WO2005019402A1

WO2005019402A1 - Method for producing detergents or cleaning agents

Info

Publication number: WO2005019402A1
Application number: PCT/EP2004/008936
Authority: WO
Inventors: Wolfgang Barthel; Birgit Burg; Salvatore Fileccia; Arno DÜFFELS; Maren Jekel; Alexander Lambotte; Christian Nitsch; Ulrich Pegelow; Ulf Arno Timmann
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2003-08-19
Filing date: 2004-08-10
Publication date: 2005-03-03
Also published as: DE10338043A1

Abstract

The invention relates to moulding methods for detergent or cleaning agent preparations, according to which the moulded preparation is de-gasified after the moulding process. Said methods permit the production of moulded bodies that are less susceptible to breakage and have an improved appearance.

Description

Process for the production of washing or cleaning agents

This application concerns detergents or cleaning agents. In particular, this application relates to a method for producing detergents or cleaning agents.

Detergents or cleaning agents are now available to consumers in a wide variety of forms. In addition to washing powders and granules, this offer also includes, for example, cleaning agent concentrates in the form of extruded or tableted compositions. These solid, concentrated or compacted offer forms are characterized by a reduced volume per dosing unit and thus lower the costs for packaging and transport. The detergent or cleaning agent tablets in particular also meet the consumer's desire for simple dosing. The corresponding agents are described in detail in the prior art.

In addition to the fixed supply forms described, detergents or cleaning agents can also be packaged as gels or pastes.

For example, the granted European patent EP 331 370 (Unilever) discloses a process for producing stable, viscous liquid compositions for use in automatic dishwashers. European patent EP 797 656 (Unilever) relates to non-aqueous liquid detergent compositions which contain polymeric hydrotropes.

Water-soluble or water-dispersible films are also particularly suitable for packaging solid or liquid detergents or cleaning agents. The detergents packaged in this way to form individual dosing units can be simply put in one or more bags directly into the washing machine or dishwasher or in their washing-up chamber, or by throwing them into a predetermined amount of water, for example in a bucket or in a hand-washing or Sink, to be dosed. Packaged detergents and cleaning agents of this type have been the subject of numerous publications.

The granted European patent EP 700 989 B1 claims, for example, a detergent packaged as a unit for dishwashing, the detergent packaged as a unit being encased in a package made of a water-soluble material which is sticky on the outside. The application WO 02/16222 (Reckitt-Benckiser) discloses water-soluble packaging for aqueous detergent compositions, the free water content of which is at least 3% by weight. ;

The subject of WO 02/16541 (Reckitt-Benckiser) are liquid detergent compositions with a water content of between 20 and 50% by weight, which are packaged in a water-soluble or water-dispersible material, have at least one polyphosphate builder and, through a certain ratio of those in the Potassium and sodium ions contained in the agent are labeled.

Despite the numerous publications in the field of detergents or cleaning agents, there is still a need for improving the cleaning performance of these agents, in particular while maintaining or reducing the amounts of washing or cleaning-active substances used per washing or cleaning cycle. There is also a need to reduce the amount of non-washing or cleaning-active materials used for packaging and packaging these agents (e.g. water-soluble or non-water-soluble polymer films of the outer packaging).

The object of the present application was to provide a process for the production of rapidly soluble washing or cleaning agents of high density. At high throughput, the process should enable detergent tablets with high breaking strength and a new look. The resulting detergents or cleaning agents should in particular not require any or only a reduced additional packaging. Furthermore, a new type of assembly for washing or cleaning agents should be provided, which is distinguished by an improved washing or cleaning performance compared to conventional assembly forms.

It has now been found that quickly soluble detergent tablets with high breaking hardness and a flat, glossy surface can be produced by means of a casting process, in which the washing or cleaning-active preparation is degassed after casting and before solidification.

A first subject of the present application is therefore a method for producing a cast body from a washing or cleaning active preparation, comprising the steps: a) pouring a washing or cleaning active preparation into the receiving trough of a molding tool; b) degassing the washing or cleaning active mixture of active substances.

The degassing of the washing- or cleaning-active preparation not only made it possible to increase the average breaking hardness of the cast bodies, it also made a difference also achieved an improvement in the optical effect of these bodies. The bodies produced by the method according to the invention do not have any unevenness or holes caused by gas inclusions on their surface. Furthermore, depending on the method used for the degassing, the bodies also have a smooth upper side in comparison with shaped detergent or cleaning product bodies produced by conventional casting methods.

Various procedures are suitable for degassing. In addition to vibration, these are in particular the action of a vacuum, ultrasound or heat on the pourable washable or cleaning-active preparation. In the context of the present application, degassing by vibration of the mold is preferred.

In the context of the present application, “vibration” or “oscillation” refers to a periodic process in which the molding tool is moved back and forth within certain limits. The vibration can take place both horizontally and vertically. Methods in which horizontal and vertical vibrations are superimposed are preferred. In preferred methods according to the invention, the vibration of the molding tool accordingly takes place in the horizontal and / or vertical spatial direction.

The vibration movement is characterized by its amplitude and frequency. The "amplitude" is the maximum deflection of the mold from the rest position. In a preferred embodiment of the present invention, the amplitude of the vibration movement in the horizontal direction is less than 10 cm, preferably less than 7 cm, particularly preferably less than 4 cm and in particular less than 2 cm. In the vertical direction, the amplitude of the vibration movement is preferably less than 4 cm, particularly preferably less than 2 cm and in particular less than 1 cm.

The number of vibrations per unit of time determines the "frequency" of this vibration. The amplitude, frequency and duration of the vibration movement are among others in the method according to the invention. determined by the viscosity and composition (for example the solids content) of the processed active washing or cleaning preparations. Frequencies between 0.1 and 1000 Hz, preferably between 0.2 and 800 Hz, particularly preferably between 0.4 and 500 Hz and in particular between 0.8 and 300 Hz are preferably realized in the method according to the invention.

In a preferred variant of the method according to the invention, the amplitude and / or frequency of the vibration used can be infinitely regulated. By continuously regulating the amplitude and / or frequency, the vibration movement can be adapted in a simple manner to the requirements of the respectively processed active washing or cleaning preparation. The need for such adjustments can change, for example, in the case of recipe changes or changes in the Process temperature (for example: temperature of the poured active washing or cleaning preparation; outside temperature during production). In the context of the present application, the amplitude and the frequency of the vibration used for degassing are preferably constant during degassing. Nevertheless, it can also be advantageous to change the amplitude and / or the frequency of the vibration during the degassing. Methods in which the amplitude and / or frequency of the vibration change during degassing are preferred according to the invention. It is conceivable, for example, that the amplitude of the vibration decreases or increases at a constant frequency. However, methods can also be carried out in which the frequency of the vibration is increased or decreased with a constant amplitude. Methods in which the frequency of the vibration is increased in the course of degassing at constant amplitude are particularly preferred in the context of the present application.

