EP0716683B1 - Spray-dried washing or cleaning product or component therefor - Google Patents

Abstract

Washing or cleaning products or a component therefor contain alk(en)yl sulphates in amounts from 5 to 30 % by weight and crystalline stratified silicates having the formula NaMSixO2x+1.yH2O, in which M stands for sodium or hydrogen, x equals a number from 1.9 to 4, preferably 2, 3 or 4, and y equals a number from 0 to 20, in amounts from 30 to 80 % by weight, in relation to the water-free active substance. These products may be obtained by spray-drying without loosing their primary and secondary washing power.

Description

The invention relates to detergents or cleaning agents or a component therefor which contain alk (en) yl sulfates as anionic surfactants and crystalline phyllosilicates as builder substance, and a process for their preparation.

Crystalline layered sodium silicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 have proven to be suitable substitutes or partial substitutes for the established builders phosphates and zeolites. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171. β-disodium disilicate is commercially available under the name SKS 7 ( ^R ), δ-sodium disilicate is available under the name SKS 6 ( ^R ) (commercial products from Hoechst AG, Federal Republic of Germany). These powders generally have a bulk density of less than 600 g / l and have high fines content, usually more than 30% by weight, with a particle size below 0.1 mm.

From European Patent EP-B-0 320 770 it is known that certain crystalline layered silicates, in particular disilicates, can be recrystallized, although it is possible that after recrystallization there is a different crystal modification than before, but ultimately a crystalline modification and there is no amorphous modification. It is essential to prepare a concentrated solution of the layered silicate, since hydrolysis occurs in dilute solution and with prolonged exposure to water, especially at higher temperatures, as a result of which the layered silicate is broken down into low-molecular fragments. Once such fragments have formed, they can no longer be converted into crystalline layered silicates. Of the The patentee has concluded from this that detergents or cleaning agents which contain crystalline phyllosilicates should also be producible by spray drying. The spraying process should be carried out at gas inlet temperatures of 70 to 300 ° C and preferably from 100 to 200 ° C. Other ingredients that may be included in the slurry to be spray dried are, for example, anionic surfactants such as alkyl benzene sulfonates and alkyl sulfates.

According to the teaching of the international patent application WO-A-92/18594, however, losses occur in the action of the crystalline layered silicates in the usual spray drying of slurries which contain crystalline layered silicates caused by the destruction of their physical structure. Crystalline layered silicates should therefore be incorporated into detergents or cleaning agents using other process methods.

Obviously, special parameters must be observed when spray-drying slurries which contain crystalline layered silicates so that the application-related advantages of the crystalline layered silicates are not lost. However, these parameters are not disclosed in European Patent EP-B-0 320 770.

Washing or cleaning agents usually contain alkyl benzene sulfonates and / or alkyl sulfates as anionic surfactants. However, alkylbenzenesulfonates have the disadvantage that they are obtained from petrochemical raw materials and are therefore not among the renewable raw materials. Although alkyl sulfates, in particular fatty alkyl sulfates, are based on renewable raw materials, it is known, on the other hand, that they are used in granular form in large amounts, ie in amounts of, for example, around 8% by weight and above, in particular in conventional spray technology and in particular in combination with nonionic surfactants lead to an unacceptable redispersion behavior. In the older German patent application DE-A-42 42 185 washing or cleaning agents with alk (en) yl sulfates in amounts above 8% by weight and crystalline layered silicates in amounts of 10 to 60% by weight are described which do not have the Spray drying the crystalline Layered silicates, but are preferably obtained by extrusion according to international patent application WO-A-91/02047.

Surprisingly, it has now been found that it is very possible to provide spray-dried detergents or cleaning agents or a component therefor which contain alk (en) yl sulfates and crystalline phyllosilicates in the spray-dried fraction without the agent having losses in the primary and secondary washing power compared to agents, which were not produced by spray drying.

Accordingly, the invention relates in a first embodiment to a washing or cleaning agent or a component therefor, which (s) alk (en) yl sulfates and crystalline phyllosilicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen means, x is a number from 1.9 to 4 and y is a number from 0 to 20, and it contains alk (en) yl sulfates in amounts between 5 and 30% by weight and crystalline phyllosilicates in amounts between 30 and Contains 80% by weight, based on the anhydrous active substance, and is in spray-dried form.

