EP0784668A1

EP0784668A1 - Improved extrusion process for manufacturing detergents

Info

Publication number: EP0784668A1
Application number: EP95933387A
Authority: EP
Inventors: Kathrin Schnepp; Monika Böcker; Manfred Greger; Dieter Jung; Norbert Kühne; Josef Markiefka; Wolfgang Seiter
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1994-09-27
Filing date: 1995-09-18
Publication date: 1997-07-23
Also published as: WO1996010070A1; DE4434500A1

Abstract

In the production of washing and cleaning agents by pressing a homogeneous pre-mixture of washing agent components into strands through perforated moulds, subsequent crushing of the extrudate and treatment in a rounding device producing a product consisting of largely uniform spherical granules with bulk densities generally in the 700g/l - 1050 g/l range, the aim is to improve the degree of homogeneity of the pre-mix used for the extrusion process and the smoothness of the surface of the extruded granules, while avoiding differences in length. This is achieved in essence by using hot drying gases to spray-dry an aqueous sludge containing a surfactant, inorganic builders and silicone oil; the spray-drying product is optionally mixed with other solid washing or cleaning agents, or washing or cleaning agents prepared in solid form, the mixture is extruded through a perforated plate and the extrudate is optionally rounded and/or pulverised.

Description

"Improved extrusion process for the production of detergents"

The invention relates to an improved method for producing granular detergents with a high bulk density.

Granular detergents with a high bulk density can be produced according to the process of international patent application WO 91/02047. This involves the extrusion of a homogeneous pre-mix of detergent ingredients over perforated molds, which preferably have an opening width of 0.5 mm to 5 mm, subsequent crushing of the extrudate and subsequent treatment in a rounding machine, which is largely uniform spherical products leads. The compacting extrusion step gives granular particles with bulk densities of generally 700 g / 1 to 1050 g / 1. These can be complete washing or cleaning agents or constituents of such agents, which are completed by admixing other components that are usually not co-extrudable, for example solid or solid bleach activators, foam regulators or enzymes.

In such a manufacturing process, the detergent ingredients provided for extrusion can usually be used in the form of solid pre-products, so-called compounds, which contain two or more customary detergent ingredients. Such granular compounds can be produced by customary processes, for example spray drying an aqueous slurry. An advantage of such a procedure is that under normal conditions liquid detergent ingredients, for example nonionic surfactants, are used with the aid of carrier materials which themselves belong to the usual detergent ingredients. for example inorganic builders, can be made up in solid form and, by simply mixing separately prepared compounds in different proportions, comes to very different premixes for the extrusion and thus also to very different end products. It should be mentioned as a disadvantage that with this procedure, ie the mixing of several powdery multi-component compounds, the homogeneity of the premix intended for the extrusion is not always given, which can have a disadvantageous effect on the homogeneity and the grain stability of the extrudate . Thus, especially in the case of surfactant-rich formulations, sometimes jagged surfaces of the extrudate grain and length differences after tapping are observed, which is due to the poor degree of rounding, that is to say deviation from the spherical shape, to a non-optimal increase in the bulk density due to the extrusion step, to increased fine and coarse particles share and generally leads to a deterioration of the product image.

Surprisingly, it has now been found that these disadvantages can be overcome and an increase in the bulk density can be achieved if a spray-dried compound which contains small amounts of a silicone oil is used to produce the premix intended for extrusion from detergent ingredients.

The invention therefore relates to a process for the preparation of detergents or cleaning agents or their constituents with a high bulk density by extrusion in the form of holes via hole shapes and subsequent comminution of the extrudate by means of a cutting device, which is characterized in that an aqueous slurry containing surfactant , inorganic builder and silicone oil, spray-dried using hot drying gases, the spray-drying product optionally mixed with further solid and / or solid-form detergent or cleaning agent components, extruded through a perforated plate and the extrudate optionally rounded and / or powdered.