In addition to the vibration described above, the application of a negative pressure, the action of ultrasound or the action of heat are also suitable for degassing the poured active washing or cleaning preparation.

In a preferred embodiment of the method according to the invention, the degassing takes place by applying a negative pressure. In this process variant, pressures below 900 mbar, preferably maintenance 700 mbar, particularly preferably below 500 mbar, very particularly preferably below 300 mbar and in particular below 100 mbar are used for degassing. The level of the negative pressure used will be based, for example, on the viscosity of the detergent-active preparation to be degassed and on the boiling temperature of active substances (e.g. non-aqueous solvents) contained in this detergent-active preparation. While it is generally preferred to avoid the simultaneous evaporation of volatile constituents during the degassing of the washing or cleaning active preparation, such evaporation, on the other hand, can be used very specifically in special processes for degassing the washing or cleaning active preparations (drag effect ). To generate the vacuum required for the degassing of the washing or cleaning-active preparation, all pumps known to the person skilled in the art for these purposes are suitable, in particular the water jet, liquid vapor jet, water ring and above usable for a rough vacuum. Koiben pumps. However, rotary vane, gate valve, trochoid and sorption pumps, as well as so-called roots blowers and cryopumps, can also be used. Rotary vane pumps, diffusion pumps, roots blowers, displacement pumps, turbomolecular pumps, sorption pumps and ion getter pumps (getters) are particularly suitable for setting a fine vacuum.

In a further preferred process variant, the degassing is carried out by the action of ultrasound. In the context of the present application, ultrasound is the name for sound, the frequencies of which are above the human hearing range (approx. 16 Hz-20 kHz) and. are below 109 Hz; Sound with frequencies greater than 109 Hz is called hypersonic. to Generation of ultrasound, mechanical or electrical vibrators can be used. Since the strength of the ultrasound is influenced by the transport medium, the absorption of the sound generally increases with the number of vibrations, the strength of the ultrasound in the use according to the invention is preferably adapted to the selected formulation of the washing or cleaning preparation. In the case of degassing by ultrasound, particular attention must be paid to the fact that the ultrasound absorption causes (local) heating of the medium, which can lead to deactivation of individual ingredients in the detergent or cleaning preparation. In a preferred embodiment of the present invention, the washing or cleaning-active preparation to be degassed therefore contains no enzymes and / or fragrances and / or dyes and / or bleaching agents and / or bleach activators.

Finally, in a further preferred process variant, the washing or cleaning-active preparation can also be degassed by the action of heat. Due to the influence of heat, The viscosity of the active washing or cleaning preparation is reduced and the escape of enclosed gas bubbles from this preparation is accelerated. As with the action of ultrasound, heating the washing-active or cleaning-active preparation can also favor the evaporation of volatile constituents, in the course of which degassing of the preparation is achieved at the same time. The temperatures reached in the degassing by the action of heat are preferably in the range from 40 to 160 ° C., preferably in the range from 50 to 140 ° C. and in particular in the range from 55 to 120 ° C. The washing or cleaning-active preparation is preferably heated by heat radiation and / or hot air and / or by heating the molding tools.

In its previously described embodiments, the method according to the invention is suitable, for example, for producing compact, molded detergent tablets. Following the degassing or in the course of the degassing, the poured active washing or cleaning preparation can also be brought into shape. Preferably, the deformable, poured active washing or cleaning preparation is brought into the mold with the formation of a hollow mold.

The hollow mold can be produced in step using different techniques. In the simplest case, a flowable mixture is poured into an appropriate mold, left to harden there and then removed from the mold. A disadvantage of this is the design of the shape, since the desired wall thicknesses of the hollow bodies formed do not allow complicated geometries to be filled quickly.

Alternatively, the solidifying mixture can be filled into a mold that is designed only as a cavity. If you let the mixture solidify there, you would get a compact body, not a hollow shape. Appropriate process control can ensure that the mixture first solidified on the wall of the mold. If the mold is turned over after a certain time t, the excess mixture flows off and leaves a lining of the mold, which itself is a hollow mold, which can be removed from the mold after complete solidification. As already mentioned, the filling can also take place before demolding; filling during the solidification process is also possible.

Preferred embodiment variants of the present invention are therefore methods for producing a cast body from a washing or cleaning active preparation, comprising the steps: a) pouring a washing or cleaning active preparation into the receiving trough of a molding tool; b) degassing the active washing mixture which is active in washing or cleaning; c) Turning the mold and pouring out excess washing or cleaning active preparation.

Depending on the solidification mechanism, the mold is preferably turned after a time t between 0 and 20 minutes, preferably after a time t between 1 and 17 minutes, particularly preferably after a time between 2 and 14 minutes, very particularly preferably between 3 and 11 minutes and especially between 4 and 8 minutes.

As an alternative to completely filling the die mold and pouring excess mixture, the receiving trough of the molding tool can only be partially filled. In these cases, the mixture is pressed against the wall of the receiving trough with a suitable stamp, where it solidifies to form the hollow body. This process variant represents an intermediate form between the "pouring technique" and the casting technique in negative molds of the hollow body. Corresponding methods in which a) washing or cleaning-active preparation is poured into the receiving trough of a molding tool in order to produce a cast body from an active washing or cleaning preparation becomes; b) the washing or cleaning active preparation is degassed; c) the washing or cleaning active preparation is pressed by a stamp on the walls of the receiving trough and a hollow form is thus produced; are therefore also preferred. A particularly advantageous feature of this method, which is also referred to as the "cold stamp method", is the possibility of producing large numbers of items with a precisely defined wall thickness of the hollow body. In addition, the process is largely insensitive to fluctuating flow properties and can also be used with higher-viscosity mixtures. In a preferred embodiment of this preferred method variant, a cooled stamp is used. The temperature of this cooled stamp is preferably between 5 and 20 ° C, particularly preferably between 8 and 19 ° C, very particularly preferably between 11 and 18 ° C and in particular between 14 and 17 ° C.

The methods described above are particularly suitable for producing hollow bodies which have a shape without undercuts, that is to say have the shape of a "shell". These "trays" can be filled and optionally closed. The resulting hollow bodies can have one, two, three, four or more individual receiving troughs, which are preferably separated from one another by cast webs.

With regard to the shape of the shells, there are no limits for the expert in the selection. From the hemisphere to angular ("cardboard-like") shells to complicated structures with a pronounced surface structure (e.g. in the form of nutshells or animal shapes), all hollow bodies can be produced.

During or after solidification, in a preferred process variant according to the invention, the noses or edges of solidified washing or cleaning active preparation hanging out of the mold are cut or scraped off by knives and / or removed with a roller from the hollow bodies produced by turning or displacing. In a particularly preferred embodiment of the method according to the invention, heated knives or scrapers or rollers are used for cutting or scraping or rolling. The temperature of these heated knives, scrapers or rollers is preferably at least 35 ° C., preferably at least 45 ° C. and in particular between 50 and 90 ° C.

