EP1081219A2 - Solid detergents - Google Patents

Abstract

Solid detergent with improved solubility comprises a core of anionic surface active compounds and an enclosing film of solubility at least 10 g/l at 20 degrees C.

Description

Field of the Invention

The invention is in the field of washing, rinsing and cleaning agents and relates to new ones coated anionic surfactants, a process for their preparation and the use of the substances for Manufacture of washing, rinsing and cleaning agents, especially in tablet form.

State of the art

So far, granules of anionic surfactants, such as sodium lauryl sulfate, have been obtained either by drying the corresponding aqueous solutions or pastes or by direct neutralization of the acidic precursors of the surfactant, ie generally the sulfonic acids or sulfuric acid semiesters. For the production of the solids, for example, fluidized-bed drying, spray mixing processes and drying in the thin layer are suitable. These processes share the task of producing products with a high surfactant content in order to be able to add the surfactants in high concentrations to detergents, dishwashing detergents and cleaning agents. Both water-soluble (eg sodium sulfate) and water-insoluble (eg zeolite) additives, which serve as carriers, are incorporated into the solids, which are preferably granules. Other additives such as defoamers, builders and the like can also be used. As a result of the manufacturing processes of the prior art, the additives or additives in the solid final preparation, for example the granules, are distributed essentially homogeneously [cf. eg WO 94/18291, WO 94/18293 (Henkel)] However, detergents of this type are by no means completely satisfactory in their properties, but rather show a strong tendency to stick and - especially when introduced into the dosing chamber of a washing machine - low solubility.

The object of the present invention was therefore to provide new detergents in solid form to provide on the basis of anionic surfactants, which - both alone and in the solid Final formulation - have a lower tendency to stick and at the same time stand out through a improved solubility, especially in the dosing chamber of washing machines and in cold water, award. Another task then also existed, detergent tablets based on the detergents mentioned, which also have an improved solubility have or easier wash-in via the dosing chamber of washing machines and dishwashers have or where the proportion of disintegrants can be reduced with the same solubility.

Description of the invention

The invention relates to detergents in solid form, which are characterized in that they are made of there are anionic surface-active compounds as the core and a layer surrounding 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 the new detergents both alone and in the Final formulation show a significantly lower tendency to stick and show up both in the cold Water as well as in the dosing chamber of washing machines through a product State of the art distinguish improved solubility. Pressed using these new fabrics Tablets also have a faster solubility or can be used with the same solubility a smaller amount of explosives. The invention closes the knowledge one that it is not distracting if part of the coating is made into the Tenside grain arrives. The coating of the surfactant grain also does not have to be complete, it is sufficient if the coating ensures that the migration of water and surfactants, in particular nonionic surfactants, in which grain is prevented.

Anionic surfactant compounds

Typical examples of anionic surfactants that form the core of the detergents are soaps, alkylbenzenesulfonates, Alkane sulfonates, olefin sulfonates, 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 for example acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, Protein fatty acid condensates (especially vegetable products based on wheat) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can be a conventional, but preferably have a narrow homolog distribution. Preferably be Coated alkyl sulfates, alkyl benzene sulfonates, olefin sulfonates, methyl ester sulfonates and mixtures thereof. The proportion of anionic surface-active compounds in the detergents can be 20 to 99, preferably 50 to 95 and in particular 85 to 90 wt .-%.

in der R für einen verzweigten, vorzugsweise jedoch linearen Alkylrest mit 10 bis 18 Kohlenstoffatomen, Ph für einen Phenylrest und X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. Insbesondere von diesen geeignet sind Dodecylbenzolsulfonate, Tetradecylbenzolsulfonate, Hexadecylbenzolsulfonate sowie deren technische Gemische in Form der Natriumsalze.Preferred alkylbenzenesulfonates preferably follow the formula (I)

in which R stands for 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. Of these, dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are particularly suitable.

