EP1086202B1 - Production of granulates containing alkylpolyglycoside - Google Patents

Abstract

The invention relates to granulates containing alkylpolyglycoside (APG) having advantageous technical application properties and which can be obtained through a method whereby an aqueous APG paste is mixed with other aqueous non-surface active granulation components and sprayed on a solid mixture being agitated in a mixer.

Description

The present invention relates to the production of alkyl polyglycoside (APG) -containing granules in a mixed granulation process.

Granular detergent and cleaning agent compositions are largely made by spray drying. When spray drying, the ingredients are like Surfactants, builders etc. with approx. 35 to 50% by weight water to form an aqueous slurry, the so-called slurry, mixed and in spray towers in a hot gas stream atomized, whereby the detergent and cleaning agent particles form. Either the facilities for this process and the implementation of the process are costly, since approx. 30 to 40% by weight of the slurry water must be evaporated. In addition, the granules produced by spray drying usually have excellent ones Solubility, but only have low bulk weights, which leads to higher packaging volumes as well as transport and storage capacities. The flowability too spray-dried granules are not due to their irregular surface structure optimal, which also affects their visual appearance. In addition, the spray drying non-ionic surfactants are associated with further problems. Because of their relative low melting points and due to their relatively high volatility tend to be non-ionic Surfactants in the spray drying process, in part with the hot gas drying stream to be carried away and to pass into the exhaust air, what the specialist is known as "pluming" or "blue smoke". Spray drying processes have one further series of disadvantages, so that there was no lack of attempts to manufacture detergents and cleaning agents without spray drying.

For example, W. Hermann de Groot, I. Adami, GF Moretti describes "The Manufacture of Modern Detergent Powders", Hermann de Groot Academic Publisher, Wassenaar, 1995, page 102 ff . various mixing and granulating processes for the production of detergents and cleaning agents. These processes have in common that premixed solids are granulated with the addition of the liquid ingredients and, if necessary, subsequently dried.

There is also a broad state of the art in non-tower manufacturing in patent literature of detergents and cleaning agents. Here is the production of surfactant granules, which contain alkyl polyglycosides (APG), are associated with further difficulties, since aqueous solutions or pastes from APG are not simply a granulating liquid can be used, as is usually the case for nonionic surfactants. If you try to apply APG solutions to moving solids, you get Granules which only have a low absorption capacity for other optional uses Have detergent and cleaning agent ingredients and also tend to clump together. This procedure also has the disadvantage that the mixture to be granulated stubbornly sticks to the mixing tools and the mixer wall and in this way continuous production prevented.

The present invention was based on the object of a method for the production To provide APG-containing granules which are free from the disadvantages mentioned. It should a granulation process can be provided which is both discontinuous and The continuous production of APG-containing granules allowed without ticking occur or the granules have adverse properties.

This task can be solved if the APG solutions or pastes are not used alone, but in a mixture with other aqueous solutions of non-surfactant granulation components used as granulation liquid.

The invention relates to a method for producing alkyl polyglycoside (APG) -containing Granules, in which an aqueous APG paste with other aqueous solutions non-surfactant granulation components are mixed and agitated in a mixer Solid mixture is sprayed on.

Alkypolyglycosides which can be used according to the invention satisfy the general formula RO (G) ₂ , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.

wobei x der um 1 verringerte oben beschriebene Glycosidierungsgrad z ist, bevorzugte Werte von x also zwischen 0 und 3, vorzugsweise zwischen 0 und 1 und insbesondere zwischen 0,1 und 0,4 liegen. Die Zahl n der Methylengruppen liegt vorzugsweise zwischen 7 und 21, bevorzugt zwischen 11 und 17, C-Atomen. Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used. These can be described using the following formula

where x is the degree of glycosidation z reduced by 1 described above, preferred values of x are therefore between 0 and 3, preferably between 0 and 1 and in particular between 0.1 and 0.4. The number n of methylene groups is preferably between 7 and 21, preferably between 11 and 17, carbon atoms.

The alkyl polyglycosides used according to the invention (hereinafter referred to as APG for short) can be prepared by known processes based on known raw materials. For example, dextrose is reacted with n-butanol to give butylpolyglycoside mixtures in the presence of an acidic catalyst, which are transglycosidated with long-chain alcohols in the presence of an acidic catalyst to give the desired alkylpolyglycoside mixtures. It is also possible to glycosidate dextrose directly with the desired long-chain alcohol to the desired alkyl polyglycoside mixtures.
The structure of the products can be varied within certain limits. The alkyl radical is determined by the choice of the long-chain alcohol. For economic reasons, the industrially accessible alcohols having 8 to 22 carbon atoms, in particular native alcohols from the hydrogenation of carboxylic acids or carboxylic acid derivatives, are preferred. The alcohols obtainable from technical alcohol syntheses, such as oxo alcohols and Ziegleral alcohols, can also be used.

