DE102006007807A1 - Packaging, especially of detergent portions, is effected by vacuum applying a film around the portion while leaving one surface film-free so as to create an opening - Google Patents

Abstract

Packaging by (i) placing a body between a film and a vacuum source and (ii) applying the film to the body by means of the vacuum is such that the body has greater than one surface and the film is applied on all n surfaces.

Description

The The present invention relates to a method for packaging moldings in a foil, packed medium portions, their enveloping foils no sealing seams and the use of these medium portions.

in the State of the art are numerous possibilities for packaging of moldings described. One of these possibilities is the moldings loose with a tubular Surround film. For technical reasons, the use of tubular bags leads to a void volume, allowing a packaged in a tubular bag moldings a larger space requirement has as the unpackaged shaped body itself. This condition carries disadvantages in the stacking and thus in the transport and storage of appropriate Products with you. Another disadvantage of the void volume is that filled Bag against mechanical influences are unstable and can burst. The circumstance of mechanical instability can be circumvented by the air is removed from the tubular bag and so the tubular bag material to the molding is created. This results in packaging in which, in particular at the corners, but also over whole surfaces of the molding away, the bag material in two or even more layers on top of each other. The packaged molding is surrounded in such a case by much more bag material, as to his serving would be necessary in principle. The one above the other lying layers of the bag material meet any stabilizing Function, but lead to an unnecessary high consumption of packaging material. These products please low consumer acceptance, as they have no smooth surface and due the overlays several bag layers also have no clear shape, but "shriveled Act".

The Coating one to be wrapped molding Delivers visually pleasing products with smoother, glossier surface and advantageous haptic properties. However, the coating is of moldings technically complex and expensive. In addition, coatings usually have a low material thickness and Therefore, a low mechanical stability.

Also in the prior art is the packaging of moldings in physically or chemically deformable films. In the described Method is formed from a first sheet a trough, filled the molding and the packaging is sealed with a second foil by the two Foils are adhered together. The products show always one or more sealing seams on, which have a low visual appeal and in addition under stress, as well as the action of solvents such as water or Dissolve heat. It result in partially or completely opened packaging, from which the molded body can emerge. For procedural reasons, the sealing seams of the Packaging the shape of a protruding edge of the film, as the Foils are sealed by next to the molded body to be packaged be placed and connected. Also, the variety of mandatory Process steps is a significant disadvantage of these processes. The time consuming process for making such packaged moldings are also characterized by a high amount of packaging material out.

Of the The present invention was based on the object, a method to the serving of moldings to provide, which does not have the aforementioned disadvantages.

in this connection should the process be particularly effective in terms of time efficiency, the number of necessary process steps, the material consumption and thus the cost to be superior to the known methods.

Surprisingly has now been found that the disadvantages by means of a packaging process handle in which a shaped body between a film and a vacuum guide is placed and the film under the action of a means of vacuum guide generated vacuum around the molding is placed.

• a) der Formkörper zwischen der Folie und einer Vakuumführung platziert wird;
• b) mittels der Vakuumführung ein Vakuum erzeugt und die Folie unter Einwirkung des Vakuums um den Formkörper gelegt wird,

wobei der Formkörper n > 1 Flächen aufweist und die Folie in dem Verfahrensschritt b) an alle n Flächen des Formkörpers angelegt wird.The subject of the present invention is therefore a process for the packaging of shaped articles, in which a film is applied by means of a vacuum to the molding, wherein

• a) the molding is placed between the film and a vacuum guide;
• b) generates a vacuum by means of the vacuum guide and the film is placed under the action of the vacuum around the shaped body,

wherein the shaped body has n> 1 areas and the film in the method step b) is applied to all n surfaces of the shaped body.

Prefers be in step b) of the method according to the invention n-1 surfaces of the molding Completely covered with the foil while the remaining area A is only partly covered. It is particularly preferred here if the area A at least 10%, preferably at least 20% and in particular at least 40% of its total area is covered with the foil.

By the inventive method can be shaped body with less time and material costs compared to known methods to pack visually appealing products. The inventive method is for packaging moldings from many areas, in particular from the washing or cleaning agents, care, pre- or post-treatment agents, Food and cosmetics suitable. Also the packaging of toys, Stationery or tool is by means of the method according to the invention possible. The process according to the invention for packaging is particularly preferred used by washing or cleaning agent portions. As to be packed moldings can in the process according to the invention any body wrapped in foil be enough high inherent stability to go through the inventive packaging process. Enough intrinsically stable within the meaning of the invention is a body that settles after 2 minutes of resting on a horizontal surface at the temperature at the packaging process is carried out per spatial direction less than 10%, preferably less than 5% of the extent of the molding in this spatial direction, has deformed. In the method according to the invention can Correspondingly, also moldings be packaged, which at 20 ° a pasty, gelatinous or liquid Have consistency, as long as the inventive method in a Temperature performed is at which the molding material one enough high inherent stability having.

Preferably is in the inventive method as a molded body, a bar, a tablet or a melt or injection molding product used. It is too possible, Multi-phase tablets such as gel phase tablets or combination products from injection molded or melted cast products with tablets and / or bars in the method according to the invention to wrap.

One Another object of the present invention is accordingly a middle portion, in particular a washing or cleaning agent portion, comprising a shaped body and a surrounding the molding, preferably water-soluble or water-dispersible film without seal seams, wherein the film on the area A of the molding an opening has, whose area smaller than this area A of the molding.

Of the moldings preferably has n surfaces on, of the n surfaces of the molding n-1 areas Completely and the area A is partially covered with film.

Of the in the method according to the invention to be packaged moldings preferably has more than 2 areas, particularly preferably 3 to 10 surfaces and in particular 6 areas on. Conceivable is the use of moldings of any shape in the Packaging process according to the invention. Preferably, the shaped body however, the shape of a prism, more preferably the shape of a straight prism and in particular the shape of a cuboid.

With Preference is the shaped body an n-sided prism, an n-sided truncated pyramid or a n-sided pyramid and therefore has n edges between the surface A and the n adjacent to this surface surfaces on. The film is preferably in the process according to the invention such by at least one of these edges, preferably by at least 2 of these edges and in particular wrapped around all these edges, that the film partially covers the surface A.

In an embodiment The inventive center portion preferably makes the area of the opening between 5 and 90%, preferably between 7.5 and 70% and in particular between 10 and 50% of the area A of the molding out.

The middle portion according to the invention is preferable to the sum of its surfaces at least 70%, preferably at least 75%, preferably at least 80%, more preferably at least 85%, more preferably at least 90% and in particular at least 95% wrapped in foil.

The inventive method allows it, moldings to pack without a protruding edge of the film is formed. Advantages of innovative center portions with flat or curved side surfaces without projecting film parts are in addition to the improved visual impression also improvements in the area of storage and transport. moreover allows the method allows a flexible adjustment of the material thickness of the Packaging material.

The inventive method can be done in many variations.

• a) ein Formkörper mit einer seiner Flächen auf einen Sockel gelegt wird, so dass zwischen der aufliegenden Fläche A des Formkörpers und dem Sockel eine Kontaktfläche B ausgebildet wird, wobei die Fläche A größer ist als die Kontaktfläche B, und eine Folie derart zugeführt wird, dass sich der Formkörper zwischen Sockel und Folie befindet; und
• b) mittels der Vakuumführung ein Vakuum erzeugt und die Folie unter Einwirkung des Vakuums an den Formkörper angelegt wird;

wobei die Fläche A in Schritt b) anteilsweise mit der Folie bedeckt wird.A preferred embodiment of the method according to the invention is a method in which

• a) a shaped body with one of its surfaces is placed on a base so that a contact area B is formed between the resting surface A of the shaped body and the base, wherein the area A is greater than the contact area B, and a film is supplied in such a way that the molding is between the base and the film; and
• b) generates a vacuum by means of the vacuum guide and the film is applied under the action of the vacuum to the molding;

wherein the surface A in step b) is partially covered with the film.

The area A is the base facing the base of the molding, which partly in contact with the pedestal stands. Preferably, the shaped body is so on the base placed that the pedestal surface Completely with the molding is covered.

Preferably is the contact surface B less than 90%, preferably less than 80%, preferably less than 70%, more preferably less than 60%, preferably less as 50%, most preferably less than 40%, with preference less than 30%, with particular preference less than 20% and in particular less than 10% of the area A.

With preference, the contact surface B is less than 100 cm ² , preferably less than 10 cm ² , preferably less than 5 cm ² , more preferably less than 2.5 cm ² , more preferably less than 2 cm ² , most preferably less than 1 , 5 cm ² , more preferably less than 1 cm ² , more preferably less than 0.5 cm ² and in particular less than 0.25 cm ² .

The vacuum guide is located in this embodiment of the method according to the invention preferably in the pedestal. However, it may also be preferable the vacuum guide outside to provide the base. In this case, a vacuum table is preferred used, which equipped with one or more sockets is. The vacuum guides are here preferably in the vacuum table surface in low Distance from the base (s). This distance is preferably smaller 2 cm, preferably less than 1.5 cm, more preferably less than 1 cm and in particular less than 0.5 cm. It is possible more than one, preferably more than two, preferably more than three and in particular more than four vacuum guides to be provided per socket.

Especially it is preferred in this embodiment of the method according to the invention, that the area A, the contact surface B and / or the base surface flat / plan is / are.

As a general rule However, the pedestal can be a dome-shaped, beveled, pointed tapered or planar top surface and a round, angular, especially three-, four-, five- or hexagonal shape, or the shape of a symbol or logo. It is too possible, the molded body to be packaged to place on several sockets. The means of such Method produced middle portions have accordingly several small openings or a big opening in the enveloping one Slide on.

• a) ein Formkörper mit einer seiner Flächen derart auf einer Folie platziert wird, dass sich der Formkörper zwischen der Folie und einer Vakuumführung befindet;
• b) mittels der Vakuumführung ein Vakuum erzeugt wird und die Folie unter Einwirkung des Vakuums an den Formkörper angelegt wird.

