EP1543100B1 - Method for the production of coated detergent or cleansing agent portions - Google Patents

Abstract

Disclosed is a simple and universally applicable method for producing detergent or cleansing agent portions that are tightly coated with water-soluble coatings. The inventive method comprises the following steps: a water-soluble bottom film is placed upon a conveyor chain or a molding tool; one or several detergent or cleansing agent portion/s is/are disposed on the bottom film; a water-soluble top film is placed upon the detergent or cleansing agent portion/s that lie/s on top of the bottom film; the top film is fixed onto the bottom film such that the detergent or cleansing agent portion/s is/are enclosed; the films are sealed and optionally cut.

Description

The present invention relates to a process for the preparation of detergent or cleaner portions having a coating of water-soluble materials which closely surrounds the compositions contained in the portion.

Portioned detergents and cleaners are widely described in the art and are becoming increasingly popular with consumers because of their ease of use. The portioning can be achieved, for example, by conversion into a compact form or by separate packaging. In the former case, the tabletting has an outstanding role, in the latter case predominantly portions are used in the field of washing or cleaning agents, which are surrounded by packages of water-soluble materials. Thus, EP-A-700 989 discloses portion-packed detergents in a water-soluble film. However, these portions have the disadvantage of not having the high degree of compactness which tablets have. The Befüllung of tubular bags on the one hand leads to a low degree of compaction, on the other hand to a technically related void volume, so that a measured for a washing or cleaning cycle amount of detergent or cleaning agent occupies a larger space than a corresponding amount in tableted form. In addition, the void volume causes filled bags are unstable to mechanical influences and can burst.

A disadvantage of the washing or cleaning tablets on the market that they still need to be provided with an outer packaging that protects the ingredients from environmental influences (especially moisture). These "flow packs" of water-insoluble materials must be removed by the consumer before dosing, which can be troublesome for the consumer and cause waste. Possible solutions to this problem are the coating of the molding with water-soluble polymers or the use of water-soluble packaging.

A coating provides visually appealing tablets with a smooth, glossy surface and advantageous haptic properties. However, the coating of tablets is technically complicated and expensive. The use of water-soluble packaging is described in the form of bags of water-soluble film in the prior art. For example, WO-A-0055 415 and GB-A-2 361 685 disclose methods of making water-soluble packages. However, these tablets have aesthetic disadvantages compared to conventional tablets. Also the consumer acceptance is low in this form of supply because the outer packaging suggests to the consumer to have to be removed - a real advantage of the water-soluble "flow packs" is therefore not visible to the consumer.

It is an object of the present invention to provide a process for producing aesthetically pleasing washing or cleaning agent portions. In this case, the method should be so variable that both tablets and other ready-made detergent or cleaning compositions such as moldings, powders, granules, extrudates, dandruff, etc. pack aesthetically pleasing. For the process alternatives in which tablets are not packaged, portions should be produced which combine the advantages of the compactness of tablets with those of the rapid solubility of portioned systems and, moreover, need not be provided with an outer packaging of water-insoluble film.

It has now been found that a wrapper of water-soluble film, which bears tightly against a tablet or particulate filling which is not a molded article, is aesthetically pleasing and is accepted by the consumer. The degree of compaction of such systems is close to conventional tablets and well above that of conventional portioned systems, with the solubility significantly exceeding that of tablets and reaching that of conventional particulate detergents or cleaners. It has further been found that a particular wrapping method is universally applicable to both particulate compositions and tablets, and provides close-serving portions.

• a) Auflegen einer wasserlöslichen Unterfolie auf eine Transportkette oder ein Form(en)werkzeug;
• b) Auflegen einer oder mehrerer Wasch- oder Reinigungsmittetportion(en) auf die Unterfolie;
• c) Auflegen einer wasserlöslichen Oberfolie auf die Wasch- oder Reinigungsmittelportion(en) auf der Unterfolie;
• d) Fixierung der Oberfolie auf der Unterfolie unter Einschluß der Wasch- oder Reinigungsmittelportion(en);
• e) Versiegeln und optionales Schneiden der Folien

gekennzeichnet ist.The subject of the present invention is therefore a process for the preparation with water-soluble coatings tightly enveloped washing or cleaning agent portions, by the steps

• a) placing a water-soluble lower film on a transport chain or a mold (s) tool;
• b) placing one or more washing or cleaning agent portions on the lower film;
• c) placing a water-soluble upper film on the washing or cleaning agent portion (s) on the lower film;
• d) fixing the upper film to the lower film, including the washing or cleaning agent portion (s);
• e) Sealing and optional cutting of the films

is marked.

The following is a description of the method according to the invention with reference to its method steps. A detailed description of the films to be used in the process according to the invention and the ingredients of the washing or cleaning agent portions can be found in connection with these statements.

In the first step of the method according to the invention, a water-soluble lower film is provided, which is placed on a transport chain or a mold (s) tool. A combination of transport chain and mold (s) tool is used according to the invention. As a transport chain in the context of the present invention, conveyor belts etc. are understood. Transport chains or belts are preferred for reasons of process economy over fixed molds. A combination of transport chain and mold (s) tool, for example, a production line, which has recesses at regular intervals.

If mold (s) tools are used, the molds may be designed as individual units, but it is also possible and preferred for reasons of process economy to use molds having a variety of shapes. About these forms, a water-soluble film is placed in step a) of the method according to the invention, to which in the next process step, one or more washing or cleaning agent portion (s) are applied.

It is possible and preferred according to the invention to preform the film which is placed on the transport chain or the mold (s) in step a). In particular, in the subsequent application of particulate compositions, it is advisable to use mold (s) tools and preform the applied film. As a result, the particles are spatially fixed, which facilitates the subsequent process steps.

Preferred processes according to the invention are characterized in that the lower film is preformed by the application of a vacuum and / or by heating. As a result, the film is provided with a cavity for receiving the particulate detergent composition. The procedure described above is not on the Dosage of particulate compositions limited, but can also be used for the inventive packaging of tablets.

It is preferred according to the invention that the water-soluble film prior to application to the mold (s) tool to temperatures above 50 ° C, preferably above 70 ° C and in particular above 90 ° C, heated. As a result, the subsequent deformation is facilitated. As an alternative to heating before placing on the mold (s) tool or in addition to it, the film can be further heated during the forming process. Here, process variants are preferred in which the deformation of the water-soluble film by heating the film to temperatures of 100 to 120 ° C is supported. A combination of the two process variants, i. Applying a heated film and further heating is possible and preferred.

The film may also be pressed into the mold by the dosage of the tablet or particulate composition. This is possible with particulate compositions, for example, by placing an annular die on top of the film over the mold and metering the particulate composition through this tube into the mold. In this case, the film can sink into the mold either because of the mass of the composition, but the metering process can also be assisted by pushing the composition into the mold, for example by means of a punch in the tubular metering device. For tablets, this dosing unit can also be used, but due to the compact shaped body structure, the tablet can also be placed without them.

If a particulate composition is used, it can also be easily precompressed to ensure the most complete possible filling of the mold. If multiphase portions are to be prepared, pressing the particulate composition first metered insures a plane interface between the two layers. Visually, such two-phase portions are closely related to the known two-layer tablets. However, the forces for pressing the particulate composition are chosen so that the range of elastic deformation is not left. The metering pressure thus does not lead to sintering together of the particles (as would be the case with tabletting), but only to the removal of bulk material cavities and to a flat surface. Here, methods according to the invention are preferred in which a particulate premix is slightly compacted by means of the punch, wherein compression forces below 1 kN are preferred.

Lightly precompacted particulate compositions can also be easily lifted out of the mold before sealing, without breaking immediately - this can be used to advantage for the position of the later seal, see below.

Preferred methods for coating particulate compositions according to the invention are characterized in that a further particulate washing or cleaning agent is metered onto the first precompressed particulate washing or cleaning agent. As a result, visually appealing portions can be produced.

When a mold is used, its depth, in combination with the height of the inserted tablet or filled particulate composition, determines how high the composition protrudes from the film plane. The subsequent placement of the top film in step c) of the method according to the invention then determines the position of the sealing seam produced later.

When the detergent or detergent composition metered into the mold is flush with the top of the mold, the sealed seam forms as a "brim" on an end face of the portion. Here can be used to seal a simple plate, however, has the disadvantage that the film that covers the top of the portion is exposed to the influence of heat.

Alternatively, you can also make the sealed seam so that it runs along the lateral surface of the portion. In this case, the portion stands out of the mold and the portion of the portion protruding from the mold is covered with another film. The seal can not be done now with a plate-like sealing tool, but takes place with an annular tool. This method has the advantage that the lowering of the annular sealing tool additionally tightens the upper foil. In addition, the heat on the portion compared to a "hot plate" is significantly reduced.

For this reason, methods according to the invention are preferred in which the washing or cleaning agent portion (s) in step b) does not terminate flush with the upper side of the mold after being placed on the lower film, but protrude from it, it being preferred that that a maximum of 50%, preferably a maximum of 40% and in particular a maximum of 30% of the greatest height of the washing or cleaning agent portion (s) are within the mold.

In extreme cases, there is no form in which the portion can be metered, i. the washing or cleaning agent composition or the washing or cleaning agent tablet is placed on a lower film, which in turn rests on a flat conveyor chain or a "conveyor belt". Inventive methods in which the lower film during the steps b) to e) is completely flat, according to the invention are preferred because of the simpler apparatus design and the simplified procedure.

The washing or cleaning agent portion to be introduced onto or into the lower film may be particulate or may consist of a majority of moldings, as previously described. In addition, it is also possible and preferred that it consists of a washing or cleaning agent tablet or a casting with washing or cleaning active ingredients. Tablets and casting bodies have the advantage that they can be deposited exactly on the foil and do not slip even when the foil is transported on a flat conveyor belt or a conveyor chain. Particle clusters can change their shape in this approach. Preferred methods according to the invention are therefore characterized in that the washing or cleaning agent portion (s) placed on the bottom foil in step b) is / are (a) washing or cleaning agent tablet (s).

Of course, it is possible according to the invention to also carry out a combination of the abovementioned possibilities by introducing both a particulate composition and one or more tablets onto or into the lower film. Instead of tablets or in addition to other shaped articles can be used alone or in combination with powders, for example, casting or powder or liquid-filled hollow body, which can be produced for example by injection molding, bottle blowing, deep drawing, etc. Gelatin capsules with powder or (preferably) liquid filling, which are introduced together with a particulate composition and / or a tablet onto or into the lower film, are particularly preferred in the context of the present invention.

With particular preference, the inventive method for the packaging of washing or cleaning active casting bodies is used, wherein it is particularly preferred that the casting in the packaging with one or more particulate washing or cleaning agents, such as powders, extrudates or granules combined. A more detailed description of the casting body preferred according to the invention will be given below in the text.

In step c) of the process according to the invention, an upper film is applied to the lower film coated with one or more washing or cleaning agent portions, which is fixed in step d) and sealed in step e). The application of the top film preferably takes place with the aid of a dome-shaped tool, which carries the top film in itself and is slipped over the washing or cleaning agent portions located on the bottom film. It is preferred that the top film is not flat, so tense, but also formed like a dome. This can be achieved by applying the top film in the tool to its wall. Preferred methods are characterized in that the top film is preformed before applying in step c) by applying a vacuum and / or by heating in a dome.

It may be advantageous to heat the top film to temperatures between 100 ° C and 200 ° C, with temperatures between 100 ° C and 120 ° C are preferred. The dome-like shape with the top film is then slipped over the washing or cleaning agent portion (s) on the bottom film. This forms an already completely surrounded by water-soluble film washing or cleaning agent portion, which is partially separated by an air cushion of the film. To ensure a skin-tight packaging, the air can be sucked through slots on the bottom surface of the upper tool. The creation of a vacuum on these slots additionally causes the top film to detach from the dome as soon as the dome-shaped mold is ventilated from above. Here, methods according to the invention are preferred in which step c) is introduced by pre-aeration from above.