The polyglycosyl radicals G _y are determined, on the one hand, by the selection of the carbohydrate and, on the other hand, by setting the average degree of polymerization (degree of glycosidation y), as is described, for example, in DE 19 43 689 . In principle, it is known that polysaccharides, for example starches, maltodextrins, dextrose, galactose, mannose, xylose, etc. can be used. The commercially available carbohydrates starch, maltodextrins and in particular dextrose are preferred. Since the economically interesting APG syntheses are not regio- and stereoselective, the alkyl polyglycosides are always mixtures of oligomers, which in turn represent mixtures of different isomeric forms. They exist side by side with α- and β-glycosidic bonds in pyranose and furanose form. The linkages between two saccharide residues are also different.

Alkyl polyglycosides which can be used according to the invention can also be prepared by mixing alkyl polyglycosides with alkyl monoglycosides. Alkyl monoglycosides can be obtained or enriched, for example, from alkyl polyglycosides using polar solvents such as acetone using the process disclosed in EP 092 355 . The degree of glycosidation of alkyl polyglycosides is usually determined by ¹ H nuclear magnetic resonance measurements.

According to the invention, the alkyl polyglycosides are in the form of aqueous solutions or pastes mixed with aqueous solutions of other non-surfactant granulation components and sprayed onto the solids. It is preferred that the APG solutions or pastes prior to mixing with the other solutions, APG levels of at least 40 % By weight, preferably at least 45% by weight and in particular at least 50% by weight, each based on the APG solution or paste.

The aqueous solutions of non-surfactant granulation components are sprayed on mixed on the solids with the APG pastes described above. As non-surfactant granulation components come from all ingredients Washing and cleaning agents in question, which are water-soluble and not from the Group of surfactants. In particular, here are silicates, polymers, complexing agents, optical brighteners and inorganic salts as non-surfactant granulation components to call.

Both crystalline and amorphous silicates can be used as silicates, the alkali metal silicates are preferred.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H 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. Such crystalline layered silicates are described, for example, in European patent application EP-A-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, it being possible, for example, to keep β-sodium disilicate by the method described in international patent application WO-A-91/08171 .

Amorphous sodium silicates with a modulus Na ₂ O: SiO 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 are delayed in dissolving and 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 also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 . Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

As polymers, water-soluble polymers come into consideration because of their secondary washing properties are often used in detergents and cleaning agents. In these The group includes in particular the polyacrylic acids or polyacrylates and the copolymers of acrylic acid with other monomers, especially unsaturated acids such as maleic acid. Acrylic acid-maleic acid copolymers are, for example, under the trade name Sokalan® CP 5 (BASF) available

Suitable complexing agents in the context of the present invention are, for example Alkali salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and also alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates. Low molecular weight hydroxycarboxylic acids such as citric acid, tartaric acid, Malic acid or gluconic acid suitable. Suitable complexing agents can also be selected from organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriaminepenta (methylenephosphonic acid) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBS-AM).

Derivatives of diaminostilbenedisulfonic acid or its alkali metal salts can be used as optical brighteners be used. 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 similarly constructed Compounds which, instead of the morpholino group, have a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Farther 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) diphenyl. Mixtures of the aforementioned Brighteners can be used.

Finally, inorganic salts can also be used as the granulation component, if desired. The alkali metal salts in particular are from this group and among them the carbonates, bicarbonates and sulfates are preferred.

The granulation components mentioned can also be used in a mixture with one another with no limits on the freedom of formulation. The mix with Other granulation components are always recommended when certain substances should not be contained in large amounts in the granules - this is how optical brighteners become usually combined with other granulation components. The salary of the aqueous solution of the granulation components of active substance before mixing with the APG paste, for example, more than 20% by weight, preferably more than 25 % By weight and in particular more than 30% by weight, in each case based on the aqueous solution.

An aqueous sodium silicate solution is particularly advantageous as the granulation component used for mixing with the APG paste, the more than 20 wt .-%, preferably more than 25% by weight and in particular more than 30% by weight of sodium silicate, in each case based on the aqueous solution.