in der R² für einen linearen oder verzweigten, aliphatischen Alkyl- und/oder Alkenylrest mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen und Y für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. Typische Beispiele für Alkylsulfate, die im Sinne der Erfindung Anwendung finden können, sind die Sulfatierungsprodukte von Capronalkohol, Caprylalkohol, Caprinalkohol, 2-Ethylhexylalkohol, Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol und Erucylalkohol sowie deren technischen Gemischen, die durch Hochdruckhydrierung technischer Methylesterfraktionen oder Aldehyden aus der Roelenschen Oxosynthese erhalten werden. Die Sulfatierungsprodukte können vorzugsweise in Form ihrer Alkalisalze und insbesondere ihrer Natriumsalze eingesetzt werden. Besonders bevorzugt sind Alkylsulfate auf Basis von C_16/18-Talg-Fettalkoholen bzw. pflanzliche Fettalkohole vergleichbarer C-Kettenverteilung in Form ihrer Natriumsalze. Im Falle von verzweigten primären Alkoholen handelt es sich um Oxoalkohole, wie sie z.B. durch Umsetzung von Kohlenmonoxid und Wasserstoff an alpha-ständige Olefine nach dem Shop-Verfahren zugänglich sind. Solche Alkoholmischungen sind im Handel unter dem Handelsnamen Dobanol® oder Neodol® erhältlich. Geeignete Alkoholmischungen sind Dobanol 91®, 23®, 25®, 45®. Eine weitere Möglichkeit sind Oxoalkohole, wie sie nach dem klassischen Oxoprozeß der Enichema bzw. der Condea durch Anlagerung von Kohlenmonoxid und Wasserstoff an Olefine erhalten werden. Bei diesen Alkoholmischungen handelt es sich um eine Mischung aus stark verzweigten Alkoholen. Solche Alkoholmischungen sind im Handel unter dem Handelsnamen Lial® erhältlich. Geeignete Alkoholmischungen sind Lial 91®, 111®, 123®, 125®, 145®. 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)

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 which 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, petroselachcohol, elaidyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained from 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 metal 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, these are oxo alcohols, as are obtainable, for example, by converting carbon monoxide and hydrogen to alpha-olefins using the shop method. 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, 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 strongly branched alcohols. Such alcohol mixtures are commercially available under the trade name Lial®. Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.

Envelopes

The detergents according to the invention contain the substances enveloping the surfactant standard on solid - preferably in total amounts from 1 to 80 wt .-%, preferably from 5 to 50 and in particular from 5 to 20% by weight. These coating substances are water-soluble compounds, which have a water solubility at 20 ° C. of at least 10 g / l, preferably at least 50 Have g / l and in particular 100 g / l and advantageously more, for the overall recipe have useful properties, such as complexing hardness and Heavy metal ions or the inhibition of gel phase formation. Alternatively, the coating with water-soluble envelopes are also made from the melt.

Wassergläser") und Alkaliphosphate genannt werden sollen. Typische Beispiele sind Magnesiumsulfat-Heptahydrat oder Borax.In a first embodiment of the invention, these substances can be the salts of inorganic mineral acids . Typical examples are the alkali and / or alkaline earth metal salts, aluminum or zinc salts of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid and silicic acid, in particular the alkali metal sulfate, alkali borates and perborates, the various alkali metal silicates (

Water glasses ") and alkali phosphates should be mentioned. Typical examples are magnesium 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, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic 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 appropriate salts in the same manner as above are the corresponding salts of succinic acid, maleic acid, fumaric acid, glutaric acid and adipic acid. Finally, salts of hydroxy-functionalized polyvalent carboxylic acids can also be used, such as the above-mentioned salts of malic acid, tartaric acid and in particular citric acid. The use of alkali metal citrates is particularly preferred here.

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

Manufacturing process

The detergents according to the invention can be produced by processes that are already in production of detergents are known. Basically, the surfactant grain is first Drying and optionally granulating an appropriate aqueous solution or paste, which is then brought into contact with an aqueous solution or melt of the coating substance becomes. This is preferably done at higher temperatures, with the coating substance on the Grain precipitates and essentially includes it. The production is generalized of the new detergents in such a way that firstly an aqueous solution or paste of the anionic surface-active compound dries and on the resulting grain from a aqueous solution or melt precipitates a coating substance, possibly during the water evaporates. It is of course immediately clear that the process is one-step or two-step can be carried out. In the latter case, you first become an appropriate surfactant solution or paste dry and the dried powder, which in turn is a conventional powder Market product can trade, then coat. In one-stage, preferably continuous Processes are either the aqueous surfactant preparations or the dried surfactant powder used together with the coating agents.

The drying device into which the aqueous surfactant preparations are introduced, preferably sprayed, can be any drying apparatus. In one process control, the drying is carried out as spray drying in a drying tower. The surfactant solutions or pastes are exposed to a drying gas stream in a finely divided form in a known manner. Anionic surfactant powders are obtained, which are then intimately mixed with the required amount of coating substances in the form of an aqueous solution in a second step. Components for this process, such as, for example, paddle mixers from Lödige or in particular spray mixers from Schugi, are advantageous, in which the surfactant powder is placed in the mixing chamber and the aqueous solutions of the coating materials are sprayed on. It is also possible to carry out the drying of the aqueous surfactant preparations and the mixing simultaneously in a fluidized bed dryer.