Another preferred embodiment of the method according to the invention is a method in which

• a) a shaped body with one of its surfaces is placed on a foil such that the shaped body is located between the foil and a vacuum guide;
• b) a vacuum is generated by means of the vacuum guide and the film is applied under the action of the vacuum to the molding.

Preferably is that or are the vacuum guides in this embodiment provide directly above the molded body to be packaged.

to Simplification is intended in the following in this embodiment, the vacuum guide facing area of the molding as area A be designated.

Preferably, the area A of the shaped body in the inventive method to at least 10%, preferably at least 20%, preferably at least 30%, more preferably at least 40%, more preferably at least 50%, most preferably at least 60%, with preference to this at least 70%, with particular preference at least 80% and in particular at least 90%.

All in all becomes the shaped body with preference to the sum of its surfaces at least 70%, preferably at least 75%, preferably at least 80%, more preferably at least 85%, more preferably at least 90% and in particular at least 95% wrapped in foil.

Prefers The film is softened before it is applied to the molding. This will be between step a) and step b) the film with preference by heating / heating or by the action of solvents, in the case of water-soluble or water-dispersible films, preferably by the action of Water or steam, softened. It may be preferable to use the film over its the whole area away or even partially soften. In the case in which the film is only partially softened, it is preferred that the film to soften only in those places, which later cover the edges of the molding.

The in step b) of the method according to the invention applied vacuum is preferably from 100 to 950 mbar, preferably from 200 to 900 mbar, particularly preferably from 300 to 850 mbar and in particular from 400 up to 800 mbar.

in the Following the process steps a) and b), the film is preferably in an additional step c) at a distance from the molding, smaller than 1 cm, preferably smaller than 0.5 cm, more preferably less than 0.1 cm, and in particular less than 0.05 cm, using of mechanical cutting tools, exposure to heat, especially using laser devices or melting tools, or by Solve the Foil using solvents, Water or steam is severed.

alternative Is it possible the supernumerary Foil not separate, but in the additional step c) to the area A to seal. Preferably, this step by the Action of heat, specifically using laser devices or melting tools, by pressure or by dissolution the film using solvents, Water or steam and the application to the molding carried out.

through of the inventive method, a middle portion is produced, their serving has an opening. Such agents have many advantages over the in the prior art described means. The average portion has no protruding film parts such as sealing seams or excess material and draws is therefore characterized by a good look and feel. The material consumption per molded article to be packaged is kept as low as possible by the inventive method. Further material savings can be carried out by enlarging the opening. It is thus preferred, in particular those shaped bodies which are stable to external influences such as Moisture or solvents are so packaged that the opening of the film on the surface A of molding a maximum of 70%, more preferably a maximum of 50% and in particular maximum 30% of the area A matter.

One substantial advantage of the medium portions over coated means is the easy removability of the packaging. In a preferred embodiment the method according to the invention is no adhesive bond between the molding and the built up in the process step b) to the molded body film. Accordingly, you can moldings and slide easily and quickly separated from each other while the coatings described in the prior art on the whole Shaped surface with This are liable and connected by the consumer easily can not be separated / removed.

In a preferred embodiment of the inventive process, the film contains a tear strip, with which the packaging is simply opened by the consumer and the molded body can be removed.

in the Case of a medium portion, which is used in aqueous medium and a water-soluble one or water-dispersible film, the film dissolves on contact with the water directly from the mold. The molded body, respectively the active ingredients contained in it are released without delay. This effect can be contained in the molding or the film Disintegration agents are still reinforced. In a coated moldings the coating has to be flat be released from the shaped body, before the active ingredients of the molding be released.

Depending on the application, it may be preferred if the molding is complete or nearly completely wrapped in foil. In a preferred embodiment of the inventive center portion, the opening is sealed with another film.

Preferably is therefore applied to the non-foil covered surface of the surface A before or after of steps a) and b) and optionally c) in a further step d) another film applied / sealed.

In a preferred embodiment of the inventive method is applied to the surface A before passing of step a) another film applied to the surface A of the molding or the area A coated with a coating. In these two cases will an adhesive connection between another film or Coating and the surface A made. The on the surface A already partially or completely with foil or coating covered moldings is subsequently in the Process steps a) and b) wrapped with foil. The steps in a) and b) applied film may subsequently be adhered to the coating or the further film are connected, so that a liquid-tight Medium portion is formed. With preference is on an adhesive connection between the other film or the coating and the dispensed in the steps a) and b) applied film.

In this embodiment it is preferable if the area A of the molding before passing through process steps a) and b) to a maximum of 99%, preferably to a maximum of 75%, more preferably to a maximum of 50% and in particular to a maximum of 25% covered with foil or coating is.

A full wrapping of the molded body to be packaged can also be achieved if on the surface A of the unpackaged molding a another film laid loosely and in the process steps a) and b) inserted film around the molding - including further film - laid becomes. In this embodiment, an adhesive connection is preferred between further, loosely on the surface A resting foil and the film applied in steps a) and b) again a liquid density To receive packaging. Especially with regard to the fast release of active substances in liquids like watery Media may be preferred, no adhesive bond between to provide these two slides. In this case, the liquid can penetrate into the middle portion and dissolve / disperse the active ingredients. A quick release of the active ingredients will also in this case accelerated by in the active ingredient-containing moldings and / or the film disintegrating agents are incorporated.

The in this embodiment the method according to the invention used additional film, which no adhesive connection with the shaped body preferably covers at most 100%, preferably maximum 85%, more preferably to a maximum of 70% and in particular to maximum 55 of the area A.

A another possibility consists in the non-foil covered surface of the surface A of the molding after Going through steps a) and b) and optionally c) in another Step d) with another film to occupy and the other film adherent with the film applied in steps a) and b) connect. Preferred may additionally formed an adhesive connection between another film and the molding become.

The further film preferably covers a maximum of 99%, preferably a maximum 75%, more preferably at most 50% and especially maximum 25% of the area A. However, it may also be preferred that the further film the area A partial or complete and also one or more other surfaces of the molding partially or completely covered. For cost reasons However, it is of interest to use the film as possible to keep low.

options for the adhesive connection between two films, between film and moldings or between film and coating are known in the art. Next the use of known adhesives becomes an adhesive bond preferably by the use of heat, especially with the help of Laser devices or melting tools, by pressure or through Solve the Foil using solvents, Water or steam produced. Depending on the nature of the molding can it is preferable not to form a continuous adhesive bond, but only a punctiform adhesive bond which acts as a perforation and the ingress of liquid allowed, but from unwanted contact of the consumer with the Shaped surface protects.

Preferably the adhesive bond is not on the side edges of the Molding, but on a shaped body surface, preferably the area A placed around protruding edges to avoid packaging material.

Preferably are at most 70%, preferably at most 60%, particularly preferably at most 50%, preferably to a maximum of 40%, with preference to a maximum of 30% and in particular a maximum of 20% of the sum of the surfaces of the molding adhering associated with film and / or coating. With preference the foil is in the inventive average portion shrunk onto the molding.

The in the method according to the invention The films used are preferably water-soluble or water-dispersible. Preferably, they contain washing or washing in addition to the film components cleaning-active components. In order to increase consumer acceptance it is preferred to use films which are transparent or have translucent properties.

Under Transparency is to be understood here as the permeability within the visible spectrum of light (410 to 800 nm) greater than 20%, preferably greater than 30%, very preferred greater than 40% and in particular greater than 50% is. Thus, once a wavelength of the visible spectrum the light a permeability greater than 20%, it is to be regarded as transparent within the meaning of the invention.

In the method according to the invention It is preferable to use a film having a thickness of 5 to 500 μm, preferably from 8.5 to 400 μm, more preferably from 12 to 300 microns, preferably from 15.5 to 200 μm and in particular from 19 to 100 μm having. Accordingly, the film in the inventive Central portion preferably a thickness of 5 to 500 microns, preferably from 8.5 to 400 μm, more preferably from 12 to 300 microns, preferably from 15.5 to 200 μm and in particular from 19 to 100 μm on.

The in the process according to the invention usable films or coating agents can be a single Material or a blend of different materials. In preferred inventive method includes water-soluble wrapping one or more materials from the group (optionally acetalized) Polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinylpyrrolidone, Polyethylene oxide, polyethylene glycol, gelatin, cellulose and theirs Derivatives, in particular MC, HEC, HPC, HPMC and / or CMC, and / or Copolymers and mixtures thereof. Possibly. can the servings Plasticizers known to those skilled in the art for increasing the flexibility of the material be mixed.

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

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

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

contain.

Commercially available polyvinyl alcohols, the as white-yellowish Powders or granules with degrees of polymerization in the range of approx. 100 to 2500 (molecular weights of about 4000 to 100,000 g / mol) offered have hydrolysis degrees of 98-99 and 87-89 mol%, respectively So still a residual content of acetyl groups. To be characterized the polyvinyl alcohols from the manufacturers by specifying the Degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

polyvinyl alcohols are dependent soluble in the degree of hydrolysis in water and a few highly polar organic solvents (Formamide, dimethylformamide, dimethyl sulfoxide); of (chlorinated) Hydrocarbons, esters, fats and oils are not attacked. Polyvinyl alcohols are classified as toxicologically harmless and are at least partially biodegradable biologically. The water solubility can be by post-treatment with aldehydes (acetalization), by Complexation with Ni or Cu salts or by treatment with dichromates, boric acid od. Borax decrease. Polyvinyl alcohol is largely impermeable to gases such as Oxygen, nitrogen, helium, hydrogen, carbon dioxide, however, leaves Pass water vapor.

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

Preferably, polyvinyl alcohols of a certain molecular weight range are used, preference being given to processes according to the invention in which the water-soluble coating comprises polyvinyl alcohols and / or PVAL copolymers whose molecular weight is in the range from 3500 to 100,000 gmol ^-1 , preferably from 10,000 to 90,000 gmol ^-1 preferably from 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 .

