EP0720644B1 - Detergent mixtures and washing or cleaning agents with improved solvent properties - Google Patents

Abstract

PCT No. PCT/EP94/03077 Sec. 371 Date Mar. 25, 1996 Sec. 102(e) Date Mar. 25, 1996 PCT Filed Sep. 14, 1994 PCT Pub. No. WO95/08616 PCT Pub. Date Mar. 30, 1995A substantially water-free detergent mixture comprising a) alkyl or alkenyl sulfates corresponding to formula (I): R1OSO3X(I) in which R1 is a linear or branched aliphatic hydrocarbon radical containing 16 to 18 carbon atoms and X is an alkali metal or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, b) alkyl or alkenyl sulfates corresponding to formula (II): R2OSO3X(II) in which R2 is a linear or branched aliphatic hydrocarbon radical containing 12 to 14 carbon atoms and X is an alkali metal or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, wherein components a) and b) are present in a ratio by weight of 90:10 to 70:30, and c) a hydrophobic structure breaker corresponding to formula (III): R4O(CH2CH2O)nH(III) in which R4 is a linear or branched alkyl or alkenyl radical containing 12 to 18 carbon atoms and n is 0 or a number of 1 to 5.

Description

The invention relates to anhydrous detergent mixtures which contain long-chain and short-chain alkyl sulfates in selected mixing ratios and hydrophobic structure breakers, and to the use of these mixtures for the production of solid detergents.

Anionic surfactants, in particular alkyl sulfates or fatty alcohol sulfates, are important components of detergents, dishwashing detergents and cleaning agents. In contrast to nonionic surfactants, which have an inverse solubility behavior and, as a result of hydrogen bonds, are more soluble in cold water than in warm water, anionic ones Conventional surfactants, i. H. their solubility increases more or less linearly with temperature until the solubility product is reached. However, for technical applications - for example with regard to the induction capacity during the washing process - there is a need for anionic surfactants which have a sufficient solubility even in cold water.

• a) die Mitverwendung von Hydrotropen und
• b) die Oberflächenvergrößerung des Tensidkorns.

In the past there has been no lack of attempts to improve the problem of the poor solubility in cold water of anionic surfactants, in particular of alkylbenzenesulfonates, fatty alcohol sulfates and α-methyl ester sulfonates. Two main concepts were pursued, namely

• a) the use of hydrotropes and
• b) the surface enlargement of the surfactant grain.

The best-known hydrotropes undoubtedly include the short-chain alkylarylsulfonates, such as, for example, toluene, xylene or cumene sulfonate. They are suitable, for example, as solubilizers for anionic and nonionic surfactants in the production of liquid detergents. The improved solubility is probably due to advantageous mixed micelle formation. In this context, reference is made to the overview by H. Stache in Fette, Seifen, Anstrichmittel 71, 381 (1969).

However, the improvement in solubility in cold water, in particular of fatty alcohol sulfates, is usually achieved by adding them as hydrotrope surfactants with high HLB values, for example highly ethoxylated polyglycol ethers (tallow alcohol 40 EO adduct) or the like. The dissolution rates that can be achieved in this way, in particular in the case of fatty alcohol sulfates, are unsatisfactory for a large number of technical applications.

According to the teaching of DE-A-41 24 701 (Henkel), solid detergents with high bulk density and improved solubility are obtained by adding mixtures of anionic and nonionic surfactants to polyethylene glycol ethers with a molecular weight in the range from 200 to 12000, preferably from 200 to 600, and then dries and / or solidifies. According to embodiment 1, a detergent preparation containing C ₁₂ -C ₁₈ fatty alcohol sulfate, C ₁₂ -C ₁₈ fatty alcohol 5 EO and C ₁₆ -C ₁₈ tallow fatty alcohol 5 EO adduct and - based on the nonionic surfactants - is not less than 45 wt .-% polyethylene glycol with a molecular weight of about 400 is disclosed, which is extruded after homogenization and processed into granules. However, the rate of dissolution of the resulting solid detergents is still unsatisfactory. In addition, the presence of the large amounts of polymer required is not desirable.

According to EP-A-0 208 534, spray-dried detergent compositions are disclosed in general form which, in addition to anionic surfactants, contain nonionic surfactants, polyacrylates and polyethylene glycol ethers with an average molecular weight in the range from 1000 to 20,000. The teaching of this document is that the dispersibility of anionic surfactants can be improved by adding nonionic surfactants, polyethylene glycol ether (PEG) and polyacrylates. The only exemplary embodiment describes a mixture comprising alkylbenzenesulfonate and fatty alcohol sulfate, to which a C ₁₂ -C ₁₃ -oxoalcohol-6.5 EO adduct, sodium polyacrylate and polyethylene glycol with a molecular weight of approx. 8000 are added. The weight ratio between nonionic surfactant and PEG is 1: 1.

DE-A-21 24 526 relates to detergent and cleaning agent mixtures with controlled foam behavior. According to Example 6, compositions are disclosed which contain tallow alcohol sulfate, alkylbenzenesulfonate and polyethylene glycol with a molecular weight of approximately 20,000.

At this point, reference is made only to further developments in processes which relate to the production of solid anionic surfactants. Solid detergents are known, for example, from international patent application WO-A-92/09676 (Henkel), which are obtained by treating aqueous alkyl sulfate pastes with soda and zeolites and then extruding them. The document does not reveal anything about the dissolution rate of the solids.