However, according to the invention it is also possible to produce hollow bodies which have only a small opening and which later fill the resulting hollow shape through this small "bunghole". Corresponding processes are usually carried out on an industrial scale with closable double molds which are filled with a quantity of solidifying mixture which is sufficient for wall lining in the desired thickness and are moved in all spatial directions. Here, all shapes are possible, from the ball to egg shapes to complicated hollow structures such as animal shapes, company logos, etc. A further preferred embodiment of the present invention therefore provides a method for producing a cast body from a washable or cleaning-active preparation a) a washing or cleaning active preparation is poured into a closable double mold; and b) the washing or cleaning active preparation is degassed.

In a preferred embodiment of the method according to the invention, the washing- or cleaning-active preparations are degassed and shaped into a hollow body. The following Solidification of the washing- or cleaning-active preparations provides a dimensionally stable hollow shape after shaping. In the context of the present invention, "solidification" denotes any hardening mechanism which, from a deformable, preferably flowable mixture or such a substance or mass, provides a body which is solid at room temperature without the need for pressing or compacting forces. "Solidification" in the sense of the present invention is therefore, for example, the curing of melts of substances which are solid at room temperature by cooling. "Solidification processes" in the sense of the present application are also the hardening of deformable masses through time-delayed water binding, through evaporation of solvents, through chemical reaction, crystallization etc. as well as the reactive hardening of flowable powder mixtures to form stable hollow bodies.

In summary, methods according to the invention are preferred in which the cast body, preferably the open hollow form, by time-delayed water binding, by cooling below the melting point, by evaporation of solvents, by crystallization, by chemical reaction (s), in particular polymerization, by changing the rheological Properties e.g. is produced by changing shear, by sintering or by means of radiation curing, in particular by UV, alpha-beta or gamma rays.

In the context of the present application, methods are preferred in which the solidification of the cast bodies takes place by cooling below the melting point. The cooling below the melting point can take place, for example, by giving off heat to the surroundings, in particular to the molding tool. However, it is particularly preferred to support the heat emission by using a cooling medium. Consequently, methods according to the invention are particularly preferred in which the mold is cooled. Suitable cooling media are, for example, (dried) cold air, dry ice or liquid nitrogen. With particular preference, however, circulating, preferably liquid, coolants are used in the mold. The mold is preferably cooled to temperatures below 20 ° C., preferably below 17 ° C., particularly preferably below 14 ° C., very particularly preferably below 11 ° C. and in particular below 8 ° C. In a further preferred process variant, the cooling is carried out to temperatures between 5 and 20 ° C., particularly preferably to temperatures between 8 and 19 ° C., very particularly preferably to temperatures between 11 and 18 ° C. and in particular to temperatures between 14 and 17 ° C.

If hollow molds are produced using the method according to the invention, they can be filled with detergents or cleaning agents during or after production. All ready-made detergents or cleaning agents can be introduced into the hollow mold in liquid, pasty, gel-like, powdered, extruded, granulated, pelletized, flaky or tableted form. However, it is not necessary to fill in a finished detergent or cleaning agent, rather individual detergents or Detergent ingredients or precursors thereof are filled into the hollow body. The following substances or classes of substances may be mentioned here as examples of substances or classes of substances:

Powder: bicarbonates, silicates, potash, soda, zeolites, polymers (PEG, maleic acid-polyacrylic acid copolymer salts, citric acid, citrates, sugar, soap, disintegrants and disintegrants, sulfates, phosphates, perborates, carboxymethyl cellulose (CMC), LAS powder ( linear alkyl benzene sulfonates), FAS powder (fatty alcohol sulfates).

Pastes: surfactant pastes (LAS paste, aqueous FAS paste), water glass

Compounds: Tower powder (spray agglomerates), LAS compounds, FAS compounds, TAED, percarbonate, enzyme extrudates, crude extrudate, nonionic surfactant compounds

Liquids: polymer solutions (maleic acid-polyacrylic acid copolymer salts in aqueous solutions), phosphonate solutions (aqueous), perfume oils, enzyme solutions, chlorine bleaching solutions, hydrogen peroxide solutions, cationic surfactant solutions, nonionic surfactants

The liquids can also be in the form of a gel (due to higher active substance concentrations or by adding thickeners, eg Tixogel ^® (Süd-Chemie)). The solids can also be processed as solutions or suspensions, the liquids as compounds in bound form.

The examples given above show that all of the substances or mixtures of substances mentioned can be introduced into the hollow bodies or into the receiving troughs of the hollow bodies. The liquid and pasty media (which occur in the upstream production stages in the aggregate states mentioned) can also be used, for example, to dry or to be absorbed on carriers.

After filling, the open hollow mold can be closed. This is necessary for liquid or pasty fillings to prevent the filling from escaping before use. In the case of fillings that remain firmly in the hollow mold, the mold may not be closed if desired. Closure can also be indicated in such cases for aesthetic reasons.

The optional closing of the hollow form can be done in different ways. In the case of moldings with a bung hole, this can be closed, for example, by inserting a suitable part. Open hollow molds in the form of hollow bodies without undercuts can be closed with foils or poured over with additional material for the hollow mold after filling. The optional sealing with foils is described below. The film, which closes the opening (s) of the hollow mold (s), is applied to the surface of the hollow mold and bonded to it, which can be done, for example, by gluing, partial melting or by chemical reaction. It is possible to apply the film to all surfaces of the hollow mold (ie not only via the opening) and to bond it firmly with it, so that the film forms a coating, a "coating" of the entire molded body. Preferred detergent and cleaning agent portions produced according to the invention are, however, characterized in that the film does not enclose the entire molded body.

For reasons of process economy and aesthetic impression, it is preferred that the film is applied only in such a way that it fulfills a function, i.e.. serves to close the mold.

The sealing film can of course also be a laminate of several differently composed films, the opening of the hollow mold can be released at certain times in the washing and cleaning cycle by means of different compositions of individual film layers.

Finally, it is particularly preferred according to the invention to close the hollow body with a prefabricated and water-soluble or water-dispersible bag ("pouch") filled with washing or cleaning-active substances.

Preferred film materials are the polymers known from the prior art. In particular films preferred, which consist of a polymer with a molecular weight between 5000 and 500,000 daltons, preferably between 7500 and 250,000 daltons and in particular between 10,000 and 100,000 daltons. With regard to the media into which detergents and cleaning agents are usually introduced, detergent tablets in which the film consists of a water-soluble polymer are particularly preferred.

Such preferred polymers can be synthetic or natural in origin. If native or partially native polymers are used as film material, film materials made from one or more substances from the group consisting of carrageenan, guar, pectin, xanthan, cellulose and their derivatives, starch and their derivatives and gelatin are preferred.

