DE19946342A1 - Shaped body with improved water solubility - Google Patents

Abstract

Shapes are proposed with improved water solubility, containing surface-active compounds and disintegrants, which are distinguished by the fact that they contain additives which consist of anionic surfactants as the core and a layer enveloping them, with the proviso that the coating substances at 20 ° C. have a water solubility of at least Have 10 g / l.

Description

Field of the Invention

The invention is in the field of solid washing, rinsing and cleaning agents and relates to new moldings with improved water solubility, which are characterized by a content of disintegrants and special coated anionic surfactants. A method is also claimed Production of the moldings which are particularly suitable for tablet production.

State of the art

So far, granules of anionic surfactants, such as. B. sodium lauryl sulfate, either by drying the corresponding aqueous solutions or pastes or by direct neutralization of the acidic ones Precursors of the surfactant, usually the sulfonic acids or sulfuric acid semiesters. Fluid bed drying, spray mixing, for example, are suitable for the production of the solids drive, as well as drying in the thin layer. Common to these processes is the task, Pro products with a high surfactant content in order to wash, To be able to add detergents and cleaning agents. Thereby, in the solids, which are preferably granules, both water-soluble (e.g. sodium sulfate) and water-insoluble Liche (e.g. zeolite) aggregates incorporated, which serve as a carrier. Also other additives, such as e.g. B. defoamers, builders and the like can also be used. As a result of the manufacturing process Ren of the prior art, the additives during the shaping, ie for example in the manufacture of tablets, essentially homogeneously distributed [cf. e.g. B. WO 94/18291, WO 94/18293 (Henkel)]. Detergent of this type are none in their properties completely satisfactory, but show a strong tendency to stick and - especially when Introducing into the dosing chamber of a washing machine - a low solubility in cold water.

The object of the present invention was therefore to create new moldings, especially tablets for detergents, dishwashing detergents and cleaning agents, based on anionic surfactants have a lower tendency to stick during manufacture and at the same time are characterized by a  improved solubility, especially in the dosing chamber of washing machines and in cold water water, or in which the proportion of disintegrants are reduced with the same solubility can.

Description of the invention

The invention relates to moldings with improved water solubility, containing surface Chenactive compounds and disintegrants, which are characterized in that they ent additives hold, which consist of anionic surfactants as the core and a layer enveloping them, with the proviso that the coating substances have a water solubility of at least 10 g / l at 20 ° C.

Surprisingly, it was found that with the use of coated anion tensi let the tablets be produced that dissolve so quickly compared to comparable products on the market Show that they are no longer in the drum, but directly over the wash-in chamber of the wash machine can be metered. The tablets also have a reduced production Stickiness, so that the amount of disintegrants is reduced compared to conventional products that can.

Anionic surfactant compounds

Typical examples of anionic surfactants, which form the core of the coated additives, are Soaps, alkyl benzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfo nate, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ethers 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 carbon acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyloli goglucoside sulfates, protein fatty acid condensates (especially vegetable products based on wheat) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these have a conventional, but preferably a narrowed homolog distribution. Before alkyl sulfates, alkyl benzene sulfonates, olefin sulfonates, methyl ester sulfonates and de coated mixtures. The proportion of anionic surface-active compounds in the Zu Substitutes (= core) can be 20 to 99, preferably 50 to 95 and in particular 85 to 90% by weight wear.  

Preferred alkylbenzenesulfonates 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 for a phenyl radical and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, Alkanolammonium or Glucammonium stands. Of these, dodecylbenzene is particularly suitable sulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in Form of sodium salts.

Alkyl and / or alkenyl sulfates, which are also often referred to as fatty alcohol sulfates, are to be understood as meaning 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 represents} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and Y represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl sulfates that can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, arylselyl alcohol, elaidyl alcohol Gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis. The sulfation products can preferably be used in the form of their alkali salts and in particular their sodium salts. 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 are particularly preferred. In the case of branched primary alcohols are Oxoalko hole, as z. B. accessible by reaction of carbon monoxide and hydrogen to alpha-olefins by the shop process. Such alcohol mixtures are commercially available under the trade name Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®. Another possibility are oxo alcohols, such as those obtained after the classic Enichema or Condea oxo process by adding 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®.

Water soluble compounds

The additives contain the substances enveloping the anionic surfactant grain - based on solids - preferably in total amounts from 1 to 25, preferably from 5 to 20 and in particular from 10 to 15 % By weight. These coating substances are preferably compounds which have a Have water solubility at 20 ° C of at least 50 g / l and in particular 100 g / l and before sometimes have other properties useful for the overall formulation, such as the complexation of hardness and heavy metal ions. Alternatively, the coating can also from the melt as long as the coating substances after drying the required water have solubility.