After the top film has laid loosely over the washing or cleaning agent portion (s) located on the lower film, the dome-like tool is fully ventilated from above. A skin-tight enclosure is preferably achieved in that a vacuum is applied to the connecting surface between the upper and lower film. Alternatively or in addition here, the dome-like tool can be acted upon with an overpressure which presses the top film onto the washing or cleaning agent portion (s). Inventive methods, which are characterized in that the steps c) and / or d) by evacuating the Interspace between the upper and lower film and / or supported by applying pressure to the upper film are preferred according to the invention.

In step d), the films are completely sealed around the washing or cleaning agent portion (s). Following sealing, the films can be stabilized by the differential pressure in the mold to prevent reforming. In addition, the mold can be cooled to keep the sealed product unchanged in shape and to shorten the residence times in the mold.

A further variant of the method envisages initially packaging the portions either in water-soluble films as disclosed above and then shrink-drying the film packaging onto the portions. This shrink film is a film that has been stretched and is contracting again when heated. In this case, it is possible to produce envelopes lying very close to the surface of the portions.

Processes which are likewise preferred according to the invention are characterized in that pre-stretched films are used as the water-soluble film (s) in steps a) and c), which are shrunk onto the detergent or cleaning agent portion (s) in step e) or subsequently.

Instead of a single-layer film, multi-layer film laminates can also be used according to the invention. Such laminates have the advantage that the individual layers can be adapted to the respective environmental conditions. Thus, for example, an inner film can be used which is inert to the composition to be filled and does not undergo any undesired reactions with the filling. An outer film, which better resists environmental influences, can protect the composition from external influences in such a two-film laminate. Of course, three-film laminates, four-film laminates, etc. can also be used according to the invention. Different functions (mechanical stabilization, vapor barrier, optics, incorporation of ingredients, etc.) can be assigned to the individual films.

The following is a description of the usable in the process according to the invention films:

The films which can be used in the process according to the invention can be a single material or a blend of different materials. In preferred processes according to the invention, water-soluble coating comprises one or more materials from the group (optionally acetalized) polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, gelatin, cellulose and derivatives thereof, in particular MC, HEC, HPC, HPMC and / or CMC, and / or copolymers and mixtures thereof. Possibly. For example, the wraps may be mixed with plasticizers known to those skilled in the art in order to increase the flexibility of the material.

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

enthalten.In the context of the present invention, polyvinyl alcohols are particularly preferred as water-soluble polymers. "Polyvinyl alcohols" (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure

in small proportions (about 2%) also structural units of the type

contain.

Commercially available polyvinyl alcohols, which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so still contain a residual content of acetyl groups. The polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically harmless and are biological at least partially degradable. The water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax. Polyvinyl alcohol is largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allows water vapor to pass through.

Preferred processes in the context of the present invention are characterized in that the water-soluble coating comprises polyvinyl alcohols and / or PVAL copolymers whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

Preferably, polyvinyl alcohols of a certain molecular weight range are used, preference being given to processes according to the invention in which the water-soluble coating comprises polyvinyl alcohols and / or PVAL copolymers whose molecular weight is in the range from 3,500 to 100,000 gmol ^-1 , preferably from 10,000 to 90,000 gmol ^-1 preferably from 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 .

The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.

Processes preferred according to the invention are characterized in that the water-soluble coating comprises polyvinyl alcohols and / or PVAL copolymers whose average degree of polymerization is between 80 and 700, preferably between 150 and 400, particularly preferably between 180 and 300 and / or their molecular weight ratio MW (50%). ) to Mw (90%) is between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.45 and 0.6.

The polyvinyl alcohols described above are widely available commercially, for example under the trademark Mowiol® (Clariant). Polyvinyl alcohols which are particularly suitable for the purposes of the present invention are, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88 and Mowiol® 8-88.

Further polyvinyl alcohols which are particularly suitable as material for the water-soluble coating are shown in the following table: description Degree of hydrolysis [%] Molecular weight [kDa] Melting point [° C] Airvol® 205 88 15-27 230 Vinex® 2019 88 15-27 170 Vinex® 2144 88 44 - 65 205 Vinex® 1025 99 15-27 170 Vinex® 2025 88 25 - 45 192 Gohsefimer® 5407 30 - 28 23,600 100 Gohsefimer® LL02 41 - 51 17,700 100

Other polyvinyl alcohols suitable as material for the water-soluble coating are ELVANOL® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK). Also suitable are ERKOL types from Wacker.

die durch radikalische Polymerisation von 1-Vinylpyrrolidon nach Verfahren der Lösungs- oder Suspensionspolymerisation unter Einsatz von Radikalbildnern (Peroxide, Azo-Verbindungen) als Initiatoren hergestellt werden. Die ionische Polymerisation des Monomeren liefert nur Produkte mit niedrigen Molmassen. Handelsübliche Polyvinylpyrrolidone haben Molmassen im Bereich von ca. 2500-750000 g/mol, die über die Angabe der K-Werte charakterisiert werden und - K-Wert-abhängig - Glasübergangstemperaturen von 130-175° besitzen. Sie werden als weiße, hygroskopische Pulver oder als wäßrige Lösungen angeboten. Polyvinylpyrrolidone sind gut löslich in Wasser und einer Vielzahl von organischen Lösungsmitteln (Alkohole, Ketone, Eisessig, Chlorkohlenwasserstoffe, Phenole u.a.).A further preferred group of water-soluble polymers which can serve as a coating according to the invention are the polyvinylpyrrolidones. These are sold, for example, under the name Luviskol® (BASF). Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinones)], abbreviation PVP, are polymers of the general formula (I)

which are prepared by free-radical polymerization of 1-vinylpyrrolidone by the method of solution or suspension polymerization using free-radical initiators (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer provides only low molecular weight products. Commercially available polyvinylpyrrolidones have molecular weights in the range from about 2500-750000 g / mol, which are characterized by the specification of the K values and, depending on the K value, have glass transition temperatures of 130-175 °. They are offered as white, hygroscopic powders or as aqueous solutions. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).

Also suitable are copolymers of vinylpyrrolidone with other monomers, in particular vinylpyrrolidone / vinyl ester copolymers, as are sold, for example, under the trademark Luviskol® (BASF). Luviskol® VA 64 and Luviskol® VA 73, in each case vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.

als charakteristischem Grundbaustein der Makromoleküle. Von diesen haben die Vinylacetat-Polymere (R = CH₃) mit Polyvinylacetaten als mit Abstand wichtigsten Vertretern die größte technische Bedeutung.
Die Polymerisation der Vinylester erfolgt radikalisch nach unterschiedlichen Verfahren (Lösungspolymerisation, Suspensionspolymerisation, Emulsionspolymerisation, Substanzpolymerisation.). Copolymere von Vinylacetat mit Vinylpyrrolidon enthalten Monomereinheiten der Formeln (I) und (II).The vinyl ester polymers are vinyl ester-accessible polymers having the moiety of the formula (II)

as a characteristic building block of the macromolecules. Of these, the vinyl acetate polymers (R = CH ₃ ) with polyvinyl acetates as by far the most important representatives of the greatest technical importance.
The polymerization of the vinyl esters is carried out free-radically by different processes (solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization). Copolymers of vinyl acetate with vinylpyrrolidone contain monomer units of the formulas (I) and (II).

Further suitable water-soluble polymers are the polyethylene glycols (polyethylene oxides), which are referred to as PEG for short. PEG are polymers of ethylene glycol which are of the general formula (III)

H- (O-CH ₂ -CH ₂ ) _n -OH (III)

satisfy, where n can take values between 5 and> 100,000.

PEGs are prepared industrially by anionic ring-opening polymerization of ethylene oxide (oxirane), usually in the presence of small amounts of water. Depending on the reaction procedure, they have molar masses in the range of about 200-5,000,000 g / mol, corresponding to degrees of polymerization of about 5 to> 100,000.

The products with molecular weights <about 25 000 g / mol are liquid sore at room temperature are referred to as actual polyethylene glycols, abbreviated PEG. These short-chain PEGs can be used in particular other water-soluble polymers, e.g. Polyvinvlalkoholen or cellulose ethers are added as plasticizer. The polyethyleneglycols which can be used according to the invention and which are solid at room temperature are termed polyethylene oxides, abbreviated PEOX. High molecular weight polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and therefore show only weak glycol properties.

Also suitable as water-soluble coating material is also gelatine according to the invention, this preferably being used together with other polymers. Gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as water-soluble coating material is extremely widespread, especially in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin has little use because of its high price compared to the polymers mentioned above.

• Celluloseether, wie Hydroxypropylcellulose, Hydroxyethylcellulose und Methylhydroxypropylcellulose, wie sie beispielsweise unter den Warenzeichen Culminal® und Benecel® (AQUALON) vertrieben werden.
  Celluloseether lassen sich durch die allgemeine Formel (IV) beschreiben,
  
  in der R für H oder einen Alkyl-, Alkenyl-, Alkinyl-, Aryl- oder Alkylarylrest steht. In bevorzugten Produkten steht mindestens ein R in Formel (III) für -CH₂CH₂CH₂-OH oder -CH₂CH₂-OH. Celluloseether werden technisch durch Veretherung von Alkalicellulose (z.B. mit Ethylenoxid) hergestellt. Celluloseether werden charakterisiert über den durchschnittlichen Substitutionsgrad DS bzw. den molaren Substitutionsgrad MS, die angeben, wieviele Hydroxy-Gruppen einer Anhydroglucose-Einheit der Cellulose mit dem Veretherungsreagens reagiert haben bzw. wieviel mol des Veretherungsreagens im Durchschnitt an eine Anhydroglucose-Einheit angelagert wurden. Hydroxyethylcellulosen sind ab einem DS von ca. 0,6 bzw. einem MS von ca. 1 wasserlöslich. Handelsübliche Hydroxyethyl- bzw. Hydroxypropylcellulosen haben Substitutionsgrade im Bereich von 0,85-1,35 (DS) bzw. 1,5-3 (MS). Hydroxyethyl- und -propylcellulosen werden als gelblich-weiße, geruch- und geschmacklose Pulver in stark unterschiedlichen Polymerisationsgraden vermarktet. Hydroxyethyl- und -propylcellulosen sind in kaltem und heißem Wasser sowie in einigen (wasserhaltigen) organischen Lösungsmitteln löslich, in den meisten (wasserfreien) organischen Lösungsmitteln dagegen unlöslich; ihre wäßrigen Lösungen sind relativ unempfindlich gegenüber Änderungen des pH-Werts oder Elektrolyt-Zusatz.

Further water-soluble polymers suitable for coating according to the invention are described below:

• Cellulose ethers, such as hydroxypropyl cellulose, hydroxyethyl cellulose and methyl hydroxypropyl cellulose, such as those sold under the trademarks Culminal® and Benecel® (AQUALON).
  Cellulose ethers can be described by the general formula (IV)
  
  in which R is H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in formula (III) is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of the cellulose reacted with the etherifying reagent or how many moles of the etherifying agent were attached on average to an anhydroglucose unit. Hydroxyethylcelluloses are water-soluble from a DS of about 0.6 or an MS of about 1. Commercially available hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS), respectively. Hydroxyethyl and propylcelluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propylcelluloses are soluble in cold and hot water as well as in some (hydrous) organic solvents but insoluble in most (anhydrous) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Preferred processes according to the invention are characterized in that the water-soluble coating comprises hydroxypropylmethylcellulose (HPMC) having a degree of substitution (average number of methoxy groups per anhydroglucose unit of the cellulose) of from 1.0 to 2.0, preferably from 1.4 to 1.9 , and a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit of cellulose) of from 0.1 to 0.3, preferably from 0.15 to 0.25.