From international patent application WO-A-91/02047 a process for the production of washable or cleaning-active extrudates with high density is known, whereby a solid and free-flowing premix containing a plasticizer and / or lubricant is extruded under pressure and the strand after exiting the hole shape can be cut to the predetermined granule size by means of a cutting device. To explain the further extrusion process, reference is also expressly made to the international patent applications WO-A-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 extrusion temperature. Under the shear action of the extruder screws, the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally, under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knife. The hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension. In this embodiment, the production of granules of an essentially uniformly predeterminable particle size succeeds, wherein in particular, the absolute particle sizes can 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 chopped-off 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 step. 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 may also 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. The extrudates can then be mixed with other constituents of washing or cleaning agents.

The object of the invention has now been to provide alkyl sulfates in such a form of supply that, after mixing with other detergent ingredients and mechanical solidification, they result in detergents or cleaning agents which are readily soluble even in cold water and whose production is free from the disadvantages described is.

The invention therefore relates in a first embodiment to a detergent mixture comprising a) alkyl and / or alkenyl sulfates of the formula (I) in which R _{1 is} a linear or branched aliphatic

R ₁ OSO ₃ X (I)

Hydrocarbon radical having 16 to 18 carbon atoms and X is an alkali or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, b) alkyl and / or alkenyl sulfates of the formula (II) in which R _{2 is} a linear or branched aliphatic hydrocarbon

R ₂ OSO ₃ X (II)

material residue with 12 to 14 carbon atoms and X as above, wherein the detergent mixture is essentially anhydrous, the components a) and b) in a weight ratio of 90: 10 to 70: 30 and c) hydrophobic structure breaker of the formula (III) in which R ₄ for a linear or variable

R ₄ O (CH ₂ CH ₂ O) _n H (III)

branched alkyl and / or alkenyl radical having 12 to 18 carbon atoms and n is 0 or numbers from 1 to 5, contains.

In the context of this invention, "essentially water-free" means that the individual solid ingredients can still contain residual amounts of water from their production, but no water is additionally added in the preparation of the detergent mixture according to the invention and the total amount of water in the detergent mixture is at values of less than 10% by weight, preferably not more than 5% by weight.

In the context of this invention, "detergent mixture" always means a mixture of the components (I), (II) and (III), as long as it is not expressly defined that a further ingredient is present in this mixture.

The detergent mixtures according to the invention can be mixed with further powdered detergent or cleaning agent ingredients and, after mechanical solidification, in particular extrusion, give solid detergents which have a significantly improved dissolution rate and show advantages in the washing-up behavior in the washing machine.

The invention includes the knowledge that only the combination of different features, namely the use of hydrophobic structure breakers and the mixing of alkyl sulfates of different C chain lengths, results in a synergistic improvement in the dissolution behavior. The weight ratio of the different alkyl sulfate types to one another has proven to be a further critical feature, since an improvement in the dissolution rate should not be bought by a deterioration in the washing properties.

The alkyl sulfates used (or synonymously: fatty alcohol sulfates) are usually prepared by sulfating alcohols with gaseous sulfur trioxide or chlorosulfonic acid and subsequent neutralization with bases. These alcohols are preferably derived from alcohols from renewable raw materials. These are, in particular, fatty alcohols which only have even-numbered C chain numbers. However, if alcohols of other origin are also used, alcohols with odd C chain numbers can also occur. In this case, however, it should apply that C ₁₅ alkyl sulfates should not be contained alone, but only in mixtures with other alkyl sulfates of the formula (I) and / or of the formula (II). However, its content should preferably not exceed 20% by weight, based on the total of the alkyl sulfates present. The described ratio of components a) and b) can be achieved in that mixtures of this type are produced specifically from C ₁₂ -C ₁₄ alkyl sulfates and C ₁₆ -C ₁₈ alkyl sulfates. However, it is also possible to use mixtures which, for example, contain C ₁₂ -C ₁₈ alkyl sulfates, that is to say already contain components a) and b), and the ratio of a) to b) described, if appropriate - if it is not already present in the mixture - by adding the appropriate shorter or longer chain alkyl sulfates. It is also possible to use various mixtures of, for example, C ₁₂ -C ₁₆ alkyl sulfate and C ₁₆ -C ₁₈ alk (en) yl sulfate or C ₁₂ -C ₁₈ alk (en) yl sulfates with only small proportions of shorter-chain C ₁₂ -C ₁₄ alkyl sulfates. The possibilities for producing the corresponding detergent mixtures are therefore varied. It is also possible for the detergent mixtures to contain further alk (en) yl sulfates whose C chain number is below 12 or above 18. Here too, depending on the source of the alcohol source, there are also odd and branched alkyl sulfates conceivable. In particular, however, it is preferred that the alcohols are linear and saturated and, like the fatty alcohols, are obtained from renewable raw materials. From an application point of view, however, it is preferred that alkyl sulfates with C chain numbers below 12 not in amounts above 20% by weight, preferably not in amounts above 10% by weight, and alk (en) yl sulfates with C chain numbers above 18 also not in amounts above 20% by weight, preferably not in amounts above 10% by weight. The quantities given relate to the total of the total alk (en) yl sulfates present. Alk (en) yl sulfate mixtures which contain a maximum of 5% by weight of alkyl sulfates with C chain numbers below 12 and are preferably free of these and a maximum of 5% by weight of alk (en) yl sulfates with C are particularly advantageous -Chain chain numbers above 18 and in particular are free of these. The quantitative data in turn relate to the sum of the total alk (en) yl sulfates present.