In a first embodiment of the invention, these envelopes can be salts ganic mineral acids. Typical examples are the alkali and / or alkaline earth salts, alumi nium or zinc salts of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid and Silica, in particular the alkali sulfate, alkali borates and perborates, the various alkali silicates ("water glasses") and alkali phosphates should be mentioned. Typical examples are Magne sodium sulfate heptahydrate or borax.

The salts of organic carboxylic acids are also suitable. Typical examples are the alkali and / or alkaline earth metal salts, aluminum or zinc salts of monocarboxylic acids with 1 to 22 carbon atoms, as there are formic acid, acetic acid, propionic acid, butyric acid, valeric acid, Ca pronic acid, caprylic acid, 2-ethylhexanoic acid. The use of sodium acetate is particularly preferred. Instead of the monocarboxylic acids, corresponding C ₂ -C ₆ dicarboxylic acids can also be used, so that the corresponding salts of succinic acid, maleic acid, fumaric acid, glutaric acid and adipic acid come into question as suitable coating substances in the same way as above. Finally, salts of hydroxy-functionalized polyvalent carboxylic acids can also be used, such as. B. the above salts of malic acid, tartaric acid and especially citric acid. The use of alkali metal citrates is particularly preferred here.

The third group of suitable coating substances are the water-soluble polymers, in which de for example, protein hydrolyzates, polyamides, polyacrylates and polyurethanes can. Urea and polyurea are also suitable. Saccharides and Polysaccharides such as e.g. B. sucrose, maltose or starch hydrolysates.

The moldings can contain the coated anionic surfactants in amounts of 1 to 50, preferably 5 to 35 and in particular 10 to 20 wt .-% - based on the moldings.  

Preparation of the coated anionic surfactants

The coated anionic surfactants can be manufactured using processes that are already in production of detergents are known and are the subject of a further patent application by the applicant. Basically, the anionic surfactant grain is first dried and optionally granulated tion of a corresponding aqueous solution or paste, which is then mixed with an aqueous Solution of the coating substance is brought into contact. This is preferably done at higher temperatures the coating substance is deposited on the grain and it is very important closes. Generally speaking, the production of the coated anionic surfactants takes place in such a way that one first dries an aqueous solution or paste of the anionic surfactant and on which bil the grain precipitates an envelope substance from an aqueous solution or melt if while the water evaporates. It is of course immediately clear that the process has one stage or can be carried out in two stages. In the latter case, you first become a corresponding ten Dry the sid solution or paste and the dried powder, which in turn is also can trade a conventional market product, then coat. In the one-stage, preferably two This continuous process is either the aqueous surfactant solutions or pastes or the dried surfactant powder used together with the coating agents.

In the drying device into which the surfactant solutions or pastes are introduced, preferably ver sprayed, it can be any drying equipment. In a process the drying is carried out as spray drying in a drying tower. This will be watery Solutions or pastes in a known manner a drying gas stream in finely divided form puts. Anionic surfactant powders are obtained, which are then combined with the required in a second step Amount of the coating substances are intimately mixed in the form of an aqueous solution. For this operation are components such as paddle mixers from Lödige or in particular spray mixers from Schugi, where the anionic surfactant powder is placed in the mixing chamber and the aqueous solutions of the envelopes are sprayed on. It is also possible to dry the anionic surfactant solution solutions or pastes and the mixing simultaneously in a fluidized bed dryer.

A particularly preferred possibility is the aqueous surfactant precursors of a vortex layer granulation ("SKET" granulation). Below is a granulation below to understand simultaneous drying, which is preferably carried out batchwise or continuously. there the anionic surfactants can be used both in the dried state and as an aqueous preparation become. The aqueous solutions or melts of the envelopes are simultaneously or after introduced into the fluidized bed via one or more nozzles. Preferably one is about a nozzle into a fluidized bed that is approximately filled with seed material blow in and dose the envelopes via a second nozzle. This corresponds to a continuous one solid / liquid production, however, presupposes that dried anionic surfactant powder already  is present. The process can also be carried out continuously in liquid / liquid form. In this case it is but make sure that the aqueous surfactant precursors at such a high temperature is brought that the droplets are dried immediately after leaving the nozzle without however, the surfactant decomposes. Conversely, the envelopes, especially the aqueous solutions, must be used in a be injected at such a low temperature that they do not drop off immediately after leaving the nozzle dry, but can deposit on the anionic surfactant grain. The necessary Be conditions depend in particular on the cross-section of the system and can be carried out by a specialist routine optimization can be found.

