EP1232242B1 - Detergent granules with an improved dissolution rate - Google Patents

Description

Field of the invention

The invention is in the field of solid detergents, dishwashing detergents and cleaners and relates to a process for the preparation of novel surfactant granules which are distinguished by an improved dissolution rate.

State of the art

For the preparation of solid detergents, dishwashing detergents and cleaning agents, it is preferred today to use surfactants in granular, virtually anhydrous form. For the preparation of such forms of application, a variety of methods have proven to be suitable. Common to the commercially available surfactant granules, however, that they have an insufficient dissolution rate, especially in cold water. Detergent tablets which are produced on the basis of anionic or nonionic surfactants, for this reason, despite the concomitant use of significant amounts of disintegrants are not used directly in the dispensing compartment of the washing machine, but must be added directly to the wash liquor.

The French patent application FR 2,147,443 discloses a powdered detergent containing oleyl polypeptides in combination with carboxymethylcellulose as a disintegrant. The German patent DE 44 33 070 discloses mild powder detergent mixtures containing a protein derivative, namely wheat protein fatty acid condensates, polyacrylate and carboxymethylcellulose.

The object of the present invention has thus been to provide surfactant granules which disintegrate particularly rapidly on contact with cold water without formation of a gel phase, so that the disadvantages of the prior art are reliably overcome.

Description of the invention

The invention relates to a process for the preparation of surfactant granules with improved dissolution rate, which is obtained by granulating and compacting surface-active proteins and / or protein derivatives, optionally together with anionic and / or nonionic surfactants in the presence of disintegrants.

Surprisingly, it has been found that the granules of the invention not only have excellent washing and cleaning performance, but also have a significantly improved dissolution rate, which in particular makes their use possible for the production of such detergent tablets, which are metered in directly via the dispensing chamber of the washing machines can be. The concomitant use of other disintegrants is often no longer necessary in the preparation of such tablets. Compared with the conventional granules, in which one has to speak of "dissolving" the product, the description "decay" is more appropriate here. The surfactant is thus released very quickly and can be active.

In the process for preparing surfactant granules with improved dissolution rate, the surface-active proteins and / or protein derivatives, optionally together with anionic and / or nonionic surfactants, are granulated and compacted in the presence of disintegrants.

Proteins and protein derivatives

As protein component are preferably protein hydrolyzates and their condensation products with fatty acids, subordinated protein hydrolyzate and quaternized protein fatty acid condensates in question. Protein hydrolysates are degradation products of animal or vegetable proteins, for example collagen, elastin or keratin and preferably almond and potato protein, and in particular wheat, rice and soy protein, which are cleaved by acid, alkaline and / or enzymatic hydrolysis and then an average molecular weight in Range of 600 to 4000, preferably 2000 to 3500 have. Although protein hydrolyzates, in the absence of a hydrophobic moiety, are not surfactants in the classical sense, they are widely used to formulate surfactants because of their dispersing properties. Overviews of the preparation and use of protein hydrolysates are, for example, from G. Schuster and A. Domsch in soaps oils Fette Wachse 108, 177 (1982 ) respectively. Cosm. 99, 63 (1984 ), from HW Steisslinger in Parf.Kosm. 72, 556 (1991 ) and F. Aurich et al. in Tens.Surf.Det. 29, 389 (1992 ) published. Preferably vegetable protein hydrolysates based on wheat gluten or rice protein are used, their preparation in the two German Patent DE 19502167 C1 and DE 19502168 C1 (Henkel ) is described. From the protein hydrolysates can be produced by condensation with C ₆ -C ₂₂ -, preferably C ₁₂ -C ₁₈ fatty acids anionic surfactants, so-called protein fatty acid condensates having comparable properties with soaps. Preferably, condensates of said hydrolyzates with caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid used.

Anionic surfactants

Typical examples of anionic surfactants which can be used together with the proteins or protein derivatives are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether). sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acylaspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates ( in particular vegetable products based on wheat) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Preference is given to using alkylbenzenesulfonates, alkyl sulfates, soaps, alkanesulfonates, olefinsulfonates, methyl ester sulfonates and mixtures thereof. Preferred alkylbenzenesulfonates preferably follow the formula (I)

R-Ph-SO ₃ X (I)

in which R is a branched, but preferably linear, alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Especially suitable of these are dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts. Alkyl and / or alkenyl sulfates, which are also frequently referred to as fatty alcohol sulfates, are the sulfation products of primary and / or secondary alcohols, which preferably follow the formula (II),

R ² O-SO ₃ Y (II)

in which R ^{2 is} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and Y is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl sulfates which can be used according to the invention are the sulfation products of caproic alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures obtained by high-pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxo synthesis. The sulfation products may preferably be in the form of their alkali metal salts and in particular their sodium salts are used. Particular preference is given to alkyl sulfates based on C _16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts. In the case of branched primary alcohols are oxo alcohols, as they are accessible, for example, by reacting carbon monoxide and hydrogen to alpha-olefins by the shop process. Such alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®. Another possibility are oxo alcohols, as obtained by the classical oxo process of Enichema or the Condea by addition of carbon monoxide and hydrogen to olefins. These alcohol mixtures are a mixture of highly branched alcohols. Such alcohol mixtures are commercially available under the trade name Lial®. Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.

Nonionic surfactants

In the context of the present invention, the nonionic surfactants which are likewise suitable as additional surfactant components of the granules may be, for example, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, alk (en) yloligoglycosides, Fatty acid N-alkylglucamides, protein hydrolysates (especially wheat-based vegetable products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Preference is given to using those nonionic surfactants which can be dried off, in particular alkyl and / or alkenyl oligoglycosides which preferably follow the formula (III),

R ³ O- [G] _p (III)

in which R ^{3 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. Representatives of the extensive literature are here on the writings EP 0301298 A1 and WO 90/03977 directed. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (III) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer
and here, above all, the values p = 1 to 6 can assume, the value p for a particular alkyloligoglycoside is an analytically determined arithmetic variable, which usually represents a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred. The alkyl or alkenyl radical R ³ can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, as obtained, for example, in the hydrogenation of technical methyl Feftsäureste or in the hydrogenation of aldehydes from the Roelen oxo synthesis. Preference is given to alkyl oligoglucosides of the chain length C ₈ -C ₁₀ (DP = 1 to 3), which are obtained as a feedstock in the distillative separation of technical C ₈ -C ₁₈ coconut fatty alcohol and with a content of less than 6 wt.% C ₁₂ alcohol may be contaminated and alkyl oligoglucosides based on technical C _9/11 -Oxoalkohole (DP = 1 to 3). The alkyl or alkenyl radical R ³ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaldyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and technical mixtures thereof which can be obtained as described above. Preference is given to alkyl oligoglucosides based on hydrogenated C _12/14 coconut alcohol having a DP of 1 to 3.

