WO2004031338A1

WO2004031338A1 - Method for the production of coated detergent or cleansing agent portions

Info

Publication number: WO2004031338A1
Application number: PCT/EP2003/010370
Authority: WO
Inventors: Alexander Lambotte; Matthias Reimann; Wolfgang Barthel
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2002-09-27
Filing date: 2003-09-18
Publication date: 2004-04-15
Also published as: AU2003262514A1; EP1543100B1; DE10245260A1; EP1543100A1; DE50303130D1; ATE324432T1; ES2263065T3

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

"Process for the production of coated detergent or cleaning agent portions"

The present invention relates to a method for producing detergent or cleaning agent portions, which have an envelope made of water-soluble materials, which closely surrounds the compositions contained in the portion.

Portioned detergents and cleaning agents are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage. The portioning can be achieved, for example, by converting it into a compact form or by separate packaging. In the former case, tableting has an outstanding role; in the latter case, in the area of detergents or cleaning agents, mainly portions are used which are surrounded by packaging made of water-soluble materials. However, these portions have the disadvantage of not having the high degree of compactness that tablets have. The filling of tubular bags leads on the one hand to a low degree of compression, and on the other hand to a technically determined empty volume, so that a quantity of a detergent or cleaning agent measured for a washing or cleaning cycle takes up a larger space than a corresponding quantity in tableted form. In addition, the empty volume means that filled bags are unstable against mechanical influences and can burst.

A disadvantage of the washing or cleaning agent containers on the market is that they still have to be provided with an outer packaging which protects the ingredients from environmental influences (in particular moisture). These "flow packs" made of water-insoluble materials must be removed by the consumer before metering, which can be annoying to the consumer and cause waste. Approaches to solving this problem are coating the molded body with water-soluble polymers or using 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 complex and expensive. The use of water-soluble packaging is described in the prior art in the form of bags made of water-soluble film. However, these tablets have aesthetic disadvantages compared to conventional tablets. Consumer acceptance too is low in this form of offer, since the outer packaging suggests to the consumer that it has to be removed - a real advantage of the water-soluble flow packs is therefore not recognizable to the consumer.

The present invention was based on the object of providing a method for producing aesthetically appealing detergent or cleaning agent portions. Here, the process should be so variable that tablets as well as differently formulated detergent or cleaning agent compositions such as castings, powders, granules, extrudates, flakes, etc. can be packaged in an aesthetically pleasing manner. For the process alternatives in which tablets are not packed, it should be possible to produce portions which combine the advantages of the compactness of tablets with those of the quick solubility of portioned systems and, moreover, do not have to be provided with an outer packaging made of water-insoluble film.

It has now been found that an envelope made of water-soluble film, which lies closely against a tablet or a particulate filling, which is not a shaped body, is aesthetically pleasing and is accepted by the consumer. The degree of compaction of such systems is close to that of conventional tablets and significantly higher than that of conventional portioned systems, the solubility clearly exceeding that of tablets and reaching that of conventional particulate detergents or cleaning agents. It has further been found that a special coating process can be used universally both for particulate compositions and for tablets and provides portions with a tight-fitting coating.

The present invention therefore relates to a process for the production with water-soluble wrappings of tightly wrapped detergent or cleaning agent portions, which comprises the steps a) placing a water-soluble bottom film on a transport chain or a mold (s); b) placing one or more detergent or cleaning agent portion (s) on the lower film; c) placing a water-soluble top film on the detergent or cleaning agent portion (s) on the bottom film; d) fixing the top film to the bottom film including the detergent or cleaning agent portion (s); e) sealing and optional cutting of the foils is marked.

There follows a description of the method according to the invention on the basis of its method steps. A detailed description of the foils to be used in the method according to the invention and the ingredients of the detergent or cleaning agent portions can be found after these explanations.

In the first step of the method according to the invention, a water-soluble bottom film is provided, which is placed on a transport chain or a mold (s). A combination of transport chain and mold (s) can also be used according to the invention. Transport belts etc. are also understood as a transport chain in the sense of the present invention. Conveyor chains or belts are preferred over fixed molds for reasons of process economy. A combination of transport chain and mold (s) is, for example, an assembly line that has recesses at regular intervals.

If mold (s) are used, the molds can be designed as individual units, but it is also possible and preferred for reasons of process economy to use molds which have a large number of shapes. In step a) of the process according to the invention, a water-soluble film is placed over these molds, onto which one or more detergent or detergent portions are placed in the next process step.

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

Preferred methods according to the invention are characterized in that the bottom film is preformed by applying a vacuum and / or by heating. As a result, the film is provided with a cavity for receiving the particulate detergent or cleaning agent composition. However, the procedure described above is not based on the Dosage of particulate compositions limited, but can also be used for the packaging of tablets according to the invention.

It is preferred according to the invention that the water-soluble film is heated to temperatures above 50 ° C., preferably above 70 ° C. and in particular above 90 ° C., before being placed on the mold (s). This will make subsequent deformation easier. As an alternative to heating before placing it on the mold (s) or in addition, the film can be heated further during the forming process. Process variants are preferred here in which the deformation of the water-soluble film is supported by heating the film to temperatures of 100 to 120 ° C. A combination of the two process variants, i.e. Placing a heated film and further heating is possible and preferred.

The film can also be pressed into the mold by metering the tablet or the particulate composition. With particulate compositions, this is possible, for example, by placing an annular tool on the film placed over the mold and metering the particulate composition into the mold through this tube. In this case, the film can either sink into the mold due to the mass of the composition, but the metering process can also be supported by pressing the composition into the mold, for example by means of a stamp in the tubular meter. This dosage unit can also be used for tablets, but due to the compact molded body structure, the tablet can also be placed without it.

If a particulate composition is used, it can also be slightly pre-compressed to ensure that the mold is filled as completely as possible. If multiphase portions are to be produced, pressing on the first metered-in particulate composition ensures a flat interface between the two layers. Visually, such two-phase portions are closely based on the known two-layer tablets. The forces for pressing the particulate composition are selected so that the area of elastic deformation is not left. The dosing pressure does not lead to the particles sintering together (as would be the case with tableting), but only to the removal of bulk material cavities and to a flat surface. Methods according to the invention are preferred here, in which a Particulate premix is slightly compressed with the aid of the stamp, compression forces below 1 kN being preferred.

Slightly pre-compressed particulate compositions can also be easily lifted out of the mold before the sealing process without breaking immediately - this can be used advantageously for the position of the subsequent sealing seam, see below.

Preferred methods according to the invention for the coating of particulate compositions are characterized in that a further particulate detergent or cleaning agent is metered onto the first pre-compressed particulate washing or cleaning agent. This makes it possible to produce visually appealing portions.

If a molding tool is used, its depth in combination with the height of the inserted tablet or the filled-in particulate composition determines how high the composition protrudes from the film level. 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 which is subsequently produced.

When the detergent or cleaning agent composition dosed into the mold is flush with the top of the mold, the sealing seam is formed as a "brim" on one end face of the portion. A simple plate can be used here for sealing, but this has the disadvantage that the film, which covers the top of the portion to which heat is applied.

Alternatively, the sealing seam can also be designed so that it runs along the outer surface of the portion. In this case, the portion protrudes from the mold and another part of the portion protruding from the mold is covered with another film. The sealing can now not be carried out with a plate-like sealing tool, but instead takes place with an annular tool. This method has the advantage that the lowering of the ring-shaped sealing tool additionally tightens the upper film. In addition, the heat effect on the portion is significantly reduced compared to a "heating plate".

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

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

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

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

The method according to the invention is used with particular preference for packaging washable or cleaning-active casting bodies, it being particularly preferred that the casting body is present in the packaging in combination with one or more particulate washing or cleaning agents, such as, for example, powders, extrudates or granules. A more detailed description of casting bodies preferred according to the invention is given below in the text.

In step c) of the process according to the invention, an upper film is placed on the bottom film topped with one or more detergent or cleaning agent portion (s), which is fixed in step d) and sealed in step e). The upper film is preferably applied with the aid of a dome-shaped tool which carries the upper film and is placed over the detergent or cleaning agent portions located on the lower film. It is preferred here that the top film is not flat, that is to say stretched, but is also formed in a dome-like manner. This can be achieved by placing the top film in the tool on its wall. Preferred methods are characterized in that the top film is preformed before being placed in step c) by applying a vacuum and / or by heating in a dome.