The alk (en) yl sulfates are the sulfuric acid half esters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ₁₀ -C ₂₀ oxo alcohols, and those of secondary alcohols thereof 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. C ₁₆ -C ₁₈ 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 C ₁₆ -C ₁₈ alk (en) yl sulfates in combination with short-chain alkyl sulfates, preferably mixtures of C ₁₂ -C ₁₄ fatty alkyl sulfates or mixtures of C ₁₂ -C ₁₈ fatty alkyl sulfates with C ₁₆ -C ₁₈ fatty alkyl sulfates and in particular C ₁₂ -C ₁₆ fatty alkyl sulfates with C16-C18 fatty alkyl sulfates. In a further preferred embodiment of the invention, however, not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length are used from preferably C ₁₆ to C ₂₂ used. Mixtures of saturated sulfated fatty alcohols predominantly consisting of C ₁₆ and unsaturated sulfated fatty alcohols predominantly consisting of C ₁₈ are particularly preferred.

The sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol of ethylene oxide (E0) or C ₁₂ - C ₁₈ 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.

The content of these alk (en) yl sulfates in the washing or cleaning agents according to the invention or in the spray-dried components therefor is preferably above 8% by weight and is in particular in amounts between 10 and 25% by weight, based in each case on the spray-dried component, in front. Amounts between 12 and 20% by weight (based in each case on the spray-dried component) of alk (en) yl sulfates are particularly advantageous.

The agents or components according to the invention can also contain further additional anionic surfactants, for example alkylbenzenesulfonates, olefin sulfonates, alkanesulfonates, esters of α-sulfofatty acids or their salts, sulfated fatty acid glycerol esters, alkyl sulfosuccinates or mixtures thereof. In a particularly preferred embodiment of the invention, however, the agents or components contain no additional anionic surfactants apart from the alk (en) yl sulfates. Only soaps, preferably in amounts of 0.2 to about 5% by weight, based on the finished washing or cleaning agent, can be present. 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. It is also possible that the soaps are not contained in the spray-dried component, but are mixed in subsequently.

The alk (en) yl sulfates and soaps 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 triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

Disilicates and, in particular, β-Katrium disilicate and δ-Katrium disilicate are used as particularly preferred crystalline sheet silicates. Their content is preferably 35 to 70% by weight and in particular 40 to 65% by weight, in each case based on the anhydrous active substance in the spray-dried component.

Detergents or cleaning agents which contain a spray-dried component with alk (en) yl sulfates and crystalline layered silicates in the stated composition have the same properties compared to agents with the same formulation, but which do not contain alk (en) yl sulfates and crystalline layered silicates in a spray-dried component Primary washing ability a significantly improved secondary washing ability. This is evident both in the incrustation inhibition and in the graying inhibition.

It was particularly surprising, however, that the spray-dried component, which is used either as a washing or cleaning agent alone or after preparation with other ingredients of washing or cleaning agents, has a very good redispersibility. The redispersibility is not only significantly improved in comparison to agents with the same formulation, which do not contain alk (en) yl sulfates and crystalline layered silicates of a spray-dried component, but also compared to products on a spray-dried basis which contain alk (en) yl sulfates and zeolite instead of the crystalline layered silicates .

It is not yet clear what causes these beneficial effects. It is possible either that the crystalline phyllosilicates used in the slurry to be spray-dried have a crystalline structure even after the spray drying, or that they have been modified in another, possibly non-crystalline, form with hitherto not elucidated structure, but this modification has at least as good a washing effect as that of the crystalline layered silicates originally used. Another assumption is that the alk (en) yl sulfates used and the crystalline phyllosilicates interact positively in the aqueous slurry, causing the alk (en) yl sulfates to gel on the one hand and the polyanions to fragment when the spray-dried granules are redissolved in water the crystalline layered silicates, on the other hand, are avoided or at least suppressed. On the other hand, it has also been shown that such aqueous slurries can be processed under relatively gentle spray drying conditions. The process specified below for the production of detergents or cleaning agents or a spray-dried component therefor is therefore also the subject of this invention.

