WO2001010994A1

WO2001010994A1 - Method for producing preparations containing co-builders

Info

Publication number: WO2001010994A1
Application number: PCT/EP2000/007230
Authority: WO
Inventors: Rene-Andres Artiga Gonzalez; Beatrix Kottwitz; Günther VOGT; Volker Bauer; Gerhard Alband
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1999-08-06
Filing date: 2000-07-27
Publication date: 2001-02-15
Also published as: CA2315136A1; AU6698100A; DE19936726A1

Abstract

The object of the invention is to improve the method for the production of bulky, powdery and flowable preparations containing co-builders and an organic and/or inorganic carrier material which are suitable for the production of particle-shaped detergent and cleaning agents. This is substantially achieved by mixing an oxidised dextrin derivative with an inorganic builder, surfactant, and a large quantity of water so that a mixture which is flowable and which can be pumped at temperatures below 80 °C is produced. Water is removed from said mixture by means of drying gases at temperatures in the range of 160 °C to 260 °C until a powdery, flowable product is obtained.

Description

Process for the preparation of preparations containing cobuilder

The present invention relates to a method for producing powdery. bulk and free-flowing preparations which contain certain cobuilders and organic and / or inorganic carrier material, and their use as premixes (compounds) for the production of particulate detergents and cleaning agents.

Detergents and cleaning agents normally contain so-called builder substances in addition to the surfactants that are indispensable for washing or cleaning performance. which have the task of supporting the performance of the surfactants by eliminating hardening agents, that is to say essentially calcium and magnesium ions, from the wash liquor in such a way that they do not interact negatively with the surfactants. A known example of such builder substances which improve the primary washing power is zeolite Na-A, which is known to be able to form complexes, in particular with calcium ions, such that their reaction with water hardness-forming anions, in particular carbonate, is suppressed to form insoluble compounds. In addition, the builders, in particular in textile detergents, are intended to prevent the redeposition of the dirt detached from the fiber or generally from the surface to be cleaned, and also from the reaction of water-hardness-forming cations with water-hardness-forming anions on the cleaned textile or the surface of the insoluble compounds. So-called co-builders are usually used for this purpose. usually polymeric polycarboxylates, which, in addition to their contribution to the secondary washing ability, advantageously also have a complexing action against the water hardness-forming cations.

Particulate detergents or cleaning agents generally consist of several separately manufactured solid components which, depending on the nature of their ingredients, require different manufacturing processes. A preferred manufacturing process for the component of such agents containing builder and surface active substance is spray drying because of its relative simplicity aqueous solution or slurry of the ingredients. Such a method, however, presupposes a thermal load capacity of the components, which, when using conventional builders, in particular based on inorganic substances such as phosphates. Zeolites or layered silicates is well guaranteed. Polymeric polycarboxylates, such as the conventional polymers made up of acrylic acid and maleic acid, but also monomeric cobuilders, such as alkali citrates, can normally be spray-dried as part of aqueous slurries in the course of the production of detergents and cleaning agents.

If you want to use organic cobuilders, which due to their molecular composition suggest a better biodegradability than the above-mentioned polymeric polycarboxylates, you are faced with the problem that these substances in particular have little thermal resistance and are more or less colored when used in conventional spray drying processes Lead powder products that can not be incorporated into particulate detergents or cleaning agents. This problem is very pronounced with cobuildem based on oligomeric or polymeric saccharides. the oxidized dextrin derivatives are particularly worth mentioning here.

The oxidized derivatives of dextrins are their reaction products with oxidizing agents. which are able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function, dextrins being understood to mean oligomers or polymers of carbohydrates which are accessible, for example, by partial hydrolysis of starch. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably oligomers or polymers with average molecular weights in the range from 440 to 500,000 or with dextrose equivalents (DE) in the range from 0.5 to 40, in particular from 2 to 30, DE being a customary measure for the reducing agent Effect of a polysaccharide compared to dextrose, which has a DE of 100, is. Both maltodextrins (DE 3 - 20) and dry glucose syrups (DE 20 - 37) as well as so-called yellow dextrins and white dextrins with higher average molecular weights in the range from about 2,000 to 30,000 can be used. A preferred dextrin is described in European patent application EP 0 703 292 - wrote. Oxidized dextrins obtainable from these dextrins and processes for their preparation are known, for example, from European patent applications EP 427 349, EP 472 042 and EP 542 496 and international patent applications WO 93/08251, WO 93/16110. WO 95/07303 and WO 95/12619 are known. A product oxidized at C _{6 of} the saccharide ring is preferably used, as can be obtained by the process according to one of the international patent applications WO 93/161 10, WO 94/28030, WO 95/20608 and WO 96/03439. In addition, preference is given above all to the use of dextrins which have been modified oxidatively at their originally reducing end, possibly with the loss of a carbon atom. When the originally reducing end of the oligosaccharide was an anhydroglucose unit. in this case there is an arabinonic acid unit after modification:

(Glucose) _n → (Glucose) _n- ι-arabinonic acid. In these, the average degree of oligomerization n, which can also take fractional numerical values as the quantity to be determined analytically, is preferably in the range from 2 to 20, in particular 2 to 10. This latter oxidative modification can be carried out, for example, with the aid of Fe, Cu or Ag. Co or Ni catalysts, as described in international patent application WO 92/18542, using Pd, Pt, Rh or Os catalysts, as described in European patent EP 0 232 202, or using a quinone / Hydroquinone system in alkaline with the addition of oxygen and optionally aftertreatment with hydrogen peroxide.

The invention relates to a process for the preparation of pulverulent, fuelable and pourable preparations which contain cobuilders and organic and / or inorganic carrier material and are suitable for the production of particulate detergents and cleaning agents by drying flowable, aqueous, surfactant-containing mixtures of their constituents, thereby characterized in that an oxidized dextrin derivative is mixed with an inorganic builder, surfactant and so much water that a flowable and pumpable mixture is formed at temperatures below 80 ° C and this by spray drying using drying gases with temperatures in the range from 160 ° C to 260 ° C removes the water to such an extent that a powdery, self-adhesive product is formed. This is normally the case with water contents of the powder product of about 2% by weight to 15% by weight, with contents here Water that can be expelled when heated to temperatures up to 200 ° C should be understood.

The term “carrier material” used here is intended to denote the other ingredients contained in the powdered preparation in addition to the cobuilder essential to the invention. These can be selected from all the usual ingredients of detergents or cleaning agents which do not interact unreasonably with the cobuilder essential to the invention in the course of production or subsequent storage, and which survive the spray drying process without undue loss of activity. The proportions of the other ingredients are essentially based on the fact that the preparation produced by the process according to the invention must be in powder form. The ingredients that are solid at room temperature will therefore by far make up by far the largest proportion of the carrier material.

Among these, inorganic builder materials should be mentioned first, in particular zeolites. Silicates. Carbonates and - where there are no ecological prejudices against their use - also phosphates. Such inorganic builders are preferred in compounds produced by the process according to the invention in amounts of 25% by weight to 75% by weight. in particular 30% by weight to 65% by weight are present.

The fine crystalline, synthetic and bound water-containing zeolite in detergent quality is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ 0 ^• (ln) K ₂ 0 ^• Al ₂ O ₃ '(2 - 2.5) SiO ₂ ' (3.5 - 5.5) H ₂ O can be described. Suitable zeolites preferably have an average particle size of less than 10 μm and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x 0 _{2x +} ι Η ₂ 0, where M is sodium or hydrogen x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Such crystalline layered silicates are described, for example, in European patent application EP 0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ 'yH ₂ O are preferred, with β-sodium disilicate being able to be obtained, for example, by the method described in international patent application WO 91/08171.

Amorphous sodium silicates with a module Na ₂ 0: Si0 ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used can be delayed release and usually also have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which delay the dissolution compared to the conventional ones Have water glasses are described for example in German patent application DE 44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

Of course, it is also possible to use the generally known phosphates as builders, provided that such use should not be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphate is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0 ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.

In addition to the oxidized dextrin, other organic cobuilders, in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, polymeric aspartic acid, polyacetals and phosphonates can be used if desired. These classes of substances are described below, although their use in the process according to the invention is not preferred. In a preferred embodiment of the invention, further organic cobuilders are used only in a minor amount compared to the oxidized dextrin derivative. In a further preferred embodiment of the invention, those listed below are missing in particular

Whole polycarboxylates / polycarboxylic acids.

Organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are Citric acid, adipic acid, succinic acid, glutaric acid. Malic acid. Tartaric acid, maleic acid, fumaric acid. Sugar acids. Amino carboxylic acids. Nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these. The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Polymeric polycarboxylates are also suitable as additional cobuilders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. As 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 particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol. preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the agents is, if desired, 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve water solubility, the polymers can also allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid. included as a monomer.