Other polymers which can be used as film materials are synthetic polymers which are preferably water-swellable and / or water-soluble. Such synthetic-based polymers can be "tailor-made" for the desired film permeability during storage and dissolution of the film when used. Particularly preferred film materials are selected from a polymer or polymer mixture, the polymer or at least 50% by weight of the polymer mixture being selected from polyvinyl alcohol. Another preferred subject of the present application is therefore a method for producing a cast body from a washing or cleaning active preparation, comprising the steps: a) pouring a washing or cleaning active preparation into the receiving trough of a molding tool; b) degassing the active washing mixture which is active in washing or cleaning; c) shape the washing or cleaning active preparation to form a hollow body; d) filling the hollow body with a further active washing or cleaning preparation; e) closing the hollow body.

All detergent or cleaning agent preparations which can be processed by casting techniques are generally suitable for processing in the method according to the invention. Particular preference is given to using active washing or cleaning preparations in the form of dispersions in the process according to the invention. In a particularly preferred embodiment of the present application, the wash-active or cleaning-active preparation poured into the receiving recess of the molding tool is a dispersion of solid particles in a dispersant, dispersions which, based on their total weight i), 10 to 85% by weight Dispersants and ii) contain 15 to 90 wt .-% dispersed substances, are particularly preferred.

In this application, dispersion is a system consisting of several phases, one of which is continuous (dispersant) and at least one other is finely divided (dispersed substances). Particularly preferred wash- or cleaning-active preparations according to the invention are characterized in that they contain the dispersant in amounts above 11% by weight, preferably above 13% by weight, particularly preferably above 15% by weight, very particularly preferably above 17% by weight. % and in particular above 19 wt .-%, each based on the total weight of the dispersion. Dispersions which have a dispersion with a proportion by weight of dispersant above 20% by weight, preferably above 21% by weight and in particular above 22% by weight, in each case based on the total weight of the dispersion, can furthermore preferably be used. The maximum dispersant content of preferred dispersions, based on the total weight of the dispersion, is preferably less than 63% by weight, preferably less than 57% by weight, particularly preferably less than 52% by weight, very particularly preferably less than 47% by weight .-% and in particular less than 37 wt .-%. In the context of the present invention are particularly ^'such washing or cleaning-active preparations which, based on their total weight, dispersion agents in amounts from 12 to 62 wt .-%, preferably 14 to 49 wt .-% and in particular 16-38 wt. -% contain. Be particularly preferred Dispersions with a dispersant content of between 16 and 30% by weight, preferably between 16 and 26% by weight and in particular between 16 and 22% by weight, in each case based on the total weight of the dispersion.

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

Suitable dispersants in the context of the present invention are preferably the water-soluble or water-dispersible polymers, in particular the water-soluble or water-dispersible nonionic polymers. The dispersant can be either a single polymer or a mixture of different water-soluble or water-dispersible polymers. In a further preferred embodiment of the present invention, the dispersant or at least 50% by weight of the polymer mixture consists of water-soluble or water-dispersible nonionic polymers from the group of polyvinylpyrrolidones, vinylpyrrolidone / vinyl ester copolymers, cellulose ethers, polyvinyl alcohols, polyalkylene glycols, in particular polyethylene glycol and / or polypropylene glycol.

Polyvinylpyrrolidones are preferred dispersants in the context of the invention. Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinones) j, abbreviation PVP, are polymers of the general formula (I)

which are produced by free-radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using free-radical formers (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer only provides products with low molecular weights. Commercial polyvinylpyrrolidones have molar masses in the range from approx. 2500-750000 g / mol, which are characterized by the specification of the K values and, depending on the K value, have glass transition temperatures of 130-175 °. They are presented as white, hygroscopic powders or as aqueous ones. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.). Vinylpyrrolidone / Vinylester copolymers, as are marketed, for example under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / inyl acetate copolymers, are particularly preferred nonionic polymers.

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

CH ₂ - CH - O

O R (ii)

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

The vinyl esters are polymerized by free radicals using various processes

(Solution polymerization, suspension polymerization, emulsion polymerization,

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

Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and methylhydroxypropyl cellulose, as sold for example under the trademark Culminal® ^® and Benecel ^® (AQUALON).

Cellulose ethers can be described by the following general formula

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

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

[-CH ₂ -CH (OH) -] _n

which in small proportions also structural units of the type

[-CH ₂ -CH (OH) -CH (OH) -CH ₂ ]

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

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

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

H- (0-CH ₂ -CH ₂ ) _n -OH (III)

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

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

H- (0-CH-CH ₂ ) _n -OH (IV) I CH ₃

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

Dispersions are particularly preferably used which contain a nonionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, the proportion by weight of the poly (ethylene) glycol in the total weight of all dispersants is preferably between 10 and 90% by weight, particularly preferably between 30 and 80% by weight and in particular between 50 and 70% by weight. Dispersions in which the dispersant is more than 92% by weight, preferably more than 94% by weight, particularly preferably more than 96% by weight, very particularly preferably more than 98% by weight are particularly preferred. and in particular 100% by weight of a poly (alkylene) glycol, preferably poly (ethylene) glycol and / or poly (propylene) glycol, but in particular poly (ethylene) glycol. Dispersing agents which, in addition to poly (ethylene) glycol, also contain poly (propylene) glycol, preferably have a ratio by weight of poly (ethylene) glycol to poly (propylene) glycol of between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, particularly preferably between 10: 1 and 1, 5: 1 and in particular between 7: 1 and 2: 1. Other preferred dispersants are the nonionic surfactants, which are used both alone, but particularly preferably in combination with a nonionic polymer. Detailed information on the nonionic surfactants that can be used can be found below in the description of detergent or cleaning substances.

Dispersions preferably used are characterized in that at least one dispersant has a melting point above 25 ° C, preferably above 35 ^C C and especially above 40 ° C. The use of dispersants with a melting point or melting range between 30 and 80 ° C., preferably between 35 and 75 ° C., particularly preferably between 40 and 70 ° C. and in particular between 45 and 65 ° C. is particularly preferred, these dispersants based on the total weight of the dispersants used, a weight fraction above 10% by weight, preferably above 40% by weight, particularly preferably above 70% by weight and in particular between 80 and 100% by weight.

Suitable dispersed substances in the context of the present application are all substances having a washing or cleaning activity which are solid at room temperature, but in particular washing or cleaning substances from the group of builders (builders and cobuilders), washing or cleaning polymers, bleaching agents and bleach activators , the glass corrosion protection agent, the silver protection agent and / or the enzymes. A more detailed description of these ingredients can be found below in the text.

The water content of the dispersions preferably used in the process according to the invention is, based on their total weight, preferably less than 30% by weight, preferably less than 23% by weight, preferably less than 19% by weight, particularly preferably less than 15% by weight .-% and in particular less than 12 wt .-%. Disperisons preferably used according to the invention are low in water or anhydrous. Disperisons used with particular preference are characterized in that, based on their total weight, their free water content is below 10% by weight, preferably below 7% by weight, particularly preferably below 3% by weight and in particular below 1% by weight. -% exhibit.