Suitable silicone oils which can be used in the context of the invention, that is to say liquid organopolysiloxanes, are customary alkyl and aryl polysiloxanes, their copolymers and block polymers with polyalkylene oxides and their acylation products with long-chain fatty acids. They can be used as such or in a mixture with other conventional defoaming agents, which include paraffins, long-chain fatty acid esters and finely divided silica, which can also be silanized or otherwise hydrophobized. Mixtures of this type consist of at least 50% by weight, preferably at least 90% by weight and in particular at least 98% by weight, of organopolysiloxane. Organopolysiloxanes containing silicic acid, in particular diethylpolysiloxane, are preferably used. The viscosity of the silicone oils used is preferably 25000 mPa.s to 38000 mPa.s at room temperature; it can be determined by customary methods, for example using a Brookfield (R) viscometer model RVT using spindle No. 5 at 10 revolutions per minute , be measured. The amount of such silicones contained in the spray drying product can vary within a very wide range and is normally up to about 1% by weight.

The spray drying product used in the process according to the invention preferably contains 25% by weight to 65% by weight, in particular 30% by weight to 60% by weight of inorganic builder, 7.5% by weight to 40% by weight , in particular 10% by weight to 30% by weight of surfactant, in particular synthetic anionic surfactant of the sulfate and / or sulfonate type, and 0.01% by weight to 0.7% by weight, in particular 0.015% by weight to 0.4% by weight silicone oil. The remainder to 100% by weight consists of the usual ingredients of spray-dried washing or cleaning agents, in particular water, preferably organic in amounts of up to 20% by weight, in particular from 8% by weight to 18% by weight Cobuilders, which preferably in amounts up to 8% by weight, in particular from 3% by weight to 6.5% by weight, discoloration inhibitors, which are preferably used in spray drying products intended for the production of detergents in amounts of up to 5% by weight, in particular 1.5% by weight to 3% by weight, and inorganic water-soluble salts, for example alkali metal sulfates and / or carbonates, which preferably in amounts of up to 20% by weight, in particular of 2 wt .-% to 12 wt .-% are included.

The spray drying product is compacted by extrusion, alone or in a mixture with other preferably solid detergent ingredients. Such further detergent ingredients, which can preferably be added in amounts of up to 50% by weight, in particular 5% by weight to 25% by weight, based on the premix to be extruded, include solid bleaching agents. oxygen-based agents, for example alkali perborates, which can be present as so-called monohydrates or tetrahydrates, or alkali percarbonates, powdered bleach activators, for example a tetraacetylethylenedia in granulate, prepared in solid form, in solid form, prepared by the process of European patent EP 0037026 Anionic surfactant compounds containing active substance, for example an alkyl sulfate compound produced according to the process of international patent application WO 93/04162, enzymes present in granular form, for example an enzyme extrudate produced according to the process of international patent application WO 91/02792 or an according to the process of German patent application DE 4339463.4 Multi-enzyme granules produced, in powder form, for example prepared by the method of German patent application DE 4408360.2, soil release active ingredient and / or a foam regulator present as a solid, for example a foam inhibitor granulate known from European patent EP 0496510, international patent application WO 91/12306 or German patent applications DE 4325881.6 and DE 4344 155.6. Customary liquid ingredients of detergents and cleaning agents, for example dyes or fragrances or additional, in particular nonionic, surfactants can, if desired, be applied to the spray-drying product and / or one of the other solid detergent ingredients mentioned before the extrusion step. The stated other detergent or cleaning agent constituents, either solid or made up in solid form, can also, alternatively to their processing via the premix to be extruded, be admixed with the extrudate in order to obtain a finished detergent or cleaning agent. A premix is preferably made from 20% by weight to 70% by weight of the spray drying product, 3% by weight to 20% by weight of anionic surfactant compound according to WO 93/04162 with a content of more than 80% by weight, in particular more than 90% Wt .-% of alkyl sulfate with alkyl chain lengths in the range of C12 to C \ Q, balance essentially inorganic salts and water, 2 wt .-% to 10 wt .-% powdered, separately added alkali carbonate, 5 wt .-% to 20 wt. % powdery, separately added polycarboxylate cobuilder, for example alkali citrate, and 10% by weight to 20% by weight of peroxy bleach, for example sodium perborate monohydrate, and up to 20% by weight, in particular 5% to 20% % By weight liquid components, for example water, aqueous alkali silicate or polycarboxylate solutions and / or liquid nonionic surfactants, produced and extruded, to which further solid or solid detergent ingredients, if desired, can be added after the extrusion.