Typical examples of alkyl sulfates that make up component a) are cetyl sulfate, stearyl sulfate and oleyl sulfate and their technical mixtures based on C ₁₆ -C ₁₈ tallow alcohol or artificial blends of comparable chain length. Typical examples of alkyl sulfates that make up component b) are lauryl sulfate and myristyl sulfate and their technical mixtures based on C ₁₂ -C ₁₄ coconut or palm kernel alcohol or artificial blends of comparable chain length.

The hydrophobic structure breakers are fatty alcohols or their adducts with a few moles of ethylene oxide. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, linolenyl alcohol and their technical mixtures and their adducts with 1 to 5 moles of ethylene oxide. The alkoxylation products can have both a conventional and, in particular, a narrow homolog distribution.

From an application point of view, hydrophobic structure breakers of the formula (III) are preferred in which R _{4 represents} a linear alkyl radical having 12 to 14 carbon atoms and n represents 0 or numbers from 1 to 3. The use of C ₁₂ -C ₁₄ coconut fatty alcohol or its 2EO adduct is particularly advantageous. The essentially water-free detergent mixtures can contain the hydrophobic structure breakers in amounts of 1 to 50, preferably 5 to 20% by weight, based on the mixtures.

In some preferred embodiments, it has proven advantageous if non-ethoxylated fatty alcohol having 12 to 18 carbon atoms is used as the hydrophobic structure breaker. Typical examples of this are, as indicated above, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol or their technical mixtures, in particular C ₁₂ -C ₁₄ -, C ₁₆ -C ₁₈ - or C ₁₂ -C ₁₈ fatty alcohol mixtures. This also includes the unsulfonated fractions from the production of the alk (en) yl sulfates according to a) and b). It is preferred that the amount of the unsulfonated components in the industrially produced alk (en) ylsulfate mixture, which apart from the alk (en) ylsulfates and the unsulfonated components usually contain further components, in particular inorganic salts, is 4.5% by weight .-% does not exceed. In particular, the unsulfonated portion should make up less than 3% by weight, advantageously less than 2% by weight, based in each case on the industrially produced alk (en) yl sulfate mixture.

As extensive investigations by the applicant have shown, the unsulfonated portion (US) contained in the alkyl sulfates, i.e. the free fatty alcohol, in the further processing to solid detergents or cleaning agents, in particular in the particularly preferred extrudates, in contrast to the additionally used fatty alcohol, have the effect that, with a constant ratio between components a) and b), the dissolving rate of the increasing US content Detergent or cleaning agent decreases again. However, this effect can be compensated for by increasing the proportion of the shorter-chain component b) within the stated limits.

A preferred embodiment of the invention therefore relates to anhydrous detergent mixtures which contain components a) and b) in a weight ratio of 90:10 to 80:20 and in which the unsulfonated components in the Components a) and b) make up a total of less than 2% by weight, based on components a) and b).

A further advantageous embodiment relates to anhydrous detergent mixtures which contain components a) and b) in a weight ratio of 70:30 to 75:25 and in which the unsulfonated components in components a) and b) total less than 4.5% by weight. % - based on components a) and b) - make up.

If other advantageous mixtures are not illustrated by the examples contained in the experimental part, the person skilled in the art can vary the parameters "US content" and ratio a: b "independently on the basis of the teaching presented, without having to be inventive in this regard.

Purified alk (en) yl sulfate mixtures which no longer contain unsulfated constituents can also be used and may even be particularly preferred for the reasons mentioned. Purified alk (en) yl sulfate mixtures of this type can be obtained, for example, by superheated steam drying. The anhydrous detergent mixtures used according to the invention preferably contain the non-ethoxylated alcohols in amounts of 1 to 50% by weight, in particular in amounts of up to 20% by weight, based in each case on the detergent mixtures. In particular, it is preferred that, in addition to the unsulphonized proportions which may already be present through the technical preparation, 1 to 20% by weight, advantageously 2 to 15% by weight, of linear alcohols with up to 16 carbon atoms and in particular 2 to 12% by weight. % Of fatty alcohols with 12 and / or 14 carbon atoms are present in the detergent mixtures used according to the invention. In a preferred embodiment of the invention, the content of C ₁₈ alcohol is not more than 2% by weight and in particular not more than 1.5% by weight, in each case based on the detergent mixture. In a further preferred embodiment of the invention, the alcohol content with a C chain number above 15 is not more than 10% by weight, preferably not more than 5% by weight and in particular not more than 3% by weight, in each case on the detergent mixture.

In order to produce readily soluble alkyl sulfates, the surfactant grain has to be structured, for which incorporation and homogeneous distribution of the optionally solidified structure breaker is required. This can be done in several ways.

A particularly simple embodiment of the method consists in presenting the alkyl sulfates (components a and b) in powder form and intimately mixing them with the required amount of the structure breaker which may have solidified. Components such as mixers from Eirich or shovel mixers from Lödige or in particular spray mixers from Schugi are advantageous for this process, in which the anionic surfactant is placed in the mixing chamber and the hydrophobic structure breaker is optionally sprayed together with a polymeric solidifying agent. It is also possible to carry out the drying of the anionic surfactant pastes and the mixing simultaneously in a fluidized bed dryer. Dry, readily soluble powders are obtained, which are subsequently subjected to further customary, solid powder detergent additives, for example spray-dried compounds, and can be processed, for example, to detergent extrudates.

The invention further relates to a process for the preparation of anhydrous detergent mixtures, in which mixtures of alkyl and / or alkenyl sulfates of the formulas (I) and (II) are impregnated with the hydrophobic structure breakers (III).