If proteins and / or protein derivatives on the one hand and anionic and / or nonionic surfactants on the other hand are used together, it is advisable to use them in a weight ratio of 1: 10 to 10: 1, preferably 1: 5 to 5: 1 and in particular 1: 2 to 2: 1 insert. The proteins and / or protein derivatives and surfactants - either individually or together - both as aqueous pastes with solids contents (= active substance contents) of, for example, 1 to 60, preferably 5 to 50 and especially 15 to 35 wt .-% or as dry solids with residual water contents typically less than 10 and preferably less than 5% by weight.

explosives

The term disintegrants means substances which are contained in the surfactant granules in order to accelerate their disintegration on contact with water. Overviews can be found eg in J. Pharm. 61 (1972 ) or Römpp Chemielexikon, 9th edition, Volume 6, p. 4440 , The disintegrants may be present homogeneously distributed macroscopically in the granules, but may, viewed microscopically, form zones of increased concentration due to their production. Preferred disintegrants include polysaccharides such as natural starch and its derivatives (carboxymethyl starch, Starch glycolates in the form of their alkali salts, agar agar, guar gum, pectins, etc.), celluloses and their derivatives (carboxymethylcellulose, microcrystalline cellulose), polyvinylpyrrolidone, collidone, alginic acid and their alkali metal salts (alginates), amorphous or partially crystalline layered silicates (bentonites), Polyurethanes, polyethylene glycols and gas generating systems. Further disintegrants which may be present within the meaning of the invention are, for example, the documents WO 98/40462 (Rettenmeyer ) WO 98/55583 and WO 98/55590 (Unilever ) and WO 98/40463 , DE 19709991 and DE 19710254 (Henkel ) refer to. The teaching of these documents is expressly incorporated by reference. To prepare the granules according to the invention, it is possible to use the surfactants and disintegrants in a weight ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1 and in particular 1: 2 to 2: 1, based in each case on the solids content. It is also advisable to adjust the water content of the disintegrants or the surfactant granules so that does not automatically swell during storage. Preferably, the residual water content should not exceed 10% by weight.

Granulation and compaction

The preparation of the surfactant granules, so the granulation and compaction can meet in the manner known for detergents. The compacting is absolutely necessary to achieve a sufficient increase in the dissolution rate.

A particularly preferred way of preparing the surfactant granules is to subject the mixtures to fluidized bed granulation ("SKET" granulation). This is to be understood as meaning a granulation with simultaneous drying, which preferably takes place batchwise or continuously. The mixtures of surfactants and disintegrants can be used both in the dried state and as an aqueous preparation. Preferably used fluidized bed apparatuses have bottom plates with dimensions of 0.4 to 5 m. Preferably, the granulation is carried out at fluidized air velocities in the range of 1 to 8 m / s. The discharge of the granules from the fluidized bed is preferably carried out via a size classification of the granules. The classification can be carried out, for example, by means of a sieve device or by a countercurrent air stream (classifier air) which is regulated so that only particles above a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed. Usually, the incoming air is composed of the heated or unheated classifier air and the heated bottom air. The soil air temperature is between 80 and 400, preferably 90 and 350 ° C. Advantageously, a starting material, for example a surfactant granulate from a previous experimental batch, is initially introduced at the beginning of the granulation.

Other methods such as compacting by extrusion or in the roll mill are explained below in the chapter "Production of detergents, dishwashing detergents and cleaning agents". The application of these techniques to the preparation of the surfactant granules according to the invention can be carried out analogously.
In order to facilitate the processing in the processes mentioned, it has proved to be advantageous to add to the surfactant granules granulating and compacting aids, for example polyethylene glycol waxes, in amounts of from 1 to 10 and preferably from 2 to 5% by weight, based on the granules. which above all improve the sliding and adhesion behavior of the products and reduce the necessary energy input. If the desired grain size distribution is not already achieved by the compaction alone, further steps, such as a classification, can be followed.

Industrial Applicability

The surfactant granules can be used for the preparation of solid detergents, dishwashing detergents and cleaning compositions in which they are used in amounts of from 1 to 90, preferably from 5 to 50 and in particular from 10 to 25,% by weight, based on the compositions. The compositions may be present in the form of powders, granules, extrudates, agglomerates or in particular tablets and contain other typical ingredients.

Primary constituents of the compositions may be, for example, further anionic, nonionic, cationic, amphoteric and / or zwitterionic surfactants, but anionic surfactants or combinations of anionic and nonionic surfactants are preferably present, provided they are not identical with the ingredients of the granules according to the invention.

The washing, rinsing and cleaning agents may further contain inorganic and organic builders, wherein as inorganic builders mainly zeolites crystalline phyllosilicates, amorphous silicates and - as far as permissible - also phosphates, such as. Tripolyphosphate be used. The amount of co-builder is to be counted towards the preferred amounts of phosphates.