It can be advantageous here to heat the top film to temperatures between 100 ° C. and 200 ° C., temperatures between 100 ° C. and 120 ° C. being preferred. The dome-like shape with the top film is then placed over the detergent or cleaning agent portion (s) on the bottom film. This forms a detergent or cleaning agent portion which is already completely surrounded by water-soluble film and which is partially separated from the film by an air cushion. In order to ensure that the packaging is as tight as possible, the air can be sucked out through slots on the foot surface of the upper tool. Applying a vacuum to these slots additionally causes the top film to detach from the dome as soon as the dome-shaped tool is ventilated from above. Methods according to the invention are preferred here, in which step c) is initiated from above by pre-ventilation.

After the top film has laid loosely over the detergent or cleaning agent portion (s) located on the bottom film, the dome-like tool is fully ventilated from above. A skin-tight covering is preferably achieved in that a vacuum is still present on the connecting surface between the top and bottom films. As an alternative or in addition to this, the dome-like tool can be subjected to an excess pressure which presses the top film onto the detergent or cleaning agent portion (s). Method according to the invention, which are characterized in that the steps c) and / or d) by evacuating the Gap between the top and bottom films and / or by applying pressure to the top film are preferred according to the invention.

In step d), the films are sealed over the entire area around the detergent or cleaning agent portion (s). Following the sealing, the films can be stabilized by the differential pressure in the mold in order to prevent re-shaping. In addition to this, the mold can be cooled in order to keep the sealed product unchanged in its shape and to shorten the dwell times in the mold.

Another variant of the method provides that the portions are either first packaged in water-soluble films according to the ones disclosed above and the film packaging is then shrunk onto the portions. This shrink film is a film that has been stretched and contracts again when heated. It is possible to produce wrappings that lie very close to the surface of the portions.

Processes which are also preferred according to the invention are characterized in that the water-soluble film (s) used in steps a) and c) are pre-stretched films which are shrunk onto the detergent or detergent 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. For example, an inner film can be used which is inert to the composition to be filled and which does not react with the filling. An outer film, which withstands the environmental influences better, can protect the composition against 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, with the individual films being able to be assigned different functions (mechanical stabilization, vapor barrier, optics, functionality by incorporating ingredients, etc.).

The films which can be used in the process according to the invention are described below: 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 methods according to the invention, water-soluble coating comprises one or more materials from the group (optionally acetalized) polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinyl pyrrolidone, polyethylene oxide, polyethylene glycol, gelatin, cellulose and their derivatives, in particular MC, HEC, HPC, HPMC and / or CMC, and / or copolymers and mixtures thereof. Possibly. Plasticizers known to the person skilled in the art can be added to the coatings to increase the flexibility of the material.

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

CH2 CH CH2 CH OH OH

which in small proportions (approx. 2%) also structural units of the type

contain.

Commercial polyvinyl alcohols, which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approximately 100 to 2500 (molar masses from approximately 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , therefore still contain a residual content of acetyl groups. The manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.

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

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

Polyvinyl alcohols of a certain molecular weight range are preferably used, with methods according to the invention being preferred 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 ^" ", preferably from 10,000 to 90,000 gmol ^"1 , particularly preferably from 12,000 to 80,000 gmol ^" 'and in particular from 13,000 to 70,000 gmol ^" '.

The degree of polymerization of such preferred polyvinyl alcohols is between approximately 200 to approximately 2100, preferably between approximately 220 to approximately 1890, particularly preferably between approximately 240 to approximately 1680 and in particular between approximately 260 to approximately 1500.

Processes which are 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 MG (50% ) to MG (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 trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88 and Mowiol ^® 8-88. Further polyvinyl alcohols which are particularly suitable as materials for the water-soluble coating can be found in the table below:

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, NM1 1Q, KZ-06 (trademark of Nippon Gohsei KK). ERKOL types from Wacker are also suitable.

Another preferred group of water-soluble polymers that can serve as a coating according to the invention are the polyvinylpyrrolidones. These are sold, for example, under the name Luviskol ^® (BASF). Polyvinylpyrrolidones [poly (l-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (I)

which are produced by free-radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using free-radical formers (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer only provides products with low molecular weights. Commercial polyvinylpyrrolidones have molecular weights in the range of approx. 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 / Vinylester copolymers, as are marketed, for example under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.

The vinyl ester polymers are polymers accessible from vinyl esters with the grouping of the formula (II)

-CH ₂ - CH -

O

C.

O (II)

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

The vinyl esters are polymerized by free radicals using various processes (solution polymerization, suspension polymerization, emulsion polymerization,

Bulk polymerization.). Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (I) and (II).

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

H- (0-CH ₂ -CH ₂ ) _n -OH (III)

are sufficient, where n can have values between 5 and> 100,000. PEGs are manufactured industrially by anionic ring opening polymerization of ethylene oxide (oxirane), usually in the presence of small amounts of water. Depending on how the reaction is carried out, they have molar masses in the range of approximately 200-5,000,000 g / mol, corresponding to degrees of polymerization of approximately 5 to> 100,000.

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

According to the invention, gelatin is also suitable as a water-soluble coating material, which is preferably used together with other polymers. Gelatin is a polypeptide (molecular weight: approx. 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 the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as a water-soluble coating material is extremely widespread, particularly in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.

Further water-soluble polymers which are suitable as coatings according to the invention are described below:

Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and methylhydroxypropyl cellulose, as sold for example under the trademark Culminal® ^® and Benecel ^® (AQUALON). Cellulose ethers can be described by the general formula (IV)

in which R represents 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 cellulose have reacted with the etherification reagent or how many moles of etherification reagent have been attached to an anhydroglucose unit on average. Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercial hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1, 35 (DS) and 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) 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 hydroxypropylmethyl cellulose (HPMC), which have a degree of substitution (average number of methoxy groups per anhydroglucose unit of the cellulose) from 1.0 to 2.0, preferably from 1.4 to 1.9 , and has a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit of cellulose) from 0.1 to 0.3, preferably from 0.15 to 0.25.

Other polymers suitable according to the invention are water-soluble amphopolymers. Ampho-polymers are amphoteric polymers, ie polymers that contain both free amino groups and free -COOH or S0 ₃ H groups in the molecule and are capable of forming internal salts, are zwitterionic polymers that contain quaternary ammo- niumgruppen and -COO ^"-. contain or -SOa ^'groups, and those polymers summarized containing -COOH or S0 ₃ H groups and quaternary ammonium groups according to the invention An example of a amphopolymer suitable is the acrylic resin commercially available as Amphomer ^® , which is a copolymer of tert-butylaminoethyl methacrylate, N- (l, 1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters, and preferred amphopolymers are composed of unsaturated ones Carboxylic acids (e.g. acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (e.g. acrylamidopropyltrimethylammonium chloride) and optionally other ionic or nonionic monomers together, as can be seen, for example, in German Offenlegungsschrift 39 29 973 and the prior art cited therein Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyl rimoniumchlorid as they are in 2001 N commercially available under the name Merquat ^®, are inventively particularly preferred amphopolymers. Other suitable amphoteric polymers are for example those available under the names Amphomer and Amphomer ^® LV-71 (DELFT NATIONAL) octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers.

Suitable water-soluble anionic polymers according to the invention include a .:

Vinyl acetate / crotonic acid copolymers, such as are commercially available for example under the names Resyn ^® (National Starch), Luviset ^® (BASF) and Gafset ^® (GAF). In addition to monomer units of the aforementioned formula (II), these polymers also have monomer units of the general formula (V):

[-CH (CH ₃ ) -CH (COOH) -] _n (V)

Vinylpyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF). A preferred polymer is that available under the name Luviflex VBM-35 ^® (BASF) vinylpyrrolidone / acrylate terpolymers. Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide 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 a mixture, 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 a mixture with other copolymerizable compounds on polyalkylene glycols, are obtained by polymerization in the heat in a homogeneous phase by the polyalkylene glycols being converted into the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid In the presence of radical formers. Suitable vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and as esters of acrylic acid or methacrylic acid, those which have low molecular weight aliphatic alcohols, in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl l-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 available.

Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula VI

H- (0-CH-CH ₂ ) _n -OH (VI)

CH,

are sufficient, where n can take values between 1 (propylene glycol) and several thousand. Technically important here are in particular di-, tri- and tetrapropylene glycol, i.e. 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 monomer of the non-ionic type, ii) at least one monomer of the ionic type, 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 non-ionic monomers can be of very different types and among these the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate,

Allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether,

Stearyl vinyl ether and 1-hexene.