Fluidized bed apparatuses which are preferably used have base plates with dimensions of 0.4 to 5 m. The granulation is preferably carried out at fluidizing air speeds in the range from 1 to 8 m / s carried out. The granules are preferably discharged from the fluidized bed in one size classification of the granules. The classification can, for example, by means of a screening device or by an opposite air flow (classifier air), which is regulated so that only particles from a certain particle size removed from the fluidized bed and smaller particles in the vortex layer can be withheld. The inflowing air usually settles out of the heated or unheated classifier air and the heated bottom air together. The soil air temperature is there between 80 and 400, preferably 90 and 350 ° C. Advantageously, at the beginning of the granule a starting mass, for example an anionic surfactant granulate from an earlier test batch, submitted. In the fluidized bed, the water evaporates from the emulsions or dispersions Dried to dried germs are formed, which are coated with further amounts of defoamer, granular be dried and again dried at the same time. As already explained, you can the aqueous solutions can also be used together with the surfactant precursors, but this can do so cause some of the coating materials to land in the grain and the coating of the grain is incomplete. This may be sufficient for the intended effect in some cases, but it is more advantageous only supply the aqueous solutions to the granulation towards the end of the drying process in order to ensure that the grain is coated very substantially. In this context, the Teaching of the German patent applications DE 43 03 211 A1 and DE 43 03 176 A1 referenced, their In is hereby expressly included. For the purposes of the invention, agglomerates can also be used be set, which arise from caking of the granules.

Explosives

The term disintegrant is to be understood as meaning substances which are added to the moldings in order to accelerate their decay when brought into contact with water. Overviews can be found e.g. B. in J. Pharm. Sci. 61 (1972) or Römpp Chemielexikon, 9th edition, volume 6, p. 4440. The explosives can be homogeneously distributed in the molded body when viewed macroscopically, microscopically  however, due to the manufacturing process, they form zones of increased concentration. Among the preferred explosives agents include polysaccharides, such as. B. 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 (carboxymethyl cellulose, microcrystalline cellulose), polyvinyl pyrrolidone, collidone, alginic acid and their alkali salts, amorphous or also partially crystalline layered silicates (bentonites), polyurethanes, Polyethylene glycols and gas generating systems. Other explosives in the sense of the invention can be present, for example, the publications WO 98/40462 (Rettenmeyer), WO 98/55583 and WO 98/55590 (Unilever) and WO 98/40463, DE 197 09 991 and DE 197 10 254 (Henkel) refer to. Reference is expressly made to the teaching of these writings. The moldings the disintegrants can be used in amounts of 0.1 to 25, preferably 1 to 20 and in particular 5 to 15 % By weight - based on the moldings.

Production of the moldings

The molded articles are generally produced by tableting or press agglomeration. The Particulate press agglomerates obtained can either be used directly as detergents or be after-treated and / or prepared beforehand using customary methods. To the usual Nachbe Actions include, for example, powdering with finely divided ingredients from washing or cleaning agents agents, whereby the bulk density is generally further increased. A preferred afterbe act, however, also represents the procedure according to the German patent applications DE 195 24 287 A1 and DE 195 47 457 A1, wherein dusty or at least finely divided ingredients (the so-called fine fractions) to the particulate process produced according to the invention Products that serve as the core, are glued on and thus create means that these so-called have called fine particles as the outer shell. This is advantageously done by a Melt agglomeration. For melting agglomeration of the fine fractions, reference is expressly made to the Of referenced in German patent applications DE 195 24 287 A1 and DE 195 47 457 A1. In in the preferred embodiment of the invention, the solid detergents are in tablet form, these tablets preferably in particular for storage and transport reasons have rounded corners and edges. The base of these tablets can be circular, for example mig or rectangular. Multilayer tablets, especially tablets with 2 or 3 layers, wel che can also be different in color, are particularly preferred. Blue-white or green-white or cyan-white tablets are particularly preferred. The tablets can also be pressed and contain unpressed parts. Shaped body with a particularly advantageous dissolution speed who obtained when the granular components of the coated anionic surfactants before pressing 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 wt .-%. A particle size is preferred External distribution in the range from 0.05 to 2.0 and particularly preferably from 0.2 to 1.0 mm.  