The washing or cleaning agent according to the invention or the spray-dried component for this purpose can also contain further, conventional ingredients of spray-dried washing or cleaning agents. These include in particular other builder substances; in a particularly preferred embodiment of the invention, however, the spray-dried component contains no zeolite. It is also preferred that the spray-dried component contains no additional carbonates. Additional carbonates used are amounts of carbonates which are not introduced into the aqueous slurry to be spray-dried by way of the production process or by impurities in the raw materials.

In a further preferred embodiment of the invention, however, the spray-dried component contains further organic builder substances. These include in particular polycarboxylic acids and / or their salts, preferably polycarboxylic acids used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids and nitrilotriacetic acid, 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. Use is particularly preferred of mixtures of dicarboxylic acids such as Sokalan DCS ( ^R ) (commercial product from BASF, Germany) and in particular of citric acid and / or citrate.

Polymeric polycarboxylates, for example sodium salts of homo- and / or copolymers of acrylic acid, can also be present in the spray-dried component. Preference is also given to using biodegradable terpolymers, for example those which contain, as monomeric salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives, or which, as monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

In a preferred embodiment of the invention, the spray-dried component has a content of 15 to 20% by weight of C ₁₆ -C ₁₈ -alk (en) yl sulfate, 0 to 2% by weight of soap and 50 to 70% by weight on the anhydrous active substance, on crystalline layered silicates. The water content of these spray-dried components is preferably 10 to 20% by weight.

In a further particularly preferred embodiment of the invention, the spray-dried component contains alk (en) yl sulfates and soap as above, 40 to 65% by weight, based on anhydrous active substance, of crystalline phyllosilicates and 2 to 30% by weight, preferably 10 to 30% by weight, and in particular 15 to 25% by weight, of polycarboxylic acids and / or their salts, water-containing citrates (sodium citrate dihydrate) being preferred. The water content of this spray-dried component is in the range given above.

The washing or cleaning agents according to the invention or the spray-dried component for this purpose can now be prepared with further conventional inorganic and / or organic ingredients of washing or cleaning agents. These primarily include bleaching agents, bleach activators, graying inhibitors such as cellulose ether or polyvinylpyrrolidone, optical brighteners, dyes and fragrances as well as enzymes and enzyme stabilizers. Foam inhibitors, particularly in granular form, can also be mixed in subsequently. In particular, it is also preferred to subsequently add nonionic, optionally also amphoteric cationic and / or zwitterionic surfactants to the spray-dried components.

Suitable nonionic surfactants are, for example, alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably 2-methyl branched or linear and may contain 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 those of coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 E0 per mole of alcohol are particularly preferred. The particularly preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohol with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

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

Other suitable nonionic surfactants are, for example, surfactants of the amine oxide type or polyhydroxy fatty acid amides, in particular fatty acid N-alkylglucamides.

The nonionic surfactants are preferably sprayed onto the spray-dried component or onto the washing or cleaning agent prepared with other solids such as bleaching agents.

Other components that can be subsequently mixed into the spray-dried component are customary builder substances such as zeolite or phosphate and polymeric polycarboxylates. However, it is preferred that the washing or cleaning agents according to the invention are free of zeolites and in particular also free of phosphates. It is also possible for polycarboxylic acids or their salts to be subsequently mixed into a finished washing or cleaning agent in the preparation of the spray-dried component. It is preferred, however, that - if polycarboxylic acid or its salts are present - these are introduced into the composition via the spray-dried component.

Due to the high alkalinity of the crystalline layered silicates, it is not absolutely necessary to add further alkaline inorganic salts such as alkali carbonates and amorphous alkali silicates. However, it is possible that these substances are used in granular components, for example as carriers, and thus get into the composition.

Bleaching agents which can be added are, for example, compounds which provide H ₂ O ₂ in water, such as sodium perborate tetrahydrate and sodium perborate monohydrate. Further bleaching agents which can be used are, for example, sodium percarbonate, citrate perhydrate and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates or diperdodecanedioic acid.

Among the compounds serving as bleach activatroen, N-acyl or O-acyl compounds which form organic peracid with H ₂ O ₂ , preferably N-N'-tetraacylated diamines and esters of polyols such as glucose pentaacetate are of particular importance. Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239.

