WO1999063044A1

WO1999063044A1 - Production of granulates containing alkylpolyglycoside

Info

Publication number: WO1999063044A1
Application number: PCT/EP1999/003565
Authority: WO
Inventors: Hans-Friedrich Kruse; Franz Gormanns; Jordi Junca
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1998-06-03
Filing date: 1999-05-25
Publication date: 1999-12-09
Also published as: DE59902356D1; ATE222288T1; EP1086202B1; EP1086202A1; DE19824742A1; JP2002517558A; ES2180333T3

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

'Production of granules containing alkyl polyglycosides'

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 produced by spray drying. In spray drying, the ingredients such as surfactants, builders etc. are mixed with about 35 to 50% by weight of water to form an aqueous slurry, the so-called slurry, and atomized in spray towers in a hot gas stream, the detergents and cleaning agents being atomized - Form particles. Both the plants for this process and the implementation of the process are costly since approximately 30 to 40% by weight of the slurry water must be evaporated. In addition, the granules produced by spray drying usually have excellent solubility, but only have low bulk densities, which leads to higher packaging volumes and transport and storage capacities. The flowability of spray-dried granules is also not optimal due to their irregular surface structure, which also affects their visual appearance. In addition, spray drying of nonionic surfactants is associated with further problems. Because of their relatively low melting points and because of their relatively high volatility, nonionic surfactants in the spray drying process tend to be entrained in part with the hot gas drying stream and to pass into the exhaust air, which is known to the person skilled in the art as "pluming" or "blue smoke". Spray drying processes have one further series of disadvantages, so that there has been no lack of attempts to carry out the production of detergents and cleaning agents completely without spray drying.

W.Hermann de Groot, I. Adami, G.F. Moretti "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 the patent literature for the non-tower manufacture of detergents and cleaning agents. The production of surfactant granules which contain alkyl polyglycosides (APG) is associated with further difficulties, since aqueous solutions or pastes from APG cannot simply be used as the granulating liquid, as is usually the case for nonionic surfactants. If you try to apply APG solutions to moving solids, you get granules that have only a low absorption capacity for other optional detergent 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 wall of the mixer and in this way prevents continuous production.

The object of the present invention was to provide a process for producing APG-containing granules which is free from the disadvantages mentioned. A granulation process should be provided which allows both the batchwise and the continuous production of APG-containing granules without the occurrence of deposits or the granules having disadvantageous properties.

This problem is solved if the APG solutions or pastes are not used alone, but in a mixture with other aqueous solutions of non-surfactant granulation components as the granulation liquid. The invention relates to a process for the production of alkyl polyglycoside (APG) -containing granules, in which an aqueous APG paste is mixed with other aqueous solutions of non-surfactant granulation components and sprayed onto a solid mixture agitated in a mixer.

Alkypolyglycosides which can be used according to the invention satisfy the general formula RO (G) _z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated ahphatic radical having 8 to 22, preferably 12 to 18, carbon 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.

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 alkylpolyglycosides 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 selection 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 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 are present side by side with α- and ß-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. For example, alkyl monoglycosides can be obtained or enriched from alkyl polyglycosides using polar solvents such as acetone using the process disclosed in EP 092 355. The Glycosi The degree of alkylation of alkyl polyglycosides is usually determined by 'H nuclear magnetic resonance measurements.

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

The aqueous solutions of non-surfactant granulation components are mixed with the APG pastes described above before being sprayed onto the solids. All the ingredients of detergents and cleaning agents that are water-soluble and do not come from the group of surfactants are suitable as non-surfactant granulation components. In particular, silicates, polymers, complexing agents, optical brighteners and inorganic salts are to be mentioned as non-surfactant granulation components.

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

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} 'H, 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, with β-sodium disilicate being able to be obtained, for example, by the method described in international patent application WO-A-91/08171 . Amorphous sodium silicates with a Na ^: SiO ₂ modulus of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, which delay the dissolution, can also be used are 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 building 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.

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

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

Derivatives of diaminostilbenedisulfonic acid or its alkali metal salts can be used as optical brighteners. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-moφholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which, instead of the morpholino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can also be used.

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

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

It is particularly advantageous to use an aqueous sodium silicate solution for mixing with the APG paste as the granulation component, which contains more than 20% by weight, preferably contains 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 here that the mixture of APG paste and other aqueous solutions of non-surfactant granulation components contains less than 70% by weight, preferably less than 65% by weight and in particular less than 60% by weight of water, based on the mixture, contains. The APG paste and the aqueous solution of the granulation components can be mixed with one another in varying ratios, a range of the ratio APG: remaining granulation components from 50: 1 to 1:50, in each case based on the active substance, being advantageous. In the context of the present invention, however, it is particularly preferred to select this range more narrowly, so that the ratio of APG to non-surfactant granulation components in the mixture is in the range from 2: 1 to 1:10, preferably in the range from 1: 1 to 1 : 5 and in particular in the range from 1: 1.5 to 1: 3, in each case based on active substance.