In a preferred embodiment of the process according to the invention, a solid premix is extruded which contains 20% by weight to 35% by weight of inorganic builder, in particular zeolite, 1% by weight to 13% by weight of organic cobuilder, in particular monomeric and / or polymeric polycarboxylate, 15% by weight to 25% by weight of surfactant, in particular anion and / or nonionic surfactant, up to 20% by weight of bleaching agent and 0.01% by weight to 0.3% by weight Contains silicone oil, the silicone oil originating entirely from a spray-dried compound and the other constituents may at least partially have been mixed in separately.

The extrusion is carried out under conditions known in principle, preferably using an extruder, into which the spray product or a homogeneous premix containing it is fed and under a pressure in the range from preferably 30 bar to 180 bar, in particular 40 bar to 80 bar, through a perforated plate with a hole diameter of preferably 1.2 mm to 2.0 mm, in particular 1.4 mm to 1.7 mm, extruded into strands and comminuted to a length that does not differ significantly from the thickness, that is to say the hole diameter becomes. The extrudate, if desired with application of powdery solids as described in particular in WO 94/01526, can then be rounded and deburred in a conventional rounding device, for example a spheronizer ( ^R ).

The following applies to the ingredients of the washing and cleaning agents which can be produced by the process according to the invention:

Suitable surfactants are selected from synthetic anionic surfactants, in particular of the sulfate or sulfonate type, nonionic surfactants, cationic surfactants and / or amphoteric surfactants.

Anionic surfactants are preferably selected from the class of alkyl sulfates, alkyl ether sulfates, sulfofatty acid disalts, alkyl sulfofatty acid esters. salts, alkanesulfonates and / or alkylbenzenesulfonates with linear Cg to Ci5 alkyl groups on the benzene nucleus. The useful surfactants of the sulfate type include in particular primary alkyl sulfates with preferably linear alkyl radicals having 10 to 20 carbon atoms, which have an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as the counter cation. The derivatives of linear alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols, are particularly suitable. Accordingly, the sulfation products of primary fatty alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. Particularly preferred alkyl sulfates contain a tallow alkyl radical, that is to say mixtures with essentially hexadecyl and octadecyl radicals. The alkyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.

In addition, the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates, can be used as the anionic surfactant component. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule.

Suitable anionic surfactants of the sulfonate type include, in addition to the alkylbenzenesulfonates with preferably 9 to 15 carbon atoms in the linear alkyl chain in particular, the sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those containing fatty acids 8 to 22 C-atoms, preferably 12 to 18 C-atoms, and linear alcohols with 1 to 6 C-atoms, preferably 1 to 4 C-atoms, sulfonation products, and the sulfofatty acid disalts that can be derived from them. The alkanesulfonates are substances which are obtained by sulfoxidation of hydrocarbons, which preferably contain 10 to 20 carbon atoms. This generally results in products with a statistical distribution of the sulfonic acid substituents which, if desired, can be separated in a known manner. Secondary alkanesulfonates with 12 to 17 are for agents according to the invention C atoms particularly suitable. Suitable cations in all cases of the anionic surfactants mentioned are, in particular, those from the group of alkali ions, ammonium or alkyl- or hydroxyalkyl-substituted ammonium ions.