Of the Degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680 and especially between about 260 to about 1500th

According to the invention preferred Processes are characterized in that the water-soluble coating polyvinyl alcohols and / or PVAL copolymers, their average degree of polymerization between 80 and 700, preferably between 150 and 400, more preferably between 180 to 300 and / or their molecular weight ratio MG (50%) to MG (90%) 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 material for the water-soluble coating are shown in the following table:

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

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

which are prepared by free-radical polymerization of 1-vinylpyrrolidone by the method of solution or suspension polymerization using free-radical initiators (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer provides only low molecular weight products. Handelsübli polyvinylpyrrolidones have molar masses in the range of about 2500-750000 g / mol, which are characterized by the specification of the K values and - depending on 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, such as for example, under the trade name Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred non-ionic polymers.

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

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

The Polymerization of the vinyl ester takes place radically according to different Process (solution polymerization, Suspension polymerization, emulsion polymerization, bulk polymerization.). Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (I) and (II).

Further suitable water-soluble polymers are the polyethylene glycols (polyethylene oxides), which are referred to as PEG for short. PEG are polymers of ethylene glycol which are of the general formula (III) H- (O-CH ₂ -CH ₂ ) _n -OH (III) satisfy, where n can take values between 5 and> 100,000.

PEGs are technically prepared by anionic ring-opening polymerization of ethylene oxide (oxirane) usually in the presence of small amounts of water. They have depending on the reaction Molar masses in the range of about 200-5 000 000 g / mol, corresponding degrees of polymerization from about 5 to> 100 000th

The Products with molecular weights <approx. 25 000 g / mol are liquid sore at room temperature as actual Polyethylene glycols, abbreviated PEG, designated. This short-chain PEGs can in particular other water-soluble Polymers, e.g. Polyvinvlalkoholen or cellulose ethers as plasticizer be added. The inventively usable, at room temperature solid polyethylene glycols are called polyethylene oxides, abbreviations PEOX, designated. High molecular weight polyethylene oxides have an extremely low Concentration of reactive hydroxy end groups and therefore show only still weak glycol properties.

Further as water-soluble shell material According to the invention, gelatin is also suitable, these preferably being used together with other polymers becomes. Gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), the primarily by hydrolysis of the skin and bones of animals Collagen is obtained under acidic or alkaline conditions. The amino acid composition The gelatin largely corresponds to that of the collagen from which they are made was obtained and varies depending on its provenance. The use of gelatin as the water-soluble coating material is in particular in pharmacy in the form of hard or soft gelatin capsules extremely far common. In the form of slides, gelatin is because of their compared to the above-mentioned polymers of high price only small Use.

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

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

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

preferred inventive method are characterized in that the water-soluble coating hydroxypropylmethylcellulose (HPMC), which has a degree of substitution (average number of Methoxy groups per anhydroglucose unit of cellulose) of 1.0 to 2.0, preferably from 1.4 to 1.9, and a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit the cellulose) from 0.1 to 0.3, preferably from 0.15 to 0.25, having.

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

• – Vinylacetat/Crotonsäure-Copolymere, wie sie beispielsweise unter den Bezeichnungen Resyn^® (NATIONAL STARCH), Luviset^® (BASF) und Gafset^® (GAF) im Handel sind. Diese Polymere weisen neben Monomereinheiten der vorstehend genannten Formel (II) auch Monomereinheiten der allgemeinen Formel (V) auf: [-CH(CH₃)-CH(COOH)-]_n (V)
• – Vinylpyrrolidon/Vinylacrylat-Copolymere, erhältlich beispielsweise unter dem Warenzeichen Luviflex (BASF). Ein bevorzugtes Polymer ist das unter der Bezeichnung Luviflex VBM-35 (BASF) erhältliche Vinylpyrrolidon/Acrylat-Terpolymere.
• – Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere, die beispielsweise unter der Bezeichnung Ultrahold^® strong (BASF) vertrieben werden.
• – Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen

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

• - Vinyl acetate / crotonic acid copolymers, such as those under the names Resyn ^® (NATIONAL STARCH), Luviset ^® (BASF) and Gafset ^® (GAF) are commercially available. These polymers also have monomer units of the formula (II) above [-CH (CH ₃ ) -CH (COOH) -] _n (V)
• Vinylpyrrolidone / vinyl acrylate copolymers, available, for example, under the trademark Luviflex (BASF). A preferred polymer is the vinylpyrrolidone / acrylate terpolymer available under the name Luviflex VBM-35 (BASF).
• - acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers sold for example under the name Ultrahold ^® strong (BASF).
• - Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in admixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols

Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in admixture with other copolymerizable compounds on polyalkylene glycols are by polymerization in the heat obtained in a homogeneous phase characterized in that the polyalkylene glycols in the monomers of vinyl esters, esters of acrylic acid or methacrylic acid, in the presence of free radical initiator.

When suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, Vinyl butyrate, vinyl benzoate and esters of acrylic acid or methacrylic acid those with low molecular weight aliphatic alcohols, ie in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, available are, proven.

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

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

• – gepfropfte und vernetzte Copolymere aus der Copolymerisation von i) mindesten einem Monomeren vom nicht-ionischen Typ, ii) mindestens einem Monomeren vom ionischen Typ, iii) von Polyethylenglycol und iv) einem Vernetzer Das verwendete Polyethylenglycol weist ein Molekulargewicht zwischen 200 und mehreren Millionen, vorzugsweise zwischen 300 und 30.000, auf. Die nicht-ionischen Monomeren können von sehr unterschiedlichem Typ sein und unter diesen sind folgende bevorzugt: Vinylacetat, Vinylstearat, Vinyllaurat, Vinylpropionat, Allylstearat, Allyllaurat, Diethylmaleat, Allylacetat, Methylmethacrylat, Cetylvinylether, Stearylvinylether und 1-Hexen. Die nicht-ionischen Monomeren können gleichermaßen von sehr unterschiedlichen Typen sein, wobei unter diesen besonders bevorzugt Crotonsäure, Allyloxyessigsäure, Vinylessigsäure, Maleinsäure, Acrylsäure und Methacrylsäure in den Pfropfpolameren enthalten sind. Als Vernetzer werden vorzugsweise Ethylenglycoldimethacrylat, Diallylphthalat, ortho-, meta- und para-Divinylbenzol, Tetraallyloxyethan und Polyallylsaccharosen mit 2 bis 5 Allylgruppen pro Molekül Saccharin. Die vorstehend beschriebenen gepfropften und vernetzten Copolymere werden vorzugsweise gebildet aus: i) 5 bis 85 Gew.-% mindesten eine Monomeren vom nicht-ionischen Typ, ii) 3 bis 80 Gew.-% mindestens eines Monomeren vom ionischen Typ, iii) 2 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-% Polyethylenglycol und iv) 0,1 bis 8 Gew.-% eines Vernetzters, wobei der Prozentsatz des Vernetzers durch das Verhältnis der Gesamtgewichte von i), ii) und iii) ausgebildet ist.
• – durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltene Copolymere: i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren, ii) ungesättigte Carbonsäuren, iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_1-18-Alkohols Unter kurzkettigen Carbonsäuren bzw. Alkoholen sind dabei solche mit 1 bis 8 Kohlenstoffatomen zu verstehen, wobei die Kohlenstoffketten dieser Verbindungen gegebenenfalls durch zweibindige Heterogruppen wie -O-, -NH-, -S_ unterbrochen sein können.
• – Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester Diese Terpolymere enthalten Monomereinheiten der allgemeinen Formeln (II) und (IV) (siehe oben) sowie Monomereinheiten aus einem oder mehreren Allyl- oder Methallyestern der Formel (VII):
  
  worin R³ für -H oder -CH₃, R² für -CH₃ oder -CH(CH₃)₂ und R¹ für -CH₃ oder einen gesättigten geradkettigen oder verzweigten C_1-6-Alkylrest steht und die Summe der Kohlenstoffatome in den Resten R¹ und R² vorzugsweise 7, 6, 5, 4, 3 oder 2 ist. Die vorstehend genannten Terpolymeren resultieren vorzugsweise aus der Copolymerisation von 7 bis 12 Gew.-% Crotonsäure, 65 bis 86 Gew.-%, vorzugsweise 71 bis 83 Gew.-% Vinylacetat und 8 bis 20 Gew.-%, vorzugsweise 10 bis 17 Gew.-% Allyl- oder Methallyletsre der Formel (VII).
• – Tetra- und Pentapolymere aus i) Crotonsäure oder Allyloxyessigsäure ii) Vinylacetat oder Vinylpropionat iii) verzweigten Allyl- oder Methallylestern iv) Vinylethern, Vinylesterrn oder geradkettigen Allyl- oder Methallylestern
• – Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinymethylether, Acrylamid und deren wasserlöslicher Salze
• – Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen verzweigten Monocarbonsäure.

In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used.

• Grafted and crosslinked copolymers from the copolymerization of i) at least one nonionic-type monomer, ii) at least one ionic-type monomer, iii) 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, on. The nonionic monomers may be of very different types and of these preferred are: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allylaurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene. The non-ionic monomers may equally be of very different types, among which particularly preferably crotonic acid, allyloxyacetic acid, vinylacetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the grafting polymers. The crosslinking agents used are preferably ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallyl sucrose having 2 to 5 allyl groups per molecule of saccharin. The grafted and crosslinked copolymers described above are preferably formed from: i) 5 to 85% by weight of at least one nonionic type monomer, ii) 3 to 80% by weight of at least one ionic type monomer, iii) 2 to 50% by weight, preferably 5 to 30% by weight of polyethylene glycol and iv) 0.1 to 8% by weight of a crosslinking agent, wherein the percentage of crosslinking agent is formed by the ratio of the total weights of i), ii) and iii) is.
• Copolymers obtained by copolymerization of at least one monomer of each of the following three groups: i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, ii) unsaturated carboxylic acids, iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or Esters of the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C _1-18 -alcohols Short-chain carboxylic acids or alcohols are to be understood as meaning those having from 1 to 8 carbon atoms, the carbon chains of these compounds being optionally substituted by divalent hetero groups such as O-, -NH-, -S_ can be interrupted.
• Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester These terpolymers contain monomer units of the general formulas (II) and (IV) (see above) and monomer units of one or more allyl or methallyl esters of the formula (VII):
  
  wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated straight or branched C _1-6 alkyl radical and the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2. The abovementioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight of vinyl acetate and 8 to 20% by weight, preferably 10 to 17% by weight .-% allyl or Methallyletsre of the formula (VII).
• - tetra- and pentapolymers from i) crotonic acid or allyloxyacetic acid ii) vinyl acetate or vinyl propionate iii) branched allyl or methallyl esters iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
• Crotonic acid copolymers with one or more monomers from the group of ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts
• Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic branched monocarboxylic acid.