Further polymers which are suitable according to the invention are water-soluble amphopolymers. Amphoteric polymers, ie polymers which contain both free amino groups and free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, are zwitterionic polymers which contain quaternary ammonium groups in the molecule and -COO ^- or -SO ₃ ^- groups, and those polymers comprising -COOH or SO ₃ H groups and quaternary ammonium groups. An example of an amphopolymer which can be used according to the invention is the acrylic resin obtainable under the name Amphomer®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acids (for example acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (for example acrylamidopropyltrimethylammonium chloride) and optionally further ionic or nonionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and the one cited therein State of the art can be seen. Terpolymers of acrylic acid, methyl acrylate and Methacrylamidopropyltrimoniumchlorid, as they are commercially available under the name Merquat®2001 N, according to the invention are particularly preferred amphopolymers. Further suitable amphoteric polymers are, for example, the octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers available under the names Amphomer® and Amphomer® LV-71 (DELFT NATIONAL).

• Vinylacetat/Crotonsäure-Copolymere, wie sie beispielsweise unter den Bezeichnungen Resyn® (NATIONAL STARCH), Luviset® (BASF) und Gafset® (GAF) im Handel sind. Diese Polymere weisen neben Monomereinheiten der vorstehend genannten Formel (II) auch Monomereinheiten der allgemeinen Formel (V) auf:
  
          [-CH(CH₃)-CH(COOH)-]_n     (V)
  
  
• Vinylpyrrolidon/Vinylacrylat-Copolymere, erhältlich beispielsweise unter dem Warenzeichen Luviflex® (BASF). Ein bevorzugtes Polymer ist das unter der Bezeichnung Luviflex® VBM-35 (BASF) erhältliche Vinylpyrrolidon/Acrylat-Terpolymere.
• Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere, die beispielsweise unter der Bezeichnung Ultrahold® strong (BASF) vertrieben werden.
• Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen
  Solche gepfropften Polymere von Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch mit anderen copolymerisierbaren Verbindungen auf Polyalkylenglycolen werden durch Polymerisation in der Hitze in homogener Phase dadurch erhalten, daß man die Polyalkylenglycole in die Monomeren der Vinylester, Ester von Acrylsäure oder Methacrylsäure, in Gegenwart von Radikalbildner einrührt.
  Als geeignete Vinylester haben sich beispielsweise Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinylbenzoat und als Ester von Acrylsäure oder Methacrylsäure diejenigen, die mit aliphatischen Alkoholen mit niedrigem Molekulargewicht, also insbesondere Ethanol, Propanol, Isopropanol, 1-Butanol, 2-Butanol, 2-Methy-1-Propanol, 2-Methyl-2-Propanol, 1-Pentanol, 2-Pentanol, 3-Pentanol, 2,2-Dimethyl-1-Propanol, 3-Methyl-1-butanol; 3-Methyl-2-butanol, 2-Methyl-2-butanol, 2-Methyl-1-Butanol, 1-Hexanol, erhältlich sind, bewährt.
  Polypropylenglycole (Kurzzeichen PPG) sind Polymere des Propylenglycols, die der allgemeinen Formel VI
  
  genügen, wobei n Werte zwischen 1 (Propylenglycol) und mehreren tausend annehmen kann. Technisch bedeutsam sind hier insbesondere Di-, Tri- und Tetrapropylenglycol, d.h. die Vertreter mit n=2, 3 und 4 in Formel VI.
  Insbesondere können die auf Polyethylenglycole gepfropften Vinylacetatcopolymeren und die auf Polyethylenglycole gepfropften Polymeren von Vinylacetat und Crotonsäure eingesetzt werden.
• gepfropfte und vernetzte Copolymere aus der Copolymerisation von
  • i) mindesten einem Monomeren vom nicht-ionischen Typ,
  • ii) mindestens einem Monomeren vom ionischen Typ,
  • iii) von Polyethylenglycol und
  • iv) einem Vernetzer
  Das verwendete Polyethylenglycol weist ein Molekulargewicht zwischen 200 und mehreren Millionen, vorzugsweise zwischen 300 und 30.000, auf.
  Die nicht-ionischen Monomeren können von sehr unterschiedlichem Typ sein und unter diesen sind folgende bevorzugt: Vinylacetat, Vinylstearat, Vinyllaurat, Vinylpropionat, Allylstearat, Allyllaurat, Diethylmaleat, Allylacetat, Methylmethacrylat, Cetylvinylether, Stearylvinylether und 1-Hexen.
  Die nicht-ionischen Monomeren können gleichermaßen von sehr unterschiedlichen Typen sein, wobei unter diesen besonders bevorzugt Crotonsäure, Allyloxyessigsäure, Vinylessigsäure, Maleinsäure, Acrylsäure und Methacrylsäure in den Pfropfpolameren enthalten sind.
  Als Vernetzer werden vorzugsweise Ethylenglycoldimethacrylat, Diallylphthalat, ortho-, meta- und para-Divinylbenzol, Tetraallyloxyethan und Polyallylsaccharosen mit 2 bis 5 Allylgruppen pro Molekül Saccharin.
  Die vorstehend beschriebenen gepfropften und vernetzten Copolymere werden vorzugsweise gebildet aus:
  • i) 5 bis 85 Gew.-% mindesten eine Monomeren vom nicht-ionischen Typ,
  • ii) 3 bis 80 Gew.-% mindestens eines Monomeren vom ionischen Typ,
  • iii) 2 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-% Polyethylenglycol und
  • iv) 0,1 bis 8 Gew.-% eines Vernetzters, wobei der Prozentsatz des Vernetzers durch das Verhältnis der Gesamtgewichte von i), ii) und iii) ausgebildet ist.
• durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltene Copolymere:
  • i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren,
  • ii) ungesättigte Carbonsäuren,
  • iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols
  Unter kurzkettigen Carbonsäuren bzw. Alkoholen sind dabei solche mit 1 bis 8 Kohlenstoffatomen zu verstehen, wobei die Kohlenstoffketten dieser Verbindungen gegebenenfalls durch zweibindige Heterogruppen wie -O-, -NH-, -S_ unterbrochen sein können.
• Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester
  Diese Terpolymere enthalten Monomereinheiten der allgemeinen Formeln (II) und (IV) (siehe oben) sowie Monomereinheiten aus einem oder mehreren Allyl- oder Methallyestern der Formel VII:
  
  worin R³ für -H oder -CH₃, R² für -CH₃ oder -CH(CH₃)₂ und R¹ für -CH₃ oder einen gesättigten geradkettigen oder verzweigten C_1-6-Alkylrest steht und die Summe der Kohlenstoffatome in den Resten R¹ und R² vorzugsweise 7, 6, 5, 4, 3 oder 2 ist.
  Die vorstehend genannten Terpolymeren resultieren vorzugsweise aus der Copolymerisation von 7 bis 12 Gew.-% Crotonsäure, 65 bis 86 Gew.-%, vorzugsweise 71 bis 83 Gew.-% Vinylacetat und 8 bis 20 Gew.-%, vorzugsweise 10 bis 17 Gew.-% Allyl- oder Methaltylester der Formel VII.
• Tetra- und Pentapolymere aus
  • i) Crotonsäure oder Allyloxyessigsäure
  • ii) Vinylacetat oder Vinylpropionat
  • iii) verzweigten Allyl- oder Methallylestern
  • iv) Vinylethern, Vinylestern oder geradkettigen Allyl- oder Methallylestern
• Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinymethylether, Acrylamid und deren wasserlöslicher Salze
• Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen in α-Stellung verzweigten Monocarbonsäure.

Water-soluble anionic polymers suitable according to the invention include:

• Vinyl acetate / crotonic acid copolymers such as, for example, under the names Resyn® (NATIONAL STARCH), Luviset® (BASF) and Gafset® (GAF) are commercially available. These polymers also have monomer units of the formula (II) above
  
  [-CH (CH ₃ ) -CH (COOH) -] _n (V)
  
  
• Vinylpyrrolidone / vinyl acrylate copolymers, available, for example, under the trademark Luviflex® (BASF). A preferred polymer is the vinylpyrrolidone / acrylate terpolymer available under the name Luviflex® VBM-35 (BASF).
• Acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers, which are sold, for example, under the name Ultrahold® strong (BASF).
• Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in admixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols
  Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in admixture with other copolymerizable compounds on polyalkylene glycols are obtained by homogeneous-phase polymerization by reacting the polyalkylene glycols in the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid, in The presence of free radical initiator stirs.
  Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and as esters of acrylic acid or methacrylic acid those with aliphatic alcohols of low molecular weight, ie in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl 1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are proven.
  Polypropylene glycols (abbreviated PPG) are polymers of propylene glycol which are of general formula VI
  
  satisfy, where n can assume values between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri- and tetrapropylene glycols, ie the representatives with n = 2, 3 and 4 in formula VI.
  In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used.
• grafted and crosslinked copolymers from the copolymerization of
  • i) at least one nonionic type monomer,
  • ii) at least one ionic-type monomer,
  • iii) of polyethylene glycol and
  • iv) a crosslinker
  The polyethylene glycol used has a molecular weight between 200 and several million, preferably between 300 and 30,000.
  The nonionic monomers may be of very different types and of these preferred are: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allylaurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene.
  The non-ionic monomers may equally be of very different types, among which particularly preferably crotonic acid, allyloxyacetic acid, vinylacetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the grafting polymers.
  The crosslinking agents used are preferably ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallyl sucrose having 2 to 5 allyl groups per molecule of saccharin.
  The grafted and crosslinked copolymers described above are preferably formed from:
  • i) from 5 to 85% by weight of at least one nonionic type monomer,
  • ii) from 3 to 80% by weight of at least one ionic-type monomer,
  • iii) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and
  • iv) from 0.1% to 8% by weight of a crosslinker, wherein the percentage of crosslinker is formed by the ratio of the total weights of i), ii) and iii).
• Copolymers obtained by copolymerization of at least one monomer of each of the following three groups:
  • i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
  • ii) unsaturated carboxylic acids,
  • iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C _8-18 -alcohols
  Short-chain carboxylic acids or alcohols are to be understood as meaning those having 1 to 8 carbon atoms, it being possible for the carbon chains of these compounds to be interrupted, if appropriate, by divalent hetero groups such as -O-, -NH-, -S--.
• Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester
  These terpolymers comprise monomer units of the general formulas (II) and (IV) (see above) and monomer units of one or more allyl or methallyl esters of the formula VII:
  
  wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated straight or branched C _1-6 alkyl radical and the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2.
  The abovementioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight of vinyl acetate and 8 to 20% by weight, preferably 10 to 17% by weight .-% allyl or Methaltylester of formula VII.
• Tetra and pentapolymers from
  • i) crotonic acid or allyloxyacetic acid
  • ii) vinyl acetate or vinyl propionate
  • iii) branched allyl or methallyl esters
  • iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
• Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts
• Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic α-branched monocarboxylic acid.

Further, preferably usable according to the invention as coating polymers are cationic polymers. Among the cationic polymers, the permanent cationic polymers are preferred. According to the invention, "permanently cationic" refers to those polymers which have a cationic group independently of the pH. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group.

• quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat® und Polymer JR® im Handel erhältlich sind. Die Verbindungen Celquat® H 100, Celquat® L 200 und Polymer JR®400 sind bevorzugte quaternierte Cellulose-Derivate.
• Polysiloxane mit quaternären Gruppen, wie beispielsweise die im Handel erhältlichen Produkte Q2-7224 (Hersteller: Dow Corning; ein stabilisiertes Trimethylsilylamodimethicon), Dow Corning® 929 Emulsion (enthaltend ein hydroxyl-aminomodifiziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Hersteller: General Electric), SLM-55067 (Hersteller: Wacker) sowie Abil®-Quat 3270 und 3272 (Hersteller: Th. Goldschmidt; diquaternäre Polydime- thylsiloxane, Quaternium-80),
• Kationische Guar-Derivate, wie insbesondere die unter den Handelsnamen Cosmedia®Guar und Jaguar® vertriebenen Produkte,
• Polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat®100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat®550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere.
• Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminomethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat®734 und Gafquat®755 im Handel erhältlich.
• Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere, wie sie unter der Bezeichnung Luviquat® angeboten werden.
• quaternierter Polyvinylalkohol

sowie die unter den Bezeichnungen

• Polyquaternium 2,
• Polyquaternium 17,
• Polyquaternium 18 und
• Polyquaternium 27

bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette. Die genannten Polymere sind dabei nach der sogenannten INCI-Nomenklatur bezeichnet, wobei sich detaillierte Angaben im CTFA International Cosmetic Ingredient Dictionary and Handbook, 5^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, finden, auf die hier ausdrücklich Bezug genommen wird.Preferred cationic polymers are, for example

• quaternized cellulose derivatives, such as those commercially available under the names Celquat® and Polymer JR®. The compounds Celquat® H 100, Celquat® L 200 and Polymer JR®400 are preferred quaternized cellulose derivatives.
• Polysiloxanes having quaternary groups, such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxyl-amino modified silicone, also referred to as amodimethicones), SM-2059 (Manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80),
• Cationic guar derivatives, in particular those sold under the trade names Cosmedia®Guar and Jaguar®,
• Polymers Dimethyldiallylammoniumsalze and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products commercially available under the names Merquat®100 (poly (dimethyldiallylammonium chloride)) and Merquat®550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers.
• Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminomethacrylate copolymers. Such compounds are commercially available under the names Gafquat®734 and Gafquat®755.
• Vinylpyrrolidone-Methoimidazoliniumchlorid copolymers, such as those offered under the name Luviquat®.
• quaternized polyvinyl alcohol

as well as those under the designations

• Polyquaternium 2,
• Polyquaternium 17,
• Polyquaternium 18 and
• Polyquaternium 27

known polymers with quaternary nitrogen atoms in the polymer main chain. The polymers mentioned are designated according to the so-called INCI nomenclature, details of which can be found in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, which are expressly incorporated herein by reference becomes.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers. Cationic cellulose derivatives, in particular the commercial product Polymer® JR 400, are very particularly preferred cationic polymers.

In the process according to the invention, the coating or the film material can contain, in addition to the water-soluble polymer or the water-soluble polymers, further ingredients which in particular improve the processability of the starting materials for the coating. In particular, plasticizers and release agents should be mentioned here. In addition, colorants and / or fragrances as well as optical brighteners can be incorporated into the water-soluble sheath in order to achieve aesthetic effects there.

Hydrophilic, high-boiling liquids can be used according to the invention as plasticizers, it also being possible to use solids which are solid at room temperature as a solution, dispersion or melt. Particularly preferred plasticizers are selected from the group glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, deca-, undeca-, dodecaethylene glycol, glycerol, neopentyl glycol, trimethylolpropane, pentaerythritol, mono -, di-, triglycerides, surfactants, in particular nonionic surfactants, and mixtures thereof.

Ethylene Glycol (1,2-Ethanediol, "Glycol") is a colorless, viscous, sweet-tasting, highly hygroscopic liquid that is miscible with water, alcohols and acetone and has a density of 1.113. The solidification point of ethylene glycol is -11.5 ° C, the liquid boils at 198 ° C. Technically, ethylene glycol is recovered from ethylene oxide by heating with water under pressure. Promising manufacturing processes can also be built on the acetoxylation of ethylene and subsequent hydrolysis or on synthesis gas reactions.

Diethylene glycol (2,2'-oxydiethanol, digol), HO- (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -OH, is a colorless, viscous, hygroscopic, sweet-tasting liquid of density 1.12 -6 ° C melts and boils at 245 ° C. With water, alcohols, glycol ethers, ketones, esters, chloroform, diglycol is miscible in any ratio, but not with hydrocarbons and oils. The diethylene glycol, which is usually abbreviated in practice to diglycol, is prepared from ethylene oxide and ethylene glycol (ethoxylation) and is therefore practically the starting element of the polyethylene glycols (see above).

Glycerin is a colorless, clear, heavy-bodied, odorless sweet-tasting hygroscopic liquid of density 1.261 that solidifies at 18.2 ° C. Glycerine was originally only one By-product of fat saponification, but today is technically synthesized in large quantities. Most technical processes are based on propene, which is processed into glycerol via the intermediates allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO ₃ contact via the step of the glycide.

Trimethylolpropane [TMP, etriol, etiol, 1,1,1-tris (hydroxymethyl) propane] is chemically exactly 2-ethyl-2-hydroxymethyl-1,3-propanediol and comes in the form of colorless, hygroscopic masses having a melting point of 57 -59 ° C and a boiling point of 160 ° C (7 hPa) in the trade. It is soluble in water, alcohol, acetone, but insoluble in aliphatic and aromatic hydrocarbons. The preparation is carried out by reaction of formaldehyde with butyraldehyde in the presence of alkalis.

Pentaerythritol [2,2-bis (hydroxymethyl) -1,3-propanediol, penta, PE] is a white, crystalline powder with a sweetish taste that is non-hygroscopic and combustible and has a density of 1.399, a melting point of 262 ° C and has a boiling point of 276 ° C (40 hPa). Pentaerythritol is readily soluble in boiling water, poorly soluble in alcohol and insoluble in benzene, carbon tetrachloride, ether, petroleum ether. Technically, pentaerythritol is prepared by reacting formaldehyde with acetaldehyde in aqueous solution of Ca (OH) ₂ or NaOH at 15-45 ° C. First, a mixed aldol reaction takes place in which reacting formaldehyde as a carbonyl component, acetaldehyde as a methylene component. Due to the high carbonyl activity of formaldehyde, the reaction of acetaldehyde with itself hardly occurs at all. Finally, the thus formed tris (hydroxymethyl) acetaldehyde is converted with formaldehyde in a crossed Cannizzaro reaction into pentaerythritol and formate.

Mono-, di-, triglycerides are esters of fatty acids, preferably longer-chain fatty acids with glycerol, wherein depending on the type of glyceride, one, two or three OH-groups of glycerol are esterified. As the acid component with which the glycerol can be esterified in mono-, di- or triglycerides which can be used according to the invention, there are, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), Undecanoic acid, etc. In the context of the present invention, the use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid) are preferred. . Hexacosanoic acid (cerotic acid), triacotinic acid (melissic acid) and the unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c octadecadienoic acid (linoleic acid), 9t, 12t octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c octadecranic acid (linolenic acid). For cost reasons, the native fatty substances (triglycerides) or the modified native fatty substances (partially hydrolyzed fats and oils) can also be used directly. Alternatively, fatty acid mixtures can also be prepared by cleavage of native fats and oils and subsequently separated, with the purified fractions subsequently being converted again to mono-, di- or triglycerides. Acids, which are here esterified with the glycerol, in particular coconut oil fatty acid (about 6 wt .-% C ₈ , 6 wt .-% C ₁₀ , 48 wt .-% C ₁₂ , 18 wt .-% C ₁₄ , 10 wt % C ₁₆ , 2% by weight C ₁₈ , 8% by weight C _{18 '} , 1% by weight C _{18 "} ), palm kernel oil fatty acid (about 4% by weight C ₈ , 5% by weight C ₁₀ , 50 wt .-% C ₁₂ , 15 wt .-% C ₁₄ , 7 wt .-% C ₁₆ , 2 wt .-% C ₁₈ , 15 wt .-% C _{18 '} , 1 wt .-% C _{18 "} ), tallow fatty acid (about 3% by weight C ₁₄ , 26% by weight C ₁₆ , 2% by weight C _{16 '} , 2% by weight C ₁₇ , 17% by weight C ₁₈ , 44 wt .-% C _{18 '} , 3 wt .-% C _18'' , 1 wt .-% C _18''' ), hardened tallow fatty acid (about 2 wt .-% C ₁₄ , 28 wt .-% C ₁₆ , 2 wt .-% C ₁₇ , 63 wt .-% C ₁₈ , 1 wt .-% C _{18 '} ), technical oleic acid (about 1 wt .-% C ₁₂ , 3 wt .-% C ₁₄ , 5 % By weight C ₁₆ , 6% by weight C _{16 '} , 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C _18' , 10% by weight C _{18 ''} , 0.5% by weight C _{18 '"} ), technical palmitic / stearic acid (about 1% by weight C ₁₂ , 2% by weight C ₁₄ , 45% by weight C ₁₆ , 2% by weight). % C ₁₇ , 47% by weight C ₁₈ , 1% by weight C _{18 '} ) and soybean oil fatty acid (approx. 2 wt .-% C ₁₄ , 15 wt .-% C ₁₆ , 5 wt .-% C ₁₈ , 25 wt .-% C _{18 '} , 45 wt .-% C _{18 "} , 7 wt .-% C _18''' ).

Surfactants, in particular nonionic surfactants, are also suitable as further plasticizers. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which for a particular product a whole or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fat ohol with 14 EO, 25 EO, 30 EO or 40 EO.

With particular preference be used as plasticizers nonionic surfactants having a melting point above room temperature. Accordingly, preferred wraps are characterized in that nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43, are used as the plasticizer , 3 ° C, are used.

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.

In a preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.

A particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, in particularly preferred processes according to the invention, ethoxylated nonionic surfactant (s) which are selected from C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).

The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.

More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Further preferred nonionic surfactants satisfy the formula

R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ],

in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula may be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is to

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

Further preferably used as plasticizers substances may be glycerol carbonate, Prpylenglycol and propylene carbonate.

Glycerol carbonate is accessible by transesterification of ethylene carbonate or dimethyl carbonate with glycerol, as by-products of ethylene glycol or methanol incurred. Another synthetic route is based on glycidol (2,3-epoxy-1-propanol), which is converted under pressure in the presence of catalysts with CO ₂ to glycerol carbonate. Glycerine carbonate is a clear, easily agitated liquid with a density of 1.398 gcm ^-3 , which boils at 125-130 ° C (0.15 mbar).

There are two isomers of propylene glycol, 1,3-propanediol and 1,2-propanediol. 1,3-Propanediol (trimethylene glycol) is a neutral, colorless and odorless, sweet-tasting liquid of density 1,0597, which solidifies at -32 ° C and boils at 214 ° C. The preparation of 1,3-propanediol succeeds from acrolein and water with subsequent catalytic hydrogenation.

Technically much more significant is 1,2-propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid, density 1.0381, which solidifies at -60 ° C and boils at 188 ° C. 1,2-Propanediol is prepared from propylene oxide by water addition.

Propylene carbonate is a water-bright, easily mobile liquid, with a density of 1.21 gcm ^-3 , the melting point is -49 ° C, the boiling point at 242 ° C. Also propylene carbonate is industrially accessible by reaction of propylene oxide and CO ₂ at 200 ° C and 80 bar.

As additional additives, which are preferably in solid form at room temperature, especially highly disperse silicas are suitable. Fumed silicas such as the commercially available Aerosil® or precipitated silicas are suitable here. Particularly preferred processes according to the invention are characterized in that as further additives one or more materials from the group (preferably highly dispersed) silica, dispersion powder, high molecular weight polyglycols, stearic acid and / or stearic acid salts, and / or from the group of inorganic salts such as sodium sulfate, calcium chloride and / or from the group of Inclusionbildner such as urea, cyclodextrin and / or from the group of super adsorbers such as (preferably crosslinked) polyacrylic acid and / or their salts such as Cabloc 5066 / CTF and mixtures thereof, is / are used.

