 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. (Per) 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 stabilizers particularly for per-compounds and enzymes are the salts of polyphosphonic acids, preferably the neutral-reacting sodium salts of, for example, l-hydroxyethane-II-diphosphonate and diethylenetriaminepentamethylenephosphonate in amounts of 0.1 to 1.5% by weight and in particular of l-hydroxyethane-l, l-diphosphonic acid. Sodium formate, for example, can also be used as stabilizers. 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 pyroboric acid (tetraboric acid H2B4O7), is particularly advantageous for stabilizing enzymes ). Derivatives of diaminosilbenesulfonic acid or their alkali metal salts can be used as optical brighteners. 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 instead of the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example 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) diphenyls. Mixtures of the aforementioned brighteners can also be used. Uniform white extrudates are obtained when, in addition to the usual brighteners, in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, even small amounts, for example 10 ~ 6 to 10 "3 wt .-%, preferably by 10" 5 wt .-%, a blue dye can be used. A particularly preferred dye is Tinoluχ ( ^R ) (commercial product from Ciba-Geigy).

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, with mixtures of 2 or 3 enzymes can be particularly beneficial, and perfume added afterwards. The extrudates can also be prepared with other finely divided dry powders before the enzymes and the other components are mixed. Examples of these are 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, given if necessary, silanized silica and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide, at least partially not extruded, but mixed subsequently with the extrudate. It is also possible that the surface of the extrudate according to the invention is first coated, for example, with zeolite or a mixture containing zeolite and then with a foam inhibitor. Such measures enable a further improvement in the flushing-in 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.

Examples

In a batch mixer equipped with a cutter head chopper, premixes M1 to M5 according to the invention and corresponding premixes VI to V2 were extruded according to the teaching of international application W0-A-91/02047. The finished extrudates were dried, but not worked up further. The compositions of the finished extrudates can be found in Tables 1 and 3, their bulk weights and their dissolving behavior can be found in Tables 2 and 4. By using alk (en) yl sulfate cuts with up to a maximum of 30% by weight of C8-Ci2-alkyl sulfates, the redispersion behavior could be further improved. The same applies when using tallow fatty alcohol sulfate to replace PEG 400 with tallow fatty alcohol with 40 E0.

The abbreviations given in the tables mean: ABS Cg-Ci3-alkylbenzenesulfonate sodium salt, calculated as 100% active substance, used as 90% by weight powder (Maranil

AOO)

TAS91 tallow fatty alcohol sulfate, calculated as 100% active substance, used as 91% by weight granules, which contained sodium carbonate and less than 1% by weight of non-chemically bound water as a carrier, produced according to the teaching of the international patent application message WO-A-93/04162

TAS84 tallow fatty alcohol sulfate, calculated as 100% active substance, used as 84% by weight granules, which contained sodium carbonate and less than 1% by weight of non-chemically bound water as a carrier, produced according to the teaching of the international patent application message W0-A-93/04162

TAS47 tallow fatty alcohol sulfate, calculated as 100% active substance, used as 47% by weight granules which contained sodium carbonate and less than 1% by weight of non-chemically bound water as a carrier, produced according to the teaching of the international patent application message WO-A-93/04162

FA5E0 Cχ2-Ci8 fatty alcohol with 5 ethylene oxide groups (E0) TA5E0 tallow fatty alcohol with 5 E0 soap Ci2-Ci8 sodium fatty acid soap, saturated Zeolite Zeolite, calculated as an anhydrous active substance

Soda sodium carbonate

Sil2.0 sodium silicate with a Na2θ: Siθ2 weight ratio of 1: 2.0

Sulphate sodium sulphate and salts from solutions

SIK foam inhibitor granules based on soda and sulfate with 15% by weight

Silicone oil PBMH perborate monohydrate CP5 Sokalan CPδ ( ^R ), copolymer of the salts of acrylic acid and

Maleic acid PEG 400 polyethylene glycol with a molecular weight of 400 HEDP 1-hydroxyethane-l, 1-diphosphonic acid tetrasodium salt

As plasticizers and / or lubricants, 2.8 wt.% Of a 20 wt.% Sokalan CPδ ( ^R ) solution and 4.1 wt. % of a 34% by weight sodium likate solution (1: 2.0) is used. Instead, 4.3% water was used in the premixes for M4, M5 and V2.

Determination of the dissolving behavior

500 ml of demineralized water (20 ° C.) were poured into a 1 l vessel, the propeller stirrer was switched on at a speed of 900 revolutions per minute, and the conductivity measuring cell was immersed. Then 5 g of the extrudate were added. The change in conductivity was recorded by a recorder. The measurement was carried out until there was no increase in conductivity. The time to reach the constant conductivity is the dissolving time of the extrudate (100%). The dissolution time at 90% resolution was calculated.