The non-ionic monomers can likewise be of very different types, of which crotonic acid, allyloxyacetic acid,

Vinyl acetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the graft polymers.

Preferred crosslinkers are ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallylsucrose with 2 to 5

Allyl groups per molecule of saccharin.

The grafted and crosslinked copolymers described above are preferably formed from: i) 5 to 85% by weight of at least one monomer of the nonionic type, ii) 3 to 80% by weight of at least one monomer of the ionic type, iii) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and iv) 0.1 to 8 wt .-% of a crosslinking agent, the percentage of the crosslinking agent by the

Ratio of the total weights of i), ii) and iii) is formed. 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 from the

Carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C ₈ * ₈ -alcohol Short-chain carboxylic acids or alcohols are understood to mean those with 1 to 8 carbon atoms, the carbon chains of these compounds being optionally by double-bonded hetero groups such as -O- , -NH-, -S_ can be interrupted.

Terpolymers of crotonic acid, vinyl acetate and an allyl or methyl ester These terpolymers contain monomer units of the general formulas (II) and (IV) (see above) and monomer units of one or more allyl or methallyesters of the formula VII: R 'R ^J

R -CC (0) -0-CH ₂ - C = CH ₂ (VII)

CH ₃

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-chain or branched C * _ ₆ alkyl radical and the sum of

Carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2.

The above-mentioned terpolymers preferably result from the copolymerization of 7 to 12% by weight crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight.

Vinyl acetate and 8 to 20 wt .-%, preferably 10 to 17 wt .-% allyl or

Methyl ester of formula VII.

Tetra- and penta-polymers of 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, vinymethyl ether, acrylamide and their water-soluble salts

Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position.

Further polymers which can preferably be used according to the invention as a covering are cationic polymers. The permanent cationic polymers are preferred among the cationic polymers. According to the invention, polymers which have a cationic group irrespective of the pH value are referred to as “permanently cationic”. These are generally polymers which contain a quaternary nitrogen atom, for example in the form of an ammonium group.

Preferred cationic polymers are, for example, quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives. Polysiloxanes with quaternary groups, such as the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicon), Dow Corning ^® 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone) , 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, such as in particular the products sold under the trade names Cosmedia ^® Guar and Jaguar ^® ,

Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers.

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as, for example, vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755.

Vinylpyrrolidone-methoimidazolinium chloride copolymers, as are offered under the name Luviquat ^® . quaternized polyvinyl alcohol and those under the names

Polyquaternium 2,

Polyquaternium 17,

Polyquaternium 18 and

Polyquaternium 27 known polymers with quaternary nitrogen atoms in the main polymer chain. The polymers mentioned are named according to the so-called INCI nomenclature, with detailed information in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^lh Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, to which express reference is made here becomes.

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

In the process according to the invention, in addition to the water-soluble polymer or the water-soluble polymers, the covering or the film material can contain further ingredients which in particular improve the processability of the starting materials for the covering. Plasticizers and release agents are particularly worth mentioning here. In addition, dyes and / or fragrances and optical brighteners can be incorporated into the water-soluble coating in order to achieve aesthetic effects there.

According to the invention, in particular hydrophilic, high-boiling liquids can be used as plasticizers, it being possible, if appropriate, to use solids as a solution, dispersion or melt even at room temperature. Particularly preferred plasticizers come from the group consisting of glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, deca-, undeca-, dodecaethylene glycol, glycerin, neopentyl glycol, trimethylol propane, pentaerythritol, mono -, Di-, triglycerides, surfactants, especially nonionic surfactants, and mixtures thereof.

Ethylene glycol (1,2-ethanediol, "glycol") is a colorless, viscous, sweet-tasting, strongly hygroscopic liquid that is miscible with water, alcohols and acetone and has a density of 1.1 13. The freezing point of ethylene glycol is around -1 1.5 ° C, the liquid boils at 198 ° C. Technically, ethylene glycol is obtained from ethylene oxide by heating with water under pressure. Promising manufacturing processes can also be based on the acetoxylation of ethylene and subsequent hydrolysis or on synthesis gas reactions.

Diethylene glycol (2,2'-oxydiethanol, digol), HO- (CH ₂ ) ₂ -0- (CH ₂ ) ₂ -OH, is a colorless, viscous, hygroscopic, sweet-tasting liquid, density 1.12, which is -6 ° C melts and boils at 245 ° C. Diglycol is miscible in any ratio with water, alcohols, glycol ethers, ketones, esters, chloroform, but not with hydrocarbons and oils. The diethylene glycol, usually called diglycol in practice, is made from ethylene oxide and ethylene glycol (ethoxylation) and is thus practically the starting link for polyethylene glycols (see above).

Glycerin is a colorless, clear, difficult to move, odorless, sweet-tasting hygroscopic liquid with a density of 1.261 that solidifies at 18.2 ° C. Glycerin was originally only one By-product of fat saponification, but is now technically synthesized in large quantities. Most technical processes are based on propene, which is processed into glycerol via the intermediate stages allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the W0 ₃ contact via the glycide stage.

Trimethylolpropane [TMP, Etriol, Ettriol, l, l, l-tris (hydroxymethyl) propane] is chemically exactly designated 2-ethyl-2-hydroxymethyl-l, 3-propanediol and comes in the form of colorless, hygroscopic masses with 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. It is produced by reacting formaldehyde with butyraldehyde in the presence of alkalis.

Pentaerythritol [2,2-bis (hydroxymethyl) -l, 3-propanediol, penta, PE] is a white, crystalline powder with a sweet taste that is not hygroscopic and flammable and has a density of 1.399, a melting point of 262 ° C. as well has a boiling point of 276 ° C (40 hPa). Pentaerythritol is readily soluble in boiling water, slightly soluble in alcohol and insoluble in benzene, carbon tetrachloride, ether, petroleum ether. Technically, pentaerythritol is produced by reacting formaldehyde with acetaldehyde in an aqueous solution of Ca (OH) ₂ or NaOH at 15-45 ° C. First, a mixed aldol reaction takes place, in which formaldehyde reacts as the carbonyl component and acetaldehyde as the methylene component. Due to the high carbonyl activity of formaldehyde, the reaction of acetaldehyde with itself almost does not occur. Finally, the tris (hydroxymethyl) acetaldehyde thus formed is converted into pentaerythritol and formate with formaldehyde in a crossed Cannizzaro reaction.

Mono-, di-, triglycerides are esters of fatty acids, preferably longer-chain fatty acids with glycerin, one, two or three OH groups of the glycerol being esterified, depending on the type of glyceride. Examples of suitable acid components with which the glycerol can be esterified in mono-, di- or triglycerides which can be used as plasticizers are 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 compound, preference is given to 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 (arachic acid), docosanoic acid (behenic acid), tetraeric acid (locanoic acid) . Hexacosanoic acid (cerotinic acid), triacotanoic 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-octadic acid, 9t-octadecenoic acid 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatreic acid (linolenic acid). For reasons of cost, 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 cleaving native fats and oils and then separated, the purified fractions later being converted into mono-, di- or triglycerides. Acids are esterified with the glycerol here, coconut oil fatty acid (in particular, about 6 wt .-% C _8, 6% by weight of C * o, 48 wt .-% C, _2, 18 wt .-% C, ₄ , 10 wt .-% C _16, 2 wt .-% C _l8, 8 wt .-% C, _8, 1 wt .-% C, _8), palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt % C, ₀ , 50% by weight C, ₂ , 15% by weight C, ₄ , 7% by weight C. ₆ , 2% by weight C ₁₈ , 15% by weight C, ₈ , 1 wt% C, ₈ ), tallow fatty acid (approx. 3 wt% C, ₄ , 26 wt% C ₁₆ , 2 wt% C, ₆ , 2 wt% C ₁₇ , 17 % By weight C ₁₈ , 44% by weight C ₁₈ , 3% by weight C _lg , 1% by weight C, ₈ ), hardened tallow fatty acid (approx. 2% by weight C, ₄ , 28% by weight) -% C, ₆ , 2 wt .-% Cι ₇ , 63 wt .-% C, ₈ , 1 wt .-% C, ₈ ), technical oleic acid (about 1 wt .-% C _{] 2} , 3 wt. -% C | ₄ , 5% by weight C, ₆ , 6% by weight C, ₆ , 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C, ₈ , 10 wt .-% C * _8, 0.5 wt .-% cis), technical palmitic / stearic acid (about 1 wt .-% C * _2, 2 wt .-% C | _4, 45 wt .-%> C | 6, 2 wt .-% C, ₇ , 47 wt .-% C, ₈ , 1 wt .-% C, ₈ ) and soybean oil fatty acid (approx. 2 wt. -% C, ₄ , 15% by weight Ciβ, 5% by weight C ₁₈ , 25% by weight C, ₈ , 45% by weight C, ₈ , 7% by weight 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 an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C * _2. * ₄ alcohols with 3 EO or 4 EO, C ^ n alcohol with 7 EO, Ci ₃ _i ₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Cι. ₂ , ₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Cι.] ₄ alcohol with 3 EO and C * _2. * ₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which are a whole for a specific product or can be 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.