The nonionic surfactants in question include, in particular, alkyl glycosides, fatty acid polyhydroxy ide, for example glucamides, as are produced, for example, in international patent application WO 92/06984, and the alkoxylates, in particular the ethoxylates and / or propoxylates of alcohols, Alkylamines, vicinal diols and / or carboxylic acid amides, which have alkyl groups with 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms. The degree of alkoxylation of these compounds is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reaction with the corresponding alkylene oxides. Products which can be prepared by alkoxylation of fatty acid alkyl esters having 1 to 4 carbon atoms in the ester part by the process of international patent application WO 90/13533 are also suitable. Preferred among the carboxamide derivatives are the ethanolamide derivatives of alkanoic acids with 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms. The alcohol alkoxylates in question include the ethoxylates and / or propoxylates of linear or branched chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms. The derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers can also be used for the preparation of usable alkoxylates. Accordingly, the ethoxylates of primary alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. It is also possible to use corresponding alkoxylates of mono- or polyunsaturated fatty alcohols, which include, for example, oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol and erucalcohol.

The alkyl glycosides suitable as nonionic surfactant components for agents according to the invention and their preparation are described, for example, in European patent applications EP 92355, EP 301 298, EP 357 969 and EP 362671 or the US Pat. No. 3,547,828. The glycoside components of such alkyl glycosides are oligo- or polymers from naturally occurring aldose or ketose monomers, which include in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allos, idose, ribose, arabinose, xylose and lyxose. The oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization, which, as an analytically determinable variable, can also assume fractional numerical values and generally between 1 and 10, in the alkyl glycosides preferably used is below a value of 1.5, in particular between 1.2 and 1.4. The preferred monomer building block is glucose because of its good availability. The alkyl part of such alkyl glycosides preferably also comes from easily accessible derivatives of renewable raw materials, in particular from the above-mentioned fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can also be used to produce usable alkyl glycosides. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. Particularly suitable alkyl glycosides contain a coconut fatty alkyl radical, that is to say mixtures with essentially dodecyl and tetradecyl radicals.

If an agent according to the invention is to contain cationic surfactants, these are preferably selected from the quaternary ammonium compounds having at least one long-chain alkyl group having 10 to 22 carbon atoms. Among these, substances with two long-chain and two short-chain alkyl chains each having 1 to 4 carbon atoms on the nitrogen atom are particularly preferred because of their known textile-softening properties. As a counter anion, such cationic surfactants usually have a halide anion, in particular chloride or bromide, or a sulfuric acid semi-ester anion, in particular methosulfate or ethosulfate, although quaternary ammonium compounds with anions which correspond to the synthetic anionic surfactants mentioned above can also be used.

Amphoteric surfactants are preferably selected from the derivatives of tertiary or quaternary aliphatic amines, the aliphatic radicals of which can be straight-chain or branched and one of which carries a carboxy, sulfo, phosphono, sulfato or phosphato group. Examples of Like compounds are NN-dimethyl-N-tetradecyl-glycine, N, N-dimethyl-N-hexadecyl-glycine, N, N-dimethyl-N-octadecyl-glycine, 3- (dimethyl-dodecylammonio) l-propanesulfonate and the commercial amphoteric surfactants sold under the names Dehyton ( ^R ) AB, CB, G and K (manufacturer Henkel).

In addition to the surfactants mentioned, the agents according to the invention can contain soap, that is to say an alkali or ammonium salt of a CQ to C22 carboxylic acid.