The finely crystalline, synthetic and bound water-containing zeolite frequently used as detergent builder is preferably zeolite A and / or P. As zeolite P, for example, zeolite MAP ^(R) (commercial product from Crosfield) is particularly preferred. Also suitable however are zeolite X and mixtures of A, X and / or P as well as Y. Of particular interest is a co-crystallized NatriumlKalium-aluminum silicate of zeolite A and zeolite X, which as VEGOBOND AX ^® (a product of Condea Augusta SpA) is commercially available. The zeolite can as spray-dried powder or as undried, still moist from their production, stabilized suspension are used. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Suitable substitutes or sub-substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2 + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in US Pat European patent application EP 0164514 A1 described. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in International Patent Application WO 91/08171 is described. Further suitable phyllosilicates are, for example, from the patent applications DE 2334899 A1 . EP 0026529 A1 and DE 3526405 A1 known. Its usability is not limited to any particular composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable layered silicates which belong to the group of water-swellable smectites are, for example, those of the general formulas

(OH) ₄ Si ₈ - _y Al _y (Mg _x Al _4-x ) O ₂₀ montmorillonite

(OH) ₄ Si _8-y Al _y (Mg _6-z Li _z ) O ₂₀ hectorite

(OH) ₄ Si _8-y Al _y (Mg _6-z Al _z ) O ₂₀ Saponite

with x = 0 to 4, y = 0 to 2, z = 0 to 6. In addition, small amounts of iron may be incorporated in the crystal lattice of the layered silicates according to the above formulas. Furthermore, the phyllosilicates may contain hydrogen, alkali, alkaline earth metal ions, in particular Na ⁺ and Ca ²⁺ , due to their ion-exchanging properties. The amount of water of hydration is usually in the range of 8 to 20 wt .-% and is dependent on the swelling state or on the type of processing. Useful phyllosilicates are for example US 3,966,629 . U.S. 4,062,647 . EP 0026529 A1 and EP 0028432 A1 known. Preferably, phyllosilicates are used which are substantially free of calcium and iron ions.

The preferred builder substances also include amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delay-delayed and have secondary washing properties. The dissolution delay compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / compaction or by over drying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that in X-ray diffraction experiments, the silicates do not give sharp X-ray reflections typical of crystalline substances but at best one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in US Pat German patent application DE 4400024 A1 described. Especially preferred are densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates. Their content is generally not more than 25 wt .-%, preferably not more than 20 wt .-%, each based on the finished agent. In some cases it has been shown that in particular tripolyphosphates, even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing power.

Useful organic builders are, for example, usable in the form of their sodium salts polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for environmental reasons, and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. The acids themselves can also be used. In addition to their builder action, the acids also typically have the property of an acidifying component and thus also serve to establish a lower and milder pH of Detergents or cleaning agents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preference is given to hydrolysis products having average molecular weights in the range from 400 to 500,000. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a customary measure for the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins having a DE of between 3 and 20 and dry glucose syrups having a DE of between 20 and 37 and also yellow dextrins and white dextrins having relatively high molecular weights in the range of 2,000 to 30,000 are useful. A preferred dextrin is disclosed in US Pat British patent application GB 9419091 A1 described. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and methods of their preparation are for example from European patent applications EP 0232202 A1 . EP 0427349 A1 . EP 0472042 A1 and EP 0542496 A1 as well as the international patent applications WO 92/18542 . WO 93/08251 . WO 93/16110 . WO 94/28030 . WO 95/07303 . WO 95/12619 and WO 95120608 known. Also suitable is an oxidized oligosaccharide according to the German patent application DE 19600018 A1 , A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Other suitable co-builders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Glycerol disuccinates and glycerol trisuccinates are particularly preferred in this context, as described, for example, in US Pat US 4,524,009 . US 4,639,325 , in the European patent application EP 0150930 A1 and the Japanese Patent Application JP 93/339896 to be discribed. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present 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 co-builders are described, for example, in the international patent application WO 95/20029 described.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular weight of 800 to 150,000 (based on acid and measured in each case against polystyrenesulfonic acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. 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 to be particularly suitable. Their molecular weight relative to free acids is generally from 5,000 to 200,000, preferably from 10,000 to 120,000 and in particular from 50,000 to 100,000 (in each case measured against polystyrene sulfonic acid). The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred. Granular polymers are usually added later to one or more basic granules. Also particularly preferred are biodegradable polymers of more than two different monomer units, for example, those according to the DE 4300772 A1 as monomers, salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to the DE 4221381 C2 as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives. Other preferred copolymers are those described in the German patent applications DE 4303320 A1 and DE 4417734 A1 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate. Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives.

Further suitable builder substances are polyacetals which are prepared by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as described in US Pat European patent application EP 0280223 A1 described, can be obtained. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Additionally, the compositions may also contain components that positively affect oil and grease washability from fabrics. The preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic Cellulose ethers, as well as known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

Other suitable ingredients of the compositions are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses which do not have outstanding builder properties, or mixtures of these; In particular, alkali metal carbonate and / or amorphous alkali silicate, especially sodium silicate with a molar ratio of Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used. The content of sodium carbonate in the final preparations is preferably up to 40% by weight, advantageously between 2 and 35% by weight. The content of sodium silicate (without any special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.

In addition to the ingredients mentioned, the compositions may contain further known additives, for example salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, defoamers, small amounts of neutral filler salts and dyes and fragrances and the like.
Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. The content of the bleaching agents is preferably from 5 to 35% by weight and in particular up to 30% by weight, it being advantageous to use perborate monohydrate or percarbonate.

As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic 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 stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-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, 2,5-diacetoxy- 2,5-dihydrofuran and those from the German patent applications DE 19616693 A1 and DE 19616767 A1 known enol esters and acetylated sorbitol and mannitol or their in the European patent application EP 0525239 A1 mixtures described (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam, from the international patent applications WO 94/27970 . WO 94/28102 . WO 94/28103 . WO 95/00626 . WO 95/14759 and WO 95/17498 are known. The from the German patent application DE 19616769 A1 known hydrophilic substituted acyl acetals and in the German patent application DE 19616 770 as well as the international patent application WO 95/14075 Acyllactame described are also preferably used. Also from the German patent application DE 4443177 A1 known combinations of conventional bleach activators can be used. Such bleach activators are contained in the customary amount range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent. In addition to or in place of the conventional bleach activators listed above, those of the European patents EP 0446982 B1 and EP 0453 003 B1 be known sulphonic imines and / or bleach-enhancing transition metal salts or transition metal complexes as so-called bleach catalysts. Among the candidate transition metal compounds include in particular from German patent application DE 19529905 A1 known manganese, iron, cobalt, ruthenium or molybdenum-salene complexes and their from the German patent application DE 19620267 A1 known N-analogues derived from the German patent application DE 19536082 A1 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes which are described in the German patent application DE 196 05 688 described manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, which from the German patent application DE 19620411 A1 known cobalt, iron, copper and ruthenium-amine complexes, which in the German patent application DE 4416438 A1 manganese, copper and cobalt complexes described in the European patent application EP 0272030 A1 Cobalt complexes described in the European patent application EP 0693550 A1 known manganese complexes from the European Patent EP 0392592 A1 known manganese, iron, cobalt and copper complexes and / or in the European patent EP 0443651 B1 or the European patent applications EP 0458397 A1 . EP 0458398 A1 . EP 0549271 A1 . EP 0549272 A1 . EP 0544490 A1 and EP 0544519 A1 described manganese complexes. Combinations of bleach activators and transition metal bleach catalysts are for example from German patent application DE 19613103 A1 and the international patent application WO 95/27775 known. Bleach-enhancing transition metal complexes, in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25 wt .-% and particularly preferably from 0.01 wt .-% to 0.1 wt .-%, each based on the total agent used.