If the structure breakers in question are liquid under normal conditions, the question arises as to how it can be ensured that the structure breaker remains in the alkyl sulfate grain, structures it permanently and does not "bleed out". A large number of investigations carried out by the applicant have surprisingly shown that the dry grain of anionic surfactants has an amazing absorption power compared to the liquid structure breakers mentioned. For example, 5 to 10, in some cases even up to 15% by weight of the liquid structure breakers can be processed with the anionic surfactants to form a solid, easily soluble product without the structure breaker gradually bleeds out and the rate of dissolution slows down with prolonged storage.

In particular when larger amounts (above 10% by weight) of the structure breakers are to be added to the anionic surfactants, it has been found that bleeding can be reliably prevented by the addition of so-called polymeric strengthening agents.

Polyethylene glycol ethers (PEG) with an average molecular weight of 12,000 to 100,000 are suitable for this purpose. Typical examples are polyethylene glycols with an average molecular weight of 12,000 to 35,000. The water-free detergent mixtures can contain the polymeric strengthening agents in amounts of 1 to 5, preferably 2 to 4% by weight, based on the hydrophobic structure breaker.

Another object of the invention relates to the use of the essentially water-free detergent mixtures according to the invention for the production of solid detergents or cleaning agents by customary methods by mixing with further powdery to granular detergent ingredients or compounds and preferably by subsequent mechanical consolidation.

Other detergent additives that can be used are, for example, other surfactants and builder substances such as zeolites, phosphates, polycarboxylates, water glass, soda, sodium sulfate and the like. If desired, component b) can also be mixed into a spray-dried compound and this mixture can in turn be added to the anhydrous mixture of components a) and c).

In a preferred embodiment of the invention, the alkyl sulfates are mixed in powder form with the optionally solidified structure breakers and the mixture is homogenized and solidified in a screw press. The extrusion is carried out via a perforated disc, so that press strands are formed which can be mechanically comminuted to extrudates or needles of the desired shape and dimension by known processes. Extrudates this form show a particularly high dissolving speed and very good washing-up behavior in the washing machine.

It has been found that the use of certain detergent mixtures according to the invention of the type specified leads to particularly advantageous performance properties of the extrudates in the production of extruded washing or cleaning agents.

In a further embodiment, the invention therefore relates to the use of the detergent mixtures mentioned for the production of detergents or cleaning agents, a non-ethoxylated alcohol having 12 to 18 carbon atoms (n equal to 0) now being used as the hydrophobic structure breaker c) and the proportion of C ₁₈ alcohol does not exceed 3% by weight, based on the detergent mixture of (I), (II) and (III).

In a further and particularly preferred embodiment of the invention, extruded detergents or cleaning agents are claimed which contain essentially water-free detergent mixtures which a) alkyl and / or alkenyl sulfates of the formula (I), in which R _{1 is} a linear or

R ₁ OSO ₃ X (I)

branched aliphatic hydrocarbon radical having 16 to 18 carbon atoms and X is an alkali or alkaline earth metal, ammonium, alkylammonium or glucammonium, b) alkyl and / or alkenyl sulfates of the formula (II), in which R _{2 is}

R ₂ OSO ₃ X (II)

is a linear or branched aliphatic hydrocarbon radical having 12 to 14 carbon atoms and X is as above, and c) hydrophobic structure breakers of the formula (III) in which R _{4 is} a linear or branched alkyl and / or alkenyl radical having 12 to 18

R ₄ O (CH ₂ CH ₂ O) _n H (III)

Carbon atoms and n stands for 0 or numbers from 1 to 5, with the proviso that they contain components a) and b) in a weight ratio of 90: 10 to 70: 30, c) being a non-ethoxylated alcohol as the hydrophobic structural breaker is used with 12 to 18 carbon atoms and the proportion of C ₁₈ alcohol does not exceed 3% by weight, based on the detergent mixture.

Surprisingly, the detergent mixtures which have non-ethoxylated alcohols as the hydrophobic structure breaker, when used according to the invention for the production of extrudates which are active in washing or cleaning, have advantages over detergent mixtures which, as the hydrophobic structure breaker, instead have ethoxylated alcohols, in particular low ethoxylated alcohols such as a C ₁₂ -C ₁₄ - Contain fatty alcohol with 3 E0 or a C ₁₂ -C ₁₈ fatty alcohol with 5 E0 or 7 E0. Due to the high viscosities and flow limits of mixtures of alkyl sulfates of the specified distribution from component a) and component b) with short-chain and non-ethoxylated fatty alcohols such as lauryl alcohol compared to the corresponding mixtures, which contain low ethoxylated fatty alcohols as a hydrophobic structural breaker, the person skilled in the art would be assume that, especially when using mixtures with non-ethoxylated fatty alcohols, extrudates are formed during the extrusion process under the action of high pressures, the surface of which is bonded by poorly soluble surfactant gels and which therefore show unfavorable dissolving properties and low dissolving speeds. It was all the more surprising that the detergent mixtures used with preference in accordance with the invention lead to extrudates which have an extremely good dissolving behavior.

Polyethylene glycol ethers with an average molecular weight of 12,000 to 100,000 are particularly suitable as polymeric solidifying agents that can be used. The essentially water-free mixtures of the different alk (en) yl sulfates, fatty alcohols and polymeric solidifying agents can be used in the latter, for example in amounts of 1 to 5% by weight, preferably in amounts of 2 to 4% by weight, based in each case on the total Mixture.