Conventional water-soluble or water-insoluble, inorganic and / or organic builder materials can be used as builder components in detergents according to the invention. Zeolites and silicates are preferred among the inorganic builder substances. The finely crystalline, synthetic and bound water-containing zeolite is preferably A-type zeolite in detergent quality. Mixtures of zeolite NaA and NaX are also suitable, the proportion of zeolite NaX in such mixtures advantageously being less than 30%. They normally have no particles larger than 30 μm and preferably consist at least 80% of particles smaller than 10 μm. Suitable zeolites have an average particle size of less than 10 μm (measurement method: Frauenhofer diffraction; mean volume distribution), preferably between 1.5 and 4.5 μm, in particular between 2.0 and 4.0 μm. Their calcium binding capacity, which can be determined according to the information in German patent application 24 12837, is in the range from 100 to 200 mg CaO / g. The content of finely divided, in particular crystalline, hydrated zeolite in the compositions is preferably 30 to 65% by weight and in particular 32 to 45% by weight, based on anhydrous active substance. The zeolite generally has a water content of 17 to 25% by weight, in particular 20 to 22% by weight. Alkali silicates which can be used additionally or instead can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na2O: SiO2 molar ratio of 1: 2 to 1: 2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil ( ^R ). Crystalline layered silicates of the formula NaMSi _x θ2χ ₊ ι + yH2θ, in which M represents sodium, x is a number of preferably, are used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application 164 514. In particular, both β- and S-sodium disilicate a2Si2θ5 ^* yH2θ are preferred, whereby β-sodium disilicate can be obtained, for example, by the process described in international patent application WO91 / 08171. The content of alkali silicates in the compositions is preferably 1 to 15% by weight and in particular 2 to 8% by weight, based on the anhydrous active substance. The weight ratio of zeolite to amorphous silicate, based in each case on anhydrous active substance, is preferably 4: 1 to 10: 1. The crystalline layered silicates are preferably used in amounts of 1 to 15% by weight and in particular 2 to 7% by weight, the weight ratio of zeolite to crystalline layered silicate, in each case based on anhydrous active substance, preferably being at least 5: 1. In compositions which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.

Suitable organic builder components are polymeric carboxylates or polymeric carboxylic acids with a relative molecular weight of at least 350 in the form of their water-soluble salts, in particular in the form of the sodium and / or potassium salts, such as oxidized polysaccharides according to international patent application WO 93 / 08251, polyacrylates, polyhydroxyacrylates, polymethacrylates, polymaleates and in particular copolymers of acrylic acid with maleic acid or maleic anhydride, preferably such from 50 to 70% acrylic acid and 50 to 10% maleic acid. The relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl ethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight. Terpolymers can also be used as the polymeric carboxylates or carboxylic acids, the two carboxylic acids and / or their salts as monomers, and the third Monomer vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate contain. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C3-Cβ-carboxylic acid and preferably from a C3-C4-monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C / j-Cβ-dicarboxylic acid, preferably an f ^ -Cβ-dicarboxylic acid, maleic acid being preferred. In this case, the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, vinyl alcohol derivatives are preferred which are an ester of short-chain carboxylic acids, for example C 1 -C 4 -carboxylic acids, with vinyl alcohol. Preferred terpolymers contain 60 to 95% by weight, in particular 70 to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate and 5 to 40% by weight. %, preferably 10 to 30% by weight of vinyl alcohol and / or vinyl acetate. Terpolymers in which the weight ratio (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2.1 and 2.5: 1. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives derives, is substituted. Preferred terpolymers contain 40 to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10 to 30% by weight, preferably 15 to 25% by weight of methyl sulfonic acid or methylene sulfonate and as a third monomer 15 to 40% by weight, preferably 20 to 40% by weight of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, saccharose being particularly preferred. By using the third monomer, predetermined breaking points are built into the polymer, which are responsible for the degradability of the polymer. The terpolymers used can be prepared by any of the known and customary processes. Terpolymers are also preferably used which are either completely or at least partially, in particular more than 50%, based on the carboxyl groups present. are neutralized. Particularly preferred terpolymers are produced by a process which is described in German patent applications DE 4221 381 and DE 4300 772.

Among the compounds which serve as bleaching agents and supply H2O2 in water, sodium perborate tetrahydrate (NaBÜ2 * H2O2 ^• 3 H2O) and monohydrate (NaBθ2 ^• H2O2) are of particular importance. However, other borates which provide H2O2 can also be used, for example the Perborax Na2B4Ü7 ^• 4 H2O2. These compounds can be partially or completely by other active oxygen carriers, in particular by peroxyhydrates, such as peroxycarbonates (Na2Cθ3 ^• 1.5 H2O2), peroxypyrophosphates, citrate perhydrates, urea-H2θ2 or melamine-H2θ2 compounds as well as by peracidic salts or peracids, such as perbenzoates , Peroxyphthalates, diperazelaic acid or diperdodecanedioic acid can be replaced.