Further, preferably usable according to the invention as a wrapper Polymers are cationic polymers. Among the cationic polymers In this case, the permanent cationic polymers are preferred. As "permanently cationic" according to the invention such Polymers referred to independently have a cationic group from the pH. These are in the Usually polymers that are quaternary Nitrogen atom, for example in the form of an ammonium group.

• – quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat^® und Polymer JR^® im Handel erhältlich sind. Die Verbindungen Celquat^® H 100, Celquat^® L 200 und Polymer JR^®400 sind bevorzugte quaternierte Cellulose-Derivate.
• – Polysiloxane mit quaternären Gruppen, wie beispielsweise die im Handel erhältlichen Produkte Q2-7224 (Hersteller: Dow Corning; ein stabilisiertes Trimethylsilylamodimethicon), Dow Corning^® 929 Emulsion (enthaltend ein hydroxyl-amino-modifiziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Hersteller: General Electric), SLM-55067 (Hersteller: Wacker) sowie Abil^®-Quat 3270 und 3272 (Hersteller: Th. Goldschmidt; diquaternäre Polydime-thylsiloxane, Quaternium-80),
• – Kationische Guar-Derivate, wie insbesondere die unter den Handelsnamen Cosmedi^® Guar und Jaguar^® vertriebenen Produkte,
• – Polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat^®100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat^®550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere.
• – Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und – methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon- Dimethylaminomethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat^®734 und Gafquat^®755 im Handel erhältlich.
• – Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere, wie sie unter der Bezeichnung Luviquat^® angeboten werden.
• – quaternierter Polyvinylalkohol sowie die unter den Bezeichnungen
• – Polyquaternium 2,
• – Polyquaternium 17,
• – Polyquaternium 18 und
• – Polyquaternium 27

bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette. Die genannten Polymere sind dabei nach der sogenannten INCI-Nomenklatur bezeichnet.Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, such as those under the names Celquat ^® and Polymer JR ^® commercially available. The compounds Celquat ^® H 100, Celquat L 200 and Polymer JR ^{® ®} 400 are preferred quaternized cellulose derivatives.
• Quaternary group polysiloxanes, such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone), Dow ^Corning® 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquaternary Polydime-thylsiloxane, quaternium-80).,
• - cationic guar derivatives such as in particular the products sold under the trade names Cosmedi ^® Guar and Jaguar ^®,
• - Polymers Dimethyldiallylammoniumsalze 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) are examples of such cationic polymers.
• Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as diethyl sulfate quaternized vinylpyrrolidone dimethylaminomethacrylate copolymers. Such compounds are sold under the names Gafquat ^® 734 and Gafquat ^® 755 commercially.
• - Vinylpyrrolidone-Methoimidazoliniumchlorid copolymers, such as those 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 polymer main chain. The polymers mentioned are designated according to the so-called INCI nomenclature.

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

in the inventive method can the serving or the film material in addition to the water-soluble polymer or the water-soluble Polymers contain other ingredients, which in particular the processability the starting materials to the cladding improve. In particular, plasticizers and release agents are used here call. About that can out Colorants and / or fragrances and optical brighteners incorporated in the water-soluble envelope be there to be aesthetic To achieve effects.

When According to the invention, plasticizers can in particular be hydrophilic, use high-boiling liquids, optionally also at room temperature solids as a solution, dispersion or melt can be used. Especially preferred Plasticizers come from the group glycol, di-, tri-, tetra-, penta-, Hexa, hepta, octa, nona, deca, undeca, dodecaethylene glycol, Glycerol, neopentyl glycol, trimethylolpropane, pentaerythritol, mono-, Di-, triglycerides, surfactants, especially nonionic surfactants, and their Mixtures.

ethylene glycol (1,2-ethanediol, "glycol") is a colorless, viscous, sweet-tasting, highly hygroscopic liquid, which is miscible with water, alcohols and acetone and a density of 1,113. The solidification point of ethylene glycol is at -11.5 ° C, the liquid boils at 198 ° C. Technically, ethylene glycol is produced from ethylene oxide by heating with Won water under pressure. Promising manufacturing process can also be applied to the acetoxylation of ethylene and subsequent Hydrolysis or build up on synthesis gas reactions.

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

Glycerin is a colorless, clear, heavy-bodied, odorless sweet-tasting hygroscopic liquid of density 1.261 that solidifies at 18.2 ° C. Glycerol was originally a 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 intermediates allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO ₃ contact via the step of the glycide.

trimethylolpropane [TMP, etriol, etiol, 1,1,1-tris (hydroxymethyl) propane] is chemical exactly denotes 2-ethyl-2-hydroxymethyl-1,3-propanediol and passes in the form of colorless, hygroscopic masses with a melting point from 57-59 ° C and a boiling point of 160 ° C (7 hPa) in the trade. It is soluble in water, alcohol, acetone, but insoluble in aliphatic and aromatic hydrocarbons. The production is done by Reaction of formaldehyde with butyraldehyde in the presence of alkalis.

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

Mono-, di-, triglycerides are esters of fatty acids, preferably longer-chain fatty acids with glycerol, wherein depending on the type of glyceride, one, two or three OH-groups of glycerol are esterified. As acid com Component with which the glycerol can be esterified in mono-, di- or triglycerides which can be used according to the invention are, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid etc .. In the context of the present invention, the use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid) are preferred. Hexacosanoic acid (cerotic acid), triacotinic acid (melissic acid) and the unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (Linolaidinsäu Re) and 9c, 12c, 15c-octadecatenic acid (linolenic acid) into consideration. For cost reasons, the native fatty substances (triglycerides) or the modified native fatty substances (partially hydrolyzed fats and oils) can also be used directly. Alternatively, fatty acid mixtures can also be prepared by cleavage of native fats and oils and subsequently separated, with the purified fractions subsequently being converted again to mono-, di- or triglycerides. Acids, which are here esterified with the glycerol, in particular coconut oil fatty acid (about 6 wt .-% Ca, 6 wt .-% C ₁₀ , 48 wt .-% C ₁₂ , 18 wt .-% C ₁₄ , 10 wt. % C ₁₆ , 2 wt.% C ₁₈ , 8 wt.% C _18. , 1 wt.% C ₁₈ ..), palm kernel oil fatty acid (about 4 wt.% C ₈ , 5 wt. C ₁₀ , 50 wt .-% C ₁₂ , 15 wt .-% C ₁₄ , 7 wt .-% C ₁₆ , 2 wt .-% C ₁₈ , 15 wt .-% C _18. , 1 wt .-% C ₁₈ ..), tallow fatty acid (about 3 wt .-% C ₁₄ , 26 wt .-% C ₁₆ , 2 wt .-% C _16. , 2 wt .-% C ₁₇ , 17 wt .-% C ₁₈ , 44% by weight C ₁₈ , 3% by weight C ₁₈ .., 1% by weight C ₁₈ ...), hardened tallow fatty acid (about 2% by weight C ₁₄ , 28% by weight C) ₁₆ , 2 wt .-% C ₁₇ , 63 wt .-% C ₁₈ , 1 wt .-% C _18. ), Technical Oleic Acid (about 1 wt .-% C ₁₂ , 3 wt .-% C ₁₄ , 5 % By weight C ₁₆ , 6% by weight C _16. , 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C _18. , 10% by weight C ₁₈ .. , 0.5 wt .-% C ₁₈ ...), technical Palmitin / stearic acid (about 1 wt .-% C ₁₂ , 2 wt .-% C ₁₄ , 45 wt .-% C ₁₆ , 2 wt. % C ₁₇ , 47% by weight C ₁₈ , 1% by weight C ₁₈ ) and soybean oil fatty acid (approx. 2 wt .-% C ₁₄ , 15 wt .-% C ₁₆ , 5 wt .-% C ₁₈ , 25 wt .-% C ₁₈ , 45 wt .-% C ₁₈ .., 7 wt .-% C ₁₈ ...).

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

With Particular preference is given to using nonionic surfactants as plasticizers, which have a melting point above room temperature. As a result, are preferred casings characterized in that as plasticizer nonionic surfactant (s) with a melting point above 20 ° C, preferably above 25 ° C, especially preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, are used.

suitable nonionic surfactants, the melting or softening points in said Temperature range, for example, low-foaming nonionic Surfactants which may be solid or highly viscous at room temperature. Become used at room temperature highly viscous nonionic surfactants, it is preferred that this is a viscosity above 20 Pas, preferably above 35 Pas and especially above 40 Pas. Also nonionic surfactants which are waxy at room temperature Consistency are preferred.

Prefers as at room temperature fixed to be used nonionic surfactants derived the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary Alcohols and mixtures of these surfactants with structurally complicated built-up surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.

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

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

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

The Nonionic surfactant preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25% by weight, especially preferably up to 20 wt .-% and in particular up to 15 wt .-% of total molecular weight of the nonionic surfactant. Especially preferred nonionic surfactants are ethoxylated monohydroxyalkanols or Alkylphenols, in addition Having polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules is involved preferably more than 30% by weight, particularly preferably more than 50 Wt .-% and in particular more than 70 wt .-% of the total molecular weight such nonionic surfactants.