These detergent mixtures are then used in the production of the extruded washing or cleaning agents, and are used as a component of the solid and free-flowing premix. The extruded washing or cleaning agents and the special process for their preparation are also the subject of this invention. The premix is then - as described, for example, in international patent application WO-A-91/02047 - extruded in a rope shape under a pressure of preferably at least 25 bar. The premix has a consistency such that the strand can be cut to the predetermined size of the granulate directly after it emerges from a hole shape by means of a cutting device. The extrudates can contain all the usual ingredients of washing or cleaning agents, including ethoxylated alcohols, in particular ethoxylated fatty alcohols, which are used as nonionic surfactants in addition to and separately from the detergent mixtures. In addition to the nonionic surfactants mentioned, these common ingredients primarily include other surfactants such as anionic, cationic, zwitterionic or amphoteric, but also other nonionic surfactants.

The finished washing or cleaning agents or the extrudates contain, for example, the known alkylbenzenesulfonates, olefin sulfonates, alkanesulfonates, sulfated fatty acid glycerol esters and / or methyl α-sulfofatty acid or their corresponding salts as anionic surfactants. However, it is preferred that the extrudates contain no more than 15% and especially no more than 10% by weight of these additional anionic surfactants. Extrudates which contain only the alk (en) yl sulfates mentioned, in particular alkyl sulfates, as anionic surfactants are very particularly preferred. At most, the extrudates can additionally contain soaps in amounts of 0.5 to 5% by weight. Saturated fatty acid soaps are 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. Unsaturated fatty acid soaps, which are derived, for example, from oleic acid, may also be present, but their proportion of the soaps should not exceed 50% by weight.

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 surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts. The content of anionic surfactants including alkyl sulfates and soaps in the washing or cleaning agents, including the extrudates, is generally between 5 and 40% by weight.

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 (E0) 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 E0 per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 E0 or 4 E0, C ₉ -C ₁₁ alcohol with 7 E0, C ₁₃ -C ₁₅ alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C ₁₂ -C ₁₈ alcohols with 3 E0, 5 E0 or 7 E0 and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 E0 and C ₁₂ -C ₁₈ alcohol with 5 E0. 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 E0 can also be used. Examples include tallow fatty alcohol with 14 E0, 25 E0, 30 E0 or 40 E0.

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, indicating the distribution of monoglycosides and oligoglycosides is any number between 1 and 10; x is preferably 1.2 to 1.4.

in der R⁵CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R⁶ 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.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (IV),

in which R ⁵ CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ⁶ 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 proportion of nonionic surfactants in the compositions is generally 2 to 25% by weight.

In anionic and nonionic surfactant mixtures, it is particularly preferred for their use in extrudates that the weight ratio of anionic surfactant: nonionic surfactant is approximately 15: 1 to 1: 1 and in particular 10: 1 to 1: 1.5.

All of the previously commonly used builder substances can be used as inorganic builder substances. These include in particular zeolites, crystalline layered silicates, even phosphates, if their use should not be avoided for ecological reasons. Their content can usually be 10 to 60% by weight. The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. However, zeolite NaX and zeolite 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 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 general formula NaMSi _z O _{2z + 1} .yH ₂ O, where M is sodium or hydrogen, z is a number from 1.9 to 4 and y is a number from 0 is to 20 and preferred values for z are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-AO 164 514. Preferred crystalline layered silicates are those in which M is sodium and z is 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

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, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of 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.

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. Terpolymers are also particularly preferred. for example, those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers (P 43 00 772.4) or which contain salts of acrylic acid and 2-alkylallylsulfonic acid as monomer and sugar derivatives DE-A-42 21 381.

Further suitable builder systems are oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application WO-A-93/16110.

In addition, the agents can also contain components which have a positive influence on the oil and fat washability from textiles. This effect becomes particularly clear 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 on 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.

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 content of sodium carbonate in the compositions is preferably up to about 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.

It is preferred in one embodiment of the invention that the alkali silicates are 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 to introduce into the process.

According to the teaching of the older German patent application P 43 19 578.4, alkali metal carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and, if appropriate, a further carboxyl and / or amino group and amino acids and / or their salts. In the context of this invention, it is preferred that the alkali metal carbonates are partially or completely replaced 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 peracid 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'-tetra-acylated 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).

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable as foam inhibitors Soaps of natural or synthetic origin, for example, which have a high proportion of C ₁₈ -C ₂₄ 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 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.

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. Here, 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. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order 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 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid (EDTMP) are suitable as stabilizers, in particular for per compounds and enzymes.

Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying. Water-soluble colloids, mostly of an 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, preference is given to cellulose ethers, such as carboxymethyl 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 polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition, used.

As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its 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 compounds of similar structure which, instead of the morpholino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, 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) diphenyls. Mixtures of the aforementioned brighteners can also be used.

The finished washing or cleaning agents can be built up uniformly from extrudates which contain the above-mentioned ingredients, including the detergent mixtures, which are also extruded as a component of the premix. In a further embodiment of the invention, however, the extrudates are processed 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 are the main component form. 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 further finely divided dry powders before the enzymes and the other components 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 partially does not extrude , 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 mixture containing zeolite 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 / l, bulk densities between 700 and 1000 g / l and in particular between 750 and 950 g / l being particularly preferred.

Examples Example 1:

In a spray mixer of Fa.Schugi the hydrophobic structure breakers are (C _12/14 - fatty alcohol 2EO adduct) and optionally the polymeric solidifying agent (polyethylene glycol, M = 12000) into a corresponding quantity sprühneutralisiertes fatty alcohol sulfate powder (components a + b) sprayed . The proportions can be found in Tab. 1. The anhydrous detergent mixtures were mixed with other customary detergent ingredients. The homogenized mixture was then first extruded in a screw press and then through a perforated disc (diameter of the holes 1.1 mm). The resulting strands were then processed into granular granules. The composition of the extrudates is shown in Table 1.