In order to achieve an improved bleaching effect when washing at temperatures below 80 ° C., in particular in the range from 40 to 60 ° C., bleach activators can be incorporated into the bleach-containing preparations. Examples of these are N-acyl or O-acyl compounds which form organic peracids with H2O, preferably N, N'-tetraacylated diamines, such as NNN '.N'-tetraacetyl-ethylenediamine, furthermore carboxylic acid anhydrides, such as benzoic anhydride and phthalic anhydride, and esters of polyols such as glucose pentaacetate. For incorporation into solid detergents, the bleach activator can be coated with coating substances in a known manner or, if necessary, be granulated using granulating aids and, if desired, contain further additives, for example dye. Carboxymethyl cellulose is used for particulate detergents loose granulated tetraacetylethylenediamine (TAED) as can be prepared by the process described in European patent EP 037026, particularly preferred.

The use of other constituents customary in detergents, in particular complexing agents for heavy metals, for example aminopolycarbon acids and / or polyphosphonic acids or their salts, graying inhibitors, for example cellulose ethers, optical brighteners, enzymes, in particular protease, aylase, lipase and / or cellulase, enzyme sta- bilisators, in particular lower carboxylic acids or calcium compounds, antimicrobial agents and colorants and fragrances are possible.

Examples

example 1

From the substances listed in Table 1, aqueous slurries were produced which contained 40 to 44% by weight of water, were heated to temperatures of about 60 ° C. to 80 ° C. and were sprayed under a pressure of 30 bar in a drying tower, where hot air (temperature 160 ° C to 220 ° C) was conducted in countercurrent. The spray drying products S1 and S2 characterized in Table 1 by their composition were obtained, which had bulk densities of about 350 grams per liter.

Table 1: Compound composition TGew .-% l

Sl S2

ABS ^a ) 11 27

Nonionic surfactant ⁰ ) 2 1

Soap 3 1

Zeolite Na-A 57 40

Sodium carbonate 3 10

Sodium silicate - 3

Polycarboxylate ^c ) 6 4 p _V pd) 2 -

Silicone oil ^e ) 0.02 0.02

Water to 100

a) Na-dodecylbenzenesulfonate b) 5-fold ethoxylated tallow alcohol (manufacturer Henkel) c) acrylic acid / maleic acid copolymer (Sokalan ( ^R ) CP 5, manufacturer BASF) d) polyvinylpyrrolidone (Sokalan ( ^R ) HP 53, manufacturer BASF)

As described in Examples 1 to 5 of WO 91/2047, the spray products specified in Table 2 below and separate ones Mixing components in the amounts specified there, granular agents Ml and M2 with a bulk density of approx. 800 g / 1 (hole diameter of the perforated plate 1.7 mm).

Table 2: Extrudate composition TGew .-% l

Ml M2

Sl 67 -

S2 - 62

S3 - -

Na Perborate - 21

FAS compound ^a ) 8 -

FAS Compoundb) - 5

Na carbonate 4 2

Na silicate 2 -

Na citrate 8 -

Polycarboxylate ^c ) - 2

Nonionic surfactant ^d ) 8 4

Water 3 4

a) containing 86% by weight Rest of Na sulfate and water, produced according to WO 93/04162 b) containing 92% by weight of C.sub.2 / 18 alkyl sulfate, rest of Na sulfate and water, produced according to WO 93/04162 c) acrylic acid / maleic acid copoly er (Sokalan ( ^R ) CP 5, manufacturer BASF) d) 3 to 5-fold ethoxylated fatty alcohol, manufacturer Henkel

For comparison, an extrudate VI was produced which, like M2, was used with the difference that a spray product free of silicone oil, which otherwise corresponded to S2 (compensation via the water content), was used. The sieve analysis shown in Table 3 shows that in the latter product only about a third have a grain size which corresponds approximately to the hole diameter of the perforated plate, while the product M2 produced by the process according to the invention still has such a grain size to far more than half, and is thus considerably more stable and the rounding survives with less decay.