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

Further preferred nonionic surfactants satisfy the formula R ¹ O [CH ₂ CH (CH ₃ ) O) _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ], in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.

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

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

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is to R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and especially from 6 to 18 Surfactants are particularly preferred in which the radicals R ¹ and R ^{2 have} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

Further Preferred substances to be used as plasticizers may include glycerol carbonate, Propylene glycol and propylene carbonate.

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

from Propylene glycol exist two isomers, the 1,3-propanediol and the 1,2-propanediol. 1,3-propanediol (Trimethylene glycol) is a neutral, colorless and odorless, sweet-tasting liquid of density 1.0597, which solidifies at -32 ° C and at 214 ° C boils. The preparation of 1,3-propanediol is possible from acrolein and Water under 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 will made of propylene oxide by Wasseranlagerung.

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

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

Further objects The present invention provides the uses of the invention Medium portion in textile cleaning and / or machine dishwashing.

Accordingly comprises the shaped body preferably washing or cleaning substances, preferably from the group of builders, Surfactants, polymers, bleaches, bleach activators, bleach catalysts Enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids, Perfumes and perfume carriers. These preferred ingredients will be described in more detail below.

builders

To the builders counting in particular the zeolites, silicates, carbonates, organic cobuilders and where no ecological Prejudices against their use exist - even the phosphates.

Preference is given to using crystalline layer-form silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, in which M represents sodium or hydrogen, x a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values x is 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layer-form silicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O are for example sold by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O, Makatite).

Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O, in which x is 2. In particular, both β- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ .yH ₂ O and furthermore especially Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O _5, natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3H ₂ O, kanemite), Na-SKS-11 (t- Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ) is preferred.

Detergents or cleaning agents preferably contain a weight fraction of the crystalline layered silicate of the formula NaMSi _x O _{2x + 1} · yH ₂ O of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular of 0 , 4 to 10 wt .-%, each based on the total weight of these agents.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle , cause.

alternative or in combination with the aforementioned amorphous sodium silicates become X-ray amorphous Silicate used, the silicate particles in electron diffraction experiments provide blurred or even sharp diffraction maxima. This is to interpret that the products microcrystalline areas the size ten up to several hundred nm, with values up to max. 50 nm and especially up to max. 20 nm are preferred. Such X-ray amorphous Silicates also have a dissolution delay over the conventional ones water glasses on.

Especially preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried roentgenoamorphous Silicates.

in the Within the scope of the present invention, it is preferred that this (s) Silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali disilicates, in detergents or cleaners in amounts of from 3 to 60% by weight, preferably from 8 to 50% by weight and in particular from 20 to 40 wt .-%, each based on the weight of the washing or cleaning agent are included.

Of course it is also a use of the well-known phosphates as builders possible, if such use is not avoided for environmental reasons should be. Among the variety of commercially available Phosphates have the alkali metal phosphates, with particular preference of Pentasodium or pentakalium triphosphate (sodium or potassium tripolyphosphate) in the washing and cleaning industry the greatest importance.

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

Technically particularly important phosphates are the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate). The sodium potassium tripolyphosphates are also preferably used according to the invention.

Become in the context of the present application phosphates as washing or cleaning active Substances used in detergents or cleaners, so included preferred agents are said phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 5 to 80 wt .-%, preferably from 15 to 75% by weight and especially from 20 to 70% by weight, respectively based on the weight of the washing or cleaning agent.

Further builders are the alkali carriers. Suitable alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention. Particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate. Also particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate. Because of their compared with other buildersub punching low chemical compatibility with the other ingredients of detergents or cleaners, the alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 wt .-% and in particular below 2% by weight, in each case based on the total weight of the washing or cleaning agent. Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.

Especially preference is given to the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of from 2 to 50% by weight, preferably from 5 to 40% by weight and in particular from 7.5 to 30 wt .-%, each based on the Weight of washing or cleaning agent. Particularly preferred Means, based on the weight of the detergent or cleaning agent less than 20% by weight, preferably less than 17% by weight, is preferred less than 13% by weight and in particular less than 9% by weight of carbonate (s) and / or bicarbonate (s), preferably alkali carbonate (s), especially preferably contain sodium carbonate.

When Organic co-builders are in particular polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) as well as phosphonates. These classes of substances are hereafter described.

useful organic builders For example, they are in the form of the free acid and / or their sodium salts usable polycarboxylic acids, where among polycarboxylic acids such carboxylic acids be understood that 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), if such an application for ecological reasons not is objectionable, as well as mixtures of these. Own the free acids In addition to their builder effect typically also the property of a acidifying and thus serve to set a lower and milder one pH of wash or detergents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.

When builders are further polymeric polycarboxylates suitable, these are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight from 500 to 70000 g / mol.

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

suitable Polymers are in particular polyacrylates, which preferably have a molecular mass of 2000 to 20,000 g / mol. Because of their superior solubility can from this group again the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and more preferably from 3000 to 5000 g / mol, may be preferred.

Suitable are furthermore copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and the acrylic acid or methacrylic acid with maleic acid. Particularly suitable are copolymers of acrylic acid with maleic which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid. Your molecular weight, based on free acids, is in general from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can either as a powder or as an aqueous one solution be used. The content of detergents or cleaners of (co) polymeric polycarboxylates is preferably from 0.5 to 20 Wt .-% and in particular 3 to 10 wt .-%.

to Improvement of water solubility can the polymers also include allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as Contain monomer.

Especially Biodegradable polymers of more than two are also preferred various monomer units, for example, those as monomers Salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Salts of acrylic acid and 2-alkylallyl sulfonic acid and sugar derivatives.

Further preferred copolymers are those which are used as monomers acrolein and Acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

As well are as further preferred builders polymeric aminodicarboxylic acids whose Salts or their precursors to call. Particular preference is given to polyaspartic acids or their salts.

Further Suitable builders are polyacetals, which by reaction of dialdehydes with polyol carboxylic acids containing 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained. preferred Polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic receive.

Further suitable organic builders are dextrins, for example Oligomers or polymers of carbohydrates by partial Hydrolysis of starches can be obtained. The hydrolysis can be carried out according to usual, for example acidic or enzyme-catalyzed processes. Preferably These are hydrolysis products with average molecular weights in the range from 400 to 500,000 g / mol. It is a polysaccharide with a Dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 preferred where DE is a common one Measure of the reducing Effect of a polysaccharide compared to dextrose, which DE of 100 is. Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrup with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher Molar masses in the range of 2000 to 30,000 g / mol.

at the oxidized derivatives of such dextrins are their reaction products with oxidants, which are able are at least one alcohol function of the saccharide ring to the carboxylic acid function to oxidize.

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

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

Furthermore can all compounds that are capable of complexes with alkaline earth ions train as builders be used.

surfactants

to Group of surfactants are the nonionic, the anionic, the cationic and the amphoteric surfactants counted.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

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

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide can 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 from that.

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

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

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

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

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

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

Particular preference is therefore given to ethoxylated nonionic surfactants consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide. These include the so-called "narrow range ethoxylates" ders preferred.

With Particular preference continues to be combinations of one or several tallow fatty alcohols with 20 to 30 EO and silicone defoamers used.

Especially preferred are nonionic surfactants which have a melting point above Have room temperature. Nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred.

suitable nonionic surfactants, the melting or softening points in said Temperature range, for example, low-foaming nonionic Surfactants which may be solid or highly viscous at room temperature. Become Used nonionic surfactants which are highly viscous at room temperature, so it is preferred that this has a viscosity above 20 Pa · s, preferably above 35 Pa · s and in particular above 40 Pa · s. Also nonionic surfactants, which are waxy at room temperature, are ever preferred according to their intended use.

nonionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-Niotenside, are also with special Preference used.

The nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule. Preferably, such PO units make up to 25% by weight, especially preferably up to 20% by weight and in particular up to 15 wt .-% of the total molecular weight of the nonionic Surfactants. Particularly preferred nonionic surfactants are ethoxylated Monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene-polyoxypropylene Have block copolymer units. The alcohol or alkylphenol content such nonionic surfactant molecules makes preferably more than 30 wt .-%, more preferably more than 50 wt .-% and in particular more than 70 wt .-% of the total Molar mass of such nonionic surfactants. Preferred means are thereby characterized in that they are ethoxylated and propoxylated nonionic surfactants contain, in which the propylene oxide in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 Make up wt .-% of the total molecular weight of the nonionic surfactant.

Prefers Surfactants to be used come from the groups of the alkoxylated Nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control out.

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

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

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

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

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or -CH (CH ₃ ) ₂ are suitable. Preference is given to using nonionic surfactants of the above formula in which R ² or R ^{3 is} a radical -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another are values of 1 or 2.

In summary, particularly preferred are nonionic surfactants having a C _9-15 alkyl group having 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. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

Surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A''O) _y - (A '''O) _z -R ² in which R ¹ and R ² independently represent a straight-chain or branched, saturated or mono- or polyunsaturated C _2-40 alkyl or alkenyl radical; A, A ', A''andA''' are independently of one another a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ - CH _{2 is} -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which are of the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² in addition to a radical R ¹ which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having from 1 to 30 carbon atoms, where x is between 1 and 90, preferably between 40 and 80, and especially between 40 and 60.

Particularly preferred are surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably represents -CH ₃ , and x and y independently of one another represent values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values for x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² , in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. When the value x ≥ 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH _z ] _k CH (OH) [CH ₂ ] _j OR ^{2 may be} different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range of 1 to 20, esp especially from 6 to 15.

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

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula zu R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

The specified C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned Nonionic surfactants represent statistical averages that are suitable for a specific Product can be a whole or a fractional number. by virtue of the manufacturing process consist of commercial products of the formulas mentioned mostly not from an individual representative, but from mixtures, which is responsible for both the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation averages and resulting in fractional numbers.

Of course, the aforementioned nonionic surfactants not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants be used. As surfactant mixtures are not mixtures nonionic surfactants referred to in their entirety one of the above general formulas, but rather such mixtures, the two, three, four or more nonionic Containing surfactants by different of the aforementioned general Formulas can be described.