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, 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. 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), are suitable as stabilizers, in particular for per-compounds and enzymes.

It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous.

Graying inhibitors have the task of 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, 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 their mixtures, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition, are preferably 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.

In a preferred embodiment of the invention, the processed washing or cleaning agents contain 15 to 35% by weight and preferably 20 to 30% by weight of anionic and nonionic surfactants, it being particularly advantageous if the nonionic surfactants consist of ethoxylated fatty alcohols and / or Alkyl glycosides exist and the weight ratio of nonionic surfactants to anionic surfactants is above 1: 1. It is particularly preferred if the anionic surfactant content, in particular alk (en) yl sulfates, is 5 to 15% by weight, is preferably 8 to 12% by weight. In a further preferred embodiment of the invention, the agents contain 25 to 50% by weight of builder substances which are composed either solely of crystalline sheet silicates (calculated as anhydrous active substance) or of crystalline sheet silicates and polycarboxylic acids or their salts and / or polymeric polycarboxylates. In such builder substance mixtures, however, the proportion of crystalline phyllosilicates, based on the total amount of builder substances, is preferably more than 50% by weight, in particular at least 60% by weight. Bleaching agents, bleach activators, enzyme granules and foam inhibitor granules can be contained in the agents in the usual amounts.

In a preferred embodiment of the invention, the washing or cleaning agents according to the invention contain amorphous silicates such as amorphous sodium disilicate or amorphous sodium trisilicate only in amounts below 5% by weight, preferably below 3% by weight and in particular below 2% by weight. The content of alkali carbonates and / or alkali bicarbonates in the particularly preferred embodiments of the washing or cleaning agents is even lower. It is preferably less than 2% by weight and in particular less than 1% by weight.

The compositions generally have a bulk density between about 300 g / l and about 550 to 600 g / l. If higher bulk densities are desired, it is advantageous either to subsequently compact the granules under customary conditions or, for example, to add nonionic surfactants under compacting conditions.

The washing or cleaning agents according to the invention or a component therefor can be prepared by adding an aqueous slurry containing crystalline phyllosilicates (calculated as anhydrous active substance) in amounts of 30 to 80% by weight and alk (en) yl sulfates in amounts of 5 contains up to 30 wt .-%, each based on the solids content of the slurry, is spray dried. It is particularly advantageous if the aqueous slurries have a concentration between 50 and 65% by weight, preferably around 60% by weight. It is advantageous if a slurry is spray dried which does not have any additional ones contains incorporated carbonates and bicarbonates. In another preferred embodiment of the invention, a slurry that does not contain zeolite is spray dried. On the other hand, it is advantageous if a slurry is spray-dried which contains polycarboxylic acids and / or their salts, preferably citric acid and / or citrate and in particular in amounts of 10 to 30% by weight, based on the solids content of the slurry. The air temperature before entering the spray drying tower can be customary values, for example above 200 ° C., such as 210 to 230 ° C. The temperature at the air outlet from the tower can still be above 100 ° C. However, it is also possible and particularly preferred to carry out the spray drying under considerably gentler conditions, namely at air inlet temperatures between 100 and 180 ° C, preferably between 120 and 160 ° C, and at air outlet temperatures below 100 ° C, preferably between 50 and 90 ° C . The temperature of the aqueous slurry before spraying is preferably less than 85 ° C, especially 60 to 75 ° C. Under these conditions, the aqueous slurries have a very low viscosity. Preferred viscosities are below 3000 mPas and in particular below 2000 mPas.

The spray-dried granules obtained in this way can then be processed with further ingredients of washing or cleaning agents. This includes the addition of, in particular, nonionic surfactants, which are preferably sprayed onto the granules, but also the addition of further solids, which are described in more detail above. In a further preferred embodiment of the invention, however, only further solids are first added subsequently to the spray-dried granules and then liquid constituents, in particular nonionic surfactants, are applied to them. If desired, the spray-dried granules or the processed detergents or cleaning agents can be compacted subsequently using conventional methods.