As mentioned at the outset, casting bodies are used in the process according to the invention as a washing or cleaning agent portion, with particular preference. As particularly advantageous starting materials for the o.g. Casting bodies have been found to be washing or cleaning agent dispersions. The processing of these dispersions into casting bodies and the subsequent packaging by means of the process according to the invention has a number of advantages. First of all, spatial shapes can be realized by the casting technology, which are not accessible by the tabletting. Furthermore, the castings, as described below against the tablets characterized by improved solubility. Finally, foundry bodies, unlike tablets, are generally ductile, and can be plastically deformed to some degree in the course of the packaging process according to the invention by the action of pressure, for example when applying the top film or during the subsequent fixing of the top film on the bottom film. As a result of this plastic deformation, irregularities in the production of the casting bodies (for example height, thickness, etc.) can be corrected and / or optically enhancing features can be embossed into the casting body.

• i) 10 bis 65 Gew.-% Dispersionsmittel und
• ii) 30 bis 90 Gew.-% dispergierte Stoffe

umfaßt.A further subject of the present application is therefore a process according to the invention in which a washing or cleaning agent portion is a washing or cleaning agent, in the form of a dispersion of solid particles in a dispersion medium, which, based on their total weight,

• i) from 10 to 65% by weight of dispersant and
• ii) 30 to 90% by weight of dispersed substances

includes.

Particularly preferred dispersions are characterized in that the dispersion has a density above 1.040 g / cm ³ . Very particularly preferably, dispersions according to the invention having a density of 1040-1670 g / cm ^3, preferably 1.120 to 1.610 g / cm ^3, particularly preferably 1.210 to 1.570 g / cm ^3, most preferably 1.290 to 1.510 g / cm ³ , and in particular between 1.340 and 1.480 g / cm ³ . The density data refer to the densities of the dispersions at 20 ° C.

As dispersion in this application a system of several phases is referred to, one of which is dispersed continuously (dispersion medium) and at least one further (dispersed substances).

Particularly preferred detergents or cleaners according to the invention are characterized in that they contain the dispersant in amounts above 11% by weight, preferably above 13% by weight, more preferably above 15% by weight, most preferably above 17% by weight. and in particular above 19 wt .-%, each based on the total weight of the dispersion. Also feasible and also preferred are agents according to the invention which have a dispersion with a proportion by weight of dispersant above 20% by weight, preferably above 21% by weight and in particular above 22% by weight, in each case based on the total weight of the dispersion. The maximum content of preferred dispersions of dispersants according to the invention, based on the total weight of the dispersion, is preferably less than 63% by weight, preferably less than 57% by weight, more preferably less than 52% by weight, very particularly preferably less than 47 Wt .-% and in particular less than 37 wt .-%. In the context of the present invention, preference is given in particular to detergents or cleaners which, based on their total weight, contain dispersants in amounts of from 12 to 62% by weight, preferably from 17 to 49% by weight and in particular from 23 to 38% by weight. % contain.

The dispersants used are preferably water-soluble or water-dispersible. The solubility of these dispersants at 25 ° C. is preferably more than 200 g / l, preferably more than 300 g / l, more preferably more than 400 g / l, very preferably between 430 and 620 g / l and especially between 470 and 580 g / l.

Suitable dispersants in the context of the present invention are preferably the water-soluble or water-dispersible polymers, in particular the water-soluble or water-dispersible nonionic polymers. The dispersant may be both a single polymer and mixtures of various water-soluble or water-dispersible polymers. In a further preferred embodiment of the present invention, the dispersant or, if the dispersant comprises substances other than the water-soluble or water-dispersible polymers, at least 50 wt .-% of the polymer mixture of water-soluble or water-dispersible nonionic polymers from the group of polyvinylpyrrolidone, vinylpyrrolidone / vinyl ester -Copolymers, cellulose ethers, polyvinyl alcohols, polyalkylene glycols, in particular polyethylene glycol and / or polypropylene glycol.

die durch radikalische Polymerisation von 1-Vinylpyrrolidon nach Verfahren der Lösungs- oder Suspensionspolymerisation unter Einsatz von Radikalbildnern (Peroxide, Azo-Verbindungen) als Initiatoren hergestellt werden. Die ionische Polymerisation des Monomeren liefert nur Produkte mit niedrigen Molmassen. Handelsübliche Polyvinylpyrrolidone haben Molmassen im Bereich von ca. 2500-750000 g/mol, die über die Angabe der K-Werte charakterisiert werden und - K-Wert-abhängig - Glasübergangstemperaturen von 130-175° besitzen. Sie werden als weiße, hygroskopische Pulver oder als wäßrige. Lösungen angeboten. Polyvinylpyrrolidone sind gut löslich in Wasser und einer Vielzahl von organischen Lösungsmitteln (Alkohole, Ketone, Eisessig, Chlorkohlenwasserstoffe, Phenole u.a.).Polyvinylpyrrolidones are preferred dispersants in the invention. Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinones)], abbreviation PVP, are polymers of the general formula (I)

which are prepared by free-radical polymerization of 1-vinylpyrrolidone by the method of solution or suspension polymerization using free-radical initiators (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer provides only low molecular weight products. Commercially available polyvinylpyrrolidones have molecular weights in the range of about 2500-750000 g / mol, which are characterized by the specification of the K values and - K value-dependent - glass transition temperatures of 130-175 ° have. They are called white, hygroscopic powder or aqueous. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).

Viliylpyrrolidone / vinyl ester copolymers, such as those sold under the trademark Luviskol® (BASF). Luviskol® VA 64 and Luviskol® VA 73, in each case vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.

als charakteristischem Grundbaustein der Makromoleküle. Von diesen haben die Vinylacetat-Polymere (R = CH₃) mit Polyvinylacetaten als mit Abstand wichtigsten Vertretern die größte technische Bedeutung.The vinyl ester polymers are vinyl ester-accessible polymers having the moiety of the formula (II)

as a characteristic building block of the macromolecules. Of these, the vinyl acetate polymers (R = CH ₃ ) with polyvinyl acetates as by far the most important representatives of the greatest technical importance.

The polymerization of the vinyl esters is carried out free-radically by different processes (solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization). Copolymers of vinyl acetate with vinylpyrrolidone contain monomer units of the formulas (I) and (II)

Cellulose ethers, such as hydroxypropyl cellulose, hydroxyethyl cellulose and methyl hydroxypropyl cellulose, such as those sold under the trademarks Culminal® and Benecel® (AQUALON).

in R für H oder einen Alkyl-, Alkenyl-, Alkinyl-, Aryl- oder Alkylarylrest steht. In bevorzugten Produkten steht mindestens ein R in Formel für -CH₂CH₂CH₂-OH oder -CH₂CH₂-OH. Celluloseether werden technisch durch Veretherung von Alkalicellulose (z.B. mit Ethylenoxid) hergestellt. Celluloseether werden charakterisiert über den durchschnittlichen Substitutionsgrad DS bzw. den molaren Substitutionsgrad MS, die angeben, wieviele Hydroxy-Gruppen einer Anhydroglucose-Einheit der Cellulose mit dem Veretherungsreagens reagiert haben bzw. wieviel mol des Veretherungsreagens im Durchschnitt an eine Anhydroglucose-Einheit angelagert wurden. Hydroxyethylcellulosen sind ab einem DS von ca. 0,6 bzw. einem MS von ca. 1 wasserlöslich. Handelsübliche Hydroxyethyl- bzw. Hydroxypropylcellulosen haben Substitutionsgrade im Bereich von 0,85-1,35 (DS) bzw. 1,5-3 (MS). Hydroxyethyl- und - propylcellulosen werden als gelblich-weiße, geruch- und geschmacklose Pulver in stark unterschiedlichen Polymerisationsgraden vermarktet. Hydroxyethyl- und -propylcellulosen sind in kaltem und heißem Wasser sowie in einigen (wasserhaltigen) organischen Lösungsmitteln löslich, in den meisten (wasserfreien) organischen Lösungsmitteln dagegen unlöslich; ihre wäßrigen Lösungen sind relativ unempfindlich gegenüber Änderungen des pH-Werts oder Elektrolyt-Zusatz.Cellulose ethers can be described by the following general formula

R is H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in formula is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of the cellulose reacted with the etherifying reagent or how many moles of the etherifying agent were attached on average to an anhydroglucose unit. Hydroxyethylcelluloses are water-soluble from a DS of about 0.6 or an MS of about 1. Commercially available hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS), respectively. Hydroxyethyl and - propylcelluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propylcelluloses are soluble in cold and hot water as well as in some (hydrous) organic solvents but insoluble in most (anhydrous) organic solvents; their watery Solutions are relatively insensitive to changes in pH or electrolyte addition.

Polyvinyl alcohols, referred to as PVAL for short, are polymers of the general structure

[-CH ₂ -CH (OH) -] _n

in small proportions also structural units of the type

[-CH ₂ -CH (OH) -CH (OH) -CH ₂ ]

contain. Since the corresponding monomer, the vinyl alcohol, is not stable in free form, polyvinyl alcohols are prepared via polymer-analogous reactions by hydrolysis, but in particular technically by alkaline catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol) in solution. By these technical methods also PVAL are accessible, which contain a predeterminable residual portion of acetate groups.

Commercially available PVAL (eg Mowiol® grades from Hoechst) come on the market as white-yellowish powders or granules with degrees of polymerization in the range of about 500-2500 (corresponding to molar masses of about 20,000-100,000 g / mol) and have different degrees of hydrolysis of 98-99 and 87-89 mol%, respectively. So they are partially hydrolyzed polyvinyl acetates with a residual content of acetyl groups of about 1-2 or 11-13 mol%.

Suitable polyalkylene glycols are, in particular, polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol, those of general formula III

H- (O-CH ₂ -CH ₂ ) _n -OH (III)

satisfy, where n can assume values between 1 (ethylene glycol) and several thousand. For polyethylene glycols there are various nomenclatures that can lead to confusion. Technically common is the indication of the average relative molecular weight following the indication "PEG", so that "PEG 200" characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210. For cosmetic ingredients, a different nomenclature is used, in which the abbreviation PEG is provided with a hyphen and directly to the Hyphen follows a number which corresponds to the number n in formula VII above. According to this nomenclature (so-called INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) are, for example, PEG-4, PEG-6, PFG-8, PEG-9 , PEG-10, PEG-12, PEG-14 and PEG-16. Commercially available are polyethylene glycols, for example under the trade names Carbowax® PEG 200 (Union Carbide), Einkapol® 200 (ICI Americas), Lipoxol® 200 MED (HUBS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rhone -Poulenc), Lutrol® E300 (BASF) and the corresponding trade name with higher numbers. The average relative molecular weight of at least one of the dispersants used in the detergents or cleaners according to the invention, in particular at least one of the poly (alkylene) glycols used, is preferably between 200 and 36,000, preferably between 200 and 6000 and more preferably between 300 and 5000.

genügen, wobei n Werte zwischen 1 (Propylenglycol) und mehreren tausend annehmen kann. Technisch bedeutsam sind hier insbesondere Di-, Tri- und Tetrapropylenglycol, d.h. die Vertreter mit n=2, 3 und 4 in Formel IV.Polypropylene glycols (abbreviated PPG) are polymers of propylene glycol which are of general formula IV

satisfy, where n can assume values between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri- and tetrapropylene glycols, ie the representatives with n = 2, 3 and 4 in formula IV.

Particularly preferred washing or cleaning agents according to the invention contain as dispersing agent a nonionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, wherein the weight fraction of the poly (ethylene) glycol on the total weight of all dispersing agents is preferably between 10 and 90% by weight, more preferably between 30 and 80% by weight and in particular between 50 and 70% by weight. Detergents or cleaning compositions according to the invention in which the dispersion medium is more than 92% by weight, preferably more than 94% by weight, more preferably more than 96% by weight, very particularly preferably more than 98, are particularly preferred Wt .-% and in particular to 100 wt .-% of a poly (alkylene) glycol, preferably poly (ethylene) glycol and / or poly (propylene) glycol, but in particular Poly (ethylene) glycol. Dispersing agents which also contain poly (propylene) glycol in addition to poly (ethylene) glycol preferably have a ratio of the weight proportions of poly (ethylene) glycol to poly (propylene) glycol between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, more preferably between 10: 1 and 1.5: 1 and in particular between 7: 1 and 2: 1 on.