Auxiliaries and additives

Other preferred ingredients of the shaped bodies according to the invention are inorganic and organic cal builder substances, whereby as inorganic builder substances mainly zeolites, crystalline Layered silicates and amorphous silicates with builder properties and - where permitted - also phosphates how tripolyphosphates are used. The builder substances are preferably in the final units riding in amounts of 10 to 60 wt .-% - based on the funds - included. If the fabrics what If they are water-soluble, they can also be used as coating materials for the inclusion of the surfactant grain. This applies, for example, to the silicates, dextrins, polyacrylates and match too.

The fine crystalline, synthetic and bound water-containing zeolite which is frequently used as a detergent builder is preferably zeolite A and / or P. As zeolite P, for example, zeolite MAP (R) (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P and Y are also suitable. Of particular interest is also a cocrystallized sodium / potassium aluminum silicate made of zeolite A and zeolite X, which is sold as VEGOBOND AX® (commercial product from Condea Augusta S. pA) is commercially available. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. 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% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. 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.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 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 Is 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A1. 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, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171. Further suitable layered silicates are known, for example, from patent applications DE 23 34 899 A1, EP 0026529 A1 and DE 35 26 405 A1. Their usability is not limited to a special 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 e.g. B. those of the general formulas

(OH) ₄ Si _8-y Al _y (Mg _x Al _4-x ) O ₂₀ Montmorrilonite
(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 can be incorporated into the crystal lattice of the layered silicates according to the above formulas. Furthermore, due to their ion-exchanging properties, the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na ⁺ and Ca ²⁺ . The amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing. Usable layered silicates are known for example from US 3,966,629, US 4,062,647, EP 0026529 A1 and EP 0028432 A1. Layer silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.

The preferred builder substances also include amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ 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 delayed release and have secondary washing properties. The release delay 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 degrees units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide 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 44 00 024 A1. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray morphous silicates.

It goes without saying that the generally known phosphates are also used as builder substances possible if such use should not be avoided for ecological reasons. Ge the sodium salts of orthophosphates, pyrophosphates and in particular are particularly suitable  the tripolyphosphate. Their content is generally not more than 25% by weight, 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 agents, in combination with other builder substances for a synergistic improvement of secondary washing power.

Useful organic builders are, for example, those in the form of their sodium salts settable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, wine acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use ecological reasons are not objectionable, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, wine acid, sugar acids and mixtures of these. The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of acidifying component and thus also serve to set a lower and milder pH value of Detergents or cleaning agents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

Other 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 processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with 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 with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30,000 can be used. A preferred dextrin is described in British patent application GB 9419091 A1. 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 processes for their preparation are known, for example, from European patent applications EP 0232202 A1, WO EP 0427349 A1, EP 0472042 A1 and EP 0542496 A1 and international patent applications 92/18542, WO 93/08251, WO 93/16110, WO 94 / 28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known. An oxidized oligosaccharide according to German patent application DE 196 00 018 A1 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably wise ethylenediamine disuccinate. Glyce are also particularly preferred in this context rindisuccinate and glycerol trisuccinate, as described, for example, in the US patent publications US 4,524,009, US 4,639,325, in European patent application EP 0150930 A1 and Japanese patent application JP 93/339896. Suitable amounts are in Formulations containing zeolite and / or silicate at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which have at least 4 Contain carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO 95120029 wrote.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid and measured against polystyrene sulfonic acid). Suitable copolymeric poly Carboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or Methacrylic acid with maleic acid. Copolymers of acrylic acid have been found to be particularly suitable Maleic acid proven to contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Their relative molecular weight, based on free acids, is generally from 5,000 to 200,000 preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (each measured against Po lystyrene sulfonic acid). The (co) polymeric polycarboxylates can either be as a powder or as an aqueous Solution are used, with 20 to 55 wt .-% aqueous solutions are preferred. Granules Polymers are usually mixed into one or more basic granules afterwards. In particular Biodegradable polymers made from more than two different mono are also particularly preferred mer units, for example those which according to DE 43 00 772 A1 as monomers salts of acrylic acid re and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE 42 21 381 C2 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives. Other preferred copolymers are those described in German patent applications DE 43 03 320 A1 and DE 44 17 734 A1 are described and as monomers preferably acrolein and acrylic have acid / acrylic acid salts or acrolein and vinyl acetate. Are also preferred as others Builder substances include polymeric aminodicarboxylic acids, their salts or their precursors call. Polyaspartic acids or their salts and derivatives are particularly preferred.

Other suitable builder substances are polyacetals, which are reacted with dialdehydes Polyolcarboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups for example as described in European patent application EP 0280223 A1 can. Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalalde  hyd and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid re received.