Biodegradable polymers of more than two different monomer units 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 or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,

Further preferred copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE 195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals will be from dialdehydes such as Glvoxal. Glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and or glucoheptonic acid.

Also oxydisuccinates and other derivatives of disuccinates. preferably ethylenediamine disuccinate. are other suitable cobuilders. Ethylene diamine N.N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts used in formulations containing zeolite and / or silicate are, if desired, from 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, especially if the agents also contain bleach, aminoalkanephosphonates. in particular to use DTPMP, or to use mixtures of the phosphonates mentioned. - 10 -

It can also use any connections that are capable. Form complexes with alkaline earth ions as additional cobuilders.

The amount of builder component, that is the sum of builder and cobuilder including the oxidized dextrin derivative essential to the invention, is usually between 40 and 80% by weight, preferably between 45 and 70% by weight and in particular between 50 and 65, in the compound produced according to the invention % By weight. The proportion of oxidized dextrin in the total builder component is preferably 5% by weight to 50% by weight, in particular 10% by weight to 25% by weight.

A surfactant is also present in the aqueous slurries to be spray-dried in accordance with the invention, it being possible to use anionic, nonionic, cationic and / or amphoteric surfactants or mixtures thereof. Mixtures of anionic and nonionic surfactants are preferred from an application point of view. The total surfactant content of the compounds produced by the process according to the invention is preferably in the range from 5% by weight to 30% by weight, in particular 7% by weight to 25% by weight.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably C .ι - alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from _2- Cι ι ₈ monoolefins with terminal or internal double bond by sulfonation with Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates, which are for example obtained from Cι ₂ .ι ₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid. Caprylic acid, capric acid, myristic acid, lauric acid. Palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C 1 -C 8 fatty alcohols, for example from coconut oil alcohol. Taig fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Cιo-C ₂ n-oxo alcohols and those half esters of secondary alcohols of these chain lengths are 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. The C ₁₂ - Ci ₆ alkyl sulfates and C ₂ -Ci ₅ alkyl sulfates and C] ₄ -Ci ₅ alkyl sulfates are preferred from a washing-technical point of view. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075.041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C ₂ ι alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C ₉ n alcohols with an average of 3.5 moles of ethylene oxide (EO) or C _2. ₈ -Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably Represent fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Here again are sulfosuccinates. whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, particularly preferred. It is also possible. Use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or its salts.

Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps, such as the salts of lauric acid, are suitable. Myristic. Palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also 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 nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example C _{_12-1} 4 alcohols containing 3 EO or 4 EO, C _9-I alcohol with 7 EO, Cι ι _3- ₅ alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, Cι _2- ι ₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ - ₁ - alcohol with 3 EO and Cι _2- ιg alcohol with 5 EO. The The given degrees of ethoxylation represent statistical mean values which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow ranks ethoxvlates. NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol for a glycose unit with 5 or 6 carbon atoms. preferably stands 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.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as they are are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N-N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (II), R ¹

R-CO-N- [Z] (II)

in the RCO for an aliphatic acyl radical having 6 to 22 carbon atoms. R 'represents hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] stands for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (III)

R'-O-R

R-CO-N- [Z] (III)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this rest. [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. According to the invention, the procedure is preferably such that 1 part by weight to 5 parts by weight, in particular 2 parts by weight to 4 parts by weight of surfactant, in particular anionic surfactant, 2 parts by weight to 15 parts by weight Mix parts, in particular 5 parts by weight to 10 parts by weight of inorganic builder, 1 part by weight of oxidized dextrin derivative and optionally further sprayable detergent or cleaning agent ingredients with so much water that a pumpable and conveyable slurry is obtained, and this spray dried, that is to say after the aqueous slurry has been distributed into small droplets and brought into contact with hot drying gas. It is preferred if the powder products resulting from the sprayed droplets never reach temperatures higher than 120 ° C. It is also preferred if the aqueous slurries provided for spray drying contain no optical brighteners, in particular no diaminostilbenedisulfonic acids or diphenylstyryls, since the color impression of the resulting powders does not appear optimal when they are present.