At Place of said surfactants or in conjunction with them may also cationic and / or amphoteric surfactants are used.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.As cationic active substances, for example, cationic compounds of the following formulas can be used:

wherein each R ^{1 group is} independently selected from C _1-6 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 is.

In automatic dishwashing detergents, is the content of cationic and / or amphoteric surfactants preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. Automatic dishwashing detergents, which contain no cationic or amphoteric surfactants particularly preferred.

polymers

to Group of polymers count in particular the washing or cleaning Poylmere, for example the rinse aid polymers and / or as a softener effective polymers. Generally in detergents or cleansers in addition to nonionic polymers also cationic, anionic and Amphoteric polymers can be used.

"Cationic Polymers "in the sense The present invention relates to polymers which are a positive charge in the polymer molecule wear. This can be present, for example, in the polymer chain (Alkyl) ammonium moieties or other positively charged groups will be realized. Particularly preferred cationic polymers are derived from the groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary Groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives the dialkylamino acrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 indicated polymers.

"Amphoteric Poylmere "in the sense of the present invention have besides a positively charged group in the polymer chain also negatively charged groups or On monomer units. These groups may be, for example to carboxylic acids, sulfonic acids or phosphonic acids act.

Preferred washing or cleaning agents, in particular preferred automatic dishwashing agents, are characterized in that they contain a polymer a) which has monomer units of the formula R ¹ R ² C =CR ³ R ⁴ in which each R ¹ , R ² , R ⁴ radical ³ , R ^{4 is} independently selected from hydrogen, derivatized hydroxy, C _1-30 linear or branched alkyl groups, aryl, aryl substituted C _1-30 linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen , at least one quaternized nitrogen atom or at least one amino group having a positive charge in the partial range of the pH range of 2 to 11, or salts thereof, with the proviso that at least one radical R ¹ , R ² , R ³ , R ^{4 is} a heteroatomic organic group having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one Aminogr uppe with a positive charge is.

bei der R¹ und R⁴ unabhängig voneinander für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen steht; R² und R³ unabhängig voneinander für eine Alkyl-, Hydroxyalkyl-, oder Aminoalkylgruppe stehen, in denen der Alkylrest linear oder verzweigt ist und zwischen 1 und 6 Kohlenstoffatomen aufweist, wobei es sich vorzugsweise um eine Methylgruppe handelt; x und y unabhängig voneinander für ganze Zahlen zwischen 1 und 3 stehen. X repräsentiert ein Gegenion, vorzugsweise ein Gegenion aus der Gruppe Chlorid, Bromid, Iodid, Sulfat, Hydrogensulfat, Methosulfat, Laurylsulfat, Dodecylbenzolsulfonat, p-Toluolsulfonat (Tosylat), Cumolsulfonat, Xylolsulfonat, Phosphat, Citrat, Formiat, Acetat oder deren Mischungen.In the context of the present application, particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula

in which R ¹ and R ⁴ are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ^{3 are} independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. X represents a counterion, preferably a counterion from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ⁴ in the above formula are selected from -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 , and - (CH ₂ CH ₂ -O) _n H.

werden im Falle von X^–= Chlorid auch als DADMAC (Diallyldimethylammonium-Chlorid) bezeichnet.Very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ¹ and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are 1 each. The corresponding monomer unit of the formula

in the case of X ^- = chloride, they are also referred to as DADMAC (diallyldimethylammonium chloride).

in der R¹, R², R³, R⁴ und R⁵ unabhängig voneinander für einen linearen oder verzweigten, gesättigten oder ungesättigen Alkyl-, oder Hydroxyalkylrest mit 1 bis 6 Kohlenstoffatomen, vorzugsweise für einen linearen oder verzweigten Alkylrest ausgewählt aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, und -(CH₂CH₂-O)_nH steht und x für eine ganze Zahl zwischen 1 und 6 steht.Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula

in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of one another are a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from -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 , and - (CH ₂ CH ₂ -O) _n H and x is an integer between 1 and 6.

werden im Falle von X^– = Chlorid auch als MAPTAC (Methyacrylamidopropyl-trimethylammonium-Chlorid) bezeichnet.For the purposes of the present application, very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ^{1 is} H and R ² , R ³ , R ⁴ and R ^{5 are} methyl and x is 3. The corresponding monomer units of the formula

in the case of X ^- = chloride, also referred to as MAPTAC (methylacrylamidopropyltrimethylammonium chloride).

According to the invention preferred Polymers are used which are diallyldimethylammonium salts as monomer units and / or acrylamidopropyltrimethylammonium salts.

The previously mentioned Amphoteric polymers have not only cationic groups, but also anionic groups or monomer units. Such anionic For example, monomer units are from the linear group or branched, saturated or unsaturated Carboxylates, linear or branched, saturated or unsaturated Phosphonates, which are linear or branched, saturated or unsaturated Sulfates or the linear or branched, saturated or unsaturated Sulfonates. Preferred monomer units are the acrylic acid, the (Meth) acrylic acid, the (dimethyl) acrylic acid, the (ethyl) acrylic acid, the cyanoacrylic acid, the vinylessing acid, the allylacetic acid, the crotonic acid, the maleic acid, the fumaric acid, the cinnamic acid and their derivatives, the allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallyl or the allylphosphonic acids.

preferred usable amphoteric polymers are from the group of alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers, and the copolymers of unsaturated Carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Prefers usable zwitterionic polymers are from the group of Acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their Alkali and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the Methacroylethylbetain / methacrylate copolymers.

Also preferred are amphoteric polymers which, in addition to one or more anionic monomers as cationic monomers Methacrylamidoalkyl-trialkylammonium chloride and dimethyl (diallyl) on include potassium chloride.

Especially preferred amphoteric polymers are from the group of the Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers as well as their alkali and ammonium salts.

Especially amphoteric polymers from the group of methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers are preferred and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers as well as their alkali and ammonium salts.

• – die Verkapselung der Polymere mittels wasserlöslicher oder wasserdispergierbarer Beschichtungsmittel, vorzugsweise mittels wasserlöslicher oder wasserdispergierbarer natürlicher oder synthetischer Polymere;
• – die Verkapselung der Polymere mittels wasserunlöslicher, schmelzbarer Beschichtungsmittel, vorzugsweise mittels wasserunlöslicher Beschichtungsmittel aus der Gruppe der Wachse oder Paraffine mit einem Schmelzpunkt oberhalb 30°C;
• – die Cogranulation der Polymere mit inerten Trägermaterialien, vorzugsweise mit Trägermaterialien aus der Gruppe der wasch- oder reinigungsaktiven Substanzen, besonders bevorzugt aus der Gruppe der Builder (Gerüststoffe) oder Cobuilder.

In a particularly preferred embodiment of the present invention, the polymers are present in prefabricated form. For the preparation of the polymers is suitable inter alia

• The encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;
• - The encapsulation of the polymers by means of water-insoluble, fusible coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C;
• - The cogranulation of the polymers with inert support materials, preferably with support materials from the group of washing or cleaning-active substances, particularly preferably from the group of builders (builders) or cobuilders.

washing or detergents contain the aforementioned cationic and / or amphoteric polymers, preferably in amounts between 0.01 and 10 % By weight, based in each case on the total weight of the washing or cleaning agent. In the context of the present application, however, such washing or detergents in which the weight fraction of the cationic and / or amphoteric polymers between 0.01 and 8 wt .-%, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4% by weight, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing detergent, is.

When softeners effective polymers are, for example, the sulfonic acid-containing Polymers which are used with particular preference.

Especially preferably as sulfonic acid-containing Polymers can be used are copolymers of unsaturated carboxylic acids containing sulfonic acid groups Monomers and optionally further ionic or nonionic Monomers.

In the context of the present invention are as unsaturated monomer carboxylic acids of the formula R ¹ (R ² ) C = C (R ³ ) COOH 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, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the above formula 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) is preferred.

In the sulfonic acid-containing monomers are those of the formula R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H 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, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas H ₂ C = CH-X-SO ₃ H H ₂ C = C (CH ₃ ) -X-SO ₃ H HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H, in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Especially preferred sulfonic acid group-containing Monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy -propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, Sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts the acids mentioned.

Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds. The content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers to be used consist only of monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH and monomers of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H.

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

besonders bevorzugt.In summary, copolymers are made of

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

particularly preferred.

• i) einer oder mehreren ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln: H₂C=CH-X-SO₃H H₂C=C(CH₃)-X-SO₃H HO₃S-X-(R⁶)C=C(R¹)-X-SO₃H, in der R⁶ und R¹ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
• iii) gegebenenfalls weiteren ionogenen oder nichtionogenen Monomeren.

Further particularly preferred copolymers consist of

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

The Copolymers can the monomers from groups i) and ii) and optionally iii) contained in varying amounts, all representatives from the group i) with all Representatives from group ii) and all representatives from the group Group iii) can be combined. Particularly preferred polymers have certain structural units on, which are described below.

For example, copolymers which are structural units of the formula are preferred - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. When the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred. The corresponding copolymers contain the structural units of the formula - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -, in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, are preferred.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, copolymers which are structural units of the formula - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) -, are particularly preferred, just as preferred as copolymers, the structural units of the formula - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred. Also preferred according to the invention are copolymers which contain structural units of the formula - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

In summary, such copolymers are preferred according to the invention, the structural units of the formulas - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m - (CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

In the polymers can the sulfonic acid groups wholly or partly in neutralized form, i. that the acidic acid atom of the sulfonic acid group in some or all of them Sulfonic acid groups against Metal ions, preferably alkali metal ions and in particular against Sodium ions, can be replaced. The use of partial or fully neutralized sulfonic acid group-containing Copolymer is preferred according to the invention.