In addition, the agents can also contain components that make the oil and fat washable made of textiles. The preferred oil and fat dissolving components include for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose a proportion of methoxyl groups from 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and those from the prior art Polymers of phthalic acid and / or terephthalic acid or their derivatives known in the art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.

Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses, which have no outstanding builder properties, or mixtures of these; in particular, alkali carbonate and / or amorphous alkali silicate, especially sodium silicate with a molar ratio Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably of 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 in the agents (without 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 agents can be further known, in washing, rinsing and cleaning additives typically used, for example salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filling salts and color and contain fragrances, opacifiers or pearlescent agents.

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 which 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. The bleaching agent content of the agents is preferably from 5 to 35% by weight and in particular up to 30% by weight, advantageously using per borate monohydrate or percarbonate.

As bleach activators, compounds which are aliphatic under perhydrolysis conditions oxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or ge optionally substituted perbenzoic acid result, are used. Substances that are suitable  O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl carry groups. Multi-acylated alkylenediamines, in particular tetraacetylethylene, are preferred diamine (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 phenol sulfonates, especially n-nonanoyl or isononanoyl oxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5- dihydrofuran and those from German patent applications DE 196 16 693 A1 and DE 196 16 767 A1 known enol esters as well as acetylated sorbitol and mannitol or their in the European The patent application EP 0525239 A1 describes mixtures (SORMAN), acylated sugars derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaa cetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N- acylated lactams, for example N-benzoylcaprolactam, which are known from international patent applications gen WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498 are known. The hydrophilic sub. Known from German patent application DE 196 16 769 A1 substituted acylacetals and those in German patent application DE 196 16 770 and the internatio Nale patent application WO 95/14075 described acyllactams are also preferably used puts. The combinations known from German patent application DE 44 43 177 A1 conventional bleach activators can be used. Such bleach activators are common Quantity range, preferably in amounts from 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total average. In addition to the conventional ones listed above Len bleach activators or in their place can also those from the European patent specifications EP 0446982 B1 and EP 0453003 B1 known sulfonimines and / or bleaching enhancers transition metal salts or transition metal complexes as so-called bleaching catalysts be included. The transition metal compounds in question include in particular those Manganese, iron, cobalt, rutheni known from German patent application DE 195 29 905 A1 um or molybdenum salt complexes and those from German patent application DE 196 20 267 A1 Known N-analog connections, which is known from German patent application DE 195 36 082 A1 manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, which in the German Patent application DE 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, Titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, derived from the German Patent application DE 196 20 411 A1 known cobalt, iron, copper and ruthenium amine complexes, the manganese, copper and cobalt described in German patent application DE 44 16 438 A1 Complexes described in the European patent application EP 0272030 A1 cobalt Complexes, the manganese complexes known from European patent application EP 0693550 A1, the manganese, iron, cobalt and copper known from European patent EP 0392592 A1 fer complexes and / or those 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 bleaching catalysts are, for example, from the German patent application DE 196 13 103 A1 and the international patent application WO 95/27775 are known. Bleaching enhancer Transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are in usual amounts, preferably in an amount up to 1 wt .-%, especially of 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the entire mean.

Enzymes in particular come from the class of hydrolases, such as proteases, Estera sen, lipases or lipolytic enzymes, amylases, cellulases or other glyco sylhydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases carry in the Laundry for removing stains, such as stains containing protein, fat or starch, and Graying at. Cellulases and other glycosyl hydrolases can be removed by removing pilling and microfibrils help to maintain color and increase the softness of the textile. To bleach or to inhibit color transfer, oxidoreductases can also be used. Especially from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens enzymatic active ingredients obtained. Preferably who the proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus the, used. There are enzyme mixtures, for example from protease and amylase or Pro tease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipoly enzymes or protease having a table action, lipase or enzymes and cellulase having a lipolytic action, in particular, however, protease- and / or lipase-containing mixtures or mixtures with lipolytic acting enzymes of particular interest. Examples of such lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also been found in some cases proven. Suitable amylases include in particular α-amylases, iso-amylases, pul lulanases and pectinases. Cellobiohydrolases, endoglucanases are preferably used as cellulases and β-glucosidases, which are also called cellobiases, or mixtures thereof. Because the different cellulase types differ in their CMCase and avicelase activities the desired activities can be set by targeted mixtures of the cellulases. The enzymes can be adsorbed on carriers and / or embedded in coating substances around them protect against premature decomposition. The percentage of enzymes, enzyme mixtures or enzyme Granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

In addition to the mono- and polyfunctional alcohols, the agents can contain further enzyme stabilizers. For example, 0.5 to 1% by weight 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 boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous. . Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. For this purpose, what are water-soluble colloids mostly organic in nature are suitable, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Furthermore, soluble starch preparations and other starch products than those mentioned above can be used, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the detergent, are preferred , used.