Table 1: Compositions from Ml to M3 and VI (in% by weight)

Ml M2 M3 VI

ABS 10 10 20 10

TAS84 10 - - -

TAS91 - 10 - -

TAS47 - - - 10

FA5E0 2 2 2 2

TA5E0 0.5 0.5 0.5 0.5

Soap 1.0 1.0 1.0 1.0

SIK 6.0 6.0 6.0 6.0

Zeolite 20 20 20 20

Soda 12 12 12 12

Sil 2.0 3.5 3.5 3.5 3.5

CP5 6.0 6.0 6.0 6.0

PBMH 18 18 18 18

PEG 400 2.0 2.0 2.0 2.0

HEDP 1.0 1.0 1.0 1.0

water and

Sulfate residue residue residue residue

Table 2: Bulk weight and dissolution times (90%) of the extrudates M1-M3 and VI

Ml M2 M3 VI

Bulk weight (g / 1) 830 808 795 810

Release time (in seconds) 210 208 229 243 Table 3: Compositions of M4 and M5 and V2 ⁽ in% by weight)

M4 M5 V2

TAS84 9 - -

TAS91 - 9 -

TAS47 - - 9

FA5E0 9 9 9

TA5E0 1 1 1

Soap 0.5 0.5 0.5

Zeolite 35 35 35

Soda 14 14 14

PBMH 16 16 16

water and

Sulfate residue residue residue residue

Table 4: Bulk weight and dissolution times (90%) of the extrudates M4-M5 and V2

M4 M5 V2

Bulk weight (g / 1) 820 812 800

Release time (in seconds) 310 216 454

Claims

claims

1. A process for the production of washable or cleaning-active extrudates with a high density, a solid premix being extruded under pressure and the strand being cut out of the hole shape by means of a cutting device to the predetermined granule dimension, characterized in that the premix is anionic and contains nonionic surfactants and the anionic surfactants are introduced into the premix only via a solid powdery or granular preparation form, the anionic surfactants being introduced at least in part via a preparation form with an anionic surfactant content of at least 50% by weight, based on the preparation form .

2. The method according to claim 1, characterized in that the Anionten¬ side at least 30% by weight, preferably at least 50% by weight, based in each case on the total amount of anionic surfactant, as a solid, powdery or granular preparation form with a Anionic surfactant content of at least 50% by weight, preferably from 60 to 100% by weight and in particular from 70 to 95% by weight, based in each case on the solid formulation, can be introduced into the process.

3. The method according to claim 1 or 2, characterized in that the anionic surfactants are introduced into the process in one or more solid preparation forms, the preparation forms in each case at least 75% by weight, preferably at least 80% by weight, of one or contain several anionic surfactants.

4. The method according to any one of claims 1 to 3, characterized in that anionic surfactants are used in amounts of 5 to 30 wt .-% in the premix.

5. The method according to any one of claims 1 to 4, characterized in that alkylbenzenesulfonates and / or alk (en) yl sulfates are used as anionic surfactants.

6. The method according to any one of claims 1 to 5, characterized in that 8 to 25 wt .-% alkylbenzenesulfonates and / or alk (en) yl sulfates are used in the premix.

7. The method according to any one of claims 1 to 6, characterized in that as anionic surfactants alkylbenzenesulfonate and alk (en) yl sulfate in a weight ratio of 0.5: 1 to 1.5: 1, preferably up to 1.2: 1 and in particular around 1: 1 in the premix.

8. The method according to any one of claims 1 to 7, characterized in that alk (en) yl sulfates are used in the premix, the proportion of short-chain alkyl sulfates such as Ci2-alkyl sulfate or even shorter-chain alkyl sulfates based on the total of the total alk ( en) ylsulfate is a maximum of 30 wt .-%.

9. The method according to any one of claims 1 to 6, characterized in that in the premix alkylbenzenesulfonates as sole anionic surfactants in the form of a highly concentrated powder, preferably as a powder with an active substance content of above 85 wt .-% are used.

10. The method according to any one of claims 1 to 9, characterized in that in the premix nonionic surfactants in amounts of 0.5 to 25 wt .-%, preferably from 2 to 20 wt .-% and in particular from 5 to 15 wt. -% are used.

11. The method according to claim 10, characterized in that 50 to 100 wt .-% of the nonionic surfactants used consist of ethoxylated alcohols.

12. The method according to any one of claims 1 to 11, characterized in that the extrudates produced are processed with further ingredients of washing or cleaning agents.