The APG paste and the aqueous solution of the granulation components are mixed and sprayed onto the solids moving in the mixer. It is preferred that the Mixture of APG paste and other aqueous solutions of non-surfactant granulation components less than 70% by weight, preferably less than 65% by weight and in particular contains less than 60% by weight of water, based on the mixture. The APG paste and the aqueous solution of the granulation components can be in varying ratios are mixed with one another, a frame of the ratio APG: remaining granulation components from 50: 1 to 1:50, based in each case on the active substance, is advantageous is. In the context of the present invention, however, it is particularly preferred to cover this area choose narrower so that the ratio of APG to non-surfactant granulation components in the mixture in the range 2: 1 to 1:10, preferably in the range of 1: 1 up to 1: 5 and in particular in the range from 1: 1.5 to 1: 3, in each case based on active substance, lies.

The solid mixture on which the mixture of APG paste and aqueous solution is non-surfactant Granulation components can be sprayed on, all usually in Detergents and cleaning agents used ingredients. These substances come from usually from the group of builders (e) and / or surfactant granules (e) and / or Bleaching agents and / or bleach activators and, if appropriate, other customary ingredients of detergents and cleaning agents.

In addition to the washing-active substances, builders are the most important ingredients of Detergents and cleaning agents. In the process according to the invention, the solid mixture all builders commonly used in detergents and cleaning agents be included, in particular thus zeolites, silicates, carbonates, organic cobuilders and where there are no ecological prejudices against their use - including phosphates.

The finely crystalline, synthetic and bound water-containing zeolite used 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 (approx ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula n Na ₂ O (1-n) K ₂ O Al ₂ O ₃ (2 - 2.5) SiO ₂ (3.5 - 5.5) H ₂ O can be described. The zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water. In preferred processes, the solid mixture moved in the mixer contains zeolite (e) in amounts of more than 10% by weight, preferably in amounts of more than 20% by weight and in particular in amounts above 30% by weight, based on the solid mixture ,

It goes without saying that the generally known phosphates are also used as builder substances possible if such use is not avoided for ecological reasons should be. The sodium salts of orthophosphates, pyrophosphates, are particularly suitable and especially the tripolyphosphates.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if provided such use is not objectionable for ecological reasons, as well as mixtures from 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 this.

The silicates already described above can also be used as a granulation component (aqueous solution mixed with the APG paste) as well as in the solid mixture be included.

In addition to the builders, the solid mixture can contain wash-active substances, which preferably come from the group of anionic and / or nonionic surfactants. These surfactants can be used as pure substances if they are the process temperature is fixed; but they can also be used as compounded raw materials or applied to carrier materials in the solid mixture.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C _9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C _12-18 monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent ones receives alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with 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. Among fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained 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 with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, Myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of 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 half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat . Nos . 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 - 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 which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 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). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Are suitable saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, 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 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, especially in the form of the sodium salts.

In the context of the present invention, it is preferred that the solid mixture 5 to 60% by weight, preferably 10 to 50% by weight and in particular 20 to 40% by weight of anionic (s) Contains surfactant (s).

When selecting the anionic surfactants which are used in the process according to the invention Are used, there are no general conditions to be complied with In the way. However, preferred solid mixtures have a soap content, which exceeds 0.2% by weight, based on the total weight of the solids presented. The preferred anionic surfactants are the alkylbenzenesulfonates, fatty alcohol sulfates, preferred solid mixtures being 2 to 20% by weight, preferably 5 to 15 % By weight and in particular 7.5 to 12.5% by weight of fatty alcohol sulfate (s), in each case based on the total weight of the submitted solids

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 fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 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 to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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, such as them 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 .

Also 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 be suitable. The amount of these nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, especially not more than half of it.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zukkers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. 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.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

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 oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated 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 be converted, for example according to the teaching of international application WO-A-95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired polyhydroxy fatty acid amides.

In the context of the present invention, it is preferred that the solid mixture 5 to 40% by weight, preferably 7.5 to 30% by weight and in particular 10 to 20% by weight of nonionic (s) Contains surfactant (s).

In addition to the constituents mentioned, in the process according to the invention, further in Detergents and cleaning agents usual ingredients from the group of bleaching agents, Bleach activators, enzymes, fragrances, perfume carriers, fluorescent agents, dyes, Foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, Color transfer inhibitors and corrosion inhibitors are used.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.

To improve the bleaching effect when washing at temperatures of 60 ° C and below To achieve this, bleach activators can be incorporated into the solid mixture. Compounds which are aliphatic under perhydrolysis conditions can be used as bleach activators Peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid are used. Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups. Are preferred polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated Triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, in particular Triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, too so-called bleaching catalysts can be incorporated into the moldings. With these fabrics are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing ones Tripod ligands as well as Co, Fe, Cu and Ru amine complexes are used as bleaching catalysts usable.

Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question. Bacterial strains or are particularly well suited Mushrooms such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or Protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but especially mixtures containing cellulase of special interest. Peroxidases or oxidases have also been found in some Cases proved to be suitable. The enzymes can be adsorbed on carriers and / or be embedded in coating substances to protect them against premature decomposition. The Proportion of enzymes, enzyme mixtures or enzyme granules in the solid mixture can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

In addition, components can also be used that allow oil and fat to be washed out from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times with a detergent according to the invention, the oil and fat-dissolving component contains, was washed. The preferred oil and fat dissolving components include for example nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ether, as well as the polymers of phthalic acid known from the prior art and / or terephthalic acid or its derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. Of these, the sulfonated ones are particularly preferred Derivatives of phthalic acid and terephthalic acid polymers.

Dyes and fragrances can be added to the aesthetic impression of the products to improve and the consumer in addition to the softness performance a visual and sensory to provide "typical and distinctive" product. As perfume oils or fragrances can individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type become. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and benzyl salicylate. The ethers include, for example Benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 C atoms, Citral, Citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone, ∝-Isomethylionon and Methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, Phenylethyl alcohol and terpineol, the hydrocarbons mainly include Terpenes like limes and pinene. However, mixtures of different are preferred Fragrances are used, which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures, such as those derived from plants Sources are accessible, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, Mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The dye content of the plasticizers according to the invention is usually lower 0.01% by weight, while fragrances make up up to 2% by weight of the total formulation can.

The fragrances can be added directly to the process according to the invention via the solid mixture be introduced, but it can also be advantageous to apply the fragrances to carriers, which increase the adhesion of the perfume to the laundry and a slower one Fragrance release ensures long-lasting fragrance of the textiles. As such carrier materials Cyclodextrins have proven themselves, for example, the cyclodextrin-perfume complexes can also be coated with other auxiliaries.

In order to improve the aesthetic impression of the agents according to the invention, they can can be colored with suitable dyes. Preferred dyes, the selection of which Specialist poses no difficulty, has a high storage stability and insensitivity compared to the other ingredients of the agents and against light and none pronounced substantivity towards textile fibers so as not to stain them.

The process according to the invention is initially carried out by dry mixing the Solids in a suitable mixer and subsequent granulation with the addition of Mixture of APG paste and aqueous solution of non-surfactant granulation components, the liquid preferably being added by spraying.

The process can be carried out in a wide variety of mixing and granulating devices become. In a suitable mixing and granulating device, for example in corresponding plants of the type of an Eirich mixer, a Lödige mixer, for example a ploughshare mixer from Lödige, or a mixer from the company Schugi, at peripheral speeds of the mixing elements are preferably between 2 and 7 m / s (ploughshare mixer) or 5 to 50 m / s (Eirich, Schugi), in particular between 15 and 40 m / s the solids and subsequently with the addition of the mixture granulated from APG and granulation components. It can be in at the same time a predetermined grain size of the granulate can be set in a known manner. The Process takes only a very short period of time, for example about 0.5 to 10 minutes, in particular about 0.5 to 5 minutes (Eirich mixer, Lödige mixer) for homogenization of the mixture to form the free-flowing granules. In the Schugi mixer however, a dwell time of 0.5 to 10 seconds is usually sufficient to to obtain a free-flowing granulate. For carrying out the method according to the invention suitable mixers are, for example, Eirich® mixers of the R or RV series (trademark the machine factory Gustav Eirich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G mixer (trademark of Fukae Powtech, Kogyo Co., Japan), the Lödige® FM, KM and CB mixers (trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais® series T or K-T (trademark of Drais-Werke GmbH, Mannheim).

The mixture of aqueous APG paste with other aqueous non-surfactant solutions Granulation components are preferably used at a temperature above Room temperature. It is preferably added to the agitated solid mixture at temperatures above 60 ° C, especially at temperatures above 70 ° C. The increased temperature of the granulating liquid has the consequence that higher liquid proportions can be used and the stickiness of the resulting granules is further reduced becomes.

Examples:

A surfactant-containing base powder which did not contain any APG was produced by spray drying and the composition of which is given in Table 1. This base powder was mixed with other solids and placed in a mixer. On the moving solid mixture were a 50 wt .-% APG paste and a 35 wt .-% sodium silicate solution sprayed (each in water). After the formation of granules a 43% by weight solution of an acrylic acid-maleic acid copolymer in water was sprayed on. In process sequence E1 according to the invention, the APG paste was sprayed on mixed with the sodium silicate solution and the mixture onto the solid mixture sprayed. In comparative example V1, the APG paste and subsequently sprayed on the sodium silicate solution.