It is particularly preferred to use nonionic surfactants which have a melting point above room temperature as plasticizers. Accordingly, preferred coatings are characterized in that non-ionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43, are used as plasticizers , 3 ° C, can be used.

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can 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 that have a waxy consistency at room temperature are also preferred.

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

In a preferred embodiment of the present invention, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C | ₆ - ₂ o-alcohol), preferably a C * ₈ alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 Mole of ethylene oxide obtained. Among these, the so-called "narrow ranks ethoxylates" (see above) are particularly preferred. Accordingly, ethoxylated nonionic surfactant (s) which are composed of C ₆ . ₂ o-monohydroxy alkanols or C ₆ - ₂ o-alkyl phenols or C ₆ - ₂ o-fatty alcohols and more than 12 mol, preferably more than 15 mol and was recovered in particular more than 20 moles of ethylene oxide per mole of alcohol (s).

The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. 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 makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants.

Other nonionic surfactants with melting points above room temperature which are particularly preferably used contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which comprises 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol 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'0 [CH ₂ CH (CH ₃ ) 0] _x [CH ₂ CH ₂ 0] _y [CH ₂ CH (0H) R ² ],

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

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R'θ [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x> 2, each R ³ in the above formula can 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, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . 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 can be different if x> 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if 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 can be joined together 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 chosen here by way of example and may well be larger, the range of variation 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 can be used

R'0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (0H) CH ₂ 0R ²

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for numbers 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 represents} H and x assumes values from 6 to 15. Further substances which can preferably be used as plasticizers are glycerol carbonate, propylene glycol and propylene carbonate.

Glycerol carbonate can be obtained by transesterification of ethylene carbonate or dimethyl carbonate with glycerin, ethylene glycol or methanol being obtained as by-products. Another synthetic route starts from glycidol (2,3-epoxy-1-propanol), which is reacted under pressure in the presence of catalysts with CO ₂ to give glycerol carbonate. Glycerol carbonate is a clear, easily movable liquid with a density of 1.398 ^"3 that 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 with a density of 1.0597 that solidifies at -32 ° C and boils at 214 ° C. 1,3-propanediol can be produced from acrolein and water with subsequent catalytic hydrogenation.

Technically far more important 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 made from propylene oxide by adding water.

Propylene carbonate is a water-bright, easily movable liquid with a density of 1, 21 like ^"3 , the melting point is -49 ° C, the boiling point is 242 ° C. Propylene carbonate is also available on an industrial scale due to the reaction of propylene oxide and C0 ₂ at 200 ° C and 80 bar accessible.

Highly disperse silicas are particularly suitable as additional additives, which are preferably in solid form at room temperature. Pyrogenic silicas such as the commercially available Aerosil ^® or precipitated silicas are available here. Particularly preferred processes according to the invention are characterized in that one or more materials from the group (preferably highly disperse) 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 inclusion formers such as urea, cyclodextrin and / or from the group of superadsorbers such as (preferably crosslinked) polyacrylic acid and / or their salts such as Cabloc 5066 / CTF and mixtures thereof. As mentioned at the outset, castings are used with particular preference as detergent or cleaning agent portions in the process according to the invention. Detergent or cleaning agent dispersions have proven to be particularly advantageous starting materials for the abovementioned castings. The processing of these dispersions into castings and the subsequent packaging by means of the method according to the invention has a number of advantages. First of all, the casting technology can be used to create spatial shapes that are not accessible through tableting. Furthermore, as described below, the castings are distinguished from the tablets by improved solubility. Finally, unlike tablets, castings are generally ductile and can be plastically deformed to a certain extent in the course of the packaging process according to the invention by the action of pressure, for example when the top film is placed on or when the top film is subsequently fixed on the bottom film. This plastic deformation allows irregularities in the production of the cast body (for example height, thickness, etc.) to be corrected and / or visually upgrading features to be impressed into the cast body.

Another object of the present application is therefore a method according to the invention, in which a detergent or detergent portion is used in the form of a dispersion of solid particles in a dispersant, which, based on their total weight, i) 10 to 65 wt .-% dispersant and ii) comprises 30 to 90 wt .-% dispersed substances.

Particularly preferred dispersions are characterized in that the dispersion has a density above 1,040 g / cm ^" . Very particular preference is given to dispersions according to the invention having a density between 1,040 and 1,670 g / cm ³ , preferably between 1, 120 and 1, 610 g / cm ^3, particularly preferably 1.210 to 1.570 g / cm ^", very particularly preferably 1.290 to 1.510 g / cm ^3, and especially 1.340 to 1.480 g / cm ^3. The information on the density relates in each case to the densities of the dispersions at 20 ° C.

In this application, dispersion is a system consisting of several phases, one of which is continuous (dispersant) and at least one other is finely divided (dispersed substances). Particularly preferred washing or cleaning agents according to the invention are characterized in that they contain the dispersing agent in amounts above 11% by weight, preferably above 13% by weight, particularly preferably above 15% by weight>, very particularly preferably above 17% by weight. -% and in particular above 19 wt .-%, each based on the total weight of the dispersion. Also realizable and preferred are compositions according to the invention which have a dispersion with a weight fraction 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 dispersants in preferred dispersions 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, particularly preferably less than 52% by weight, very particularly preferably less than 47 % By weight and in particular less than 37% by weight. In the context of the present invention, particular preference is given to those washing or cleaning agents which, based on their total weight, contain dispersing agents in amounts of 12 to 62% by weight, preferably 17 to 49% by weight and in particular 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 / 1, preferably more than 300 g / 1, particularly preferably more than 400 g / 1, very particularly preferably between 430 and 620 g / 1 and in particular between 470 and 580 g / 1.

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 can be either a single polymer or a mixture of different 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, consists of at least 50% by weight of the polymer mixture of water-soluble or water-dispersible nonionic polymers from the group of the polyvinylpyrrolidones, vinylpyrrolidone / vinyl esters Copolymers, cellulose ethers, polyvinyl alcohols, polyalkylene glycols, in particular polyethylene glycol and / or polypropylene glycol. Polyvinylpyrrolidones are preferred dispersants in the context of the invention. Polyvinylpyrrolidones [poly (l-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (I)

which are produced by free-radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using free-radical formers (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer only provides products with low molecular weights. Commercial polyvinylpyrrolidones have molar masses in the range from approx. 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 presented as white, hygroscopic powders or as aqueous ones. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).

Vinylpyrrolidone / Vinylester copolymers, as are marketed, for example under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.

- CH ₂ - CH

O

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

Bulk polymerization.). Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (I) and (II)

Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and

Methylhydroxypropylcellulose, such as are for example sold under the trademark Culminal® ^® and Benecel ^® (AQUALON).

Cellulose ethers can be described by the following general formula

in R represents H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in the 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 cellulose have reacted with the etherification reagent or how many moles of etherification reagent have been attached to an anhydroglucose unit on average. Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 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). Hydroxyethyl and propyl celluloses are marketed as yellowish white, odorless and tasteless powders in widely differing degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; their watery Solutions are relatively insensitive to changes in pH or electrolyte addition.

Polyvinyl alcohols, abbreviated as PVAL, are polymers of the general structure

[-CH ₂ -CH (OH) -] _n

which 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 in solution via polymer-analogous reactions by hydrolysis, but technically in particular by alkaline-catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol). These technical processes also make PVAL accessible which contain a predeterminable residual proportion of acetate groups.

Commercial PVAL (eg Mowiol ^® types from Hoechst) are commercially available as white-yellowish powders or granules with degrees of polymerization in the range of approx. 500-2500 (corresponding to molar masses of approx. 20,000-100,000 g / mol) and have different degrees of hydrolysis from 98-99 and 87-89 mole%, respectively. They are therefore partially saponified polyvinyl acetates with a residual acetyl group content of approx. 1-2 or 11-13 mol%.

Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol which have the general formula III

H- (0-CH ₂ -CH ₂ ) _n -OH (III)

are sufficient, where n can take values between 1 (ethylene glycol) and several thousand. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and directly to the Dash one "number follows, corresponding to the number n in the above formula VII. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^lh Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997 ) are, for example PEG-4, PEG-6, PEG-8, PEG-9, PEG 10, PEG 12, PEG 14 and PEG-16 can be used. Also commercially available are polyethylene glycols, for example, under the trade names Carbowax ^® PEG 200 (Union Carbide), Emkapol ^® 200 (ICI Americas), Lipoxol ^® 200 MED (HÜLS America), Polyglycol ^® E-200 (Dow Chemical), Alkapol ^® PEG 300 (Rhone-Poulenc), Lutrol ^® E300 (BASF) and the corresponding trade names with higher numbers The average relative molecular weight of at least one of the dispersing agents used in the washing or cleaning agents according to the invention, in particular at least one of the poly (alkylene) glycols used, is preferably between 200 and 36,000, preferably t between 200 and 6000 and particularly preferably between 300 and 5000.

Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula IV

H- (0-CH-CH ₂ ) _n -OH (IV)

CH,

are sufficient, where n can take values between 1 (propylene glycol) and several thousand. Technically important here are in particular di-, tri- and tetrapropylene glycol, i.e. the representatives with n = 2, 3 and 4 in formula IV.

Particularly preferred washing or cleaning agents according to the invention contain a nonionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, the proportion by weight of the poly (ethylene) glycol in the total weight of all dispersants is preferably between 10 and 90% by weight, particularly preferably between 30 and 80% by weight and in particular between 50 and 70% by weight. Washing or cleaning agents according to the invention are particularly preferred in which the dispersant comprises more than 92% by weight, preferably more than 94% by weight, particularly preferably more than 96% by weight, very particularly preferably more than 98% % By weight and in particular 100% by weight of a poly (alkylene) glycol, preferably poly (ethylene) glycol and / or poly (propylene) glycol, but in particular Poly (ethylene) glycol. Dispersing agents which, in addition to poly (ethylene) glycol, also contain poly (propylene) glycol, preferably have a ratio by weight of poly (ethylene) glycol to poly (propylene) glycol of between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, particularly preferably between 10: 1 and 1.5: 1 and in particular between 7: 1 and 2: 1.

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

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is branched linearly or preferably in the 2-position methyl may or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C * _2. * ₄ alcohols with 3 EO or 4 EO, C ₉ . ₁ - Alcohol with 7 EO, C, ₃ _i ₅ -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, -Cι _2. * ₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as Mixtures of C * _2. * ₄ alcohol with 3 EO and C * _2. * ₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4. Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (V),

R ¹

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

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

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

R ^! -0-R ²

R-CO-N- [Z]

in the R for a linear or branched alkyl or alkenyl radical with 7 to 12

Carbon atoms, R for a linear, branched or cyclic alkyl radical or one

Aryl radical with 2 to 8 carbon atoms and R for a linear, branched or cyclic Alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C ₄ alkyl or phenyl radicals are preferred and [Z] stands for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this residue.

[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. The cleaning agents according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols.

Agents according to the invention which contain a nonionic surfactant which has a melting point above room temperature are particularly preferred. Accordingly, preferred dishwashing detergents are characterized in that they have nonionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43, 3 ° C.

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

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

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C * 6- ₂ alcohol), preferably a Cg-alcohol and at least 12 moles, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide won. Among these, the so-called "narrow ranks ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred dishwashing detergents according to the invention contain ethoxylated nonionic surfactant (s) which are composed of C6. ₂ o-monohydroxy alkanols or C ₆ - ₂ o-alkyl phenols or C ₁ 0- ₂₀ - fatty alcohols and more than 12 mol, preferably more than 15 mol and was recovered in particular more than 20 moles of ethylene oxide per mole of alcohol (s).

The nonionic surfactant, which is solid at room temperature, preferably has additional propylene oxide units in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. 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 makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass 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 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 Make up surfactants. Other nonionic surfactants with melting points above room temperature which are particularly preferably used contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which comprises 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol 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 that 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)

RO [CH ₂ CH (CH ₃ ) 0] _x [CH ₂ CH ₂ 0] _y [CH ₂ CH (OH) R ² ], (VI)

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

R'θ [CH ₂ CH (R) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x> 2, each R ³ in the above formula can 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, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} special for the radical R ³ 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 in the above formula can be different if x> 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if 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 can be joined together 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 chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

R'0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (0H) CH ₂ 0R ²

simplified. In the last-mentioned formula, R ¹ , R ² and R ^'are as defined above and x stands for numbers 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 represents} H and x assumes values from 6 to 15.

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

R'θ [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ], OR ²

contain, in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type R'0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (0H) CH ₂ 0R ²

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

In the context of the present invention, weakly foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants. Among these, surfactants with EO-AO-EO-AO blocks are preferred, one to ten EO or AO groups being bonded to one another before a block follows from the other groups. Machine dishwashing detergents according to the invention which contain surfactants of the general formula VII as nonionic surfactant (s) are preferred here

R'-0- (CH ₂ -CH ₂ -0) _w - (CH ₂ -CH-0) _x - (CH ₂ -CH ₂ -0) _y - (CH ₂ -CH-0) _z -H (VII )

R ¹ R ³

in which R ¹ is a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ - ₂ 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 ) and the indices w, x, y, z independently of one another represent integers from 1 to 6.

The preferred nonionic surfactants of the formula VII can be prepared by known methods from the corresponding alcohols R'-OH and ethylene or alkylene oxide. The radical R ¹ in formula VII above can 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 generally not shown, the linear radicals being of alcohols of native origin with 12 to 18 carbon atoms, for example coconut, palm, tallow or Oleyl alcohol are preferred. Alcohols accessible from synthetic sources are, for example, Guerbet alcohols or residues which are methyl-branched in the 2-position or linear and methyl-branched residues in a mixture, as are usually present in oxo alcohol residues. 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 Dishwashing detergents are preferred in which R ¹ in formula VII represents an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

In addition to propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit. However, other alkylene oxides in which R ² or R ³ are selected independently of one another from - CH ₂ CH ₂ -CH ₃ or CH (CH) ₂ are also suitable. Preferred automatic dishwashing agents are characterized in that R ² or R ³ for a radical -CH ₃ , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.

In summary, nonionic surfactants which have a Cg.u-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 with particular preference according to the invention.

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

R'θ [CH ₂ CH (R ³ ) 0] _x R ² (VIII)

in which R '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 is preferably between 1 and 5 have hydroxyl groups and are preferably further functionalized with an ether group, R ^{3 is} H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2- Butyl radical, x stands for values between 1 and 40.

In the case of 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'0 [CH ₂ CH ₂ 0] _x R ² (IX)

those nonionic surfactants are particularly preferred in which R '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 group-capped poly (oxyalkylated) nonionic surfactants which are of the formula (X)

R'θ [CH ₂ CH ₂ 0] _x CH ₂ CH (OH) R ² (X)

in addition to a radical R ¹ , which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 have up to 30 carbon atoms R ² , which is adjacent to a monohydroxylated intermediate group - CH ₂ CH (OH). x in this formula stands for values between 1 and 40. Such end-capped poly (oxyalkylated) nonionic surfactants can be obtained, for example, by reacting a terminal epoxide of the formula R ² CH (0) CH ₂ with an ethoxylated alcohol of the formula R'θ [CH ₂ CH ₂ 0] _x ., CH ₂ CH ₂ OH obtained.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the above-mentioned nonionic surfactants represent statistical mean values which can be an integer or a fraction for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned usually do not consist of an individual representative, but of mixtures, which can result in mean values and fractional numbers for the C chain lengths as well as for the degrees of ethoxylation or alkoxylation.

Particularly preferred washing or cleaning agents according to the invention contain at least one nonionic surfactant, preferably at least one end group-capped poly (oxyalkylated) nonionic surfactant, the weight fraction of the nonionic surfactants on the total weight of all dispersants is preferably between 1 and 60% by weight, particularly preferably between 2 and 50% by weight and in particular between 3 and 40% by weight. Washing or cleaning agents according to the invention are particularly preferred, in which the total weight of the nonionic surfactant (s) in relation to the total weight of the agent according to the invention is between 0.5 and 40% by weight, preferably between 1 and 30% by weight, 5% is preferably between 2 and 25 and in particular between 2.5 and 23% by weight.