Table 3: Grain size distribution TGew% 1

M2 VI on sieve 01.6 mm 65 33 on sieve 00.6 mm 30 67 on sieve 00.4 mm 5 0

Claims

claims

1. A process for the production of detergents or cleaning agents and their constituents with a high bulk density by extrusion through perforated shapes and subsequent comminution of the extrudate by means of a cutting device, characterized in that an aqueous slurry containing surfactant and inorganic builders and silicone oil, spray-drying using hot drying gases, the spray-drying product optionally mixed with further solid and / or solid detergent or cleaning agent components, extruded through a perforated plate and the extrudate optionally rounded and / or powdered.

2. The method according to claim 1, characterized in that as Sili¬ oils alkyl and aryl polysiloxanes, their copolymers and block polymers with polyalkylene oxides and their acylation products with long-chain fatty acids or their ab ischung with paraffins, long-chain fatty acid esters or finely divided silica , which can also be silanized or otherwise hydrophobized.

3. The method according to claim 2, characterized in that the silicone oil from at least 50 wt .-%, preferably at least 90 wt .-% and in particular at least 98 wt .-% consist of organopolysiloxane.

4. The method according to any one of claims 1 to 3, characterized in that an organopolysiloxane containing silicic acid, in particular dimethylpolysiloxane, is used as the silicone oil.

5. The method according to any one of claims 1 to 4, characterized in that the viscosity of the silicone oil used at room temperature is 25000 mPa.s to 38000 mPa.s.

6. The method according to any one of claims 1 to 5, characterized in that the spray drying product 25 wt .-% to 65 wt .-%, in particular 30 wt .-% to 60 wt .-% inorganic builder, 7.5 wt .-% % to 40% by weight, in particular 10% by weight to 30% by weight, of surfactant, in particular synthetic anionic surfactant of the sulfate and / or sulfonate type, and

Contains 0.01% by weight to 0.7% by weight, in particular 0.015% by weight to 0.4% by weight, of silicone oil.

7. The method according to claim 6, characterized in that the remainder to 100 wt .-% of the spray drying product from up to 20 wt .-%, in particular 8 wt .-% to 18 wt .-% water, up to 8 wt. %, in particular 3% by weight to 6.5% by weight of organic cobuilder, up to 5% by weight, in particular 1.5% by weight to 3% by weight of discoloration inhibitors, and up to 20 % By weight, in particular 2% by weight to 12% by weight, of inorganic water-soluble salts.

8. The method according to any one of claims 1 to 7, characterized in that a premix comprising 20% by weight to 70% by weight of the spray drying product, 3% by weight to 20% by weight of anionic surfactant compound from more than 80% by weight, in particular more than 90% by weight, of alkyl sulfate with alkyl chain lengths in the range from C12 to C \%, remainder essentially inorganic salts and water, 2% by weight to 10% by weight in powder form, separately added alkali carbonate, 5% by weight to 20% by weight powdery, separately added polycarboxylate cobuilder and 10% by weight to 20% by weight peroxobleach, and up to 20% by weight, in particular 5% by weight. -% to 20 wt .-% extruded liquid components.

9. The method according to any one of claims 1 to 7, characterized in that extruding a premix, the 20 wt .-% to 35 wt .-% of inorganic builders, 1 wt .-% to 13 wt .-% organic cobuilders, in particular monomeric and / or polymeric polycarboxylate, 15% by weight to 25% by weight of surfactant, in particular anionic and / or nonionic surfactant, up to 20% by weight of bleaching agent and 0.01% by weight to 0, 3 wt .-% silicone oil ent.

10. The method according to any one of claims 1 to 9, characterized in that under a pressure in the range of 30 bar to 180 bar, in particular 40 bar to 80 bar, through a perforated plate with a hole diameter of 1.2 mm up to 2.0 mm, especially 1.4 mm to 1.7 m pressed in shape and crushed to a length that does not differ significantly from the hole diameter.