A particularly preferred option is then to use the preferably aqueous surfactant precursors of fluidized bed granulation ( SKET "granulation). This means granulation with simultaneous drying, which is preferably carried out batchwise or continuously. The anionic surfactants can be used both in the dried state and as an aqueous preparation. The aqueous solutions or melts of the coating materials become simultaneous or one after the other through one or more nozzles into the fluidized bed. Preferably, one nozzle is continuously blown into a fluidized bed filled with germ material and surfactant powder is metered in via a second nozzle. This corresponds to a continuous solid / liquid production, but sets The process can also be carried out continuously in liquid / liquid form, but in this case it must be ensured that the aqueous surfactant preparation is introduced at a temperature which is so high that the Droplets are dried immediately after leaving the nozzle without the anionic surfactant decomposing. Conversely, the coating materials, especially the aqueous solutions, must be injected at such a low temperature that they do not dry out immediately after leaving the nozzle, but can be deposited on the surfactant grain. The conditions required for this depend in particular on the cross section of the system and can be found by the person skilled in the art by routine optimization.

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. The granules are preferably discharged from the fluidized bed via a size classification of the granules. The classification can take place, for example, by means of a sieve device or by means of an opposing air flow (classifier air) which is regulated in such a way that only particles of a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed. The inflowing air is usually 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. A starting mass, for example a surfactant granulate from an earlier test batch, is advantageously introduced at the start of the granulation. In the fluidized bed, the water evaporates from the emulsions or dispersions, producing dried to dried germs, which are coated with further amounts of anionic surfactant, granulated and again dried at the same time. As already explained, the aqueous solutions of the coating substances can also be used together with the surfactant precursors, but this can lead to some of the coating materials ending up in the grain and the coating of the grain being incomplete. In some cases this may be sufficient for the intended effect, but it is more advantageous to add the aqueous solutions to the granulation only at the end of the drying process in order to ensure that the grain is coated to a very substantial extent. In this context, reference is made to the teaching of German patent applications DE 4303211 A1 and DE 4303176 A1 , the content of which is hereby expressly included. For the purposes of the invention, it is also possible to use agglomerates which result from the granules caking together.

Industrial applicability

Another object of the present invention relates to the use of the invention Detergents as wash raw materials for the production of detergents and dishwashing detergents, preferably Those with a high anionic surfactant content (e.g. 5 to 25% by weight) and in the form of powders, granules, extrudates, agglomerates or tablets. Other preferred ingredients of detergents, dishwashing detergents and cleaning agents used using the inventive Salt additives are obtained are inorganic and organic builder substances, being inorganic Builder substances mainly with zeolites, crystalline layered silicates and amorphous silicates Builder properties and - where permissible - also phosphates such as tripolyphosphates are used. The builder substances are preferably in the final preparations in amounts of 10 to 60 % By weight - based on the funds - included. If the substances are water-soluble, they come at the same time also suitable as envelopes for the inclusion of the surfactant grain. This applies, for example, to the im the following described silicates, dextrins, polyacrylates and the like.

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 as VEGOBOND AX ^® (commercial product from Condea Augusta SpA) 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 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, it being possible, for example, to obtain β-sodium disilicate by the process described in international patent application WO 91/08171 . Further suitable layered silicates are known, for example, from patent applications DE 2334899 A1, EP 0026529 A1 and DE 3526405 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-compatible smectites, are, for example, 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. Useful layer 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 delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles in the electron diffraction experiments yield washed-out or even unhappy diffraction maxima. 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 4400024 A1 . Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

Of course, it is also possible to use the generally known phosphates as builders, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. Their content is generally not more than 25% by weight, preferably not more than 20% by weight, in each case based on the finished composition. In some cases, it has been shown that tripolyphosphates in particular, 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 ability.

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

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 2,000 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 , EP 0427349 A1 , EP 0472042 A1 and EP 0542496 A1 as well as from international patent applications WO 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 19600018 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 ethylenediamine disuccinate . Also particularly preferred in this context are glycerol disuccinates and glycerol trisuccinates , as described, for example, in US Pat . Nos . 4,524,009 , 4,639,325 , in European patent application EP 0150930 A1 and in Japanese patent application JP 93/339896 . Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.

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

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid and measured in each case against polystyrene sulfonic 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 relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (measured in each case 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 subsequently mixed into one or more basic granules. Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which, according to DE 4300772 A1, as salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or as DE 4221381 C2 as monomer salts of acrylic acid and the 2-alkylallylsulfonic acid and sugar derivatives. Further preferred copolymers are those which are described in German patent applications DE 4303320 A1 and DE 4417734 A1 and which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers. Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred.