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. The use of dispersants with a melting point or melting range between 30 and 80 ° C., preferably between 35 and 75 ° C., particularly preferably between 40 and 70 ° C. and in particular between 45 and 65 ° C. is particularly preferred, these dispersants based on the total weight of the dispersants used, a weight fraction above 10% by weight, preferably above 40% by weight, particularly preferably above 70% by weight and in particular between 80 and 100% by weight.

Preferred agents according to the invention are dimensionally stable at 20 ° C. Agents according to the invention are considered to be dimensionally stable if they have an inherent dimensional stability which enables them to assume a non-disintegrating spatial shape under the usual conditions of manufacture, storage, transport and handling by the consumer, this spatial shape also under longer conditions under the conditions mentioned Time, preferably 4 weeks, particularly preferably 8 weeks and in particular 32 weeks, did not change, that is to say, under the usual conditions of manufacture, storage, transport and handling by the consumer, in the spatial-geometric form resulting from the manufacture , that is, does not melt.

The water content of the above-mentioned 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. Washing or cleaning agents preferred according to the invention are low in water or anhydrous. Particularly preferred washing or cleaning agents according to the invention are characterized in that the dispersion, based on its total weight, contains free Has water below 10 wt .-%, preferably below 7 wt .-%, particularly 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 . Particularly preferred dispersants are water-soluble or water-dispersible polymers with a density (20 ° C.) above 1,040 g / cm ³ , preferably between 1,040 and 1,670 g / cm ³ , preferably between 1,120 and 1,610 g / cm ³ , particularly preferably between 1,210 and 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 ^" .

Detergents or cleaning agents preferred according to the invention are distinguished in that they are in water (40 ° C.) in less than 12 minutes, preferably less than 10 minutes, preferably in less than 9 minutes, particularly preferably in 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 dishwasher (Miele G 646 PLUS). The main wash cycle of a standard wash program (45 ° C) is started. The solubility is determined by measuring the conductivity, which is recorded by a conductivity sensor. The dissolving process ends when the maximum conductivity is reached. In the conductivity diagram, this maximum corresponds to a plateau. The conductivity measurement begins with the insertion of the circulation pump in the main wash cycle. The amount of water used is 5 liters.

The following is a description of the ingredients that can be contained in the portions coated with the aid of the method according to the invention:

The detergent or cleaning agent portions coated with the aid of the method according to the invention can contain all the usual constituents of washing or cleaning agents, which are briefly described below.

The detergent or cleaning agent portions coated with the method according to the invention preferably contain surfactant (s), it being possible to use anionic, nonionic, cationic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants in textile detergents, the proportion of anionic surfactants being greater than the proportion of nonionic surfactants. The The total surfactant content of the detergent 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 detergent substances in the detergents.

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

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

Other suitable surfactants are polyhydroxy fatty acid amides of the formula VIII below,

R ¹

R-CO-N- [Z] VIII

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which 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.

The group of polyhydroxy fatty acid amides also includes compounds of the formula IX below,

R'-OR ²

I

R-CO-N- [Z] IX

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C ₄ alkyl or phenyl radicals are preferred and [Z] stands for a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives thereof 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 preferred non-ionic surfactants in detergent or cleaning agent portions which are suitable for textile washing and which are produced using the method according to the invention is 5 to 20% by weight, preferably 7 to 15% by weight and in particular 9 to 14% by weight, in each case based on the entire mean.

Low-foaming nonionic surfactants are preferably used in automatic dishwashing detergents.

Anionic, cationic and / or amphoteric surfactants can also be used in conjunction with the surfactants mentioned, these surfactants due to their foaming behavior machine dishwashing detergents are of minor importance and mostly used only in amounts below 10% by weight, mostly even below 5% by weight, for example from 0.01 to 2.5% by weight, in each case based on the agent become. In contrast, these surfactants are of significantly greater importance in detergents. The detergent or cleaning agent portions produced according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as the surfactant component.

The agents according to the invention can contain, for example, cationic compounds of the formulas X, XI or XII as cationic active substances:

R '

R -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (X)

(CH ₂ ) _n -TR ²

R ¹

R'-N ^w - (CH2) _n -CH-CH2 (XI)

R 'T T

R ² R ²

_D ι

R ³ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (XII)

R ⁴

wherein each group R ^{1 is} independently selected from Cι_6-alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group 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.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants are sulfonate-type

fonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from C _2. ₈ monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C ₁ -C ₈ -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. 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.

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₂ -C ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The Cι -C ₆ alkyl sulfates and Cj ₂ -Cι ₅ - alkyl sulfates and Cι ₄ -C | ₅ alkyl sulfates are preferred. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants. The sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 mol of ethylene oxide. ₂ j-alcohols, such as 2-methyl-branched C ^ π alcohols with an average of 3.5 moles of ethylene oxide (EO) or Cι ₂ .ι ₈ fatty alcohols with 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-0 ₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

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

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

The anionic surfactant content of preferred textile detergents according to the invention 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 composition.

In the context of the present invention, preferred agents additionally contain one or more substances from the group of builders, bleaching agents, bleach activators, enzymes, Electrolytes, non-aqueous solvents, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, silicone oils,

Anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, phobing and impregnating agents, UV and anti-slip agents as well as UV and anti-slip agents.

The builders that can be contained in the agents according to the invention include, 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 builder substances is possible according to the invention, provided that such use should not be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.

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

Sodium dihydrogen phosphate, NaH P0 ₄ , exists as a dihydrate (density 1.91, preferably ^"3 , melting point 60 °) and as a monohydrate (density 2.04, preferably ^{" 3} ). Both salts are white, water-soluble powders that lose the crystal water when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ 0 ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ θ9) and Maddrell's salt (see below). NaH ₂ P0 _{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 (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PU, is a white salt with a density of 2.33 ^"3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 ₃ ) _x ] and is easily soluble in water. Disodium hydrogen phosphate (secondary sodium phosphate), Na HP0 ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly ^"3 , water loss at 95 °), 7 mol. (Density 1.68 gladly ^{" 3} , melting point 48 ° with loss of 5 H ₂ 0) and 12 mol. Water ( Density 1.52 ^"3 , melting point 35 ° with loss of 5 H ₂ 0), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ θ7 when heated more. Disodium hydrogenphosphate is used by neutralizing phosphoric acid with soda solution made from phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HP0 ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na P0 ₄ , are colorless crystals, which like dodecahydrate a density of 1.62 ^'3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20%) P ₂ 0 ₅ ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40%) P ₂ 0 ₅ ) have a density of 2.536 like ^'3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or three-base potassium phosphate), K ₃ P0 ₄ , is a white, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction Heating of Thomas slag with coal and potassium sulfate Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred in the cleaning agent industry over corresponding sodium compounds.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ 0 ₇ , exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1, 815-1, 836 like ^{" 3} , melting point 94 ° with water loss). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ 0 ₇ is formed by heating 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 formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ 0 ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 ^"3 , which is soluble in water, the pH value being 1%) solution at 25 ° is 10.4. Condensation of the NaH ₂ P0 ₄ or the KH ₂ P0 produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's 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 Oιo (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (0) (ONa) -0] _n that crystallizes with 6 H ₂ 0 - Well with n = 3. About 17 g of the salt of water free of water of crystallization dissolve in 100 g of water at room temperature, about 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15%> diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ PO | ₀ (potassium tripolyphosphate), for example in the form of a 50 wt .-% solution (>23%> P ₂ 0 ₅ , 25%> K ₂ 0) on the market. The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaP0 ₃ ) ₃ + 2 KOH -> NajKΛOio + H ₂ 0

According to the invention, these can be used just like 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 0 _{x +} ι Η 0, 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 Layered silicates of the formula given are those in which M is sodium and x is 2 or 3. In particular, both ß- and δ-sodium disilicate

Na ₂ Si ₂ 0 ₅ -yH ₂ 0 preferred.

Amorphous sodium silicates with a module Na ₂ 0: Si0 ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

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

nNa ₂ 0 '(ln) K ₂ 0 ^• A1 ₂ 0 ₃ ^■ (2 - 2.5) Si0 ₂ ^■ (3.5 - 5.5) H ₂ 0 can be described. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production. In the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C | ₂ -C | ₈ fatty alcohols with 2 to 5 ethylene oxide groups, -C ₂ -C | ₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Other important builders are in particular the carbonates, citrates and silicates. Trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicates and / or metasilicates are preferably used.