Suitable enzymes are, in particular, those from the class of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases carry in the laundry for the removal of stains, such as proteinaceous, fat or starchy stains, and Graying at. Cellulases and other glycosyl hydrolases can contribute to color retention and increase the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer. Particularly suitable are enzymatic agents obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof used. Since the different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of the cellulases can be used to set the desired activities. The enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation. The proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.

In addition to the mono- and polyfunctional alcohols, the agents may contain other enzyme stabilizers. For example, 0.5 to 1 wt .-% sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. In addition to calcium salts, magnesium salts also serve as stabilizers. However, the use of boron compounds, for example of boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H ₃ BO ₃ ), of metaboric acid (HBO ₂ ) and of pyroboric acid (tetraboric acid H ₂ B ₄ O ₇

Grayness inhibitors have the task to keep suspended from the fiber debris suspended in the fleet and so prevent the re-raising of the dirt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and other than the above-mentioned starch products can be used, eg degraded starch, aldehyde strengths, etc. Also, polyvinylpyrrolidone is useful. However, preference is given to cellulose ethers, such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and polyvinylpyrrolidone, for example, in amounts of from 0.1 to 5% by weight, based on the compositions, used.

The agents may contain as optical brighteners derivatives of Diaminostilbendisulfonsäure or their alkali metal salts. Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which are used in place of the morpholino Group a Diethanolaminogruppe, a methylamino group, an anilino group or a 2-Methoxyethylaminogruppe carry. Furthermore, brighteners of the substituted diphenylstyrene type may be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brightener can be used. Uniformly white granules are obtained when the means except the usual brighteners in conventional amounts, for example between 0.1 and 0.5 wt .-%, preferably between 0.1 and 0.3 wt .-%, even small amounts , For example, 10 ^-6 to 10 ^-3 wt .-%, preferably 10 to ⁵ wt .-%, of a blue dye. A particularly preferred dye is Tinolux® (commercial product of Ciba-Geigy).

Suitable soil repellents are those which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate being in the range from 50:50 to 90:10. More specifically, the molecular weight of the linking polyethylene glycol units is in the range of 750 to 5,000, that is, the degree of ethoxylation of the polymers containing polyethylene glycol groups may be about 15 to 100. The polymers are characterized by an average molecular weight of about 5000 to 200,000 and may have a block, but preferably a random structure. Preferred polymers are those having molar ratios of ethylene terephthalate / polyethylene glycol terephthalate of from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Further preferred are those polymers comprising linking polyethylene glycol units having a molecular weight of from 750 to 5,000, preferably from 1000 to about 3000 and a molecular weight of the polymer of about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhöne-Poulenc).

As defoamers waxy compounds can be used. "Waxy" is understood as meaning those compounds which have a melting point at atmospheric pressure above 25 ° C. (room temperature), preferably above 50 ° C. and in particular above 70 ° C. The waxy defoamer substances are practically insoluble in water, ie at 20 ° C. they have water in 100 g a solubility below 0.1 wt .-% on. In principle, all known from the prior art waxy defoamer substances may be included. Suitable waxy compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic esters of monohydric and polyhydric alcohols and paraffin waxes or mixtures thereof. Alternatively, it is of course also possible to use the silicone compounds known for this purpose.

Suitable paraffin waxes generally represent a complex mixture without a sharp melting point. For characterization is usually determined its melting range by differential thermal analysis (DTA), as in " The Analyst "87 (1962), 420 , described, and / or its solidification point. This is the temperature at which the paraffin passes from the liquid to the solid state by slow cooling. In this case, at room temperature completely liquid paraffins, that is those with a solidification point below 25 ° C, according to the invention not useful. For example, those can be used EP 0309931 A1 known paraffin wax mixtures of, for example, 26 wt .-% to 49 wt .-% microcrystalline paraffin wax having a freezing point of 62 ° C to 90 ° C, 20 wt .-% to 49 wt .-% hard paraffin with a solidification point of 42 ° C to 56 ° C and 2 wt .-% to 25 wt .-% soft paraffin with a solidification point of 35 ° C to 40 ° C. Preferably, paraffins or paraffin mixtures are used which solidify in the range of 30 ° C to 90 ° C. It should be noted that even at room temperature appearing paraffin wax mixtures may contain different proportions of liquid paraffin. In the case of the paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and is preferably completely absent. Thus, particularly preferred paraffin wax mixtures at 30 ° C have a liquid content of less than 10 wt .-%, in particular from 2 wt .-% to 5 wt .-%, at 40 ° C, a liquid content of less than 30 wt .-%, preferably from 5 Wt .-% to 25 wt .-% and in particular from 5 wt .-% to 15 wt .-%, at 60 ° C, a liquid content of 30 wt .-% to 60 wt .-%, in particular of 40 wt .-%. % to 55 wt .-%, at 80 ° C, a liquid content of 80 wt .-% to 100 wt .-%, and at 90 ° C, a liquid content of 100 wt .-% to. The temperature at which a liquid content of 100% by weight of the paraffin wax is reached is, in the case of particularly preferred paraffin wax mixtures, still below 85 ° C., in particular at 75 ° C. to 82 ° C. The paraffin waxes may be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.