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

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 anionic and / or nonionically modified derivatives of these. Of these are particularly preferred 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 other known detergents, dishwashing detergents and cleaning agents commonly used additives, for example salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filling salts as well as 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 5 to 35% by weight and in particular up to 30% by weight, advantageously using perborate monohydrate or percarbonate.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-acetiacetyl, ethylene glycol 2,5-dihydrofuran and the enol esters known from German patent applications DE 19616693 A1 and DE 19616767 A1 as well as acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0525239 A1 (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose , Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkyl ized glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are known from 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 hydrophilically substituted acylacetals known from German patent application DE 19616769 A1 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE 4443177 A1 can also be used. Bleaching equivalents of this type are present in the customary quantitative 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 the conventional bleach activators listed above or in their place, the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0446982 B1 and EP 0453 003 B1 can also be present as so-called bleaching catalysts. The transition metal compounds in question include in particular the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE 19529905 A1 and their N-analog compounds known from German patent application DE 19620267 A1 , which are known from German Patent application DE 19536082 A1 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium described in German patent application DE 196 05 688 - and copper complexes with nitrogen-containing tripod ligands known from the German patent application DE 19620411 A1 cobalt, iron, copper and ruthenium-ammine complexes, the manganese described in the German patent application DE 4416438 A1, copper and cobalt complexes, the cobalt complexes described in European patent application EP 0272030 A1, which are known from the European patent application EP 0693550 A1 manganese Complexes, the manganese, iron, cobalt and copper complexes known from European patent EP 0392592 A1 and / or those described in European patent EP 0443651 B1 or European patent applications EP 0458397 A1 , EP 0458398 A1 , EP 0549271 A1 , Manganese complexes described in EP 0549272 A1 , EP 0544490 A1 and EP 0544519 A1 . Combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 19613103 A1 and international patent application WO 95/27775 . Bleach-enhancing transition metal complexes, in particular with 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% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.

Enzymes in particular come from the class of hydrolases, such as 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 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 be Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus, used. Enzyme mixtures, for example of 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 acting enzymes or protease, lipase or lipolytically acting enzymes and cellulase, 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 to be suitable in some cases proven. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases are preferably used as cellulases and β-glucosidases, which are also called cellobiases, or mixtures thereof. Since 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 monofunctional 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. Water-soluble colloids of mostly organic nature are suitable for this, 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. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. 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.

As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, 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 the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example 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. Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, and also in small amounts, for example ^Contain 10 ^-6 to 10 ^-3 wt .-%, preferably by 10 ^-5 wt .-%, of a blue dye. A particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).

As dirt-repellent polymers ( soil repellants ") are those substances 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.

The molecular weight of the linking polyethylene glycol units is in particular in the range of 750 to 5000, i.e. the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approx. 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 Preferred are those polymers which link polyethylene glycol units with a 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" are understood to mean 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 wax-like defoamer substances are practically insoluble in water, ie at 20 ° C. a solubility of less than 0.1% by weight in 100 g of water. In principle, all wax-like defoamer substances known from the prior art can be present. Suitable wax-like compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohols and paraffin waxes or mixtures thereof, or alternatively the silicone compounds known for this purpose can of course also be used.

Suitable paraffin waxes generally represent a complex mixture of substances without a damaged 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 its solidification point . This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling. Paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C., cannot be used according to the invention. For example, the paraffin wax mixtures known from EP 0309931 A1 of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point of 62 ° C. to 90 ° C., 20% by weight to 49% by weight hard paraffin can be used 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. Paraffins or paraffin mixtures which solidify in the range from 30 ° C. to 90 ° C. are preferably used. It should be noted that even paraffin wax mixtures that appear solid at room temperature 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 and is preferably absent entirely. Particularly preferred paraffin wax mixtures at 30 ° C have a liquid fraction of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid fraction of less than 30% by weight, preferably of 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 40% by weight % to 55% by weight, at 80 ° C a liquid content of 80% by weight to 100% by weight, and at 90 ° C a liquid content of 100% by weight. The temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still below 85 ° C. in particularly preferred paraffin wax mixtures, in particular at 75 ° C. to 82 ° C. The paraffin waxes can be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.

Suitable bisamides as defoamers are those which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18 C atoms and from alkylenediamines with 2 to 7 C atoms. Suitable fatty acids are lauric acid, myristic acid, stearic acid, arachic acid and behenic acid and mixtures thereof, as can be obtained from natural fats or hydrogenated 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 bismyristoylethylene diamine, bispalmitoylethylene diamine, bisstearoylethylene diamine and mixtures thereof and the corresponding derivatives of hexamethylene diamine.