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

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

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred washing or cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

bleach

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

Farther can Also bleach from the group of organic bleach used become. Typical organic bleaches are the diacyl peroxides, such as. Dibenzoyl. Other typical organic bleaches are the peroxyacids, Examples being the alkyl peroxyacids and the aryl peroxyacids become. Preferred representatives are (a) the peroxybenzoic acid and their ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and Magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, like peroxylauric acid, Peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaliminoperoxyhexanoic acid (PAP)], o-Carboxybenzamidoperoxycapronsäure, N-Nonenylamidoperadipic acid and N-Nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic, such as 1,12-diperoxy carboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebacinsäure, diperoxybrassylic, the diperoxyphthalic acids, 2-Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronate).

When Bleach can Chlorine or bromine releasing substances are used. Among the suitable chlorine or bromine releasing materials come for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

According to the invention Washing or cleaning preparations, in particular automatic dishwashing detergents, preferably 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15 Wt .-% bleach, preferably sodium percarbonate.

Of the Active oxygen content of detergents or cleaners, in particular the automatic dishwashing detergent, is, in each case based on the total weight of the composition, preferably between 0.4 and 10 wt .-%, particularly preferably between 0.5 and 8 wt .-% and in particular between 0.6 and 5 wt .-%. Especially preferred Means have an active oxygen content above 0.3 wt .-%, preferably above 0.7 wt .-%, more preferably above 0.8 wt .-% and in particular above 1.0% by weight.

Bleach activators

Bleach activators are used in laundry detergents or cleaners, for example, to achieve an improved bleaching effect when cleaned at temperatures of 60 ° C and below. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA) and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, esp pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose, as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl caprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used.

These Bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight, and especially preferably 2 to 6 wt .-%, each based on the total weight the bleach activator-containing agent used.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist.Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula

in which R ¹ is -H, -CH _3, a C _2-24 -alkyl or -alkenyl radical, a substituted C _2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C _1-24 -alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) - CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion.

in der R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt sind aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, wobei R⁴ zusätzlich auch -H sein kann und X ein Anion ist, wobei vorzugsweise R⁵ = R⁶ = -CH₃ und insbesondere R⁴ = R⁵ = R⁶ = -CH₃ gilt und Verbindungen der Formeln (CH₃)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂-CN X^–, oder (HO-CH₂-CH₂)₃N⁽⁺⁾CH₂-CN X^– besonders bevorzugt sind, wobei aus der Gruppe dieser Substanzen wiederum das kationische Nitril der Formel (CH₃)₃N⁽⁺⁾CH₂-CN X^–, in welcher X^– für ein Anion steht, das aus der Gruppe Chlorid, Bromid, Iodid, Hydrogensulfat, Methosulfat, p-Toluolsulfonat (Tosylat) oder Xylolsulfonat ausgewählt ist, besonders bevorzugt wird.Particularly preferred is a cationic nitrile of the formula

in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , wherein R ⁴ additionally also -H may be and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (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 ^{- are} particularly preferred, wherein from the group of these substances turn the cationic Nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- in which X ^{- represents} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is particularly preferred.

bleach catalysts

In addition to The conventional bleach activators or in their place may also so-called bleach catalysts are used. For these substances These are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are useful as bleach catalysts.

Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate in usual Quantities, preferably in an amount up to 5 wt .-%, in particular from 0.0025 wt.% to 1 wt.%, and more preferably from 0.01 Wt .-% to 0.25 wt .-%, each based on the total weight of inventive agent used. In special cases can However, more bleach activator can be used.

It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the inventive compositions containing as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1,5,9-trimethyl-1,5, 9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and / or 2-methyl-1,4,7-triazacyclononane ( Me / TACN). Suitable manganese complexes are, for example, [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₂ (μ-OAc) ₁ (TACN ) ₂ ] (BPh ₄ ) ₂ , [Mn ^IV ₄ (μ-O) ₆ (TACN) ₄ ] (ClO ₄ ) ₄ , [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (Me-TACN ) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₁ (μ-OAc) ₂ (Me-TACN) ₂ ] (ClO ₄ ) ₃ , [Mn ^IV ₂ (μ-O) ₃ ( Me-TACN) ₂ ] (PF ₆ ) ₂ and [Mn ^IV ₂ (μ-O) ₃ (Me / Me-TACN) ₂ ] (PF ₆ ) ₂ (OAc = OC (O) CH ₃ ).

enzymes

To increase the washing or cleaning performance of detergents or cleaners enzymes can be used. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 × 10 ^-6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Under Proteases are preferred to those of the subtilisin type. Examples therefor are the subtilisins BPN 'and Carlsberg and its advanced forms, the protease PB92, subtilisins 147 and 309, the Bacillus alkaline protease lentus, subtilisin DY and the subtilases, but not anymore the enzymes subtilisins in the strict sense, thermitase, Proteinase K and the proteases TW3 and TW7.

Examples for inventively usable Amylases are the α-amylases from Bacillus licheniformis, from 8, amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as those for use in washing and Detergents improved developments of the aforementioned Amylases. Furthermore are for this purpose the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Usable according to the invention are still lipases or cutinases, especially because of their Triglyceride-splitting activities, but also to in situ peracids from suitable precursors produce. These include for example, the original one from Humicola lanuginosa (Thermomyces lanuginosus) available, respectively further developed lipases, in particular those with the amino acid exchange D96L. Furthermore, for example, the cutinases can be used, the original from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose starting enzymes originally from Pseudomonas mendocina and Fusarium solanii have been isolated.

Farther can Enzymes are used, which are summarized by the term hemicellulases. These include for example mannanases, xanthan lyases, pectin lyases (= pectinases), Pectinesterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

Especially Preference is given to using perhydrolases in the compositions according to the invention.

to increase the bleaching effect oxidoreductases according to the invention, for example, oxidases, oxygenases, catalases, peroxidases, such as Halo, chloro, bromo, lignin, glucose or manganese peroxidases, Dioxygenases or laccases (phenol oxidases, polyphenol oxidases) be used. Advantageously, organic, particularly preferably aromatic, interacting with the enzymes Compounds added to the activity of the respective oxidoreductases to reinforce (Enhancer) or at very different redox potentials between the oxidizing enzymes and the soiling the electron flow to ensure (Mediators).

The Enzymes can used in any form established in the prior art become. These include for example, by granulation, extrusion or lyophilization obtained solid preparations or, especially in liquid or gelatinous Means, solutions the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers.

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or by extrusion of the enzyme solution together with one preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core with a water, air and / or chemical impermeable protective layer is coated. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

Farther Is it possible, to assemble two or more enzymes together, making one individual granules has several enzyme activities.

One Protein and / or enzyme may be particularly harmful during storage against damage such as inactivation, denaturation or decay, for example through physical influences, Oxidation or proteolytic cleavage are protected. In microbial Obtaining the proteins and / or enzymes is inhibiting the Proteolysis particularly preferred, especially if the means Contain proteases. Detergents or cleaners can contain stabilizers for this purpose; the provision of such funds represents a preferred embodiment of the present invention.

Prefers are one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, in Amounts of 0.1 to 5 wt .-%, preferably from 0.2 to 4.5 wt .-% and in particular from 0.4 to 4 wt .-%, each based on the total enzyme-containing agents used.

Glass corrosion inhibitors

Glass corrosion inhibitors prevent the occurrence of cloudiness, Streaks and scratches but also iridescence of the glass surface of mechanically cleaned glasses. Preferred glass corrosion inhibitors come from the group of Magnesium and zinc salts as well as the magnesium and zinc complexes.

The Spectrum of the invention preferred Zinc salts, preferably organic acids, more preferably organic Carboxylic acids, ranges from salts that are heavy or insoluble in water, so a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 mg / L, to such salts dissolved in water a solubility above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubility at 20 ° C water temperature). The first group of zinc salts includes, for example, zinc citrate, the zinc oleate and the zinc stearate, to the group of soluble Zinc salts belong for example, zinc formate, zinc acetate, zinc lactate and the zinc gluconate.

With Particular preference is given as a glass corrosion inhibitor at least one Zinc salt of an organic carboxylic acid, more preferably one Zinc salt from the group of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, Zinc lactate and zinc citrate used. Also zinc ricinoleate, zinc abietate and zinc oxalate are preferred.

In the context of the present invention, the content of zinc salt in detergents or cleaners is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight. , or the content of zinc in oxidized form (calculated as Zn ²⁺ ) between 0.01 to 1 wt .-%, preferably between 0.02 to 0.5 wt .-% and in particular between 0.04 to 0, 2 wt .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.

Silver corrosion inhibitors

Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. According to the invention, preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts, these substances being particularly preferably used in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2 Wt .-%, particularly preferably 0.01 to 0.04 wt .-% are used. Preferred acids for salt formation are hydrochloric acid, Sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric and succinic acid. Especially effective are 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5-isononyl, 5-versatic-10-alkyl-3-amino-1,2,4-triazoles and mixtures of these substances.

you In addition, cleaning agent formulations often contain active chlorine Means that can significantly reduce the corrosion of the silver surface. In Chlorine-free cleaners are especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds used. Also salt- and complex-like inorganic compounds, such as salts of Metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Prefers here are the transition metal salts, the selected are from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds for preventing the Corrosion on the items to be washed be used.

Instead of from or in addition to the silver protectants described above, for example the Benzotriazoles, can redox-active substances are used. These substances are preferably inorganic redox-active substances from the group manganese, titanium, zirconium hafnium, Vanadium, cobalt and cerium salts and / or complexes wherein the metals preferably in one of the oxidation states II, III, IV, V or VI available.

The used metal salts or metal complexes should at least partially soluble in water be. The counterions suitable for salt formation include all common ones mono-, di- or tri-negatively charged inorganic anions, e.g. Oxide, sulphate, nitrate, fluoride, but also organic anions such as Stearate.