Suitable bisamides as defoamers are those which are derived from saturated fatty acids containing 12 to 22, preferably 14 to 18, carbon atoms and alkylenediamines having 2 to 7 carbon atoms. Suitable fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof, such as those obtainable from natural fats or hardened oils, such as tallow or hydrogenated palm oil. Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine. Preferred diamines are ethylenediamine and hexamethylenediamine. Particularly preferred bisamides are Bismyristoylethylenediamine, Bispalmitoylethylendiamin, Bisstearoylethylendiamin and mixtures thereof and the corresponding derivatives of hexamethylenediamine.

Suitable carboxylic esters as defoamers are derived from carboxylic acids having 12 to 28 carbon atoms. In particular, they are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid. The alcohol portion of the carboxylic acid ester contains a monohydric or polyhydric alcohol having 1 to 28 carbon atoms in the hydrocarbon chain. Examples of suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut oil, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol and also ethylene glycol, glycerol, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol. Preferred esters are those of ethylene glycol, glycerol and sorbitan, wherein the acid portion of the ester is selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid. Candidate polyhydric alcohol esters include xylitol monopalmitate, pentarythritol monostearate, glycerol monostearate, ethylene glycol monostearate and sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate and mixed tallow alkyl sorbitan mono- and diesters. Useful glycerol esters are the mono-, di- or triesters of glycerol and said carboxylic acids, the mono- or diesters being preferred. Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glyceryl distearate are examples of this. Examples of suitable natural esters as defoamers are beeswax, which consists mainly of the esters CH ₃ (CH ₂ ) ₂₄ COO (CH ₂ ) ₂₇ CH ₃ and CH ₃ (CH ₂ ) ₂₆ COO (CH ₂ ) ₂₅ CH ₃ , and carnauba wax , which is a mixture of carnaubaic acid alkyl esters, often in combination with small amounts of free carnaubaic acid, other long chain acids, high molecular weight alcohols and hydrocarbons.

Suitable carboxylic acids as further defoamer compound are, in particular, behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid, and mixtures thereof, which are obtainable from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil. Preferred are saturated fatty acids having 12 to 22, in particular 18 to 22 C-atoms.

Suitable fatty alcohols as further antifoam compounds are the hydrogenated products of the fatty acids described.

Furthermore, dialkyl ethers may additionally be present as defoamers. The ethers may be asymmetric or symmetrical, ie containing two identical or different alkyl chains, preferably containing 8 to 18 carbon atoms. Typical examples are di-n-octyl ether, di-i-octyl ether and di-n-stearyl ether, particularly suitable are dialkyl ethers having a melting point above 25 ° C, in particular above 40 ° C.

Further suitable defoamer compounds are fatty ketones, which can be obtained by the relevant methods of preparative organic chemistry. For their preparation one starts, for example, from carboxylic acid magnesium salts, which are pyrolyzed at temperatures above 300 ° C with elimination of carbon dioxide and water, for example according to the German patent application DE 2553900 OS. Suitable fatty ketones are those prepared by pyrolysis of the magnesium salts of lauric, myristic, palmitic, palmitoleic, stearic, oleic, elaidic, petroselic, arachidic, gadoleic, behenic or erucic acid.

Further suitable defoamers are fatty acid polyethylene glycol esters, which are preferably obtained by basic homogeneously catalyzed addition of ethylene oxide to fatty acids. In particular, the addition of ethylene oxide to the fatty acids takes place in the presence of alkanolamines as catalysts. The use of alkanolamines, especially triethanolamine, results in extremely selective ethoxylation of the fatty acids, especially when it comes to producing low ethoxylated compounds. Within the group of fatty acid polyethylene glycol esters, preference is given to those which have a melting point above 25 ° C., in particular above 40 ° C.

Within the group of waxy defoamers, the paraffin waxes described are particularly preferably used alone as waxy defoamers or in admixture with one of the other waxy defoamers, wherein the proportion of paraffin waxes in the mixture is preferably more than 50% by weight, based on waxy defoamer mixture. The paraffin waxes can be applied to carriers as needed. As carrier material, all known inorganic and / or organic carrier materials are suitable. Examples of typical inorganic carrier materials are alkali metal carbonates, aluminosilicates, water-soluble phyllosilicates, alkali metal silicates, alkali metal sulphates, for example sodium sulphate, and alkali metal phosphates. The alkali metal silicates are preferably a compound having a molar ratio of alkali metal oxide to SiO _{2 of} from 1: 1.5 to 1: 3.5. The use of such silicates results in particularly good Komeigenschaften, in particular high abrasion stability and yet high dissolution rate in water. The aluminosilicates referred to as support material include, in particular, the zeolites, for example zeolite NaA and NaX. The compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass. Furthermore, silicates can be used, which are under the name Aerosil® or Sipernat® commercially. Suitable organic support materials are, for example, film-forming polymers, for example polyvinyl alcohols, polyvinylpyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch. Useful cellulose ethers are, in particular, alkali metal carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose and so-called cellulose mixed ethers, such as, for example, methylhydroxyethylcellulose and methylhydroxypropylcellulose, as well as their mixtures. Particularly suitable mixtures are composed of sodium carboxymethylcellulose and methylcellulose, wherein the carboxymethylcellulose usually has a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methylcellulose has a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit. The mixtures preferably contain alkali metal carboxymethylcellulose and nonionic cellulose ethers in weight ratios of from 80:20 to 40:60, in particular from 75:25 to 50:50. Native starch composed of amylose and amylopectin is also suitable as the carrier. Native starch is starch, as it is available as an extract from natural sources, such as rice, potatoes, corn and wheat. Native starch is a commercial product and thus easily accessible. As carrier materials, one or more of the abovementioned compounds can be used, in particular selected from the group of alkali metal carbonates, alkali metal sulphates, alkali metal phosphates, zeolites, water-soluble phyllosilicates, alkali silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch. Particularly suitable are mixtures of alkali metal carbonates, in particular sodium carbonate, alkali metal silicates, in particular sodium silicate, alkali metal sulphates, in particular sodium sulphate and zeolites.