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 part 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 as well as ethylene glycol, glycerin, 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. Eligible esters of polyhydric alcohols are, for example, xylitol monopalmitate, pentarythritol monostearate, glycerol monostearate, ethylene glycol monostearate and sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan dilaurate, sorbitan dististearate, sorbitan dandghenoate and mixed sorbitan dibehenate, and sorbitan dandebehenate, and sorbitan dandebehenate, as well as sorbitan dandebehenate and mixed sorbitan dibehenate. 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 carnauba acid alkyl esters, often in combination with small amounts of free

Carnauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons, is.

Suitable carboxylic acids as a further defoamer compound are, in particular, behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid and mixtures thereof, as can be obtained from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil. 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 the fatty acids described.
Dialkyl ethers may also be present as defoamers. The ethers can be constructed asymmetrically or symmetrically, ie contain two identical or different alkyl chains, preferably with 8 to 18 carbon atoms. Typical examples are di-n-octyl ether, di-i-octyl ether and di-n-stearyl ether; dialkyl ethers which have a melting point above 25 ° C., in particular above 40 ° C., are particularly suitable.

Other 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 the elimination of carbon dioxide and water, for example according to the German laid-open specification DE 2553900 OS. Suitable fat ketones are those which are prepared by pyrolysis of the 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.

Other suitable defoamers are fatty acid polyethylene glycol esters , which are preferably obtained by base-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, leads to an 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 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 carbonates, aluminosilicates, water-soluble sheet silicates, alkali silicates, alkali sulfates, for example sodium sulfate, and alkali 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 ethers 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 referred to as 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 can have a content of finely divided silica, which in turn can also be silanized. Such organopolysiloxanes are described, for example, in European patent application EP 0496510 A1 . Polydiorganosiloxanes which are known from the prior art are particularly preferred. However, compounds crosslinked via siloxane can also be used, as are known to the person skilled in the art under the name silicone resins. As a rule, the polydiorganosiloxanes contain finely divided silica, which can also be silanized. Silica-containing dimethylpolysiloxanes are particularly suitable. The polydiorganosiloxanes advantageously 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 carrier materials. Suitable carrier materials have already been described in connection with the paraffins. The carrier materials are generally present in amounts of 40 to 90% by weight, preferably in amounts of 45 to 75% by weight, based on defoamers.

Individual fragrance compounds , for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances . Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexylpropylatepylatepylatepylatepionate, stally. The ethers include, for example, benzyl ethyl ether, the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the jonones, α-isomethylionone and methylcedryl ketone the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, 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 perfume adheres to the laundry intensify and ensure a long-lasting fragrance of the textiles through a slower fragrance release. Cyclodextrins, for example, have proven successful as such carrier materials, the cyclodextrin-perfume complexes can also be coated with other auxiliaries.

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

Manufacture of washing, washing-up and cleaning agents

The washing, rinsing and cleaning agents obtainable using the detergents according to the invention can be produced in the form of powders, extrudates, granules, agglomerates or tablets or be used. To produce such agents, the corresponding ones are from the prior art known methods. The agents are preferably prepared in that different Particulate components containing the ingredients are mixed together.

The particulate components can be spray dried, simple mixed or complex Granulation processes, for example fluidized bed granulation, are produced. Is preferred in particular that at least one surfactant-containing component by fluidized bed granulation will be produced. It can furthermore be particularly preferred if aqueous preparations of the alkali silicate and the alkali carbonate together with other ingredients in a drying facility can be sprayed, and granulation can take place simultaneously with the drying.

The drying device into which the aqueous preparation is sprayed can be any drying apparatus. In a preferred process, the drying is carried out as spray drying in a drying tower. The aqueous preparations are exposed to a drying gas stream in finely divided form in a known manner. Patent publications by Henkel describe an embodiment of spray drying with superheated steam. The working principle disclosed there is hereby expressly made the subject of the present disclosure of the invention. Reference is made here in particular to the following publications: DE 4030688 A1 and 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 surfactant grain.

In another, especially when high bulk density agents are to be obtained, preferred Variant, the mixtures are then subjected to a compacting step, with further Ingredients are only added to the agents after the compacting step. The compacting of the ingredients takes place in a preferred embodiment of the invention in a press agglomeration process instead of. The press agglomeration process to which the solid premix (dried base preparation) subject can be realized in various devices. Depending on A distinction is made between the type of agglomerator used and different press agglomeration processes. The four most common press agglomeration processes preferred in the context of the present invention are extrusion, roll pressing or compacting, hole pressing (Pelletizing) and tabletting, so that preferred press agglomeration processes within the scope of the present invention Extrusion, roll compacting, pelletizing or tableting processes are.