The dispersions, which are preferably used as washing or cleaning active preparations, are distinguished by a high density. Dispersions with a density above 1.040 g / cm ³ are particularly preferably used. Processes which are preferred according to the invention are characterized in that the washing and cleaning-active preparation has a density above 1.040 g / cm ³ , preferably above 1.15 g / cm ³ , particularly preferably above 1.30 g / cm ³ and in particular above 1. 40 g / cm ³ . This high density not only reduces the total volume of a dosing unit cast body but also improves its mechanical stability. Particularly preferred methods according to the invention are therefore characterized in that the dispersion particularly has a density between 1,050 and 1,670 g / cm ³ , preferably between 1, 120 and 1, 610 g / cm ³ preferably between 1, 210 and 1, 570 g / cm, very particularly preferably between 1, 290 and 1, 510 g / cm ³ , and in particular between 1, 340 and 1, 480 g / cm ³ each on the densities of the media at 20 ° C. In order to avoid segregation processes during the processing of these dispersions, in particular in the course of the vibration of the molds, dispersing agents and dispersed substances preferably have densities which are less than 0.6 g / cm ³ , preferably less than 0.4 g / cm ³ and differ in particular by less than 0.3 g / cm ³ .

Dispersions preferably used according to the invention as a detergent or cleaning preparation are distinguished in that they disperse in water (40 ° C.) in less than 9 minutes, preferably less than 7 minutes, preferably in less than 6 minutes, particularly preferably in less than 5 Minutes, especially in less than 4 minutes. To determine the solubility, 20 g of the dispersion are introduced into the interior of a dishwasher (Miele G 646 PLUS). The main wash cycle of a standard wash program (45 ° C) is started. The solubility is determined by measuring the conductivity, which is recorded by a conductivity sensor. The dissolving process ends when the maximum conductivity is reached. In the conductivity diagram, this maximum corresponds to a plateau. The conductivity measurement begins with the insertion of the circulation pump in the main wash cycle. The amount of water used is 5 liters.

The active washing or cleaning preparations processed in the process according to the invention and / or the substances or substance mixtures filled into the hollow bodies produced according to the invention in a preferred process variant contain one or more customary constituents of washing and cleaning agents, preferably from the group of builders, surfactants, polymers , Bleaching agents, bleach activators, enzymes, dyes, fragrances, electrolytes, pH adjusting agents, perfume carriers, fluorescent agents, hydrotopes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, antimicrobial agents, antimicrobial agents, antimicrobial agents , Corrosion inhibitors, antistatic agents, ironing aids, phobing and impregnating agents, swelling and anti-slip agents, plasticizers and / or UV absorbers. These substances will be described in more detail below.

builders

In the context of the present application, the builders include, in particular, the zeolites,

Silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also phosphates.

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

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

In the context of the present invention, it is preferred that these silicate (s), preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, in detergents or cleaning agents in amounts of 10 to 60% by weight, preferably 15 to 50% by weight. % and in particular from 20 to 40 wt .-%, each based on the weight of the detergent or cleaning agent, are included.

If the silicates are used as a component of automatic dishwashing detergents, these detergents preferably contain at least one crystalline layered silicate of the general formula NaMSi _x 0 _{2x + 1} ^• y H ₂ 0, in which M represents sodium or hydrogen, x is a number from 1.9 to 22 , preferably from 1, 9 to 4, and y represents a number from 0 to 33. The crystalline layered silicates of the formula NaMSi _x 0 _{2x + 1} ^• y H ₂ 0 are sold, for example, by Clariant GmbH (Germany) under the trade name Na-SKS, for example Na-SKS-1 (Na ₂ Si22θ45'xH2θ, Kenyait ), N / A-

SKS-2 (Na ₂ Si ₁₄ θ29-xH2θ, magadiite), Na-SKS-3 (Na ₂ Sig0 ₁₇ -χH ₂ 0) or Na-SKS-4

(Na ₂ Si ₄ 0 ₉ -χH2θ, makatite). For the purposes of the present invention, crystalline sheet silicates of the formula (I) in which x is 2 are particularly suitable. Of these, Na-SKS-5 (α-Na ₂ Si2θ ₅ ), Na-SKS-

7 (β-Na ₂ Si ₂ 0 ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ 0 ₅ Η ₂ 0), Na-SKS-10 (NaHSi ₂ 0 ₅ -3H ₂ 0, kanemite), Na-SKS -11 (t-Na ₂ Si ₂ 0 ₅ ) and Na-SKS-13 (NaHSi ₂ 0 ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ 0 ₅ ).

If the silicates are used as a component of automatic dishwashing detergents, these detergents contain, in the context of the present application, a proportion by weight of the crystalline viscous silicate of the formula NaMSi _x 0 _{2x + 1} ^' y H ₂ 0 of 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular from 0.4 to 10% by weight, in each case based on the total weight of these compositions. It is particularly preferred if such automatic dishwashing detergents have a total silicate content below 7% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably below 4% by weight, very particularly preferably below 3% by weight .-% and in particular below 2.5 wt .-%, with this silicate, based on the total weight of the silicate contained, preferably at least 70 wt .-%, preferably at least 80 wt .-% and in particular at least 90 wt .-% is silicate of the general formula NaMSi _x 0 _{2x + 1} 'y H ₂ 0.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and is represented by the formula nNa ₂ 0 '(1-n) K ₂ 0 ^■ Al ₂ 0 ₃ ^■ (2 - 2.5) Si0 ₂ ^• ( 3.5 - 5.5) H ₂ 0

can be described. The zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. This applies in particular to the use of agents according to the invention as automatic dishwashing agents, which is particularly preferred in the context of the present application. Among the multitude of Commercially available phosphates, the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) are of the greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0 ₃ ) _n and orthophosphoric acid H ₃ P0 in addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to cleaning performance.

Suitable phosphates are, for example, sodium dihydrogen phosphate, NaH P0 ₄ , in the form of the dihydrate (density 1.91, preferably ^"3 , melting point 60 °) or in the form of the monohydrate (density 2.04, preferably ^{" 3} ), the disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HP0 ₄ , which is anhydrous or with 2 mol. (Density 2.066 like ^"3 , water loss at 95 °), 7 mol. (Density 1, 68 like ^{" 3} , melting point 48 ° with loss of 5 H ₂ 0) and 12 Mol. Water (density 1, 52 like ^"3 , melting point 35 ° with loss of 5 H ₂ 0) can be used, but especially the trisodium phosphate (tertiary sodium phosphate) Na ₃ P0, which as dodecahydrate, as decahydrate (corresponding to 19-20 % P ₂ 0 ₅ ) and in anhydrous form (corresponding to 39-40% P ₂ 0 ₅ ) A further preferred phosphate is tripotassium phosphate (tertiary or tri-base potassium phosphate), K ₃ P0 _4. Tetrasodium diphosphate ( Sodium pyrophosphate), Na ₄ P ₂ 0 ₇ , which in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1, 815-1, 836 like ^{" 3} , melting point 94 ° with loss of water), as well as the corresponding potassium salt potassium diphosphate (potassium pyrophosphate) , K ₄ P ₂ 0 ₇ .