The extrudates were subjected to sieve analysis, whereby 5 fractions were obtained: F1 > 1.6 mm F2 1.6 to 1.4 mm F3 1.4 to 1.25 mm F4 1.25 to 1.0 mm F5 <1.0 mm FG Full spectrum

Mixtures R1 and R2 are according to the invention, and mixtures V1 to V4 are used for comparison. Tab. 1: Extrudate compositions / percentages as% by weight Components V1 % V2 % V3 % V4 % R1 % R2 % C _16/18 -FAS 18.0 20.2 15.5 18.0 15.5 15.5 C _12/14 -FAS - - 2.5 - 2.5 2.5 C _12/14 -FA2 - - - 2.2 2.2 2.2 PEG12000 - - - - - 0.1 C _16/18 -FA40 5.0 5.0 5.0 5.0 5.0 5.0 Zeolite A (anhydrous) 35.0 35.0 35.0 35.0 35.0 35.0 Sodium perborate 16.0 16.0 16.0 16.0 16.0 16.0 Water glass 7.0 7.0 7.0 7.0 7.0 7.0 Water and salts ad 100 Legend: C _16/18 -FAS: C _16/18 -Fatty alcohol sulfate sodium salt spray-dried ex sulfopon ^(R) T powder, Henkel KGaA, Düsseldorf / FRG.
C _12/14 -FAS: C _12/14 fatty alcohol sulfate sodium salt spray dried
C _12/14 -FA2: C _12/14 fatty alcohol 2E0 adduct
C _16/18 -FA40: C _16/18 fatty alcohol 40E0 adduct
PEG12000: polyethylene glycol ether (M = 12000)

To investigate the solubility, 32 g of extrudate were dissolved or dispersed in 4 l of water (30 ° C., 16 ° d). After 95 s, the solutions or dispersions were filtered off, the residue was dried and weighed out. The results are summarized in Tab. 2: Tab. 2: Solubility tests / percentages in% by weight Extrudate Residue in the fractions F1 % F2 % F3 % F4 % F5 % FG % R1 29.3 24.1 13.5 8.1 0.3 16.4 R2 29.1 23.9 12.1 7.0 0.2 15.1 V1 57.1 55.0 49.3 42.0 14.8 55.4 V2 60.0 59.1 51.0 44.0 14.9 59.0 V3 45.0 39.1 39.1 30.5 10.0 31.9 V4 45.0 39.1 32.7 25.6 8.9 20.4

Example 2:

ABS

C₉-C₁₃-Alkylbenzolsulfonat-Natriumsalz,

FAS-M

Mischung aus Sulfopon T^(R) (C₁₆-C₁₈-Fettalkylsulfat, pulverförmig; Handelsprodukt des Anmelders) und Texapon LS 35^(R) (C₁₂-C₁₄-Fettalkylsulfat, flüssig; Handelsprodukt des Anmelders) im Gewichtsverhältnis 80:20. Der Anteil an unsulfiertem C₁₆-C₁₈-Fettalkohol aus dem Sulfopon T^(R) betrug 1,45 Gew.-% und an C₁₂-C₁₄-Fettalkohol aus dem Texapon LS 35^(R) betrug 0,2 Gew.-%, jeweils bezogen auf die Mischung aus den beiden alkylsulfathaltigen Rohstoffen.

FA

Laurylalkohol

TA40

Talgfettalkohol mit 40 Ethylenoxidgruppen (E0)

Nio

C₁₂-C₁₈-Fettalkohol mit 5 E0 und C₁₂-C₁₄-Fettalkohol 3 E0 im Gewichtsverhältnis 4:1

Seife

gesättigte C₁₂-C₁₈-Fettsäureseife, Natriumsalz

Zeolith

Zeolith, berechnet als wasserfreie Aktivsubstanz

CP5

Sokalan CP5^(R), Copolymeres der Salze der Acrylsäure und der Maleinsäure; Handelsprodukt der BASF, Bundesrepublik Deutschland

Sil3,0

amorphes Natriumsilikat mit einem Gewichtsverhältnis Na₂O:SiO₂ von 1:3,0

Soda

Natriumcarbonat

Per

Perboratmonohydrat

TAED

Tetraacetylethylendiamin

SIK

Silikonöl

Enzym

Protease-Granulat

A premix of the compositions given below was prepared in a continuous 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 bulk density of the extrudates according to the invention and the comparative extrudates was between 750 and 900 g / l. The compositions of the extrudates can be found in the following table. The abbreviations mentioned mean:

SECTION

C ₉ -C ₁₃ alkylbenzenesulfonate sodium salt,

FAS-M

Mixture of sulfopone T ^(R) (C ₁₆ -C ₁₈ fatty alkyl sulfate, powdery; commercial product of the applicant) and Texapon LS 35 ^(R) (C ₁₂ -C ₁₄ fatty alkyl sulfate, liquid; commercial product of the applicant) in a weight ratio of 80:20. The proportion of unsulfated C ₁₆ -C ₁₈ fatty alcohol from the sulfopone T ^(R) was 1.45% by weight and that of C ₁₂ -C ₁₄ fatty alcohol from the Texapon LS 35 ^(R) was 0.2% by weight. %, each based on the mixture of the two alkyl sulfate-containing raw materials.