Suitable silicones are customary organopolysiloxanes which may have a finely divided silica content, which in turn may also be silanated. Such organopolysiloxanes are for example in the European Patent Application EP 0496510 A1 described. Particularly preferred are polydiorganosiloxanes known in the art. However, compounds crosslinked via siloxane can also be used, as are known to the person skilled in the art under the name silicone resins. In general, the polydiorganosiloxanes contain finely divided silica, which may also be silanated. Particularly suitable are siliceous dimethyl polysiloxanes. Advantageously, the polydiorganosiloxanes have a Brookfield viscosity at 25 ° C in the range from 5,000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas. The silicones are preferably applied to support materials. Suitable carrier materials have already been described in connection with the paraffins. The support materials are usually in amounts of 40 to 90 wt .-%, preferably in amounts of 45 to 75 wt .-% - based on defoamer - included.

As perfume oils or fragrances, individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, α-isomethylionone and methyl cedryl ketone, the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.

The fragrances can be incorporated directly into the compositions of the invention, but it may also be advantageous to apply the fragrances on carriers, which enhance the adhesion of the perfume on the laundry and provide a slower fragrance release for long-lasting fragrance of the textiles. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.

If desired, the final preparations may also contain inorganic salts as fillers or leveling agents, such as, for example, sodium sulfate, which is preferably present in amounts of from 0 to 10, in particular from 1 to 5,% by weight, based on the composition.

Production of washing, rinsing and cleaning agents

The preparations obtainable using the surfactant granules according to the invention can, as already mentioned, be prepared or used in the form of powders, extrudates, granules or agglomerates. These may be both universal and fine or color detergents, if appropriate in the form of compactates or super compacts. For the preparation of such agents, the corresponding methods known from the prior art are suitable. Preferably, the agents are prepared by mixing together various particulate components containing detergent ingredients. The particulate components can be prepared by spray drying, simple mixing or complex granulation processes, for example fluidized bed granulation. It is preferred in particular that at least one surfactant-containing component is produced by fluidized bed granulation. Furthermore, it may be particularly preferred if aqueous preparations of the alkali silicate and of the alkali carbonate are sprayed together with other detergent ingredients in a drying device, wherein granulation can take place simultaneously with the drying.

In the drying device, in which the aqueous preparation is sprayed, it may be any dry equipment. In a preferred process, the drying is carried out as spray drying in a drying tower. The aqueous preparations are exposed in a known manner a drying gas stream in finely divided form. Patent publications by Henkel describe an embodiment of spray drying with superheated steam. The working principle disclosed therein is hereby expressly also made the subject of the present invention disclosure. Reference is made in particular to the following publications: DE 4030688 A1 as well as the further publications according to DE 4204035 A1 ; DE 4204090 A1 ; DE 4206050 A1 ; DE 4206521 A1 ; DE 4206495 A1 ; DE 4208773 A1 ; DE 4209432 A1 and DE 4234376 A1 , This process has already been presented in connection with the production of the defoamer com.

In another preferred variant, especially when agents of high bulk density are to be obtained, the mixtures are subsequently subjected to a compaction step, with further ingredients being added to the compositions only after the compaction step. The compaction of the ingredients takes place in a preferred embodiment of the invention in a press-agglomeration process. The pressing agglomeration process, to which the solid premix (dried base detergent) is subjected, can be realized in various apparatuses. Depending on the type of agglomerator used different Preßagglomerationsverfahren be distinguished. The four most common and preferred in the present invention Preßagglomerationsverfahren are the extrusion, the roll pressing or compaction, the hole pressing (pelletizing) and the tableting, so that in the present invention are preferred Preßagglomerationsvorgänge extrusion, Walzenkompaktierungs-, pelletizing or Tabletting operations are.

All methods have in common that the premix is compacted under pressure and plasticized and the individual particles are pressed together to reduce the porosity and adhere to each other. In all processes (in the case of tabletting with restrictions), the tools can be heated to higher temperatures or cooled to dissipate the heat generated by shearing forces.

In all methods, one or more binders can be used as an aid for compaction. However, it should be made clear that the use of several different binders and mixtures of different binders is always possible. In a preferred embodiment of the invention, a binder is used, that at temperatures up to 130 ° C, preferably up to 100 ° C and especially to 90 ° C is already completely present as a melt. The binder must therefore be selected depending on the process and process conditions or the process conditions, in particular the process temperature, must - if a particular binder is desired - be adapted to the binder.

The actual compression process is preferably carried out at processing temperatures which correspond at least in the compression step at least the temperature of the softening point, if not even the temperature of the melting point of the binder. In a preferred embodiment of the invention, the process temperature is significantly above the melting point or above the temperature at which the binder is present as a melt. In particular, however, it is preferred that the process temperature in the compression step is not more than 20 ° C above the melting temperature or the upper limit of the melting range of the binder. Although it is technically quite possible to set even higher temperatures; However, it has been found that a temperature difference to the melting temperature or to the softening temperature of the binder of 20 ° C in general is quite sufficient and even higher temperatures cause no additional benefits. Therefore, it is particularly preferred, especially for energetic reasons, to work above, but as close as possible to the melting point or at the upper temperature limit of the melting range of the binder. Such a temperature control has the further advantage that even thermally sensitive raw materials, such as peroxy bleach such as perborate and / or percarbonate, but also enzymes, can increasingly be processed without serious losses of active substance. The possibility of precise temperature control of the binder in particular in the decisive step of the compression, ie between the mixing / homogenization of the premix and the shaping, allows an energetically very favorable and extremely gentle for the temperature-sensitive components of the premix process, since the premix for a short time the is exposed to higher temperatures. In preferred Preßagglomationsverfahren the working tools of the Preßagglomerators (the worm (s) of the extruder, the roller (s) of the Walzenkompaktors and the press roll (s) of the pellet press) a temperature of at most 150 ° C, preferably at most 100 ° C and in particular at most 75th ° C and the process temperature is 30 ° C and in particular at most 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder. Preferably, the duration of the effect of temperature in the compression region of the pressing agglomerators is a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.