The agents can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyle type may be present, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4'- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. Uniform white granules are obtained if the agents, in addition to the usual brighteners, are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, even small amounts , for example 10 ^-6 to 10 ^-3 wt .-%, preferably around 10 ^-5 wt .-%, of a blue dye. A particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).

Suitable soil-repellants are substances which preferably Contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio Ethylene terephthalate to polyethylene glycol terephthalate can range from 50:50 to 90:10. The molecular weight of the linking polyethylene glycol units is in particular in the range of 750 to 5000, d. that is, the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 up to 100. The polymers have an average molecular weight of about 5000 to 200,000 and can have a block, but preferably a random structure. Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Next  preferred are those polymers which link polyethylene glycol units with one mole molecular weight from 750 to 5000, preferably from 1000 to about 3000 and a molecular weight of Have polymers from about 10,000 to about 50,000. Examples of commercially available polymers are Products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).

Wax-like compounds can be used as defoamers. As "waxy" sol che understood compounds that have a melting point at atmospheric pressure above 25 ° C (room temperature temperature), preferably above 50 ° C and in particular above 70 ° C. The waxy Ent foaming agents are practically insoluble in water, d. H. at 20 ° C in 100 g of water solubility below 0.1% by weight. In principle, all known from the prior art wax-like defoamer substances can be included. Suitable wax-like compounds are in for example bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohol len as well as paraffin waxes or mixtures thereof. Alternatively, of course, you can also use them Purpose known silicone compounds are used.

Suitable paraffin waxes are generally a complex mixture of substances without a sharp one Melting point. For characterization, one usually determines its melting range by Differential thermal analysis (DTA) as described in "The Analyst" 87 (1962), 420, and / or his Freezing point. This is the temperature at which the paraffin slowly slows down cooling changes from the liquid to the solid state. Thereby are complete at room temperature liquid paraffins, that is to say those with a solidification point below 25 ° C., are not according to the invention useful. For example, the Paraf known from EP 0309931 A1 can be used finwax mixtures of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax a solidification point of 62 ° C to 90 ° C, 20 wt .-% to 49 wt .-% hard paraffin with a solid point of 42 ° C to 56 ° C and 2 wt .-% to 25 wt .-% soft paraffin with a solidification point from 35 ° C to 40 ° C. Paraffins or paraffin mixtures are preferably used, which in Solidify the range from 30 ° C to 90 ° C. It should be noted that it is solid even at room temperature Apparent paraffin wax mixtures can contain different proportions of liquid paraffin. In the paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible Lich and preferably completely missing. For example, particularly preferred paraffin wax mixtures at 30 ° C a liquid content of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C. Liquid content of less than 30% by weight, preferably from 5% by weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular from 40% by weight to 55% by weight, at 80 ° C. a liquid fraction from 80% by weight to 100% by weight, and at 90 ° C a liquid content of 100 wt .-%. The temperature at which a liquid content of 100% by weight of the paraffin wax is reached, is still particularly preferred paraffin wax mixtures below 85 ° C, especially at 75 ° C to 82 ° C. The paraffin waxes can be petrolatum, act microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.  

Suitable bisamides as defoamers are those which differ from saturated fatty acids with 12 to 22, preferably derived from 14 to 18 carbon atoms and from alkylenediamines with 2 to 7 carbon atoms. Appropriate nete fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof, such as it is obtained from natural fats or hardened oils, such as tallow or hydrogenated palm oil are. Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethy lendiamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine. Before pulled diamines are ethylenediamine and hexamethylenediamine. Bisamides are particularly preferred Bismyristoylethylenediamine, bispalmitoylethylenediamine, bisstearoylethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine.

Suitable carboxylic acid esters as defoamers are derived from carboxylic acids with 12 to 28 carbon atoms. In particular, these 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 mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain. Examples of suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 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, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid. Suitable esters of polyvalent alcohols include xylitol monopalmitate, Pentarythritmonostearat, monostearate of glycerol, ethylene glycol and rat sorbitan, sorbitan Sorbitanmonolau, Sorbitandilaurat, sorbitan, sorbitan dioleate, and sorbitan mixed tallow and diesters. Glycerol esters which can be used are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred. Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this. Examples of suitable natural esters as defoamers are beeswax, which mainly consists 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 a further defoamer compound are in particular behenic acid, stea rinic acid, oleic acid, palmitic acid, myristic acid and lauric acid as well as their mixtures as they are natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil are. Saturated fatty acids with 12 to 22, in particular 18 to 22, carbon atoms are preferred.

Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of be written fatty acids.  

Dialkyl ethers may also be present as defoamers. The ethers can be asym be constructed metrically or symmetrically, d. H. two identical or different alkyl chains preferably contain 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 which have a melting point above Have 25 ° C, especially above 40 ° C.

Other suitable defoamer compounds are fatty ketones, which are based on the relevant methods of preparative organic chemistry can be obtained. One goes to their manufacture example of carboxylic acid magnesium salts, which at temperatures above 300 ° C below Elimination of carbon dioxide and water are pyrolyzed, for example according to the German Publication DE 25 53 900 OS. Suitable fat ketones are those obtained by pyrolysis of the Ma magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, Elaidic acid, petroselinic acid, arachic acid, gadoleic acid, behenic acid or erucic acid become.

Other suitable defoamers are fatty acid polyethylene glycol esters, preferably by ba sisch homogeneously catalyzed addition of ethylene oxide to fatty acids can be obtained. In particular Ethylene oxide is added to the fatty acids in the presence of alkanolamines as catalyzes sators. The use of alkanolamines, especially triethanolamine, leads to an extremely selective one Ethoxylation of the fatty acids, especially when it comes to low ethoxylated verbin to manufacture Within the group of fatty acid polyethylene glycol esters, those before moves that have a melting point above 25 ° C, especially above 40 ° C.

Within the group of wax-like defoamers, the paraffin waxes described are particularly preferably used alone as wax-like defoamers or in a mixture with one of the other wax-like defoamers, the proportion of paraffin waxes in the mixture preferably making up more than 50% by weight, based on the wax-like defoamer mixture . The paraffin waxes can be applied to carriers if necessary. All known inorganic and / or organic carrier materials are suitable as carrier materials. Examples of typical inorganic carrier materials are alkali metal carbonates, aluminum silicates, water-soluble sheet silicates, alkali metal silicates, alkali metal sulfates, for example sodium sulfate, and alkali metal phosphates. The alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO ₂ of 1: 1.5 to 1: 3.5. The use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water. The aluminosilicates referred to as carrier 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. Silicates which are commercially available under the name Aerosil® or Sipemat® can also be used. Examples of suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch. Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof. Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit. The mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ether in weight ratios of 80:20 to 40:60, in particular 75: 25 to 50:50. Also suitable as a carrier is native starch, which is composed of amylose and amylopectin. Starch is called native starch, as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat. Native starch is a commercially available product and is therefore easily accessible. Carrier materials which can be used individually or more than one of the abovementioned compounds, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, cellulose ethers, polyacrylate polymethacrylate and starch. Mixtures of alkali carbonates, in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate and zeolites are particularly suitable.

Suitable silicones are conventional organopolysiloxanes, which contain finely divided silica in turn can also be silanized. Such organopolysiloxanes are, for example described in European patent application EP 0496510 A1. Are particularly preferred Polydiorganosiloxanes, which are known from the prior art. But it can also use siloxane cross-linked compounds are used, as they are known to the person skilled in the art under the name of silicon har ze are known. As a rule, the polydiorganosiloxanes contain finely divided silica, which is also sila can be kidneyed. Silica-containing dimethylpolysiloxanes are particularly suitable. Advantageously the polydiorganosiloxanes have a Brookfield viscosity at 25 ° C in the range of 5,000 mPas up to 30,000 mPas, in particular from 15,000 to 25,000 mPas. The silicones are preferably on Trä germ materials applied. Suitable carrier materials are already in connection with the Par affine. The carrier materials are generally in amounts of 40 to 90% by weight, preferably in amounts of 45 to 75% by weight, based on defoamers.

As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic pro Products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used the. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert.- Butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, Benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzylsa  licylate. The ethers include, for example, benzyl ethyl ether, the aldehydes z. B. the linear Alka nale with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitro nellal, lilial and bourgeonal, to the ketones z. B. the Jonone, α-Isomethylionon and Methylcedrylke clay, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpi neol, the hydrocarbons mainly include terpenes such as limonene and pinene. Before however, mixtures of different odoriferous substances are used, which together address one Generate the appropriate fragrance. Such perfume oils can also contain natural fragrance mixtures, as they are accessible from plant sources, e.g. B. pine, citrus, jasmine, patchouly, rose or Ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the agents according to the invention, but they can also be advantageous to apply the fragrances on carriers, which the adhesion of the perfume on the Wä strengthening and slower fragrance release for long-lasting fragrance of textiles For example, cyclodextrins have proven themselves as such carrier materials, the cyclo dextrin-perfume complexes can also be coated with other auxiliaries.