Condensation of the NaH ₂ P0 ₄ or the KH ₂ P0 ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (0) (ONa) -0] _n that crystallizes with 6 H ₂ 0 -Na with n = 3. The corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P ₂ 0 ₅ , 25% K ₂ 0). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. Further also exist Sodium potassium tripolyphosphates, which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaP0 ₃ ) ₃ + 2 KOH - »Na ₃ K ₂ P ₃ O ₁₀ + H ₂ 0

According to the invention, these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

If, in the context of the present application, phosphates are used as washing or cleaning-active substances in washing or cleaning agents, preferred agents contain these 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 wt .-% and in particular from 20 to 70 wt .-%, each based on the weight of the detergent or cleaning agent.

It is particularly preferred to use potassium tripolyphosphate and sodium tripolyphosphate in a weight ratio of more than 1: 1, preferably more than 2: 1, preferably more than 5: 1, particularly preferably more than 10: 1 and in particular more than 20: 1. It is particularly preferred to use exclusively potassium tripolyphosphate without admixtures of other phosphates.

Other builders are the alkali carriers. Examples of alkali carriers include alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, the alkali silicates mentioned, alkali metal silicates, and mixtures of the abovementioned substances, the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, preferably being used for the purposes of this invention. A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred. A builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred. Because of their low chemical compatibility with the other ingredients of detergents or cleaning agents compared to other builder substances, the alkali metal hydroxides are preferably used only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, particularly preferably below 4 wt .-% and in particular below 2 wt .-%, each based on the total weight of the detergent or cleaning agent used. Agents which contain less than 0.5% by weight and in particular no alkali metal hydroxides, based on their total weight, are particularly preferred. It is particularly preferred to use carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonate (s), particularly preferably sodium carbonate, in amounts of 2 to 50% by weight, preferably 5 to 40% by weight and in particular from 7.5 to 30% by weight, based in each case on the weight of the detergent or cleaning agent. Agents which, based on the weight of the washing or cleaning agent (ie the total weight of the combination product without packaging) are less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight, and are particularly preferred contain in particular less than 9% by weight of carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonates, particularly preferably sodium carbonate.

Organic cobuilders include, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

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

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

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

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids be used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

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

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

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and are particularly preferred.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid. Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.

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

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

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

surfactants

In addition to the nonionic surfactants, the anionic, cationic and amphoteric surfactants are also included in the group of surfactants.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is branched linearly or preferably in the 2-position methyl may or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, C _{12- 4} alcohols containing 3 EO or 4 EO, _C9-11 alcohol containing 7 EO, C _13-15 -AIkohole with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ _ι alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

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

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

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

R ¹ I R-CO-N- [Z] (I)

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

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

R ¹ -0-R ²

R-CO-N- [Z]

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, 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 propylated Derivatives of this remainder.

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

Low-foaming nonionic surfactants are used as preferred surfactants. The cleaning agents according to the invention for machine dishwashing contain with particular preference nonionic surfactants, especially nonionic surfactants from the group of alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, C _{12- 4} alcohols containing 3 EO or 4 EO, _C9-11 alcohol containing 7 EO, C _13-15 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-1 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Nonionic surfactants which have a melting point above room temperature are particularly preferred, nonionic surfactants having a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43.3 ° C, are particularly preferred.

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

Preferred nonionic surfactants to be used at room temperature originate from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complicated surfactants such as

Polyoxypropylene / Polyoxyethylene / Polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

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

A particularly preferred nonionic surfactant which is solid at room temperature is made from a straight-chain fatty alcohol having 16 to 20 carbon atoms (Cι _6-2 o-alcohol), preferably a C- | ₈ - Alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide. Among these, the so-called "narrow rank ethoxylates" (see above) are particularly preferred.

Accordingly, ethoxylated nonionic surfactants, which are derived from C ₆ . ₂ o-monohydroxy alkanols or alkylphenols, or C _6- ₂₀ Cι _6-20 fatty alcohols and more than 12 moles, preferably more than 15 mol were won in particular more than 20 moles of ethylene oxide per mole of alcohol.

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

Other nonionic surfactants with melting points above room temperature which are particularly preferably used contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer bend which contains 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25% by weight. -% of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethyloipropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethyloipropane.

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

In detergents or cleaning agents, preferably in dishwashing detergents, the nonionic surfactant of the formula (II)

R 0 [CH ₂ CH (CH ₃ ) 0] _x [CH ₂ CH ₂ 0] _y [CH ₂ CH (OH) R ² ], (II) in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y stands for a value of at least 15.

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

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

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

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

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

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (OH) CH ₂ OR ²

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

If the latter statements are summarized, the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] I _j ΛO -R ²

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

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (OH) CH ₂ OR ²

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

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

R ¹ -0- (CH ₂ -CH ₂ -0) _w - (CH ₂ -CH-0) _x - (CH ₂ -CH ₂ -0) _y - (CH ₂ -CH-0) _z -H (III ) IIR ² R ³

in which R ^{1 represents} 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 represent integers from 1 to 6.

The preferred nonionic surfactants of the formula III can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in formula III above can vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is generally not shown, the linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, being preferred. Alcohols accessible from synthetic sources are, for example, Guerbet alcohols or residues which are methyl-branched in the 2-position or linear and methyl-branched residues in a mixture, as are usually present in oxo alcohol residues. Regardless of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, preferred dishwasher detergents according to the invention are those in which R ¹ in formula III for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 is up to 11 carbon atoms.

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

In summary, nonionic surfactants are particularly preferred which have a C ₉ , ₁₅ -alkyl radical with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used with particular preference according to the invention.

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

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x R ² (IV)

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

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

R ¹ 0 [CH ₂ CH ₂ 0] _x R ² (V) those nonionic surfactants are particularly preferred in which R ^{1 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, R ^{2 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and x stands for values between 1 and 40.

Those end group-capped poly (oxyalkylated) nonionic surfactants which, according to the formula (VI) R ¹ 0 [CH ₂ CH ₂ 0] _x CH ₂ CH (OH) R ² (VI)

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

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

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C _8-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C ₁₂ . ₁₈ -monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) yl suifates are the alkali and, in particular, the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred from a washing-technical point of view. 2,3-alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol ethylene oxide, such as 2-methyl-branched C ₉ n alcohols with an average of 3.5 mol ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

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

Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, and hydrogenated Erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.

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

If the anionic surfactants are part of machine dishwashing detergents, their content, based on the total weight of the detergents, is preferably less than 4% by weight, preferably less than 2% by weight and very particularly preferably less than 1% by weight. Automatic dishwashing agents that do not contain anionic surfactants are particularly preferred.