Further preferred dispersants are the nonionic surfactants, which are used alone, but particularly preferably in combination with a nonionic polymer.

As nonionic surfactants are preferably used alkoxylated, preferably ethoxylated, especially primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

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

wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

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

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic Alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C _1-4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this radical.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, the machine dishwashing detergents according to the invention contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols.

Particular preference is given to compositions according to the invention which comprise a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred dishwashing detergents are characterized in that they contain nonionic surfactant (s) having a melting point above 20 ° C., preferably above 25 ° C., more preferably between 25 and 60 ° C. and in particular between 26.6 and 43, 3 ° C, included.

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If highly viscous nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as Polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also distinguished by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.

A particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred dishwashing agents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants. Preferred dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic Surfactants are included.

More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants which may be used with particular preference are available, for example, under the name Poly Tergent® SLF-18 from Olin Chemicals.

A further preferred dishwashing detergent according to the invention contains nonionic surfactants of the formula (VI)

R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ], (VI)

in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula may be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly prefers. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is to

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

Summarizing the latter statements, dishwashing agents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

in which x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃; -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Machine dishwashing agents according to the invention which contain surfactants of the general formula VII as nonionic surfactant (s) are preferred here

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently of one another are integers from 1 to 6.

The preferred nonionic surfactants of formula VII can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in formula VII above may vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually undisplayed, wherein the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, mechanical ones according to the invention are Dishwashing agents are preferred in which R ¹ in formula VII is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ are suitable. Preferred automatic dishwashing agents are characterized in that R ² and R ³ are each a residue -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.

In summary, nonionic surfactants which have a C _9-15 -alkyl radical with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units are particularly preferred for use in the agents according to the invention. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula (VIII)

R ¹ O [CH ₂ CH (R ³ ) O] _x R ² (VIII)

in which R ^{1 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{2 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably between 1 and have 5 hydroxy groups and are preferably further functionalized with an ether group, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2- Butyl radical, x for values between 1 and 40.

In particularly preferred nonionic surfactants of the above formula (XIII), R ^{3 is} H. In the resulting end-capped poly (oxyalkylated) nonionic surfactants of the formula (IX)

R ¹ O [CH ₂ CH ₂ O] _x R ² (IX)

In particular those nonionic surfactants are preferred in which R ^{1 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, R ^{2 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and x stands for values between 1 and 40.

In particular, those end-capped poly (oxyalkylated) nonionic surfactants are preferred, which according to the formula (X)

R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² (X)

in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical with 1 have up to 30 carbon atoms R ² , which is a monohydroxylated intermediate group -CH ₂ CH (OH) - adjacent. In this formula, x stands for values between 1 and 40. Such end-capped poly (oxyalkylated) nonionic surfactants can be prepared, for example, by reacting a terminal epoxide of the formula R ² CH (O) CH ₂ with an ethoxylated alcohol of the formula R ¹ O [CH ₂ CH ₂ O] _x-1 CH ₂ CH ₂ OH.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.

Particularly preferred detergents or cleaners according to the invention contain as dispersing agent at least one nonionic surfactant, preferably at least one end-capped polyoxyalkylenated nonionic surfactant, the proportion by weight of the nonionic surfactant in the total weight of all dispersants preferably between 1 and 60 wt .-%, more preferably between 2 and 50 wt .-% and in particular between 3 and 40 wt.%. Particular preference is given to washing or cleaning agents according to the invention in which the total weight of the nonionic surfactant (s) in the total weight of the composition according to the invention is between 0.5 and 40% by weight, preferably between 1 and 30% by weight, especially preferably between 2 and 25 and in particular between 2.5 and 23 wt .-% is.

Preferred washing or cleaning agents according to the invention are characterized in that at least one dispersing agent has a melting point above 25 ° C., preferably above 35 ° C. and in particular above 40 ° C. Particularly preferred is the use of dispersants having a melting point or melting range between 30 and 80 ° C, preferably between 35 and 75 ° C, more preferably between 40 and 70 ° C and in particular between 45 and 65 ° C, these dispersants, based on the total weight of the dispersants used, a weight fraction above 10 wt .-%, preferably above 40 wt .-%, more preferably above 70 wt.% And in particular between 80 and 100 wt .-%.

Preferred agents according to the invention are dimensionally stable at 20 ° C. As dimensionally stable means according to the invention which have an intrinsic dimensional stability, which enables them to assume a non-disintegrating spatial form under normal conditions of manufacture, storage, transport and handling by the consumer, said space form under the conditions mentioned over longer Time, preferably 4 weeks, more preferably, 8 weeks and especially 32 weeks, not changed, that is, under the usual conditions of manufacture, storage, transport and handling by the consumer remains in the caused by the production spatial-geometric shape that is, does not melt away.

The water content of the abovementioned dispersions, based on their total weight, is preferably less than 30% by weight, preferably less than 23% by weight, preferably less than 19% by weight, particularly preferably less than 15% by weight and in particular less than 12% by weight. According to preferred detergents or cleaners are low in water or anhydrous. Particularly preferred washing or cleaning agents according to the invention are characterized in that the dispersion, based on their total weight, a content of free Water below 10 wt .-%, preferably below 7 wt .-%, more preferably below 3 wt .-% and in particular below 1 wt .-%.

The density of the dispersants used at 20 ° C. is preferably between 0.8 and 1.4 g / cm ³ . Are particularly preferred as dispersants water-soluble or water-dispersible polymers having a density (20 ° C) above 1.040 g / cm ^3, preferably 1040-1670 g / cm ^3, preferably 1.120 to 1.610 g / cm ^3, particularly preferably 1.210 to 1.570 g / cm ³ , very particularly preferably between 1.290 and 1.510 g / cm ³ , and in particular between 1.340 and 1.480 g / cm ³ used.

Detergents or cleaning compositions which are preferred according to the invention are characterized in that they are dissolved in water (40 ° C.) in less than 12 minutes, preferably less than 10 minutes, preferably less than 9 minutes, more preferably less than 8 minutes, and in particular dissolve in less than 7 minutes. To determine the solubility, 20 g of the dispersion are introduced into the interior of a dishwashing machine (Miele G 646 PLUS). The main rinse of a standard rinse program (45 ° C) is started. The determination of the solubility is carried out by the measurement of the conductivity, which is recorded via a conductivity sensor. The dissolution process is completed when the maximum conductivity is reached. In the conductivity diagram, this maximum corresponds to a plateau. The conductivity measurement starts with the replacement of the circulation pump in the main wash cycle. The amount of water used is 5 liters.

The following is an illustration of the ingredients that may be included in the portions coated with the aid of the method according to the invention:

The washing or cleaning agent portions coated with the aid of the method according to the invention may contain all customary constituents of detergents or cleaners, which will be briefly described below.

The washing or cleaning agent portions coated with the process according to the invention preferably comprise surfactant (s), wherein anionic, nonionic, cationic and / or amphoteric surfactants can be used. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants in the case of textile detergents, where the proportion of anionic surfactants should be greater than the proportion of nonionic surfactants. Of the Total surfactant content of the washing or cleaning agent portions is preferably below 30% by weight, based on the total agent. Nonionic surfactants have already been described above as optional plasticizers for the coating. The same substances can also be used as detergents in the compositions.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

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

wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which are customary can be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

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

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.

[Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

The content of detergent or cleaning agent portions of nonionic surfactants which is suitable for textile washing and which is produced by the process according to the invention is from 5 to 20% by weight, preferably from 7 to 15% by weight and in particular from 9 to 14% by weight, based in each case on the entire remedy.

In dishwasher detergents, low-foaming nonionic surfactants are preferably used.

In connection with the surfactants mentioned anionic, cationic and / or amphoteric surfactants can be used, which, because of their foaming behavior in automatic dishwashing detergents have only minor importance and mostly only in amounts below 10 wt .-%, usually even below 5 wt .-%, for example from 0.01 to 2.5 wt .-%, each based on the agent used become. In detergents, however, these surfactants have a significantly higher importance. The washing or cleaning agent portions prepared according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as surfactant component.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_nT-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.As cationic active substances, the agents according to the invention may contain, for example, cationic compounds of the formulas X, XI or XII:

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each group R ^{2 is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also, 2,3-alkyl sulfates prepared, for example, according to U.S. Patents 3,234,258 or 5,075,041, which can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and in particular from natural fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.

The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The content of preferred textile detergents according to the invention on anionic surfactants is 5 to 25% by weight, preferably 7 to 22% by weight and in particular 10 to 20% by weight, in each case based on the total agent.

In the context of the present invention, preferred agents additionally comprise one or more substances from the group of builders, bleaches, bleach activators, enzymes, Electrolytes, nonaqueous solvents, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, crease inhibitors, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids , Phobic and impregnating agents, swelling and anti-slip agents and UV absorbers.

Builders which may be present in the compositions according to the invention are in particular phosphates, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

The use of the generally known phosphates as builders is possible according to the invention, unless such use should not be avoided for ecological reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium phosphate, KDP), KH ₂ PO ₄ , is a white salt of 2.33 gcm ^-3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are used according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x + 1} H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Preferred crystalline Phyllosilicates of the formula given are those in which M is sodium and x takes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification 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 do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a dissolution delay compared with the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula

nNa ₂ O • (1-n) K ₂ O • Al ₂ O ₃ • (2 - 2.5) SiO ₂ • (3.5-5.5) H ₂ O

can be described. The zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Other important builders are in particular the carbonates, citrates and silicates. Preference is given to using trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicatic builders from the class of disilicates and / or metasilicates.

As further constituents alkali carriers may be present. Suitable alkali carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances, preference being given for the purposes of this invention to using the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate.

Particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate.

Also particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.

In addition, further ingredients may be present, with washing, rinsing or cleaning agents according to the invention being preferred which additionally contain one or more substances from the group of acidifying agents, chelating agents or coating-inhibiting polymers.

Acidifying agents are both inorganic acids and organic acids, provided that they are compatible with the other ingredients. For reasons of consumer protection and handling safety in particular the solid mono-, oligo- and polycarboxylic acids are used. Again preferred from this group are citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and also polyacrylic acid. The anhydrides of these acids can also be used as acidifying agents in particular maleic anhydride and succinic anhydride are commercially available. Organic sulfonic acids such as sulfamic acid are also usable. Commercially available and likewise preferably usable as acidifying agent in the context of the present invention is Sokalan® DCS (trademark of BASF), a mixture of succinic acid (maximum 31% by weight), glutaric acid (maximum 50% by weight) and adipic acid ( at most 33% by weight).

Another possible group of ingredients are the chelating agents. Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". In this case, normally stretched compounds are closed by complex formation via an ion into rings. The number of bound ligands depends on the coordination number of the central ion.

Common and preferred chelating agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Also, complex-forming polymers, ie polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and react with suitable metal atoms generally with the formation of chelate complexes, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.

Complexing groups (ligands) of conventional complexing polymers are iminodiacetic, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cyclic) polyamino, mercapto, 1,3-dicarbonyl and Crown ether residues with z. T. very specific. Activities towards ions of different metals. Base polymers of many also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided by polymer-analogous transformations with other ligand functionalities.