FA

Lauryl alcohol

TA40

Tallow fatty alcohol with 40 ethylene oxide groups (E0)

NOK

C ₁₂ -C ₁₈ fatty alcohol with 5 E0 and C ₁₂ -C ₁₄ fatty alcohol 3 E0 in a weight ratio of 4: 1

Soap

saturated C ₁₂ -C ₁₈ fatty acid soap, sodium salt

Zeolite

Zeolite, calculated as an anhydrous active substance

CP5

Sokalan CP5 ^(R) , copolymer of the salts of acrylic acid and maleic acid; Commercial product from BASF, Federal Republic of Germany

Sil3.0

Amorphous sodium silicate with a weight ratio Na ₂ O: SiO ₂ of 1: 3.0

soda

sodium

By

Perborate monohydrate

TAED

Tetraacetylethylenediamine

SIK

Silicone oil

enzyme

Protease granules

A 35% by weight aqueous sodium silicate solution (1: 3.0) was used as the plasticizer and / or lubricant. In M1, a mixture of 9 parts FAS-M with 1 part FA was first produced in a Lödige mixer. This was then incorporated into the premix. The finished extrudates were dried and mixed with TAED and the enzyme. Table 3: Compositions of the extrudate R3 according to the invention and of the comparative extrudate V5 (in% by weight) R3 V5 SECTION ---- 18th FAS-M 18th ---- FA 2.2 ---- NOK ---- 2.2 Soap 1 1 TA40 2.5 2.5 Zeolite 28 28 CP5 4th 4th soda 5 5 Sil3.0 2nd 2nd By 20th 20th TAED 6 6 SIK 0.6 0.6 enzyme 1.2 1.2 Water and salts from raw materials rest rest

Determination of the washing-in behavior in the washing machine (residue in g)

To determine the induction behavior of the extrudates, the extrudates were tested in household drum washing machines with an induction drawer at a water pressure of 0.5 bar. Test machines were Miele W918 and Quelle Privileg 1100. 5 determinations were carried out in each machine. The mean value given below was then formed from the 10 results. For this purpose, 80 g of the extrudates were added to the induction chamber per wash. The tap water with which the extrudates were washed into the respective machine, which was loaded with 3.5 kg of dry laundry, had a water hardness from 16 ° d. After the wash-in was completed, the detergent residues from the wash-in drawer and the wash-in chamber were placed separately on a watch glass with a rubber wiper and weighed out. 30% moisture was subtracted from these moist residues. The "dry residues" from the drawer and chamber were added and the mean was formed from the sum, which is given in Table 4 for R3 and V5.

Determination of the residue behavior in the simulated hand wash test (HW in%)

In a bowl, 32 g of the agent were pre-dissolved in 4 liters of water (16 ° d) at a temperature of 30 ° C for 15 seconds by hand. Then a Nicki sweater was submerged three times, pressed and turned by 90 °. After a minute, the sweater was removed from the wash water and wrung out. The wash liquor was decanted off, the residues were transferred to a sieve and dried at 40 ° C. The residues are given in%. The results are also shown in Table 4. Table 4: Injection and residue behavior of the extrudates Extrudate Induction residue in g Hand wash residue in% R3 2.2 12.7 V5 17.9 21.1

The table shows that both the flushing-in behavior and the residue behavior of the extrudates in the hand-washing test are significantly better with the extrudate R3 according to the invention than with the comparative example V5.

Claims (20)

1. Detergent mixtures containing

   a) alkyl and/or alkenyl sulfates corresponding to formula (I):
   
           R₁OSO₃X     (I)
   
   in which R₁ is a linear or branched aliphatic hydrocarbon radical containing 16 to 18 carbon atoms and X is an alkali metal or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium,

   b) alkyl and/or alkenyl sulfates corresponding to formula (II):
   
           R₂OSO₃X     (II)
   
   in which R₂ is a linear or branched aliphatic hydrocarbon radical containing 12 to 14 carbon atoms and X is an alkali metal or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium,

   characterized in that the detergent mixture is substantially water-free and contains components a) and b) in a ratio by weight of 90:10 to 70:30 and
   c) hydrophobic structure breakers corresponding to formula (III):
   
           R₄O(CH₂CH₂O)_nH     (III)
   