Instead of the surfactants mentioned or in conjunction with them, cationic and / or amphoteric surfactants can also be used.

For example, cationic compounds of the formulas VII, VIII or IX can be used as cationic active substances:

R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _π -TR ² (VII)

(CH ₂ ) _n -TR ²

R ¹ R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -CH-CH ₂ (VIII)

R ¹ TTIIR ² R ²

R ¹

R ³ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (IX)

R ⁴

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

In automatic dishwashing detergents, the content of cationic and / or amphoteric surfactants is 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 agents which do not contain any cationic or amphoteric surfactants are particularly preferred.

polymers

The group of polymers includes in particular the wash- or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners. In general, in addition to nonionic polymers, cationic, anionic and amphoteric polymers can also be used in washing or cleaning agents. Polymers effective as softeners are, for example, the polymers containing sulfonic acid groups, which are used with particular preference.

Copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionic monomers can be used particularly preferably as polymers containing sulphonic acid groups.

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

R ¹ (R ² ) C = C (R ³ ) COOH (X),

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

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

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

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

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

Preferred among these monomers are those of the formulas Xla, Xlb and / or Xlc,

H ₂ C = CH-X-S0 ₃ H (Xla), H ₂ C = C (CH ₃ ) -X-S0 ₃ H (Xlb), H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (Xlc),

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 represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and - C (0) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (0) NH-CH (CH ₂ CH ₃ ) in formula Xla), 2-acrylamido-2-propanesulfonic acid (X = - C (0) NH-C (CH ₃ ) ₂ in formula Xla), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (0) NH- CH (CH ₃ ) CH ₂ - in formula Xla) , 2-methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (0) NH- CH (CH ₃ ) CH ₂ - in formula Xlb), 3-methacrylamido-2-hydroxy-propanesulfonic acid (X = -C ( 0) NH-CH ₂ CH (OH) CH ₂ - in formula Xlb), allylsulfonic acid (X = CH ₂ in formula XI la), methallylsulfonic acid (X = CH ₂ in formula Xlb), allyloxybenzenesulfonic acid (X = -CH ₂ -0 -C ₆ H ₄ - in formula Xla), methallyloxybenzenesulfonic acid (X = -CH ₂ -0-C ₆ H ₄ - in formula Xlb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2- propen1-sulfonic acid (X = CH ₂ in formula Xlb), styrene sulfonic acid (X = C ₆ H in formula Xla), vinyl sulfonic acid (X not present in formula Xla), 3-sulfopropyl acrylate (X = -C (0) NH-CH ₂ CH ₂ CH ₂ - in formula Xla ), 3-sulfopropyl methacrylate (X = -C (0) NH- CH ₂ CH ₂ CH ₂ - in formula Xlb), sulfomethacrylamide (X = -C (0) NH- in formula Xlb), sulfomethyl methacrylamide (X = -C ( 0) NH-CH ₂ - in formula Xlb) and water-soluble salts of the acids mentioned.

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

In summary, copolymers are made of

i) unsaturated carboxylic acids of formula X.

R ¹ (R ² ) C = C (R ³ ) COOH (X),

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

ii) Monomers of the formula XI containing sulfonic acid groups

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

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

iii) optionally further ionic or nonionic monomers

particularly preferred.

Further particularly preferred copolymers consist of i) one or more unsaturated carboxylic acids from the group consisting of acrylic acid, methacrylic acid and / or maleic acid ii) one or more monomers of the formulas Xla, Xlb and / or Xlc containing sulfonic acid groups:

H ₂ C = CH-X-S0 ₃ H (Xla), H ₂ C = C (CH ₃ ) -X-S0 ₃ H (Xlb), H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) - X-S0 ₃ H (Xlc),

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 represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and - C (0) -NH-CH (CH ₂ CH ₃ ) - iii) optionally further ionic or nonionic monomers. The copolymers can contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group üi). Particularly preferred polymers have certain structural units, which are described below.

For example, copolymers which have structural units of the formula XII are preferred

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

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

These polymers are produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which is also preferred. The corresponding copolymers contain the structural units of the formula XIII

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

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

Completely analogously, acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Copolymers are those which have structural units of the formula XIV

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

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

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

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

Instead of or in addition to acrylic acid and / or methacrylic acid, maleic acid can also be used as a particularly preferred monomer from group i). In this way, copolymers preferred according to the invention are obtained which have structural units of the formula XVI

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

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

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

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

In summary, according to the invention, those copolymers are preferred which have structural units of the formulas XII and / or XIII and / or XIV and / or XV and / or XVI and / or XVII

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (XII), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC ( 0) -Y-S0 ₃ H] _p - (XIII), - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (XIV), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (XV), - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (XVI), - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) 0-Y-S0 ₃ H] _p - (XVII),

The sulfonic acid groups in the polymers may be wholly or partly in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.

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

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

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 intended use. Preferred detergent or cleaning agent compositions are characterized in that the copolymers have molecular weights of 2,000 to 200,000 gmol ^"1 , preferably 4,000 to 25,000 gmol ^{" 1} and in particular 5,000 to 15,000 gmol ^"1 .

With particular preference, amphoteric or cationic polymers continue to be used. These particularly preferred polymers are characterized in that they have at least one positive charge. Such polymers are preferably water-soluble or water-dispersible, that is to say they have a solubility in water at 25 ° C. above 10 mg / ml.

Cationic or amphoteric polymers particularly preferably contain at least one ethylenically unsaturated monomer unit of the general formula R ¹ (R ² ) C = C (R ³ ) R ⁴

in which R ¹ to R ⁴ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above, a heteroatomic group with at least one positively ended group, a quaternized nitrogen atom or at least one amine group with a positive charge in the pH range between 2 and 11 or for -COOH or -COOR ⁵ , where R ^{5 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Examples of the aforementioned (non-polymerized) monomer units are diallylamine, methyldiallylamine, dimethyldimethylammonium salts, acrylamidopropyl (trimethyl) ammonium salts (R ¹ , R ² , and R ³ , = H, R ⁴ = C (0) NH (CH ₂ ) ₂ N ⁺ ( CH ₃ ) ₃ X ^" ), methacrylamidopropyl (trimethyl) ammonium salt (R ¹ and R ² = H, R ³ = CH ₃ H, R ⁴ = C (0) NH (CH ₂ ) ₂ N ⁺ (CH ₃ ) ₃ X ^" ).