Alkali carriers can be present as further constituents. Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the abovementioned substances are considered to be alkali carriers, alkali metal carbonates, in particular sodium carbonate, in particular sodium bicarbonate or sodium sesquicarbonate being used for the purposes of this invention.

A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred.

A builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.

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

Both inorganic acids and organic acids are suitable as acidifiers, provided that these are compatible with the other ingredients. The solid mono-, oligo- and polycarboxylic acids can be used in particular for reasons of consumer protection and handling safety. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. The anhydrides of these acids can also be used as acidifying agents are, in particular maleic anhydride and succinic anhydride are commercially available. Organic sulfonic acids such as amidosulfonic acid can also be used. A commercially available as an acidifier in the context of the present invention also preferably be used is Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%>), glutaric acid (max. 50 wt .-%>), and Adipic acid (max. 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 point on a central atom, i. H. is at least "bidentate". In this case, normally elongated compounds are closed to form rings by complex formation via an ion. The number of ligands bound depends on the coordination number of the central ion.

Common chelate complexing agents preferred in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Complex-forming polymers, that is to say polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and generally react with suitable metal atoms to form 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 can 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 complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cycl.) Polyamino, mercapto, 1, 3-dicarbonyl - And crown ether residues with z. T. very specific Activities against ions of different metals. The base polymers of many commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided with further ligand functionalities by polymer-analogous conversions. In the context of the present invention, detergent or cleaning agent containers which contain one or more chelate complexing agents from the groups of

(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% by weight, preferably above 0.5% by weight>, particularly preferably above 1% by weight> and in particular above 2.5% by weight>, in each case based on the weight of the agent.

All complexing agents of the prior art can be used in the context of the present invention. These can belong to different chemical groups. The following are preferably used individually or in a mixture:

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, 3-nitridodiacetic acid, nitridodiacetic acid , N-Di- (ß-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 l-hydroxyethane-l, l-diphosphonic acid (HEDP), their higher homologues with up to 8 carbon atoms and derivatives thereof, containing hydroxyl or amino groups, and l-aminoethane-l, l-diphosphonic acid, their higher Homologs with up to 8 carbon atoms as well as derivatives thereof containing hydroxyl or amino groups, d) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methyle nphosphonic acid) or nitrilotri (methylenephosphonic acid), e) phosphonopolycarboxylic acids such as 2-phosphonobutane-l, 2,4-tricarboxylic acid and f) cyclodextrins.

In the context of this patent application, polycarboxylic acids a) are understood to mean 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. At 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 immaterial whether they are introduced in the form of acids or in the form of salts. When used as salts, alk ^' ali, ammonium or alkyl ammonium salts, in particular sodium salts, are preferred.

Deposit-inhibiting polymers can also be contained in the agents according to the invention. These substances, which can have different chemical structures, originate, for example, from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, polymers with molecular weights below 15,000 daltons being preferred.

Deposit-inhibiting polymers can also have cobuilder properties. Organic cobuilders which can be used in the dishwasher detergents according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to establish a lower and milder pH value for washing or Detergents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Polymeric polycarboxylates are also suitable as builders or scale inhibitors; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights 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 to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given 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 with molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1000 to 4000 g / mol, can in turn be preferred from this group.

Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention. The copolymers containing sulfonic acid groups 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 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 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 agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

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

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred which, in addition to cobuilder properties, also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. 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.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used. 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 at C _{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate.

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition to the substances from the classes of substances mentioned, the agents according to the invention can contain further usual ingredients of washing, rinsing or cleaning agents, whereby bleaches, bleach activators, enzymes, silver preservatives, dyes and fragrances are of particular importance. These substances are described below.

Among the compounds which serve as bleaching agents and supply H ₂ 0 ₂ in water, 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 -supplying acid salts or peracids such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the detergent tablets. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOS1), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, especially triacetine, diacetoxy-2,5-dihydrofuran.

further particularly preferred bleach activators are cationic nitrile of the formula below

R ¹

R ² -N ⁽⁺⁾ - (CH ₂ ) -CN X (-)

R ^J

in the R ¹ for -H, -CH ₃ , a C. ₂ 4-alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a Cι_ ₂₄ alkyl group, or for a substituted alkyl or Alkenylarylrest with a Cι. ₂ 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 -0) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion ,

This general formula includes a large number of cationic nitriles which can be used in the context of the present invention. The agents according to the invention particularly advantageously 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, where one or both radicals can advantageously also be a cyanomethylene radical. In the table below, preferred cationic nitriles of the formula (I) are characterized by their radicals R ¹ , R ² and R ³ :

For reasons of easier synthesis, compounds are preferred 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 ^" . Cationic nitriles of the formula below are particularly preferred

R ⁴

R ⁵ -_MN ⁽ ^ ⁺⁾ - / ('CtHr _2. ) - C'NM γ X ⁽ ' - ⁾

R ⁶

in which R ⁴ , R ⁵ and R ⁶ are selected independently of one another from -CH ₃ , -CH -CH ₃ , -CH ₂ -CH ₂ - CH ₃ , -CH (CH ₃ ) -CH ₃ , where R ⁴ additionally -H can be and X is an anion, 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 ^(_) come 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, so-called bleach catalysts can also be incorporated into the moldings. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxireductases can also be used to bleach or inhibit the transfer of color. Bacterial strains or are particularly well suited Fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are enzymatic active ingredients. Proteases of the subtle isin type and in particular proteases obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active * enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.12 to about 2% by weight.

Detergent containers according to the invention for machine dishwashing can contain corrosion inhibitors to protect the wash ware or the machine, silver protection agents in particular being particularly important in the area of machine dishwashing. The known substances of the prior art can be used. In general, silver protection agents 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. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogaliol or derivatives thereof Classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

A wide number of different salts can be used as electrolytes from the group of inorganic salts. 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 agents according to the invention is usually 0.5 to 5% by weight.

In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or bases can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually 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 colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards textile fibers in order not to dye them.

Foam inhibitors that can be used in the agents according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials. Suitable anti-redeposition agents, which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose 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 ethers 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 anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of the phthalic acid and terephthalic acid polymers are particularly preferred.

Optical brighteners (so-called "whiteners") can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances attach to the fibers and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and results in pure white with the yellow tone of the grayed or yellowed laundry. Suitable compounds come, for example, from the substance classes of 4,4'-diamino-2,2'-stilbene disulfonic acids ( Flavonic acids), 4,4'-distyryl-biphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid imides, benzoxazole, benzisoxazole and benzimidazole systems as well as pyrene derivatives substituted by heterocycles. The optical brighteners are usually in amounts 0.05 and 0.3 wt .-%, based on the finished agent used.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof in amounts of 0.1 to 5% by weight, based on the composition, are preferably used

The agents according to the invention can also be provided with additional benefits. Here are, for example, color-transfer-inhibiting compositions, agents with an “anti-gray formula”, agents with ironing relief, agents with special fragrance release, agents with improved dirt detachment or prevention of re-soiling, antibacterial Formulations, UV protection agents, color-refreshing agents, etc. can be formulated. Some examples are explained below:

Since textile fabrics, in particular made from rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers prevent bending and kinking. If pressing and squeezing across the grain are sensitive, the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

To combat microorganisms, the agents according to the invention can contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halogenophenols and phenol mercuriacetate, and these compounds can also be dispensed with entirely in the agents according to the invention.

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

An increased wearing comfort can result from the additional use of antstatics, which are additionally added to the agents according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided 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 softening effect. 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 agents according to the invention. These additionally improve the rinsing behavior of the agents according to the invention due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are wholly or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which can 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 at 25 ° C. are in the range between 100 and 100,000 centistokes, it being possible for the silicones to be used in amounts between 0.2 and 5% by weight, based on the total agent.

Finally, the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid are also suitable.

If machine dishwashing detergents are produced with the aid of the method 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 dishwashing 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 nonionic monomers

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

R '(R ^z ) C = C (R ³ ) COOH (XIII), in which R ¹ to R ^' 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 represents -COOH or - COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids that can be described by formula XIII are 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) preferred.