   in which R₄ is a linear or branched alkyl and/or alkenyl radical containing 12 to 18 carbon atoms and n is 0 or a number of 1 to 5.
2. Detergent mixtures as claimed in claim 1, characterized in that components a) and b) are present in a ratio by weight of 90:10 to 80:20 and the total unsulfonated content of components a) and b) is less than 4.5% by weight, preferably less than 3% by weight and more preferably less than 2% by weight, based on the industrially produced alk(en)yl sulfate mixture.
3. Detergent mixtures as claimed in claim 1 or 2, characterized in that they contain compounds corresponding to formula (III), in which R₄ is a linear alkyl radical containing 12 to 18 carbon atoms and n is 0 or a number of 1 to 3, as hydrophobic structure breakers.
4. Detergent mixtures as claimed in any of claims 1 to 3, characterized in that they contain the hydrophobic structure breakers in quantities of 1 to 50% by weight, based on the mixtures.
5. Detergent mixtures as claimed in any of claims 1 to 4, characterized in that they contain polyethylene glycol ethers with an average molecular weight of 12,000 to 100,000 as polymeric compacting agents.
6. Detergent mixtures as claimed in any of claims 1 to 5, characterized in that they contain the polymeric compacting agents in quantities of 1 to 5% by weight, based on the hydrophobic structure breakers.
7. A process for the production of the detergent mixtures claimed in any of claims 1 to 6, in which mixtures of alkyl and/or alkenyl sulfates corresponding to formulae (I) and (II) are impregnated with the hydrophobic structure breakers (formula III).
8. The use of the detergent mixtures claimed in any of claims 1 to 6 for the production of solid detergents or cleaning formulations by mixing with other powder-form ingredients of detergents or cleaning formulations and, preferably, subsequent mechanical compacting.
9. The use of detergent mixtures as claimed in claim 8, characterized in that a non-ethoxylated alcohol containing 12 to 18 carbon atoms is used as the hydrophobic structure breaker c) and the percentage content of C₁₈ alcohol does not exceed 3% by weight, based on the detergent mixture of a), b) and c).
10. The use of detergent mixtures as claimed in claim 8 or 9, characterized in that the detergent mixtures used contain alkyl sulfates with less than 12 carbon atoms in quantities of not more than 20% by weight and preferably in quantities of not more than 10% by weight, based on the sum total of alk(en)yl sulfates present.
11. The use of detergent mixtures as claimed in any of claims 8 to 10, characterized in that the detergent mixtures used contain alk(en)yl sulfates, preferably alkyl sulfates, with more than 18 carbon atoms in quantities of no more than 20% by weight and preferably in quantities of no more than 10% by weight, based on the sum total of alk(en)yl sulfates present.
12. The use of detergent mixtures as claimed in any of claims 8 to 11, characterized in that the detergent mixtures used contain alkyl sulfate mixtures containing at most 5% by weight of alkyl sulfates with less than 12 carbon atoms, the alkyl sulfate mixtures preferably being free from such alkyl sulfates.
13. The use of detergent mixtures as claimed in any of claims 8 to 12, characterized in that the detergent mixtures used contain alk(en)yl sulfate mixtures containing at most 5% by weight of alk(en)yl sulfates with more than 18 carbon atoms, the alk(en)yl sulfate mixtures preferably being free from such alk(en)yl sulfates.
14. The use of detergent mixtures as claimed in any of claims 8 to 13, characterized in that the detergent mixtures used contain industrially produced alk(en)yl sulfate mixtures which contain no more than 4.5% by weight, preferably less than 3% by weight and more preferably less than 2% by weight, based on the industrially produced alk(en)yl sulfate mixture, of unsulfonated components.
15. The use of detergent mixtures as claimed in any of claims 8 to 14, characterized in that the detergent mixtures used contain no more than 2% by weight and preferably no more than 1.5% by weight, based on the detergent mixture, of C₁₈ alcohols.
16. The use of detergent mixtures as claimed in any of claims 8 to 15, characterized in that the detergent mixtures used contain alcohols with more than 15 carbon atoms in quantities of no more than 10% by weight, preferably in quantities of no more than 5% by weight and, more preferably, in quantities of no more than 3% by weight, based on the detergent mixture.
17. The use of detergent mixtures as claimed in any of claims 8 to 16, characterized in that the detergent mixtures used contain 1 to 20% by weight, based on the detergent mixture, and preferably 2 to 15% by weight of linear alcohols containing up to 14 carbon atoms and, more particularly, 2 to 12% by weight of fatty alcohols containing 12 and/or 14 carbon atoms in addition to any unsulfonated components already present from the industrial production process.
18. An extruded detergent or cleaning formulation containing substantially water-free detergent mixtures which contain a) alkyl and/or alkenyl sulfates corresponding to formula (I):
    
            R₁OSO₃X     (I)
    
    in which R₁ is a linear or branched aliphatic hydrocarbon radical containing 16 to 18 carbon atoms and X is an alkali metal or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, b) alkyl and/or alkenyl sulfates corresponding to formula (II):
    
            R₂OSO₃X     (II)
    
    in which R₂ is a linear or branched aliphatic hydrocarbon radical containing 12 to 14 carbon atoms and X is as defined above, and c) hydrophobic structure breakers corresponding to formula (III):
    
            R₄O(CH₂CH₂O)_nH     (III)
    
    in which R₄ is a linear or branched alkyl and/or alkenyl radical containing 12 to 18 carbon atoms and n is 0 or a number of 1 to 5, with the proviso that they contain components a) and b) in a ratio by weight of 90:10 to 70:30, the hydrophobic structure breaker c) being a non-ethoxylated alcohol containing 12 to 18 carbon atoms and the percentage content of C₁₈ alcohol not exceeding 3% by weight, based on the detergent mixture.
19. A process for the production of high-density washing- or cleaning-active extrudates in which a solid free-flowing compound containing a plasticizer and/or lubricant is extruded under pressure to form strands and, after leaving the multiple-bore extrusion die, the strands are cut to the predetermined granule size by means of a cutting unit, characterized in that detergent mixtures containing a) alkyl and/or alkenyl sulfates corresponding to formula (I):
    
            R₁OSO₃X     (I)
    
    in which R₁ is a linear or branched aliphatic hydrocarbon radical containing 16 to 18 carbon atoms and X is an alkali metal or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, b) alkyl and/or alkenyl sulfates corresponding to formula (II):
    
            R₂OSO₃X     (II)
    
    in which R₂ is a linear or branched aliphatic hydrocarbon radical containing 12 to 14 carbon atoms and X is as defined above, and c) hydrophobic structure breakers corresponding to formula (III):
    
            R₄O(CH₂CH₂O)_nH     (III)
    
    in which R₄ is a linear or branched alkyl and/or alkenyl radical containing 12 to 18 carbon atoms and n is 0, with the proviso that the detergent mixture is substantially water-free, components a) and b) are used in a ratio by weight of 90:10 to 70:30 and the percentage content of C₁₈ alcohol is 3% by weight, based on the detergent mixture.
20. A process as claimed in claim 19, characterized in that the extrudates produced are blended with other ingredients of detergents or cleaning formulations.