If desired, the final preparations can also contain inorganic salts as fillers or fillers contain, such as sodium sulfate, which is preferably in amounts of 0 to 10, in particular whose 1 to 5 wt .-% - based on agent - is included.

Examples Manufacturing example H1

A fluidized bed was powdered with up to 70% of the fluidized bed capacity filled according to dodecylbenzenesulfonate sodium salt as seed material. Subsequently, a Bo air temperature of 160 ° C (i.e. a temperature of approx. 95 ° C in the fluidized bed) is another ten sid powder is introduced continuously by means of a first nozzle. Through a second nozzle, Be Layering the tenside grain introduced a 50 wt .-% aqueous sodium acetate solution. The Material flows were coated by regular control of the discharged and classified Granules from the fluidized bed were adjusted so that the acetate content in the end product was 42% by weight.

Manufacturing example H2

Example H1 was made using powdered coconut alcohol sulfate sodium salt (Sulfopon® 1218 G, Cognis GmbH, Düsseldorf / FRG) repeated. The coating was done with a 37 wt .-% aqueous solution of sodium citrate dihydrate. The material flows were set so that the content of sodium citrate in the end product was 20% by weight.

Application tests

The two coated anionic surfactants according to the invention Nulate H1 and H2 as well as the two uncoated starting materials were used in detergent formulations used. The preparations were pressed into tablets (weight 40 g), packed airtight and then stored at 40 ° C for 2 weeks. The composition of the detergent tablets is Table 1. Formulations 1 and 2 are according to the invention, formulations V1 and V2 serve for comparison. To assess the dissolution behavior, the tablets were placed on a wire frame placed in water (0 ° d, 25 ° C). The tablets were completely surrounded by water give. The disintegration time from immersion to complete dissolution was measured. The decay times are also shown in Table 1.  

Table 1

Test formulation for detergent tablets and solubility tests (figures in% by weight, water ad 100%)

Claims (13)

1. Shaped body with improved water solubility, containing surface-active compounds and disintegrants, characterized in that they contain additives which consist of anionic surfactants as the core and a layer enveloping them, with the proviso that the coating substances at 20 ° C a water solubility of at least 10 g / l. 2. Shaped body according to claim 1, characterized in that it contains anionic surface as the core contain active compounds which are selected from the group formed by Soaps, alkyl benzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glyceri ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfa ten, 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, fat acid sarcosinates, fatty acid taurides, N-acylamino acids, alkyl oligoglucoside sulfates, protein fat acid condensates and alkyl (ether) phosphates and mixtures thereof. 3. Shaped body according to claims 1 and / or 2, characterized in that it is the core Al kyl sulfates, alkylbenzenesulfonates, olefin sulfonates, methyl ester sulfonates and mixtures thereof hold. 4. Shaped body according to at least one of claims 1 to 3, characterized in that the enveloping layer consists of water-soluble salts of mineral acids. 5. Shaped body according to at least one of claims 1 to 3, characterized in that the enveloping layer consists of water-soluble salts of organic carboxylic acids. 6. Shaped body according to at least one of claims 1 to 3, characterized in that the enveloping layer consists of water-soluble polymers. 7. Shaped body according to at least one of claims 1 to 3, characterized in that the enveloping layer consists of water-soluble saccharides and / or polysaccharides. 8. Shaped body according to at least one of claims 1 to 3, characterized in that it coated anionic surfactants in amounts of 1 to 50 wt .-% - based on the moldings - ent hold.   9. Shaped body according to at least one of claims 1 to 8, characterized in that it Contain explosives that are selected from the group formed by Polysacchari the, polyvinylpyrrolidone, collidone, alginic acid and their alkali salts, amorphous or partially se crystalline layered silicates, polyurethanes and polyethylene glycols. 10. Shaped body according to at least one of claims 1 to 9, characterized in that it Disintegrants in amounts of 0.1 to 25 wt .-% - based on the moldings. 11. Shaped body according to at least one of claims 1 to 10, characterized in that it are detergent tablets, detergent tablets. 12. A process for the production of moldings according to claim 1, characterized in that the disintegrants and the other additives are compressed by press agglomeration. 13. The method according to claim 12, characterized in that the granular components before Compress a proportion of particles that have a diameter outside the range of 0.02 have up to 6 mm, have less than 20 wt .-%.