The solid mixture, onto which the mixture of APG paste and aqueous solution of non-surfactant granulation components is sprayed, can contain all of the ingredients normally used in washing and cleaning agents. These substances usually come from the group of builders (e) and / or surfactant granules (e) and / or bleaching agents and / or bleach activators as well as, where appropriate, other conventional ingredients of washing and cleaning agents.

In addition to the wash-active substances, builders are the most important ingredients in detergents and cleaning agents. In the process according to the invention, all builders normally used in washing and cleaning agents can be present in the solid mixture, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the 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 (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.0 ^• (ln) 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 type 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 is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these this. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The silicates already described above can also be present both as a granulation component (aqueous solution in a mixture with the APG paste) and in the solid mixture.

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 solid at the process temperature; however, they can also be incorporated into the solid mixture as compounded raw materials or applied to carrier materials.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C ₉ . ₁₃ - alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene sulfonates and hydroxyalkane, and the disulfonates obtained, for example obtained from C ₁₂ _ ₁₈ -Monoolefmen with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation into consideration. Alkanesulfonates which are derived from C ₁₂ are also suitable. ₁₈ -alkanes can be obtained, 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. 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 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fat 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.

The alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₁₀ -C ₂₀ -oxoalcohols 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, straight-chain alkyl radical which is produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. From the washing C _I2 -C ₆ alkyl sulfates and C ₁₂ -C _I5 are - alkyl sulfates and C ₁₄ -Cι preferably ₅ alkyl sulfates. 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.

Also, the Schwefelsäuremonoester the ethoxylated with 1 to 6 moles of ethylene oxide, linear or branched C ₇ _ ₂₁ alcohols such as 2-methyl-branched C. ₉ _M alcohols containing on average 3.5 mol ethylene oxide (EO) or _C12., ₈ fatty alcohols containing 1 to 4 EO, are also 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. Likewise 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. Saturated fatty acid soaps are suitable, 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 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.

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

When selecting the anionic surfactants that are used in the process according to the invention, there are no general conditions to be observed that prevent freedom of formulation. However, preferred solid mixtures have a soap content which exceeds 0.2% by weight, based on the total weight of the solids initially introduced. 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), based in each case 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 has a methyl or linear branching in the 2-position can be or linear and can contain methyl-branched radicals in the mixture, as are usually present in oxo alcohol residues. 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 " _π alcohol with 7 EO, C, ₃ . _1S - alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C, ₂ . 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 of this are 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 as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-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 (I), R ^J

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

in which RCO stands for an ahphatic acyl radical with 6 to 22 carbon atoms, R * 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.

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

R ^Ϊ -OR ^

R-CO-N- [Z] (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 represents an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C _M - alkyl or phenyl radicals being preferred and [Z] representing 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, into the desired polyhydroxyfatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

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

In addition to the constituents mentioned, other 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 can be used in the process according to the invention be 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 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the solid mixture. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acy- lated triazine derivatives, in particular l, 5-diacetyl-2,4-dioxohexahydro-l, 3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates , in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular 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, so-called bleach catalysts can also be incorporated into the moldings. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of 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 be used which have a positive influence on the washability of oil and fat from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

Dyes and fragrances can be added to improve the aesthetic impression of the products and, in addition to the softness, provide the consumer with a visually and sensorially "typical and distinctive" product. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclionylylylylylylylylylylylylylpylylylylpylylylpylylylpylylylpylylylpylylpylalylateylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatylatyl. The ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, oc-isomethylionone and methyl -cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example 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, galbana 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 less than 0.01% by weight, while fragrances can make up up to 2% by weight of the entire formulation.

The fragrances can be introduced directly into the process according to the invention via the solids mixture, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, it being possible for the cyclodextrin-perfume complexes to be additionally coated with further auxiliaries.