Preferred binders which can be used alone or in admixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols. The modified polyalkylene glycols include, in particular, the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols having a molecular weight between 600 and 12,000 and in particular between 1,000 and 4,000. Another group consists of mono- and / or disuccinates of the polyalkylene glycols in turn, relative molecular masses between 600 and 6,000, preferably between 1,000 and 4,000. For a more detailed description of the modified polyalkylene glycol ethers, refer to the disclosure of the international patent application WO 93/02176 directed. In the context of this invention, polyethylene glycols include polymers in the production of which, in addition to ethylene glycol, C ₃ -C ₅ glycols and also glycerol and mixtures thereof are used as starting molecules. Also included are ethoxylated derivatives such as trimethylolpropane having 5 to 30 EO. The polyethylene glycols preferably used may have a linear or branched structure, with particular preference being given to linear polyethylene glycols. Particularly preferred polyethylene glycols include those having molecular weights between 2,000 and 12,000, advantageously about 4,000, wherein polyethylene glycols having molecular weights below 3,500 and above 5,000, in particular in combination with polyethylene glycols having a molecular weight of about 4,000 can be used and Such combinations advantageously have more than 50% by weight, based on the total amount of polyethylene glycols, of polyethylene glycols having a molecular weight between 3,500 and 5,000. However, polyethylene glycols which are present in liquid state at room temperature and a pressure of 1 bar can also be used as binders; Here is mainly of polyethylene glycol with a molecular weight of 200, 400 and 600 the speech. However, these per se liquid polyethylene glycols should be used only in a mixture with at least one other binder, said mixture must meet the requirements of the invention again, ie must have a melting point or softening point of at least above 45 ° C. Likewise suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives of these having molecular weights of not more than 30,000. Preference is given here to molecular weight ranges between 3,000 and 30,000, for example around 10,000. Polyvinylpyrrolidones are preferably not used as sole binders but in combination with others. especially in combination with polyethylene glycols used.
The compacted material preferably has temperatures not exceeding 90 ° C. directly after leaving the production apparatus, temperatures between 35 and 85 ° C. being particularly preferred. It has been found that outlet temperatures - especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, are particularly advantageous.

In a preferred embodiment, the detergent according to the invention is prepared by means of an extrusion, as for example in the European Patent EP 0486592 B1 or the international patent applications WO 93/02176 and WO 94/09111 respectively. WO 98/12299 to be discribed. In this case, a solid premix is extruded under pressure extruded and cut the strand after exiting the hole shape by means of a cutting device to the predeterminable granule dimension. The homogeneous and solid premix contains a plasticizer and / or lubricant which causes the premix to be plastically softened and extrudable under the pressure of specific work. Preferred plasticizers and / or lubricants are surfactants and / or polymers. To explain the actual extrusion process, reference is hereby expressly made to the abovementioned patents and patent applications. Preferably, the pre-mixture is preferably supplied to a planetary roller extruder or a 2-screw extruder with co-rotating or counter-rotating screw guide, whose housing and its extruder granulating head can be heated to the predetermined extrusion temperature. Under the shearing action of the extruder screws, the premix under pressure, which is preferably at least 25 bar, at extremely high throughputs depending on the apparatus used but also may be below, compacted, plasticized, extruded in the form of fine strands through the hole die plate in the extruder head and finally Preferably, the extrudate is reduced by means of a rotating doctor blade to approximately spherical to cylindrical granules. The hole diameter of the hole nozzle plate and the strand cut length are matched to the selected granule dimension. Thus, the production of granules succeeds a substantially uniformly predictable particle size, in particular, the absolute particle sizes can be adapted to the intended use. In general, particle diameters of at most 0.8 cm are preferred. Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range of 0.5 to 5 mm and in particular in the range of about 0.8 to 3 mm. The length / diameter ratio of the chopped primary granules is preferably in the range from about 1: 1 to about 3: 1. Furthermore, it is preferable to supply the still plastic primary granules to a further shaping processing step; In this process, edges present on the raw extrudate are rounded, so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired, small amounts of dry powder, for example, zeolite powder, such as zeolite NaA powder, may be included in this stage. This shaping can be done in commercially available Rondiergeräten. It is important to ensure that only small amounts of fine grain content occur in this stage. Drying, which is described in the above-mentioned prior art documents as a preferred embodiment, is subsequently possible, but not absolutely necessary. It may just be preferable to stop drying after the compaction step. Alternatively, extrusions can also be carried out in low-pressure extruders, in the Kahl press (Amandus Kahl) or in the Bexx Bextruder. Preferably, the temperature control in the transition region of the screw, the pre-distributor and the nozzle plate is designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least achieved, but preferably exceeded. The duration of the action of temperature in the compression region of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.

The detergents according to the invention can also be prepared by means of roll compaction. Here, the premix is selectively metered between two smooth or provided with wells of defined shape rollers and rolled between the two rollers under pressure to form a sheet-like Kompaktat, the so-called scoop. The rollers exert a high line pressure on the premix and can be additionally heated or cooled as required. When using smooth rolls, smooth, unstructured flake tapes are obtained, while by using structured rolls, correspondingly structured flakes can be produced in which, for example, certain shapes of the later detergent particles can be specified. The sling strip is subsequently broken by a tee and crushing process into smaller pieces and can be processed in this way to granules, which can be refined by further known per se surface treatment method, in particular brought into approximately spherical shape. Also in the case of roll compaction, the temperature of the pressing tools, ie the rolls, is preferably not more than 150 ° C., preferably not more than 100 ° C. and in particular not more than 75 ° C. Particularly preferred production processes work in the case of roll compaction with process temperatures which are 10 ° C., in particular at most 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder. In this case, it is further preferred that the duration of the action of temperature in the compression region of the smooth rolls or rolls provided with depressions of defined shape amounts to a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.