• (i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
• (ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,
• (iii) geminalen Diphosphonsäuren,
• (iv) Aminophosphonsäuren,
• (v) Phosphonopolycarbonsäuren,
• (vi) Cyclodextrine

in Mengen oberhalb von 0,1 Gew.-%, vorzugsweise oberhalb von 0,5 Gew.-%, besonders bevorzugt oberhalb von 1 Gew.-% und insbesondere oberhalb von 2,5 Gew.-%, jeweils bezogen auf das Gewicht des Mittels, enthalten.In the context of the present invention, washing or cleaning agent tablets which contain one or more chelate complexing agents from the groups of the group are particularly preferred

• (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
• (ii) nitrogen-containing mono- or polycarboxylic acids,
• (iii) geminal diphosphonic acids,
• (iv) aminophosphonic acids,
• (v) phosphonopolycarboxylic acids,
• (vi) cyclodextrins

in amounts above 0.1 wt .-%, preferably above 0.5 wt .-%, more preferably above 1 wt .-% and in particular above 2.5 wt .-%, each based on the weight of By means of, included.

• a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt wie Gluconsäure,
• b) stickstoffhaltige Mono- oder Polycarbonsäuren wie Ethylendiamintetraessigsäure (EDTA), N-Hydroxyethylethylendiamintriessigsäure, Diethylentriaminpentaessigsäure, Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N,N-Di-(β-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-asparaginsäure oder Nitrilotriessigsäure (NTA),
• c) geminale Diphosphonsäuren wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon und 1-Aminoethan-1,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon,
• d) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure), Diethylentriaminpenta(methylenphosphonsäure) oder Nitrilotri(methylenphosphonsäure),
• e) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure sowie
• f) Cyclodextrine.

In the context of the present invention, all complexing agents of the prior art can be used. These can belong to different chemical groups. Preferably, used individually or in admixture with each other:

• a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid,
• b) nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N, N-di (β-hydroxyethyl) glycine, N- (1,2- Dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA),
• c) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), their higher homologues having up to 8 carbon atoms and hydroxy- or amino-containing derivatives thereof and 1-aminoethane-1,1-diphosphonic acid whose higher homologues with up to 8 carbon atoms and hydroxyl- or amino-containing derivatives thereof,
• d) aminophosphonic acids, such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or nitrilotri (methylenephosphonic acid),
• e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and
• f) cyclodextrins.

For the purposes of this patent application, polycarboxylic acids a) are understood as meaning carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl groups and the hydroxyl groups contained in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. In the case of the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

Scale-inhibiting polymers can likewise be present in the agents according to the invention. These substances, which could be constructed chemically different, for example, from the groups of low molecular weight polyacrylates having molecular weights between 1000 and 20,000 daltons, with polymers having molecular weights below 15,000 daltons are preferred.

Scale-inhibiting polymers may also have co-builder properties. As organic cobuilders, it is possible in particular to use polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates in the dishwasher detergents according to the invention. These classes of substances are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if 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 thereof.

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 for setting a lower and milder pH of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

As a builder or coating inhibitor further polymeric polycarboxylates are suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 500 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 1000 to 10 000 g / mol, and particularly preferably from 1000 to 4000 g / mol, may again be preferred from this group.

Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers are particularly preferably used in the compositions according to the invention. The sulfonic acid group-containing copolymers are described in detail below.

Also suitable are copolymeric polycarboxylates, 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 from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives , Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, 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 common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.

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. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition to the substances from the mentioned substance classes, the compositions according to the invention may contain further customary ingredients of detergents, dishwashing detergents or cleaners, wherein especially bleaching agents, bleach activators, enzymes, silver protectants, dyes and fragrances are of importance. These substances will be described below.

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder-Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist.In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the detergent tablets. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.
Further particularly preferred bleach activators are cationic nitrile of the formula below

in the R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or Alkenylarylrest with a C _1-24 alkyl group, or a substituted alkyl or Alkenylaryl radical having a C _1-24 -alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ - CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ - OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion.

This general formula covers a large number of cationic nitriles which can be used in the context of the present invention. With particular advantage, the compositions according to the invention contain cationic nitriles in which R ^{1 is} methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n Hexadecyl or n-octadecyl radical. R ² and R ³ are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, wherein one or both radicals may advantageously also be a Cyanomethylenrest. In the following table, preferred cationic nitriles of the formula (I) according to the invention are characterized by their radicals R ¹ , R ² and R ³ : R ¹ R ² R ³ -H -CH ₃ -CH ₃ -H -CH ₂ -CH ₃ -CH ₃ -H -CH ₂ -CH ₂ -CH ₃ -CH ₃ -H -CH (CH ₃ ) -CH ₃ -CH ₃ -H -CH ₂ -OH -CH ₃ -H -CH ₂ -CH ₂ -OH -CH ₃ -H -CH (OH) -CH ₃ -CH ₃ -H -CH ₂ -CH ₂ -CH ₂ -OH -CH ₃ -H -CH ₂ -CH (OH) -CH ₃ -CH ₃ -H -CH (OH) -CH ₂ -CH ₃ -CH ₃ -H - (CH ₂ CH ₂ -O) ₁ H -CH ₃ -H - (CH ₂ CH ₂ -O) ₂ H -CH ₃ -H - (CH ₂ CH ₂ -O) ₃ H -CH ₃ -H - (CH ₂ CH ₂ O) ₄ H -CH ₃ -H - (CH ₂ CH ₂ O) ₅ H -CH ₃ -H - (CH ₂ CH ₂ O) ₆ H -CH ₃ -CH ₃ -CH ₃ -CH ₃ -CH ₃ -CH ₂ -CH ₃ -CH ₃ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₃ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₃ -CH ₃ -CH ₂ -OH -CH ₃ -CH ₃ -CH ₂ -CH ₂ -OH -CH ₃ -CH ₃ -CH (OH) -CH ₃ -CH ₃ -CH ₃ -CH ₂ -CH ₂ -CH ₂ -OH -CH ₃ -CH ₃ -CH ₂ -CH (OH) -CH ₃ -CH ₃ -CH ₃ -CH (OH) -CH ₂ -CH ₃ -CH ₃ -CH ₃ - (CH ₂ CH ₂ -O) ₁ H -CH ₃ -CH ₃ - (CH ₂ CH ₂ -O) ₂ H -CH ₃ -CH ₃ - (CH ₂ CH ₂ -O) ₃ H -CH ₃ -CH ₃ - (CH ₂ CH ₂ O) ₄ H -CH ₃ -CH ₃ - (CH ₂ CH ₂ O) ₅ H -CH ₃ -CH ₃ - (CH ₂ CH ₂ O) ₆ H -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₃ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -OH -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -OH -CH ₃ -CH ₂ -CH ₃ -CH (OH) -CH ₃ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₂ -OH -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH (OH) -CH ₃ -CH ₃ -CH ₂ -CH ₃ -CH (OH) -CH ₂ -CH ₃ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -OH -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -OH -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH (OH) -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₂ -OH -CH ₂ -CH ₃ -CH ₂ -CH, -CH ₂ -CH (OH) -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH (OH) -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -OH -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH ₂ OH -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH (OH) -CH ₃ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₂ -OH -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH (OH) -CH ₃ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH (OH) -CH ₂ -CH ₃ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -OH -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -OH -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH (OH) -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₂ -OH -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH (OH) -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH (OH) -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -OH -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH ₂ -OH -CH ₃ -CH (CH ₃ ) -CH ₃ -CH (OH) -CH ₃ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH ₂ -CH ₂ -OH -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH (OH) -CH ₃ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH (OH) -CH ₂ -CH ₃ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₃ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -OH -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH ₂ -OH -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH (OH) -CH ₃ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH ₂ -CH ₂ -OH -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH ₂ -CH (OH) -CH ₃ -CH ₂ -CH ₃ -CH (CH ₃ ) -CH ₃ -CH (OH) -CH ₂ -CH ₃ -CH ₂ -CH ₃

in der R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt sind aus -CH₃, -CH₂-CH₃, -CH₂-CH_2-CH₃, -CH(CH₃)-CH₃, wobei R⁴ zusätzlich auch -H sein kann und X ein Anion ist, wobei vorzugsweise R⁵ = R⁶ = -CH₃ und insbesondere R⁴ = R⁵ = R⁶ = -CH₃ gilt, sind erfindungsgemäß besonders bevorzugtFor ease of synthesis, preference is given to compounds in which the radicals R ¹ to R ^{3 are} identical, for example (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^-, (CH ₃ CH ₂ CH _{2) 3} N ⁽⁺⁾ CH ₂ -CN X ^-, (CH ₃ CH (CH _{3)) 3} N ⁽⁺⁾ CH ₂ -CN X ^-, or (HO -CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- . Particularly preferred are cationic nitriles of the following formula

are independently in the R ^4, R ⁵ and R ⁶ are selected from -CH _3, -CH ₂ -CH _3, -CH ₂ -CH ₂ -CH _3, -CH (CH ₃₎ -CH _3, wherein R ⁴ is additionally also -H and X is an anion, wherein preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ , are particularly preferred according to the invention

Preferred anions X ^(-) are selected from the group chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate), cumene sulfonate or xylene sulfonate.

In addition to the conventional bleach activators or in their place also so-called bleach catalysts can be incorporated into the moldings. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer. Particularly suitable are from bacterial strains or Fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. These are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation. The proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.12 to about 2 wt .-%.

Detergent tablets for machine dishwashing according to the invention may contain corrosion inhibitors for the protection of the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these Classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

As electrolytes from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl ₂ in the agents according to the invention is preferred. The proportion of electrolytes in the inventive compositions is usually 0.5 to 5 wt .-%.

In order to bring the pH of the agents according to the invention in the desired range, the use of pH adjusting agents may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited. Usually, the amount of these adjusting agents does not exceed 5% by weight of the total formulation.

In order to improve the aesthetic impression of the agents according to the invention, they can be dyed with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to textile fibers so as not to stain them.

Suitable foam inhibitors which can be used in the compositions according to the invention are, for example, soaps, paraffins or silicone oils, which may optionally be applied to support materials. Suitable anti-redeposition agents, which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether and the polymers known from the prior art Phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.

Optical brighteners (so-called "whiteners") can be added to the compositions according to the invention in order to eliminate graying and yellowing of the treated textiles. These fabrics impinge on the fiber and cause whitening and bleaching by transforming invisible ultraviolet radiation into visible longer wavelength light, emitting ultraviolet light absorbed from the sunlight as faint bluish fluorescence, and pure yellow with the yellowed or yellowed wash White results. Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives. The optical brighteners are usually used in amounts between 0.05 and 0.3 wt .-%, based on the finished composition.

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatine, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful. However, preference is given to using cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the compositions

The compositions according to the invention can also be provided with further added benefits. Here are, for example, color transfer inhibiting compositions, anti-gray formula agents, ironing facilitators, fragrance release agents, soil repellency improvers, antibacterial agents Agents, UV protectants, color-enhancing agents, etc. can be formulated. Some examples are explained below:

Since textile fabrics, in particular of rayon, rayon, cotton and their mixtures, can crumple because the individual fibers against bending, kinking. Pressing and squeezing transverse to the fiber direction are sensitive, the compositions of the invention may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, - alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

For controlling microorganisms, the compositions of the invention may contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistats and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, and the compounds according to the invention can be completely dispensed with.

In order to prevent undesirable changes in the agents and / or the treated textiles caused by oxygen and other oxidative processes, the agents may contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

An increased wearing comfort can result from the additional use of antistatic agents which are additionally added to the agents according to the invention. Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges. External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable as antistatic agents for textiles or as an additive to detergents, with an additional finishing effect being achieved.

To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, for example, silicone derivatives can be used in the compositions according to the invention. These additionally improve the rinsing out of the compositions according to the invention by their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones are in the range between 100 and 100,000 centistokes at 25 ° C, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total agent can be used.

Finally, the agents according to the invention may also contain UV absorbers which are absorbed by the treated textiles and improve the light resistance of the fibers. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2 and / or 4 position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.