Examples

Agents of the compositions given in Table 1 were prepared, the agents M1 and M2 according to the invention containing a spray-dried component (Table 2), while the comparative products V1 and V2 were obtained by mixing the various constituents. In all cases, the nonionic surfactant was subsequently sprayed onto the granules together with the polyethylene glycol. As a further comparative example V3, an agent of the prior art was used, that 8% by weight of C ₁₆ -C ₁₈ fatty alkyl sulfate and as builder substances 25% by weight of zeolite (based on anhydrous active substance), 5.5% by weight of one Contained copolymers of acrylic acid, 12% by weight sodium carbonate and 0.4% by weight hydroxyethane diphosphonate.

The application test was carried out under practical conditions in household washing machines. For this purpose, the machines were loaded with 3.0 kg of clean laundry and 0.5 kg of test fabric, some of the test fabric being impregnated with conventional test soils for testing the primary washability and part of which consisted of white fabric for testing the incrustation inhibition and the graying inhibition. Strips of bleaching nettle (BN), knitwear (cotton tricot; B) and terry cloth (FT) were used as the white test fabric.

Washing conditions: tap water of 23 ° d (equivalent to 230 mg CaO / l, ratio calcium: magnesium 5: 1), amount of detergent used per detergent and machine 98 g, washing temperature 90 ° C, liquor ratio (kg of laundry: liter of washing solution) 3.5 : 20, 4 times rinsing with tap water, spinning and drying, number of washes: 25 each

The primary washability of agents M1 and V1 as well as M2 and V2 was comparable in each case. The same was true for the comparison of M1 and M2 or V1 and V2 with V3, apart from the washing results for cosmetic soiling. Here M1, V1, M2 and V2 had a significantly better primary washing power than V3 (difference of 8 to 10 remission units).

When determining the incrustation inhibition (% by weight of ash; Table 3), the agents M1 and M2 according to the invention showed clear advantages over the mixed products V1 and V2. Even with the graying inhibition, advantages for the agents M1 and M2 according to the invention were found on some fabrics (Table 4). What was surprising, however, was above all that the flushing-in behavior of agents M1 and M2 according to the invention was in some cases even after storage for 4 weeks to 8 weeks (30 ° C., relative atmospheric humidity 80%) better than that of comparative examples V1 and V2 (table 5). The same applies to the residue behavior (Table 6).

To determine the induction behavior, conditions were simulated that correspond to an induction device of a household washing machine operated under critical conditions. In each case, 100 g of the agent were introduced into the test device (Zanussi induction channel). After a rest period of 1 minute, 10 liters of tap water were fed in within 80 seconds. The amount of the remaining residue (in grams, g) is shown in Table 5.

Note 1:

einwandfrei, keine erkennbaren Rückstände

Note 2:

tolerierbare, vereinzelte, noch nicht störende Rückstände

Note 3:

erkennbare, bei kritischer Beurteilung bereits störende Rückstände

ab Note 4:

deutlich erkennbare und störende Rückstände in steigender Anzahl und Menge

Tabelle 1: Zusammensetzungen der Mittel M1/V1 und M2/V2 M1/V1 M2/V2 C₁₆-C₁₈-Fettalkylsulfat 8,5 9,2 C₁₂-C₁₈-Fettsäureseife, Na-Salz 0,8 0,8 C₁₂-C₁₄-Fettalkohol mit 3 EO und C₁₂-C₁₈-Fettalkohol mit 5 EO im Gew.-Verhältnis 20:80 16,5 15,8 Polyethylenglykol (relative Molekülmasse von 400) 2,0 2,0 kristallines Schichtsilikat (SKS 6^(R), berechnet als wasserfreie Aktivsubstanz) 33,5 24,0 Natriumcitrat-dihydrat --- 12,0 Natriumcarbonat 0,3 0,3 amorphes Natriumsilikat (1:2,0) 1,2 1,2 Perboratmonohydrat 16,0 16,0 Tetraacetylethylendiamin 6,0 6,0 Protease-Granulat 1,3 1,3 Silikonöl 0,01 0,01 Paraffinentschäumer-Granulat 0,6 0,6 Wasser 8,8 6,4 Natriumsulfat 3,5 3,5 Salze aus Lösungen (einschließlich Natriumhydroxid) Rest Rest Tabelle 2: Zusammensetzungen der sprühgetrockneten Komponenten von M1 und M2 M1 M2 C₁₆-C₁₈-Fettalkylsulfat 16,35 17,5 C₁₂-C₁₈-Fettsäureseife, Na-Salz kristallines Schichtsilikat 1,55 1,5 (SKS 6^(R), berechnet als wasserfreie Aktivsubstanz) 64,55 45,35 Natriumcitrat-dihydrat --- 22,8 Wasser 16,11 11,35 Salze aus Lösungen (einschließlich Natriumhydroxid) Rest Rest Tabelle 3: Inkrustationsinhibierung: Gew.-% Asche M1 V1 M2 V2 Anfangswert BN 3,42 3,63 1,88 2,74 0,09 FT 2,93 4,22 1,62 2,24 0,28 B 2,84 4,07 1,09 1,35 0,77 Tabelle 4: Vergrauungsinhibierung (% Remission) M1 V1 M2 V2 Anfangswert BN 81,6 79,4 80,4 79,7 85,4 FT 79,5 76,9 78,9 78,7 86,6 B 76,6 76,5 76,7 75,8 85,9 Tabelle 5: Einspülverhalten (Rückstand in g) M1 V1 M2 V2 V3 nach 2 Tagen 4,0 8,5 3,0 2,9 16,6 nach 4 Wochen 0,6 1,4 0,5 0,5 7,9 nach 8 Wochen 0,3 0,4 0,1 0,2 2,9 Tabelle 6: Rückstandsverhalten (visuelle Benotung) M1 V1 M2 V2 nach 2 Tagen 2,0 2,0 1,9 4,5 nach 4 Wochen 3,2 6,4 2,9 6,0 nach 8 Wochen 2,6 5,7 2,5 6,2 To determine the residue behavior, 30 l of water were initially introduced into a tub washing machine, 98 g of the respective agent were added and the mixture was dissolved by stirring. The laundry, consisting of various dark-colored, easy-care delicate items made of wool, cotton, polyamide and polyacrylonitrile, was then inserted and the machine heated to a temperature of 30 ° C. After this temperature had been reached, the laundry was washed for 10 minutes by actuating the agitator, then the washing liquor was drained off, rinsed three times with 30 l of water each time and the laundry was spun for 15 seconds. The laundry was dried with an infrared heater and graded by 5 trained people according to the following scheme (averaging):

Note 1:

flawless, no discernible residues

Grade 2:

tolerable, isolated, not yet disturbing residues

Note 3:

recognizable residues that are already annoying in the event of a critical assessment

from grade 4:

clearly recognizable and annoying residues in increasing number and quantity

Table 1: Compositions of agents M1 / V1 and M2 / V2 M1 / V1 M2 / V2 C ₁₆ -C ₁₈ fatty alkyl sulfate 8.5 9.2 C ₁₂ -C ₁₈ fatty acid soap, Na salt 0.8 0.8 C ₁₂ -C ₁₄ fatty alcohol with 3 EO and C ₁₂ -C ₁₈ fatty alcohol with 5 EO in a weight ratio of 20:80 16.5 15.8 Polyethylene glycol (molecular weight 400) 2.0 2.0 crystalline layered silicate (SKS 6 ^(R) , calculated as anhydrous active substance) 33.5 24.0 Sodium citrate dihydrate --- 12.0 sodium 0.3 0.3 amorphous sodium silicate (1: 2.0) 1.2 1.2 Perborate monohydrate 16.0 16.0 Tetraacetylethylenediamine 6.0 6.0 Protease granules 1.3 1.3 Silicone oil 0.01 0.01 Paraffin defoamer granules 0.6 0.6 water 8.8 6.4 Sodium sulfate 3.5 3.5 Salts from solutions (including sodium hydroxide) rest rest Compositions of the spray-dried components of M1 and M2 M1 M2 C ₁₆ -C ₁₈ fatty alkyl sulfate 16.35 17.5 C ₁₂ -C ₁₈ fatty acid soap, Na salt crystalline layered silicate 1.55 1.5 (SKS 6 ^(R) , calculated as an anhydrous active substance) 64.55 45.35 Sodium citrate dihydrate --- 22.8 water 16.11 11.35 Salts from solutions (including sodium hydroxide) rest rest Incrustation inhibition:% by weight of ash M1 V1 M2 V2 Initial value BN 3.42 3.63 1.88 2.74 0.09 FT 2.93 4.22 1.62 2.24 0.28 B 2.84 4.07 1.09 1.35 0.77 Graying inhibition (% remission) M1 V1 M2 V2 Initial value BN 81.6 79.4 80.4 79.7 85.4 FT 79.5 76.9 78.9 78.7 86.6 B 76.6 76.5 76.7 75.8 85.9 Induction behavior (residue in g) M1 V1 M2 V2 V3 after 2 days 4.0 8.5 3.0 2.9 16.6 after 4 weeks 0.6 1.4 0.5 0.5 7.9 after 8 weeks 0.3 0.4 0.1 0.2 2.9 Residue behavior (visual grading) M1 V1 M2 V2 after 2 days 2.0 2.0 1.9 4.5 after 4 weeks 3.2 6.4 2.9 6.0 after 8 weeks 2.6 5.7 2.5 6.2