In procedure E1 according to the invention, 6% by weight of the copolymer solution can be applied without problems (based on the finished granulate), a fine, dry and free-flowing granulate being obtained. If one does not proceed according to the invention (V1), only a reduced amount of the copolymer solution can be applied, since otherwise coarse lumps form and the mixer contents stick together and the mixer is clogged. Even with the reduced amount of copolymer solution, sticky granules are obtained, which were also significantly coarser. Because of the smaller possible amounts of copolymer solution that could be added in the comparative example, the relative proportions (figures in% by weight) of the other ingredients have changed compared to example E1 according to the invention; the absolute amounts (in kg) that were used are the same in both examples except for the copolymer solution. The percentage composition of the granules is shown in Table 2, the physical data of the granules obtained by process routes E1 and V1 are shown in Table 3. Composition of the base powder [% by weight]: C _9-13 alkyl benzene sulfonate 26.0 Soap 4.0 sodium 43.0 sodium silicate 12.0 Acrylic acid-maleic acid copolymer 7.5 Na-hydroxyethane-1,1-diphosphonate 2.0 Water, salts rest Composition of the granules [% by weight] E1 V1 Granular surfactant (Table I) 36.40 37.27 Zeolite A 32,30 33.08 C _12-18 fatty alcohol sulfate 5.10 5.20 C _9-13 alkyl benzene sulfonate, 97% 7.95 8.14 C _12-18 fatty alcohol with 7 EO 5.25 5.38 opt. brighteners 0.3 0.31 Sodium silicate solution, 35% by weight 3.47 2.63 APG paste, 50% by weight 1.80 1.89 Sokalan® CP 5 (43% by weight solution) 5.93 4.55 Water, salts rest rest Sokalan® CP 5 is an acrylic acid-maleic acid copolymer (BASF) physical data of the granules E1 V1 Bulk density [g / l] 800 830 Sieving numbers: [%] > 1.6 mm 22 27 > 0.8 mm 24 26 > 0.4 mm 35 30 > 0.2 mm 16 13 > 0.1 mm 3 3.5 <0.1 mm - 0.5

Claims (11)

1. A process for the production of granules containing alkyl polyglycosides (APG), characterized in that a water-containing APG paste is mixed with other aqueous solutions of non-surfactant granulation components and the resulting mixture is sprayed onto a mixture of solids agitated in a mixer.
2. A process as claimed in claim 1, characterized in that the water-containing APG paste contains at least 40% by weight, preferably at least 45% by weight and more preferably at least 50% by weight of alkyl polyglycosides, based on the paste.
3. A process as claimed in claim 1 or 2, characterized in that the APG used has a degree of glycosidation of 1.0 to 4.0, preferably 1.0 to 2.0 and more preferably 1.1 to 1.4.
4. A process as claimed in any of claims 1 to 3, characterized in that an alkyl polyglucoside is used as the APG.
5. A process as claimed in any of claims 1 to 4, characterized in that the other aqueous solutions of non-surfactant granulation components are selected from the group of aqueous solutions of silicates, polymers, complexing agents, optical brighteners and inorganic salts.
6. A process as claimed in any of claims 1 to 5, characterized in that a sodium silicate solution containing more than 20% by weight, preferably more than 25% by weight and more preferably more than 30% by weight of sodium silicates, based on the aqueous solution, is used as the aqueous granulation component.
7. A process as claimed in any of claims 1 to 6, characterized in that the mixture of solids agitated in the mixer contains builder(s) and/or surfactant granule(s) and/or bleaching agents and/or bleach activators and optionally other typical ingredients of detergents.
8. A process as claimed in any of claims 1 to 7, characterized in that the mixture of solids agitated in the mixer contains zeolite(s) in quantities of more than 10% by weight, preferably in quantities of more than 20% by weight and more preferably in quantities of more than 30% by weight, based on the mixture of solids.
9. A process as claimed in any of claims 1 to 8, characterized in that the mixture of APG paste with other aqueous solutions of non-surfactant granulation components contains less than 70% by weight, preferably less than 65% by weight and more preferably less than 60% by weight of water, based on the mixture.
10. A process as claimed in any of claims 1 to 9, characterized in that the ratio of APG to non-surfactant granulation components in the mixer is in the range from 2:1 to 1:10, preferably in the range from 1:1 to 1:5 and more preferably in the range from 1:1.5 to 1:3, based on active substance.
11. A process as claimed in any of claims 1 to 10, characterized in that the mixture of water-containing APG paste and other aqueous solutions of non-surfactant granulation components has a temperature above 60°C and preferably above 70°C when sprayed onto the agitated mixture of solids.