The detergent according to the invention can also be produced by means of pelleting. Here, the premix is applied to a perforated surface and pressed by means of a pressure-emitting body under plasticization through the holes. In conventional embodiments of pellet presses, the premix is compacted under pressure, plasticized, pressed by means of a rotating roller in the form of fine strands through a perforated surface and finally comminuted with a knock-off device to granules. Here are the most diverse designs of pressure roller and perforated die conceivable. For example, flat perforated plates are used as well as concave or convex ring matrices, through which the material is pressed through one or more pressure rollers. The press rollers may also be conically shaped in the plate devices, in the annular devices can matrices and press roll (s) have co-rotating or opposite sense of rotation. An apparatus suitable for carrying out the method is described, for example, in German Offenlegungsschrift DE 3816842 A1 described. The ring die press disclosed in this document consists of a rotating ring die interspersed by press channels and at least one press roll operatively connected to its inner surface, which presses the material supplied to the die space through the press channels into a material discharge. In this case, ring die and pressing roller are drivable in the same direction, whereby a reduced shear stress and thus lower temperature increase of the premix can be realized. Of course, but also in the pelleting with heatable or coolable rolls to set a desired premix temperature. Also in pelleting, the temperature of the pressing tools, so the pressure rollers or press rolls, preferably at a maximum of 150 ° C, preferably at a maximum of 100 ° C and in particular at a maximum of 75 ° C. Particularly preferred production processes work in the case of roll compaction with process temperatures which are 10 ° C., in particular at most 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.

The production of moldings, preferably those in tablet form, is usually carried out by tabletting or press agglomeration. The resulting particulate Preßagglomerate can either be used directly as a detergent or aftertreated by conventional methods and / or processed. The usual post-treatments include, for example, powdering with finely divided ingredients of detergents or cleaners, whereby the bulk density is generally further increased. However, a preferred aftertreatment is also the procedure according to the German patent applications DE 19524287 A1 and DE 19547457 A1 in which dust-like or at least finely divided ingredients (the so-called fines) are adhered to the particulate process end products according to the invention, which serve as a core, and thus arise means which have these so-called fines as the outer shell. Advantageously, this is again done by melt agglomeration. For melt agglomeration of the fines on is expressly to the disclosure in the German patent applications DE 19524287 A1 and DE 19547457 A1 directed. In the preferred embodiment of the invention, the solid detergents are in tablet form, these tablets preferably having rounded corners and edges, in particular for storage and transport reasons. The base of these tablets may, for example, be circular or rectangular. Multi-layer tablets, especially tablets with 2 or 3 layers, which may also be different in color, are especially preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred. The tablets can also contain pressed and unpressed portions. Moldings having a particularly advantageous dissolution rate are obtained when the granular constituents before pressing have a proportion of particles which have a diameter outside the range from 0.02 to 6 mm of less than 20, preferably less than 10% by weight. A particle size distribution in the range from 0.05 to 2.0 and particularly preferably from 0.2 to 1.0 mm is preferred.

Examples

Production Example H1 . 100 g of cellulose (Technocel® 150) were mixed with 200 g of protein fatty acid condensate (Lamepon® SCE-B, 95% strength by weight, powder, Cognis Deutschland GmbH / DE) and compacted using a gear roller mill. Subsequently, a sieve fraction was taken between 1.2 and 1.6 mm.

Preparation Example H2. 1000 g of cellulose (Technocel® 150) were mixed with 300 g of protein fatty acid condensate (Lamepon® SCE-B), 200 g of cocoalkyl oligoglucoside (Glucopon® 600 CSUP, 50% by weight aqueous paste, Cognis Deutschland GmbH / DE) and 150 g of a polyethylene glycol wax having an average molecular weight of 4000 mixed in a mixer and the water content reduced by drying to 12 wt .-%. Subsequently, the extrusion was carried out at 45 ° C through a sieve plate (diameter of the holes: 2 mm). The crude product was crushed and removed a sieve fraction between 1.2 and 1.6 mm.

Production Example H3 . 100 g of cellulose (Technocel® 150) were mixed with 100 g of protein fatty acid condensate (Lamepon® SCE-B) and 20 g of coconut alkyl sulfate sodium salt (Sulfopon® 1218 G, residual water content 5 wt .-%, Cognis Germany GmbH / DE)) and a Gear wheelchair compacted. Subsequently, a sieve fraction was taken between 1.2 and 1.6 mm.

Comparative Example C1 . Surfactant granules consisting of 50% by weight of protein fatty acid condensate (Lamepon® SCE-B), 5% by weight of cocoalkyl sulfate sodium salt, 5% by weight of sodium carbonate, 10% by weight of sodium silicate and 30% by weight of sodium sulfate; Sieve fraction between 1.2 and 1.6 mm.

Comparative Example V2 . Surfactant granules consisting of 95% by weight of protein fatty acid condensate (Lamepon® SCE-B), sieve fraction between 1.2 and 1.6 mm.

Application testing . A quantity of the granulate, corresponding in each case 10 g of surfactant, was added with constant stirring in 1 l of water (15 ° C.). The solution was filtered through a sieve (mesh size: 0.2 mm) after 30 s (T1), 60 s (T2) and 180 s (T3). The filter residue was washed briefly with acetone, dried and then weighed. The results are summarized in Table 1: <b><u> Table 1 </ u></b> Dissolution rate (s) of surfactant granules V1 V2 H1 H2 H3 Quantity - T0 [g] 13 12 16 39 40 Backlog - T1 [g] 12 11 6 1 1 Residue - T2 [g] 10 9 1 0 0 Backlog - T3 [g] 5 6 0 0 0

Claims (6)

1. A process for the production of surfactant granules with an improved dissolving rate in which surface-active protein hydrolyzates and/or protein fatty acid condensates are granulated and compacted in the presence of disintegrators.
2. A process as claimed in claim 1, characterized in that the proteins and/or protein derivatives are used together with anionic and/or nonionic surfactants.
3. A process as claimed in at least one of claims 1 to 2, characterized in that the proteins and/or protein derivatives on the one hand and the anonic and/or nonionic surfactants on the other hand are used in a ratio by weight of 1:10 to 10:1.
4. A process as claimed in at least one of claims 1 to 3, characterized in that the proteins and/or protein derivatives are used in the form of water-containing pastes or dry solids.
5. A process as claimed in at least one of claims 1 to 4, characterized in that disintegrators selected from the group consisting of polysaccharides, polyvinyl pyrrolidone, polyurethanes, polyacrylates, polyethylene glycols, Kollidon, alginic acids, alginates and layer silicates are used.
6. A process as claimed in at least one of claims 1 to 5, characterized in that the proteins and/or protein derivatives and the disintegrators are used in a ratio by weight of 1:10 to 10:1, based on their solids contents.