If automatic dishwasher detergents are prepared by means of the process according to the invention, they preferably contain further substances which improve the cleaning result and / or perform further functions. A particularly preferred ingredient for automatic dishwasher detergents is a polymer which contains sulfonic acid groups. Preferred compositions according to the invention are therefore characterized in that they comprise at least one copolymer of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers

In the context of the present invention, unsaturated carboxylic acids of the formula XIII are preferred as the monomer,

R ¹ (R ² ) C = C (R ³ ) COOH (XIII),

in the R ¹ to R ³ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the formula XIII, in particular acrylic acid (R ¹ R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H, R ³ = CH ₃ ) and / or maleic acid ( R ¹ = COOH; R ² = R ³ = H) is preferred.

In the sulfonic acid-containing monomers, those of the formula XIV are preferred,

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XIV),

in the R ⁵ to R ⁷ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas XIVa, XIVb and / or XIVc,

H ₂ C = CH-X-SO ₃ H (XIVa),

H ₂ C = C (CH ₃ ) -X-SO ₃ H (XIVb),

HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XIVc),

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which selected is composed of - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₂ CH ₃ ) in formula XIVa), 2-acrylamido-2-propanesulfonic acid (X = -C ( O) NH-C (CH ₃ ) ₂ in formula XIVa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula XIVa), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula XIVb), 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C (O) NH-CH ₂ CH (OH) CH ₂ - in formula XIVb), allylsulfonic acid (X = CH ₂ in formula XIVa), methallylsulfonic acid (X = CH ₂ in formula XIVb), allyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ in formula XIVa), methallyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula XIVb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid (X = CH ₂ in formula XIVb), styrenesulfonic acid (X = C ₆ H ₄ in formula XIVa), vinylsulfonic acid (X not present in formula XIVa), 3-sulfopropyl acrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ -in formula XIVa), 3-sulfopropyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula XIVb), sulfomethacrylamide (X = -C (O) NH- in formula XIVb), sulfomethylmethacrylamide (X = -C (O) NH-CH ₂ - in formula XIVb) and water-soluble salts of said acids.

Suitable further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds. The content of the monomers used according to the invention to monomers of group iii) is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers to be used consist only of monomers of groups i) and ii).

• i) ungesättigten Carbonsäuren der Formel X.
  
          R¹(R²)C=C(R³)COOH     (XII),
  
  in der R¹ bis R³ unabhängig voneinander für -H -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,
• ii) Sulfonsäuregruppen-haltigen Monomeren der Formel XIV
  
          R⁵(R⁶)C=C(R⁷)-X-SO₃H     (XIV),
  
  in der R⁵ bis R⁷ unabhängig voneinander für -H -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
• iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

besonders bevorzugt.In summary, copolymers are made of

• i) unsaturated carboxylic acids of the formula X.
  
  R ¹ (R ² ) C = C (R ³ ) COOH (XII),
  
  in the R ¹ to R ³ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
• ii) sulfonic acid group-containing monomers of the formula XIV
  
  R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XIV),
  
  in the R ⁵ to R ⁷ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -
• iii) optionally further ionic or nonionic monomers

particularly preferred.

• i) einer oder mehrerer ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln XIVa, XIVb und/oder XIVc:
  
          H₂C=CH-X-SO₃H     (XIVa),
  
          H₂C=C(CH₃)-X-SO₃H     (XIVb),
  
          HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H     (XIVc),
  
  in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NHCH(CH₂CH₃)-
• iii)gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren.

Particularly preferred copolymers consist of

• i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid
• ii) one or more sulfonic acid group-containing monomers of the formulas XIVa, XIVb and / or XIVc:
  
  H ₂ C = CH-X-SO ₃ H (XIVa),
  
  H ₂ C = C (CH ₃ ) -X-SO ₃ H (XIVb),
  
  HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XIVc),
  
  in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NHCH (CH ₂ CH ₃ ) -
• iii) optionally further ionic or nonionic monomers.

The copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii). Particularly preferred polymers have certain structural units, which are described below.

Thus, for example, preferred are compositions according to the invention which are characterized in that they contain one or more copolymers which contain structural units of the formula XV

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XV),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. Copolymerizing the sulfonic acid-containing acrylic acid derivative with methacrylic acid, one arrives at another polymer whose use in the compositions according to the invention is likewise preferred and characterized in that the compositions contain one or more copolymers which contain structural units of the formula XVI

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XVI),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, compositions according to the invention which contain one or more copolymers which are structural units of the formula XVII

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XVII),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, preferably, also a preferred embodiment of the present invention, just as preferred are compositions which are characterized in that they contain one or more copolymers, the structural units of the formula XVIII

[CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XVIII)

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred compositions which are characterized are characterized in that they contain one or more copolymers, the structural units of the formula XIX

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XIX),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred and to compositions, which are characterized in that they contain one or more copolymers, the structural units of the formula XX

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (XX),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In summary, compositions according to the invention which contain one or more copolymers which contain structural units of the formulas III and / or IV and / or V and / or VI and / or VII and / or VIII

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XV),

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XVI),

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XVII),

[CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XVIII)

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XIX),

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (XX),

in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y is -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH -C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are preferred.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. Corresponding compositions which are characterized in that the sulfonic acid groups are partially or fully neutralized in the copolymer are preferred according to the invention.

The monomer distribution of the copolymers used in the compositions according to the invention in the case of copolymers containing only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight. % Of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.

In the case of terpolymers, particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,

The molecular weight of the above-described sulfo-copolymers used in the compositions according to the invention can be varied in order to adapt the properties of the polymers to the desired use. Preferred compositions are characterized in that the copolymers have molecular weights of from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

Further preferred ingredients for machine dishwashing detergents prepared according to the invention are agents which are capable of providing corrosion protection for glassware during cleaning and / or rinsing operations of a dishwashing machine. They preferably come from the group of the compounds of zinc, aluminum, silicon, tin, magnesium, calcium, strontium, titanium, zirconium, manganese and / or lanthanum. Of the compounds mentioned, the oxides are particularly preferred.

A preferred agent for providing anticorrosive protection to glassware during dishwashing and / or rinsing operations of a dishwashing machine is zinc in oxidized form, i. Zinc compounds in which zinc is cationic. Similarly, magnesium salts are also preferred. Here, both soluble and poorly soluble or insoluble zinc or magnesium compounds can be used. Preferred compositions according to the invention comprise one or more magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid.

The acids in question preferably come from the group of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the Amino acids and / or the polymeric carboxylic acids, the unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acids having at least 8 carbon atoms and / or resin acids.

Although all magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids may be contained according to the invention, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids are selected from the groups of unbranched saturated or unsaturated monocarboxylic acids, branched saturated or unsaturated monocarboxylic acids, saturated and unsaturated dicarboxylic acids, aromatic mono-, di- and tricarboxylic acids, sugar acids, hydroxy acids, oxo acids, amino acids and / or polymeric carboxylic acids. Within these groups, the acids mentioned below are again preferred in the context of the present invention:

From the group of unbranched saturated or unsaturated monocarboxylic acids: methanoic acid (formic acid), ethanoic acid (acetic acid), propionic acid (propionic acid), pentanoic acid (valeric acid), hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), Decanoic acid (capric acid), undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (Lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid), 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c , 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatenic acid (linolenic acid).

From the group of branched saturated or unsaturated monocarboxylic acids: 2-methylpentanoic acid, 2-ethylhexanoic acid, 2-propylheptanoic acid, 2-butyloctanoic acid, 2-pentylnonanoic acid, 2-hexyldecanoic acid, 2-heptylundecanoic acid, 2-octyldodecanoic acid, 2-nonyltridecanoic acid, 2-decyltetradecanoic acid, 2-undecylpentadecanoic acid, 2-dodecylhexadecanoic acid, 2-tridecylheptadecanoic acid, 2-tetradecyloctadecanoic acid, 2-pentadecylnonadecanoic acid, 2-hexadecyleicosanoic acid, 2-heptadecylheneicosanoic acid.

From the group of unbranched saturated or unsaturated di- or tricarboxylic acids: propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanedioic acid ( Sebacic acid), 2c-butenedioic acid (maleic acid), 2t-butenedioic acid (fumaric acid), 2-butynedicarboxylic acid (acetylenedicarboxylic acid).

From the group of aromatic mono-, di- and tricarboxylic acids: benzoic acid, 2-carboxybenzoic acid (phthalic acid), 3-carboxybenzoic acid (isophthalic acid), 4-carboxybenzoic acid (terephthalic acid), 3,4-dicarboxybenzoic acid (trimellitic acid), 3,5-dicarboxybenzoic acid (Trimesionsäure).

From the group of sugar acids: galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, 2-deoxy-ribonic acid, alginic acid.

From the group of hydroxy acids: hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), malic acid (malic acid), 2,3-dihydroxybutanedioic acid (tartaric acid), 2-hydroxy-1,2,3-propanetricarboxylic acid (citric acid), ascorbic acid, 2 Hydroxybenzoic acid (salicylic acid), 3,4,5-trihydroxybenzoic acid (gallic acid).

From the group of oxo acids: 2-oxopropionic acid (pyruvic acid), 4-oxopentanoic acid (levulinic acid).

From the group of amino acids: alanine, valine, leucine, isoleucine, proline, tryptophan, phenylalanine, methionine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, lysine, arginine, histidine.

From the group of polymeric carboxylic acids: polyacrylic acid, polymethacrylic acid, alkylacrylamide / acrylic acid copolymers, alkylacrylamide / methacrylic acid copolymers, alkylacrylamide / methylmethacrylic acid copolymers, copolymers of unsaturated carboxylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers.

The spectrum of the inventively preferred zinc salts of organic acids, preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / L, preferably below 10 mg / L, in particular have no solubility, to such salts having a solubility in water above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature). The first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate:

In a further preferred embodiment of the present invention, the compositions according to the invention contain at least one zinc salt but no magnesium salt of an organic acid, which is preferably at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt selected from zinc stearate, zinc oleate, zinc gluconate, zinc acetate , Zinc lactate and / or zinc citrate. Furthermore, zinc ricinoleate, zinc abietate and zinc oxalate are also preferably used.

Claims (8)

1. Process for producing washing or cleaning composition portions tightly enveloped by water-soluble envelopes, characterized by the steps of

   a) placing a water-soluble lower film onto a transport chain or a mould;

   b) placing one or more washing or cleaning composition portion(s) onto the lower film (in the case that a mould is used in step a), the washing or cleaning composition portion(s), after being placed onto the lower film, do(es) not conclude flush with the upper side of the mould, but rather project(s) from it in such a way that not more than 50%, preferably not more than 40% and in particular not more than 30% of the maximum height of the washing or cleaning composition portion(s) is within the mould);

   c) placing a water-soluble upper film onto the washing or cleaning composition portion(s) on the lower film;

   d) fixing the upper film to the lower film to envelop the washing or cleaning composition portion(s);

   e) sealing and optional cutting of the films.
2. Process according to Claim 1, characterized in that the lower film is preshaped by the application of a vacuum and/or by gentle heating.
3. Process according to Claim 1, characterized in that the lower film is entirely planar during steps b) to e).
4. Process according to one of Claims 1 to 3, characterized in that the washing or cleaning composition portion(s) which is/are placed onto the lower film in step b) is/are (a) washing or cleaning composition tablet(s).
5. Process according to Claims 1 to 4, characterized in that the upper film, before it is placed on in step c), is preshaped by applying a vacuum and/or by gentle heating in a dome.
6. Process according to Claim 5, characterized in that step c) is initiated by preliminary airing from above.
7. Process according to one of Claims 1 to 6, characterized in that steps c) and/or d) are supported by the evacuation of the intermediate space between upper film and lower film and/or by application of pressure to the upper film.
8. Process according to one of Claims 1 to 7, characterized in that the water-soluble film(s) used in steps a) and c) are preoriented films which are shrunk onto the washing or cleaning composition portion(s) in step e) or thereafter.