All processes have in common that the premix is compressed and plasticized under pressure and the individual particles are pressed together and the porosity is reduced be liable. The tools can be used in all processes (with tableting with restrictions) heat up to higher temperatures or dissipate the shear forces Cool heat.

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

The actual compression process is preferably carried out at processing temperatures that at least in the compression step at least the temperature of the softening point, if not correspond to the temperature of the melting point of the binder. In a preferred embodiment the process temperature is significantly above the melting point or above the temperature at which the binder is in the form of 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. It is technical quite possible to set even higher temperatures; but it has been shown that a Temperature difference from the melting temperature or softening temperature of the binder of 20 ° C is generally sufficient and even higher temperatures no additional advantages cause. Therefore - especially for energy reasons - it is particularly preferred above, but as close as possible to the melting point or the upper temperature limit of the melting range of the binder. Such a temperature control has the other Advantage that also thermally sensitive raw materials, for example peroxy bleaching agents such as perborate and / or percarbonate, but also enzymes, increasingly processed without serious loss of active substance can be. The possibility of precise temperature control of the binder in particular in the decisive step of compression, i.e. between the mixing / homogenization of the Premix and the shape, allows an energetically very favorable and for the temperature sensitive Components of the premix extremely gentle process management, because the premix is only exposed to the higher temperatures for a short time. In preferred press agglomeration processes show the working tools of the press agglomerator (the screw (s) of the extruder, the roller (s) of the roller compactor and the press roller (s) of the pellet press) have a temperature of a maximum of 150 ° C, preferably a maximum of 100 ° C and in particular a maximum of 75 ° C and the process temperature is 30 ° C and in particular a maximum of 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder. The duration is preferably the temperature effect in the compression area of the press agglomerators a maximum of 2 minutes and is particularly in a range between 30 seconds and 1 minute.

Preferred binders which can be used alone or in a mixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and also 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 with a relative 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, which again have relative molecular weights between 600 and 6,000, preferably between 1,000 and 4,000. For a more detailed description of the modified polyalkylene glycol ethers, reference is made to the disclosure of the international patent application WO 93/02176 . In the context of this invention, polyethylene glycols include those polymers which, in addition to ethylene glycol, also use C ₃ -C ₅ glycols and glycerol and mixtures of these as starting molecules. Ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included. The polyethylene glycols which are preferably used can have a linear or branched structure, linear polyethylene glycols in particular being preferred. The particularly preferred polyethylene glycols include those with relative molecular weights between 2,000 and 12,000, advantageously around 4,000, polyethylene glycols with relative molecular weights below 3,500 and above 5,000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4,000, and can be used Such combinations advantageously have more than 50% by weight, based on the total amount of polyethylene glycols, of polyethylene glycols with a relative molecular weight between 3,500 and 5,000. However, polyethylene glycols can also be used as binders, which are per se in liquid state at room temperature and a pressure of 1 bar; Here we are mainly talking about polyethylene glycol with a relative molecular mass of 200, 400 and 600. However, these per se liquid polyethylene glycols should only be used in a mixture with at least one further binder, this mixture again having to meet the requirements according to the invention, that is to say having a melting point or softening point of at least above 45 ° C. Likewise suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights of up to a maximum of 30,000. Relative molecular weight ranges between 3,000 and 30,000, for example around 10,000 are preferred. Polyvinylpyrrolidones are preferably not used as sole binders but in combination with other used in particular in combination with polyethylene glycols.

The compressed material preferably has temperatures immediately after it leaves the production apparatus not above 90 ° C, with temperatures between 35 and 85 ° C particularly preferred are. 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 final preparations are produced by means of an extrusion , as described, for example, in European patent EP 0486592 B1 or international patent applications WO 93/02176 and WO 94/09111 or WO 98/12299 . In this case, a solid premix is pressed in the form of a strand under pressure and the strand is cut to the predeterminable size of the granulate after it has emerged from the hole shape by means of a cutting device. The homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry 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 patents and patent applications mentioned above. The premix is preferably fed to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guidance, the housing and the extruder pelletizing head of which can be heated to the predetermined extrusion temperature. Under the shear action of the extruder screws, the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally, under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knife. The hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension. In this way, the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use. In general, particle diameters up to 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 from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm. The length / diameter ratio of the chopped-off primary granules is preferably in the range from about 1: 1 to about 3: 1. It is also preferred to feed the still plastic primary granules to a further shaping processing step; edges present on the crude extrudate are rounded off 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, can also be used in this step. This shape can be done in standard rounding machines. It is important to ensure that only small amounts of fine coma are produced in this mare. Drying, which is described as a preferred embodiment in the abovementioned prior art documents, is subsequently possible, but not absolutely necessary. It may just be preferable not to carry out any drying after the compacting step. Alternatively, extrusions / pressing can also be carried out in low-pressure extruders, in the Kahl press (from Amandus Kahl) or in the Bepex extruder. The temperature control in the transition region of the screw, the pre-distributor and the nozzle plate is preferably designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but preferably exceeded. The duration of the temperature influence in the compression range of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.