Particularly preferred metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - (1-hydroxyethane-1,1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ , and mixtures thereof, such that the metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) _{3 are used} with particular preference ,

The inorganic redox-active substances, in particular metal salts or metal complexes are preferably coated, i. completely with a waterproof, but easily soluble at the cleaning temperatures Material coated, to their premature decomposition or oxidation during storage too prevent. Preferred coating materials which, according to known methods, such as Sandwik's melt coating process from the food industry, are applied are paraffins, microwaxes, waxes of natural origin like carnauba wax, candellila wax, beeswax, higher melting Alcohols such as hexadecanol, soaps or fatty acids.

The mentioned metal salts and / or metal complexes are in cleaning agents, preferably in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, each based on the total agent,

disintegration aid

Around the disintegration of prefabricated moldings to facilitate, it is possible Disintegration aids, so-called tablet disintegrants, in to incorporate these agents to reduce disintegration times. Under Tablet disintegrants or disintegrators are adjuvants understood that for the rapid disintegration of tablets in water or other media and for the swift one Release of the active ingredients.

These Substances that are also referred to as "explosives" due to their effect increase when water enters their volume, on the one hand increasing the intrinsic volume (swelling), on the other hand also about the Release of gases can create a pressure on the tablet can disintegrate into smaller particles. Well-known Disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can be used. Swelling disintegration aids are for example synthetic Polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified Natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Preference is given to disintegration aids in amounts of from 0.5 to 10% by weight, preferably from 3 to 7 Wt .-% and in particular 4 to 6 wt .-%, each based on the total weight of the disintegration assistant-containing agent used.

Preferred disintegrating agents are cellulosic disintegrating agents, so that preferred washing or cleaning agents comprise such cellulose-based disintegrants in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight. % contain. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.

The Cellulose used as disintegration aid is preferably not used in finely divided form, but before mixing transferred to the premixes to be compressed in a coarser form, for example, granulated or compacted. The particle sizes of such Disintegrating agents are usually above 200 microns, preferably at least 90 wt .-% between 300 and 1600 microns and in particular at least 90 wt .-% between 400 and 1200 microns.

When another disintegrating agent based on cellulose or as an ingredient This component can be used microcrystalline cellulose. This microcrystalline cellulose is made by partial hydrolysis of Celluloses obtained under such conditions, only the amorphous ones Areas (about 30% of the total cellulose mass) of the celluloses attack and completely dissolve, the crystalline areas (about 70%) but leave undamaged. A subsequent disaggregation of the resulting from the hydrolysis microfine celluloses provide the microcrystalline celluloses, the primary particle sizes of approx. 5 μm and compactable, for example, to granules having an average particle size of 200 microns are.

preferred Disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are in disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 wt .-%, each based on the total weight of the disintegrant-containing agent.

According to the invention preferred can about that in addition, gas-evolving effervescent systems as tablet disintegration aids be used. The gas-developing effervescent system can from a consist of a single substance which releases a gas on contact with water. Among these compounds is in particular the magnesium peroxide to call, which releases oxygen on contact with water. Usually However, the gas-releasing effervescent system in turn from at least two components that are together under gas formation react. While here a variety of systems is thinkable and executable, for example Nitrogen, oxygen or hydrogen will release the both in the detergents and cleaners used effervescent system on the basis of economic as well as ecological Select points of view to let. Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifier, the is suitable to release carbon dioxide from the alkali metal salts in aqueous solution.

When Acidifying agents consisting of the alkali salts in aqueous solution Carbon dioxide release, for example, boric acid as well Alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, preference is given used organic Acidifizierungsmittel, wherein the citric acid a particularly preferred acidifying agent. Preferred are Acidifier in effervescent system from the group of organic Di-, tri- and oligocarboxylic acids or mixtures.

fragrances

When Perfume oils or Fragrances can in the context of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, Ketones, alcohols and hydrocarbons are used. Prefers However, mixtures of different fragrances are used, the together create an appealing scent. Such perfume oils can also natural Contain fragrance mixtures, as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.

Around to be perceptible, a fragrance must be volatile, being next to the Nature of the functional groups and the structure of the chemical Compound also plays a role in the molecular weight. So own most fragrances have molecular weights up to about 200 daltons, while molar masses from 300 daltons and above constitute an exception. Due to the different volatility changed by fragrances the smell of a compound of several fragrances perfumes or perfume during Evaporation, whereby the odor impressions in "top note", "middle note" (middle note or body) and "base note" (end note or dry divided out). Because the smell perception to a large extent too on the smell intensity is based, the top note of a perfume or fragrance is not alone from volatile Connections while the base note for the most part from less volatile, i.e. adherent fragrances. When composing perfumes can be easier volatile For example, fragrances can be bound to specific fixatives. which prevents it from evaporating too quickly. At the following Classification of the fragrances in "lighter volatile or "adherent" fragrances So over the smell impression and about it, whether the corresponding perfume perceived as a head or middle note nothing is said.

The Fragrances can can be processed directly, but it can also be beneficial to the Fragrances on carrier The slow release of fragrance for long-lasting Provide scent. As such carrier materials For example, cyclodextrins have proven useful, with the cyclodextrin-perfume complexes additionally still can be coated with other excipients.

dyes

preferred Dyes whose selection does not present any difficulty to the skilled person have a high storage stability and insensitivity to the rest Ingredients of the agents and against light and no pronounced substantivity to the with the dye-containing agents to be treated substrates such as for example textiles, glass, ceramics or plastic dishes, so as not to stain them.

When choosing the colorant, it must be taken into account that the colorants have a high storage stability and insensitivity to light. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, colorant concentrations are typically selected in the range of a few 10 ^-2 to 10 ^-3 % by weight. By contrast, in the case of the particularly preferred, but less readily water-soluble, pigment dyes due to their brilliance, the suitable concentration of the colorant in detergents or cleaners is typically about 10 ^-3 to 10 ^-4 % by weight.

It become colorants preferably, which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be beneficial proved, colorants to be used in water or at room temperature in liquid organic Substances are soluble. Suitable are, for example, anionic colorants, e.g. anionic Nitroso.

Claims (21)

A process for packaging shaped articles, in which a film is applied to the molding by means of a vacuum, wherein a) the molding is placed between the film and a vacuum guide; b) generates a vacuum by means of the vacuum guide and the film is placed under the action of the vacuum around the shaped body, characterized in that the shaped body has n> 1 surfaces and the film in the process step b) is applied to all n surfaces of the molding. Method according to claim 1, characterized in that that in step b) n-1 areas the molded body completely with the film will be covered while the remaining area A is only partly covered. Method according to claim 2, characterized in that that the area A at least 10%, preferably at least 20% and in particular at least 40% of its total area is covered with the foil. Method according to one of claims 1 to 3, characterized that a) a shaped body with one of his surfaces is placed on a pedestal, wherein between the resting surface A of the molding and the socket a contact surface B is formed, the area A is larger as the contact surface B and a film supplied in such a way that will be the molding located between base and foil; b) by means of the vacuum guide Vacuum is generated and the film under the action of the vacuum the shaped body is created; characterized in that the area A in Step b) is partially covered with the film. Method according to one of claims 1 to 3, characterized that a) a shaped body with one of his surfaces is placed on a film such that the molding between the film and a vacuum guide is; b) a vacuum is generated by means of the vacuum guide and the film is applied to the molded body under the influence of the vacuum becomes. Method according to claim 4, characterized in that that the area A, the contact surface B and / or the base surface flat / plan is / are. Method according to one of claims 4 or 6, characterized that the shaped body is placed on the base so that the base surface completely with the shaped body is covered. Method according to one of claims 1 to 7, characterized that the shaped body more than 2 areas, preferably 3 to 10 surfaces and in particular 6 areas having. Method according to one of claims 1 to 8, characterized that the shaped body the shape of a prism, preferably the shape of a straight prism and in particular has the shape of a cuboid. Method according to one of claims 1 to 9, characterized that the shaped body an n-sided prism, a. n-sided truncated pyramid or a n-sided pyramid, therefore n edges between the surface R and the n to this area bordering areas and the film around at least one of these edges, preferably by at least 2 of these edges and in particular by all laying around these edges, the film partially covers the surface A. Method according to one of claims 1 to 10, characterized that the slide in an additional Step c) at a distance from the molding which is smaller than 1 cm, preferably less than 0.5 cm, particularly preferably less than 0.1 cm and in particular less than 0.05 cm, by means of mechanical cutting tools, Action of heat, specifically using laser devices or melting tools, or by loosening the film using solvents, Water or steam is severed, Method according to one of claims 1 to 11, characterized that supernumerary Film not separated, but in an additional step c) to the area A is sealed. Method according to one of claims 1 to 12, characterized that on the non-foil-covered surface of the surface A before or after passing through of steps a) and b) and optionally c) in a further step d) another film is applied / sealed. Method according to one of claims 1 to 13, characterized that the film used has a thickness of 5 to 500 microns, preferably from 8.5 to 400 μm, more preferably from 12 to 300 microns, preferably from 15.5 to 200 μm and in particular from 19 to 100 μm having. Medium portion, in particular washing or cleaning agent portion, comprising a shaped body and a shaped body surrounding, preferably water-soluble or water-dispersible film without sealed seams, characterized that the film is on the surface A of the molding an opening has, whose area smaller than this area A of the molding. Medium portion according to claim 15, characterized that the shaped body n surfaces and from the n surfaces of the molding n-1 areas Completely and the area A is partially covered with film. Medium portion according to one of claims 15 or 16, characterized in that the area of the opening is between 5 and 90%, preferably between 7.5 and 70% and in particular between 10 and 50% of the area A of the molding out. Medium portion according to one of claims 15 to 17, characterized in that the opening with a further film is sealed. 19. Middle portion according to one of claims 15 to 18, characterized in that the film shrunk onto the molding is. Medium portion according to one of claims 15 to 19, characterized in that the film has a thickness of 5 to 500 μm, preferably from 8.5 to 400 μm, more preferably from 12 to 300 microns, preferably from 15.5 to 200 μm and in particular from 19 to 100 μm having. Use of a medium portion according to a the claims 15 to 20 in a textile cleaning process. Use of a medium portion according to a the claims 15 to 20 in a automatic dishwashing process.