The spray-drying of the aqueous slurries takes place in systems usually provided for this purpose, so-called spray towers, in the upper part of which the slurry is sprayed into fine droplets by pressure nozzles, which move under the action of gravity into the lower part of the spray tower and come into contact with hot drying gases which are guided in cocurrent or preferably in countercurrent to the particles to be dried. It is important to ensure that the temperature of the drying gases is not too high. In the context of the invention, this means that the temperature of the drying gases does not exceed a value of 260 ° C. and is preferably in the range from 160 ° C. to 240 ° C., in particular from 180 ° C. to 220 ° C., the drying gas temperature being the hottest Location of the drying tower, the so-called ring channel, is measured.

The compounds prepared according to the invention can be admixed with other particulate constituents of detergents or cleaning agents, in particular bleaching agents, bleach activators, particulate-made enzymes such as proteases, amylases, lipases, cellulases and mixtures thereof, particulate-made foam regulator active ingredients or fragrances (so-called fragrance pearls) are to be converted into corresponding finished products. Liquid ingredients, Among these, in particular nonionic surfactants and fragrances and, if appropriate, optical brighteners mixed with water and or nonionic surfactant can be mentioned, can be sprayed onto the compounds produced according to the invention beforehand or during the mixing. It is also possible to use the compounds produced according to the invention, optionally in a mixture with other ingredients. post-compacting treatment. For the production of agents with increased bulk density, in particular in the range from 650 g / 1 to 950 g / 1, a method known from European patent EP 0 486 592 and having an extrusion step is preferred. A further preferred production using a granulation process is described in European patent EP 0 642 576. For the preparation of tablets, which can be single-phase or multi-phase, single-color or multi-color and in particular consist of one or more layers, in particular two layers, the procedure is preferably such that all constituents - optionally one layer each - are mixed mixed together and the mixture is pressed by means of conventional tablet presses, for example eccentric presses or rotary presses. In the case of multi-layer tablets in particular, it can be advantageous if at least one layer is pre-compressed. A tablet produced in this way preferably has a weight of 10 g to 50 g, in particular of 15 g to 40 g. The shape of the tablets is arbitrary and can be round, oval or angular, intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm.

Examples

Aqueous slurries S1, S2 and S3 were produced from the raw materials given in Table 1. These slurries were heated to temperatures of approximately 60 ° C. to 80 ° C. and sprayed under pressure in a drying tower, hot air (temperature approx. 200 ° C. in the ring channel) being passed in countercurrent. Free-flowing powder Ml. M2 and M3 with average grain sizes of around 300 μm were obtained, which were free of particles over 1.6 mm in diameter, had dust contents (diameter under 0.1 mm) of at most 1% by weight, and the water contents given in Table 2 (H ₂ O;% by weight) had bulk densities (SG; grams per liter) and standard color values (Y)

Table 1: Composition [kg] of the aqueous slurries

Table 2

Claims

claims

1. A process for the preparation of powdery, stoking and pourable preparations which contain cobuilders and organic and / or inorganic carrier material and are suitable for the production of particulate detergents and cleaning agents, by drying flowable, aqueous, surfactant-containing mixtures of their constituents, characterized in that mixes an oxidized dextrin derivative with inorganic builder, surfactant and so much water that a flowable and pumpable mixture is formed at temperatures below 80 ° C, and this by spray drying using drying gases with temperatures in the range of 160 ° C to 260 ° C the water to the extent that a powdery, free-flowing product is produced.

2. The method according to claim 1, characterized in that the proportion of oxidized dextrin in the total builder component is 5 wt .-% to 50 wt .-%, in particular 10 wt .-% to 25 wt .-%.

3. The method according to claim 1 or 2, characterized in that one uses as a dextrin derivative at its originally reducing end oxidatively, optionally with loss of a carbon atom, modified dextrin.

4. The method according to any one of claims 1 to 3, characterized in that the dextrin derivative of the formula (glucose) _n -ι-arabinonic acid obeys, the average degree of oligomerization n being in the range from 2 to 20, in particular from 2 to 10.

5. The method according to any one of claims 1 to 4, characterized in that drying gases are used at temperatures in the range from 160 ° C to 240 ° C, in particular from 180 ° C to 220 ° C.

6. Powdered preparation prepared by the process according to one of claims 1 to 5, suitable for the production of particulate washing and cleaning agents, characterized in that it contains inorganic builders in amounts of 25% by weight up to 75% by weight. in particular 30% by weight to 65% by weight. and / or surfactant in amounts of 5% by weight to 30% by weight. contains in particular from 7% by weight to 25% by weight.