The agents can also be produced by means of roller compaction . Here, the premix is metered in between two smooth rollers or with recesses of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe. The rollers exert a high line pressure on the premix and can be additionally heated or cooled as required. When using smooth rollers, smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs can be produced in which, for example, certain shapes of the later particles can be specified. The sliver belt is subsequently broken up into smaller pieces by a knocking-off and crushing process and can be processed into granules in this way, which can be refined by further known surface treatment processes, in particular in an approximately spherical shape. In the case of roller compaction, too, the temperature of the pressing tools, that is to say of the rollers, is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at a maximum of 75 ° C. Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder. It is further preferred that the duration of the temperature effect in the compression area of the smooth rollers or with depressions of a defined shape is a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.

The final preparations can also be made by pelleting . The premix is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization. In conventional embodiments of pellet presses, the premix is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted into granules using a knock-off device. The most varied configurations of the pressure roller and perforated die are conceivable here. For example, flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers. The press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation. An apparatus suitable for carrying out the method is described, for example, in German laid-open specification DE 3816842 A1 . The ring die press disclosed in this document consists of a rotating ring die interspersed with press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge. In this case, the ring die and the press roller can be driven in the same direction, so that a reduced shear stress and thus a small increase in the temperature of the premix can be achieved. Of course, pelleting can also be carried out with heatable or coolable rollers in order to set a desired temperature of the premix. In pelleting too, the temperature of the pressing tools, that is to say the pressure rollers or pressure rollers, is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at a maximum of 75 ° C. Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.

Another press agglomeration process that can be used to produce the inventive is tableting. Because of the size of the molded articles produced, it may be useful for tableting to add conventional disintegration aids, for example cellulose and its derivatives, in particular in coarser form, or crosslinked PVP in addition to the binder described above, which facilitate the disintegration of the compacts in the wash liquor. The particulate press agglomerates obtained can either be used directly or aftertreated and / or prepared beforehand by customary methods. The usual aftertreatments include, for example, powdering with finely divided ingredients from washing or cleaning agents, which generally further increases the bulk density. However, a preferred aftertreatment is also the procedure according to German patent applications DE 19524287 A1 and DE 19547457 A1 , in which dusty or at least finely divided ingredients (the so-called fine fractions) are adhered to the particulate end products of the process, which serve as the core, and thus give rise to agents , which have these so-called fines as an outer shell. In turn, this advantageously takes place by melting agglomeration. For melt agglomeration of the fine fractions, reference is expressly made to the disclosure in German patent applications DE 19524287 A1 and DE 19547451 A1 . In the preferred embodiment of the invention, the solid end preparations are in tablet form, these tablets preferably having rounded corners and edges, in particular for storage and transport reasons. The base of these tablets can be circular or rectangular, for example. Multi-layer tablets, in particular tablets with 2 or 3 layers, which can also have different colors, are particularly preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred. The detergent tablets generally contain a disintegrant which is intended to cause the tablet to dissolve quickly or to disintegrate rapidly in the aqueous liquor. In this context, reference is expressly made to the content of the German patent applications DE 19709991 A1 and DE 19710254 A1 , in which preferred cellulose-based disintegrant granules are described.

Examples

Manufacturing example H1. A fluidized bed was filled with powdered dodecylbenzenesulfonate sodium salt as the seed material with up to 70% of the fluidized bed capacity. Subsequently, at a soil air temperature of 160 ° C (ie a temperature of approx. 95 ° C in the fluidized bed), further surfactant powder was continuously introduced using a harvested nozzle. A 50% by weight aqueous sodium acetate solution was introduced through a second nozzle to coat the surfactant grain. The material flows were adjusted by regularly checking the discharged and classified coated granules from the fluidized bed in such a way that the acetate content in the end product was 42% by weight.

Manufacturing example H2. Example H1 was repeated using powdered coconut alcohol sulfate sodium salt (Sulfopon® 1218 G, Cognis GmbH, Dusseldorf / FRG). The coating was carried out with a 37% by weight aqueous solution of sodium citrate dihydrate. The material flows were adjusted so that the content of sodium citrate in the end product was 20% by weight.