Claims (16)

1. A detergent or cleaning composition or a component therefor which contains alk(en)yl sulfates and crystalline layer silicates corresponding to the general formula NaMSi_xO_2x+1·yH₂O, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, characterized that the detergent or cleaning composition or the component therefor contains alk(en)yl sulfates in quantities of 5 to 30% by weight and crystalline layer silicates in quantities of 30 to 80% by weight, based on the water-free active substance, and being present in spray-dried form.
2. A detergent or cleaning composition as claimed in claim 1, characterized in that it contains alk(en)yl sulfates in quantities above 8% by weight, preferably in quantities of 10 to 25% by weight and more preferably in quantities of 12 to 20% by weight, based on the spray-dried component.
3. A detergent or cleaning composition as claimed in claim 1 or 2, characterized in that it contains 35 to 70% by weight and preferably 40 to 65% by weight, based on the water-free active substance content, of crystalline layer silicates, more particularly disilicates of the βand/or 6-type, in the spray-dried component.
4. A detergent or cleaning composition as claimed in any of claims 1 to 3, characterized in that it does not contain any zeolite in the spray-dried component.
5. A detergent or cleaning composition as claimed in any of claims 1 to 4, characterized in that it does not contain any additional carbonates in the spray-dried component.
6. A detergent or cleaning composition as claimed in any of claims 1 to 5, characterized in that it contains polycarboxylic acids and/or salts thereof, preferably citric acid and/or citrate, more particularly in quantities of 10 to 30% by weight, based on the spray-dried component.
7. A detergent or cleaning composition as claimed in any of claims 1 to 6, characterized in that it is processed with other ingredients of detergents or cleaning compositions.
8. A process for the production of the detergent or cleaning composition or the component therefor claimed in any of claims 1 to 7, characterized in that a slurry containing crystalline layer silicates (expressed as water-free active substance) in quantities of 30 to 80% by weight and alk(en)yl sulfates in quantities of 5 to 30% by weight, based on the solids content of the slurry, is spray-dried.
9. A process as claimed in claim 8, characterized in that the concentration of the slurry is in the range from 50 to 65% by weight and preferably of the order of 60% by weight.
10. A process as claimed in claim 8 or 9, characterized in that a slurry which does not contain any zeolite is spray-dried.
11. A process as claimed in claims 8 to 10, characterized in that a slurry which does not contain any additionally incorporated carbonates and bicarbonates is spray-dried.
12. A process as claimed in any of claims 8 to 11, characterized in that a slurry containing polycarboxylic acids and/or salts thereof, preferably citric acid and/or citrate, more particularly in quantities of 10 to 30% by weight, based on the solids content of the slurry, is spray-dried.
13. A process as claimed in any of claims 8 to 12, characterized in that spray drying is carried out air entry temperatures of 100 to 180°C and at air exit temperatures below 100°C.
14. A process as claimed in any of claims 8 to 13, characterized in that the temperature of the aqueous slurry before spraying is below 85°C and the viscosity of the slurry under these conditions is below 3,000 mPas.
15. A process as claimed in any of claims 8 to 14, characterized in that the spray-dried granules obtained are processed with other ingredients of detergents or cleaning compositions.
16. A process as claimed in any of claims 8 to 15, characterized in that they spray-dried granules obtained are subsequently compacted.