In the case of the monomers containing sulfonic acid groups, preference is given to those of the formula XIV

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (XIV),

in which 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 represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group , which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (0) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas XlVa, XlVb and / or XIVc,

H ₂ C = CH-X-S0 ₃ H (XlVa),

H ₂ C = C (CH ₃ ) -X-S0 ₃ H (XlVb),

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (XIVc),

in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) and X represents an optionally present spacer group which is selected is from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (0) - NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-l-propanesulfonic acid (X = -C (0) NH-CH (CH ₂ CH ₃ ) in the formula XlVa), 2-acrylamido-2-propanesulfonic acid (X = -C ( 0) NH-C (CH ₃ ) ₂ in formula XIV a), 2-acrylamido-2-methyl-l-propanesulfonic acid (X = -C (0) NH-CH (CH ₃ ) CH ₂ - in formula XlVa), 2-methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (0) NH-CH (CH ₃ ) CH ₂ - in formula XlVb), 3-methacrylamido-2-hydroxy-propanesulfonic acid (X = -C (0 ) NH-CH ₂ CH (OH) CH ₂ - in formula XlVb), allyl sulfonic acid (X = CH ₂ in formula XlVa), methyl lysulfonic acid (X = CH ₂ in formula XlVb), allyloxybenzenesulfonic acid (X = -CH ₂ -0 -C ₆ Hι- in formula XlVa), methallyloxybenzenesulfonic acid (X = -CH O-CβHr in formula XlVb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenl sulfonic acid (X = CH ₂ in formula XlVb), styrene sulfonic acid (X = CβH ₄ in formula XlVa), vinyl sulfonic acid (X not present in formula XlVa), 3-sulfopropyl acrylate (X = -C (0) NH-CH ₂ CH ₂ CH ₂ - in For mel XlVa), 3-sulfopropyl methacrylate (X = -C (0) NH-CH ₂ CH ₂ CH ₂ - in formula XlVb), sulfomethacrylamide (X = -C (0) NH- in formula XlVb), sulfomethyl methacrylamide (X = - C (0) NH-CH ₂ - in formula XlVb) and water-soluble salts of the acids mentioned.

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

In summary, copolymers are made of

i) unsaturated carboxylic acids of formula X.

R '(R ² ) C = C (R ³ ) COOH (XII),

in which 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, - OH or - COOH-substituted alkyl or alkenyl radicals as defined above or represents -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) Monomers of the formula XIV containing sulfonic acid groups

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (XIV),

in which 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 represents -COOH or - COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group , which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (0) -NH-CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers

particularly preferred.

Particularly preferred copolymers consist of

i) one or more unsaturated carboxylic acids from the group consisting of acrylic acid,

Methacrylic acid and / or maleic acid

ii) one or more monomers of the formulas XlVa, XlVb and / or XIVc containing sulfonic acid groups:

H ₂ C = CH-X-S0 ₃ H (XlVa),

H ₂ C = C (CH ₃ ) -X-S0 ₃ H (XlVb),

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (XIVc), in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected is from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (0) -NH- CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers.

The copolymers can 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.

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

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (XV),

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

These polymers are produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the sulfonic acid group-containing acrylic acid derivative is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the compositions according to the invention is also preferred and is characterized in that the compositions contain one or more copolymers which have structural units of the formula XVI

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (0) -Y-Sθ ₃ H] _p - (XVI), contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -0- (CH ₂ ) _n - with n = 0 to 4, represents - © - (CeH _t ) -, represents -NH- C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , are preferred.

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

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (XVII),

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

- [CH ₂ -C (CH ₃ ) C00H] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (XVIII),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -0- (CH ₂ ) _n - with n = 0 to 4, for

represents -NH- C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are preferred.

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

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (XIX),

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

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) 0-Y-S0 ₃ H] _p - (XX),

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

- [CH ₂ -CHCOOH], _n - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (XV),

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (XVI),

- [CH ₂ -CHC00H] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (XVII),

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (XVIII),

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (XIX),

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) 0-Y-S0 ₃ H] _p - (XX),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals with 1 to 24 carbon atoms, with spacer groups in which Y for -0- (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 preferred.

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

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

In the case of terpolymers, those which contain 20 to 85% by weight> monomer from group i), 10 to 60% by weight> monomer from group ii) and 5 to 30% by weight> monomer from the group are particularly preferred iii) included.

The molar mass of the sulfo copolymers described above used in the compositions according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Preferred compositions are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol ^" ", preferably from 4000 to 25,000 gmol ^" " and in particular from 5000 to 15,000 gmol ^" '.

Further preferred ingredients for machine dishwashing agents produced according to the invention are agents which are able to provide corrosion protection for glassware during cleaning and / or washing operations of a dishwasher. They preferably originate from the group of 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 corrosion protection for glassware during cleaning and / or rinsing processes in a dishwasher is zinc in oxidized form, ie zinc compounds in which zinc is present in a cationic manner. Analogously, magnesium salts are also preferred. Here, both soluble and poorly or insoluble zinc or magnesium compounds can be used. Preferred compositions according to the invention contain one or more magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid.

The acids in question preferably originate from the group 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, etc. Amino acids and / or the polymeric carboxylic acids, the unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acids with at least 8 carbon atoms and / or resin acids.

Although according to the invention all magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids can be present, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the groups of the 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. Within the scope of the present invention, the acids mentioned below are again preferred within these groups:

From the group of unbranched saturated or unsaturated monocarboxylic acids: methanoic acid (formic acid), ethanoic acid (acetic acid), propanoic 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, dodecanoic (lauric), tridecanoic, tetradecanoic (myristic), pentadecanoic, hexadecanoic (palmitic acid), heptadecanoic acid (margaric), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanoic (Lignoceric acid), hexacosanoic acid (cerotinic acid), triacotanoic acid (melissic acid), 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselaidic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid) acid, 9 , 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatreic 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-

Contains 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) (azelaic 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 the sugar acids: galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, 2-deoxy-ri bonic acid, alginic acid.

From the group of hydroxy acids: hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), hydroxysuccinic acid (malic acid), 2,3-

Dihydorxybutanedioic acid (tartaric acid), 2-hydroxy-l, 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, alkyl acrylamide / acrylic acid copolymers, alkyl acrylamide / methacrylic acid copolymers,

Alkyl acrylamide / methyl methacrylic acid copolymers, copolymers of unsaturated carboxylic acids, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers.

The spectrum of the zinc salts of organic acids, preferably organic carboxylic acids preferred according to the invention, extends from salts which are sparingly or not soluble in water, ie have a solubility below 100 mg / L, preferably below 10 mg / L, in particular no solubility, up to such salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, particularly 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; 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, it preferably being at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group consisting of zinc stearate, zinc oleate, zinc gluconate and zinc acetate , Zinc lactate and / or zinc citrate. Zinc ricinoleate, zinc abietate and zinc oxalate can also be used with preference.

Claims

claims

1. Process for the production with water-soluble wrappings of tightly wrapped detergent or cleaning agent portions, characterized by the steps a) placing a water-soluble bottom film on a transport chain or a mold (s); b) placing one or more detergent or cleaning agent portion (s) on the lower film; c) placing a water-soluble top film on the detergent or cleaning agent portion (s) on the bottom film; d) fixing the top film to the bottom film, including the detergent or cleaning agent portion (s); e) sealing and optional cutting of the foils.

2. The method according to claim 1, characterized in that the lower film is preformed by applying a vacuum and / or by heating.

3. The method according to any one of claims 1 or 2, characterized in that the detergent or cleaning agent portion (s) in step b) after placing on the bottom film does not end / close flush with the top of the mold, but protrudes / protrudes from it It is preferred that a maximum of 50%, preferably a maximum of 40% and in particular a maximum of 30% of the greatest height of the detergent or cleaning agent portion (s) are within the mold.

4. The method according to claim 1, characterized in that the lower film is completely flat during steps b) to e).

5. The method according to any one of claims 1 to 4, characterized in that the detergent or detergent portion (s), which is / are placed in step b) on the lower film, is (are) detergent or detergent tablet (s) ,

6. The method according to any one of claims 1 to 5, characterized in that the top film is preformed before being placed in step c) by applying a vacuum and / or by heating in a dome.

7. The method according to claim 6, characterized in that step c) is initiated by pre-ventilation from above.

8. The method according to any one of claims 1 to 7, characterized in that steps c) and / or d) are supported by the evacuation of the space between the top and bottom film and / or by applying pressure to the top film.

9. The method according to any one of claims 1 to 8, characterized in that as the water-soluble film (s) in steps a) and c) pre-stretched films are used, which in step e) or subsequently to the detergent or detergent portion (s) ) are shrunk.