Application test. The two granules according to the invention and the non-coated comparison products were each compacted together with other additives at a pressure of 25 kN to give tablets (40 g). The tablets were then placed on a wire rack, which was in water (0 ° d, 25 ° C). The tablets were completely surrounded by water. The disintegration time from immersion to complete dissolution was measured. The composition of the tablets and the disintegration times are summarized in Table 1. It should be taken into account that the coated surfactants each have a surfactant content of 30% by weight at an application concentration of 52 or 38% by weight (analogous to the comparative examples). Table 2 contains a number of formulation examples. Composition of detergent tablets and disintegration times (in% by weight) composition 1 2nd V1 V2 Dodecylbenzenesulfonate sodium salt acc. Ex. H1 52.0 - - - Dodecylbenzenesulfonate sodium salt - - 30.0 - Coconut fatty alcohol sulfate sodium salt acc. Ex. H2 - 38.0 - - Coconut fatty alcohol sulfate sodium salt - - - 30.0 Microcrystalline cellulose 5.0 5.0 5.0 5.0 Calcium carbonate 18.0 22.0 40.0 40.0 Sodium sulfate 25.0 25.0 25.0 25.0 Disintegration time [s] 7 5 22 25th

Claims (15)

Solid detergents, characterized in that they consist of anionic surface-active compounds as the core and a layer surrounding them, with the proviso that the coating substances have a water solubility of at least 10 g / l at 20 ° C. Detergents according to claim 1, characterized in that they contain anionic surface-active compounds as the core, which are selected from the group consisting of soaps, alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol 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 arcosinate acids, fatty acid sulfonate fatty acids, fatty acid tolaminate fatty acids, fatty acid tolaminate fatty acids, fatty acid tolaminate fatty acids, fatty acid tolaminate fatty acids, fatty acid tolaminate fatty acids, fatty acid tolaminate fatty acids, fatty acid tolaminate fatty acids, fatty acid tolaminate fatty acids, fatty acid tolaminate fatty acids, fatty acid tolaminate fatty acids, fatty acid tolaminate fatty acids, fatty acid tolaminate fatty acids, fatty acid sulfate succinate acids, fatty acid sulfate succinate acids, fatty acid sulfate succinate acids, fatty acid sulfate succinate acids, fatty acid sulfate succinate acids, fatty acid sulfate succinate fatty acids, fatty acid sulfate succinate fatty acids, fatty acid tolate fatty acid fatty acid fatty acid fatty acid, and Alkyl (ether) phosphates and mixtures thereof. Detergents according to Claims 1 and / or 2, characterized in that they contain, as the core, alkyl sulfates, alkylbenzenesulfonates, olefin sulfonates, methyl ester sulfonates and mixtures thereof. Detergents according to at least one of Claims 1 to 3, characterized in that they contain the anionic surface-active compounds in amounts of 20 to 99% by weight. Detergents according to at least one of claims 1 to 4, characterized in that the covering layer consists of water-soluble salts of mineral acids. Detergents according to at least one of claims 1 to 4, characterized in that the covering layer consists of water-soluble salts of organic carboxylic acids. Detergents according to at least one of claims 1 to 4, characterized in that the covering layer consists of water-soluble polymers. Detergents according to at least one of claims 1 to 4, characterized in that the covering layer consists of water-soluble saccharides and / or polysaccharides. Detergents according to at least one of Claims 1 to 8, characterized in that they contain the coating substances in amounts of 1 to 80% by weight. A process for the preparation of detergents in solid form, characterized in that firstly an aqueous solution or paste of the anionic surface-active compounds is dried and a coating substance is deposited on the grain formed from an aqueous solution or melt while the water evaporates. Process according to claim 10, characterized in that the aqueous solutions or pastes of the anionic surface-active compounds are subjected to spray drying, the resulting powders are intimately mixed with the aqueous solutions or melts of the coating substances and, if appropriate, the water is removed in the process. Process according to Claim 10, characterized in that the aqueous preparations of the anionic surface-active compounds and the aqueous solutions of the coating substances are subjected to simultaneous drying and granulation in the fluidized bed. Process according to Claim 10, characterized in that dry powders of the anionic surface-active compounds and aqueous solutions or melts of the coating substances are dried and granulated in the fluidized bed. Use of detergents according to claim 1 for the production of washing, rinsing and cleaning agents. Use according to claim 14 for the production of washing, rinsing and cleaning agents in the form of powders, granules, extrudates, agglomerates or tablets.