In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to textile fibers, in order not to dye 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 the 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. In a suitable mixing and granulating device, for example in appropriate systems of the type of an Eirich mixer, a Lödige mixer, for example a ploughshare mixer from the Lödige company, or a mixer from the Schugi company, at peripheral speeds of the mixing elements, 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 are introduced and then granulated with the addition of the mixture of APG and granulation components. At the same time, a predetermined grain size of the granules can be set in a manner known per se. The process requires only a very short period of time, for example, of about 0.5 to 10 minutes, in particular about 0.5 to 5 minutes (Eirich mixer, Lödige mixer) to homogenize the mixture with formation of the free-flowing granules. In the Schugi mixer, on the other hand, a residence time of 0.5 to 10 seconds is usually sufficient to obtain a free-flowing granulate. Eirich ^® mixer Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi ^® Flexomix, the Fukae ^® are, for example FS-G mixers (trade marks of Fukae Powtech for carrying out the method according to the invention suitable mixer, Kogyo Co., Japan), the Lödige ^® FM, KM and CB mixers (trademarks of Lödige Maschinenbau GmbH, Paderborn) or the Drais ^® series T or KT (trademarks of Drais- Werke GmbH, Mannheim).

The mixture of aqueous APG paste with other aqueous solutions of non-surfactant granulation components is preferably used at a temperature which is above room temperature. The addition to the agitated solid mixture is preferably carried out at temperatures above 60 ° C., in particular 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.

Examples:

A surfactant-containing base powder which did not contain any APG and whose composition is given in Table 1 was produced by spray drying. This base powder was mixed with other solids and placed in a mixer. A 50% by weight APG paste and a 35% by weight sodium silicate solution (each in water) were sprayed onto the agitated solid mixture. 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 mixed with the sodium silicate solution before spraying on, and the mixture was sprayed onto the solid mixture. In Comparative Example VI, the APG paste and then the sodium silicate solution were sprayed on first.

In procedure E 1 according to the invention, 6% by weight of the copolymer solution can be applied without problems (based on the finished granules), fine, dry and free-flowing granules being obtained. If the procedure according to the invention is not followed (VI), only a reduced amount of the copolymer solution can be applied, since otherwise coarse lumps form and the contents of the mixer stick together and add to the mixer. Even with the reduced amount of copolymer solution, sticky granules are obtained, which were also significantly coarser. Due to the smaller possible amounts of copolymer solution that could be added in the comparative example, the relative proportions (data 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 VI are shown in Table 3. Table 1: Composition of the base powder [% by weight]:

Table 2: Composition of the granules [% by weight]

Sokalan ^® CP 5 is an acrylic acid-maleic acid copolymer (BASF) Table 3: physical data of the granules

Claims

Claims:

1. A process for the preparation of alkyl polyglycoside (APG) -containing granules, characterized in that an aqueous APG paste is mixed with other aqueous solutions of non-surfactant granulation components and sprayed onto a solid mixture agitated in a mixer.

2. The method according to claim 1, characterized in that the aqueous APG paste contains at least 40% by weight, preferably at least 45% by weight and in particular at least 50% by weight, of alkypolyglycosides, based on the paste.

3. The method according to any one of claims 1 or 2, characterized in that the APG used has a degree of glycosidation from 1.0 to 4.0, preferably from 1.0 to 2.0 and in particular from 1.1 to 1.4.

4. The method according to any one of claims 1 to 3, characterized in that an alkyl polyglucoside is used as APG.

5. The method according to any one 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. The method according to any one of claims 1 to 5, characterized in that a sodium silicate solution is used as the aqueous granulation component, the more than 20 wt .-%, preferably more than 25 wt .-% and in particular more than 30 wt .-% sodium silicates , based on the aqueous solution.

7. The method according to any one of claims 1 to 6, characterized in that the solid mixture moved in the mixer builders (e) and / or surfactant granules (e) and / or Contains bleaching agents and / or bleach activators as well as, where appropriate, other usual ingredients of washing and cleaning agents.

8. The method according to any one of claims 1 to 7, characterized in that the solid mixture moved in the mixer zeolite (e) in amounts of more than 10 wt .-%, preferably in amounts of more than 20 wt .-% and in particular in amounts contains above 30 wt .-%, based on the solid mixture.

9. The method according to any one of claims 1 to 8, characterized in that the mixture of APG paste with other aqueous solutions of non-surfactant granulation components less than 70 wt .-%, preferably less than 65 wt .-% and in particular less than 60 wt. -% water, based on the mixture contains.

10. The method according to any one of claims 1 to 9, characterized in 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 from 1: 1 to 1: 5 and in particular in the range from 1: 1.5 to 1: 3, in each case based on active substance.

11. The method according to any one of claims 1 to 10, characterized in that the mixture of aqueous APG paste and other aqueous solutions of non-surfactant granulation components when sprayed onto the moving solid mixture has a temperature above 60 ° C, preferably above 70 ° C.