Unsaturated carboxylic acids of the general formula are particularly preferred as a constituent of the amphoteric polymers

R ¹ (R ² ) C = C (R ³ ) COOH

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

Particularly preferred amphoteric polymers contain, as monomer units, derivatives of diallylamine, in particular dimethyldiallylammonium salt and / or methacrylamidopropyl (trimethyl) ammonium salt, preferably in the form of the chloride, bromide, iodide, hydroxide, phosphate, sulfate, hydrosulfate, ethyl sulffasts, methyl sulfate, mesylate, tosylate, formate or acetates in combination with monomer units from the group of ethylenically unsaturated carboxylic acids.

bleach

Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and supply H ₂ 0 ₂ in water. Further bleaching agents which can be used are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, Peroxophthalate, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. According to the invention, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-

Phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP)], o-

, N-nonenylamidoperadipic acid and N- nonenylamidopersuccinates Carboxybenzamidoperoxycapronsäure, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12- diperoxyacid, 1, 9-diperoxyazelaic acid, Diperocysebacinsäure, diperoxybrassylic acid, diperoxyphthalic acids, the 2-decyldiperoxybutane-1,4-dioic acid, N , N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid,

Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Bleach activators

Bleach activators are used in detergents or cleaning agents, for example, to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C and below. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetoxy and 2,5-diacetyloxy and 2,5-glycethylacetyl, ethylene glycol 2,5-dihydrofuran. Further bleach activators which are preferably used in the context of the present application are compounds from the group of the cationic nitriles, in particular cationic nitriles of the formula R ¹

R ² -N ⁽⁺⁾ - (CH ₂ ) -CN X ^H ,

R ³

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

A cationic nitrile of the formula R ⁴ is particularly preferred

R -N j ( ⁺ ) '.- (CH ₂ ) -CN X ⁽ (-)

R ^D

in which R ⁴ , R ⁵ and R ⁶ are selected independently of one another from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , - CH (CH ₃ ) -CH ₃ , where R ⁴ additionally can also be -H 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, the cationic in turn from the group of these substances 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, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate is selected, is particularly preferred.

As bleach activators it is also possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with 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 C atom number mentioned and / or optionally substituted benzoyl groups. Preferred are polyacylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA) as well as acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams are also preferably used. Combinations of conventional bleach activators can also be used.

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

If further bleach activators are to be used in addition to the nitrile quats, bleach activators from the group of polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyloxy- or isononosulfonates, are preferred. n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-%, each based on the total weight of the bleach activator-containing agents used.

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 consisting of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, the manganese sulfate are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular 0.0025% by weight .-% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total weight of the bleach activator-containing agents. But in special cases, more bleach activator can be used.

Glass corrosion inhibitors

Glass corrosion inhibitors prevent the appearance of cloudiness, streaks and scratches but also the iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and / or zinc salts and / or magnesium and / or zinc complexes. A preferred class of compounds that can be used to prevent glass corrosion are insoluble zinc salts.

Insoluble zinc salts in the sense of this preferred embodiment are zinc salts which have a solubility of at most 10 grams of zinc salt per liter of water at 20 ° C. Examples of insoluble zinc salts which are particularly preferred according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn ₂ (OH) ₂ C0 ₃ ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn ₃ (P0 ₄ ) ₂ ), and zinc pyrophosphate (Zn ₂ (P ₂ 0 ₇ )).

The zinc compounds mentioned are preferably used in amounts which have a zinc ion content of between 0.02 and 10% by weight, preferably between 0.1 and 5.0% by weight and in particular between 0.2 and 1.0 % By weight, in each case based on the total glass corrosion inhibitor-containing agent. The exact content of the zinc salt or zinc salts in the detergents naturally depends on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration in the detergents should be.

Since the insoluble zinc salts remain largely unchanged during the dishwashing process, the particle size of the salts is a criterion to be observed so that the salts do not adhere to glassware or machine parts. Means are preferred in which the insoluble zinc salts have a particle size below 1.7 millimeters.

If the maximum particle size of the insoluble zinc salts is below 1.7 mm, there is no fear of insoluble residues in the dishwasher. The insoluble zinc salt preferably has an average particle size which is significantly below this value in order to further minimize the risk of insoluble residues, for example an average particle size of less than 250 μm. This, in turn, is all the more the less the zinc salt is soluble. In addition, the glass corrosion inhibiting effectiveness increases with decreasing particle size. In the case of very poorly soluble zinc salts, the average particle size is preferably below 100 μm. For even more poorly soluble salts, it can be even lower; For example, average particle sizes below 100 μm are preferred for the very poorly soluble zinc oxide.

Another preferred class of compounds are magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid. These have the effect that even with repeated use the surfaces of glassware do not change corrosively, in particular no clouding, streaks or scratches but also no iridescence of the glass surfaces.

Although all magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids can be used, as described above, the magnesium and / or Zinc salts of monomeric and / or polymeric organic acids from the groups of the unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred.

The spectrum of the zinc salts of organic acids, preferably organic carboxylic acids preferred according to the invention, extends from salts which are sparingly or not soluble in water, ie have a solubility below 100 mg / L, preferably below 10 mg / L, in particular no solubility, up to such Salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, particularly preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature). The first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

It is particularly preferred to use at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group consisting of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate, as the glass corrosion inhibitor. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

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

corrosion inhibitors

Corrosion inhibitors serve to protect the items to be washed or the machine, with silver protection agents in particular being particularly important in the area of automatic dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. The following may be mentioned as examples of the 3-amino-5-alkyl-1, 2,4-triazoles which are preferably to be used according to the invention: 5-propyl, butyl, pentyl, heptyl, octyl, nonyl -, -Decyl-, -Undecyl-, -Dodecyl-, -Isononyl-, -Versatic-10-acid alkyl-, -Phenyl-, -p-Tolyl-, - (4-tert.butylphenyl) -, - (4- Methoxyphenyl) -, - (2-, -3-, -4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2-furyl) -, - (5-oxo-2-pyrrolidinyl) -, -3-amino-1, 2,4-triazole. The dishwasher detergents contain the alkylamino-1, 2,4-triazoles or their physiologically tolerable salts in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04% by weight. Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulfurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid. 5-Pentyl-, 5-heptyl-, 5-nonyl-, 5-undecyl-, 5-isononyl-, 5-versatic-10-acid-alkyl-3-amino-1, 2,4-triazoles and mixtures are very particularly effective of these substances.

In addition, detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

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

The metal salts or metal complexes used are said to be at least partially soluble in water. The counterions suitable for salt formation include all customary one, two or three times negatively charged inorganic anions, e.g. B. oxide, sulfate, nitrate, fluoride, but also organic anions such. B. stearate.

For the purposes of the invention, metal complexes are compounds which consist of a central atom and one or more ligands and, if appropriate, additionally one or more of the abovementioned anions. The central atom is one of the metals mentioned in one of the oxidation states mentioned above. The ligands are neutral molecules or anions that are monodentate or multidentate; the term “ligands” in the sense of the invention is explained in more detail, for example, in “Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507”. If the charge of the central atom and the charge of the ligand (s) do not add up to zero in a metal complex, then depending on whether there is a cationic or an anionic excess of charge, either one or more of the above anions or one or more cations, e.g. B. sodium, potassium, ammonium ions for the charge compensation. Suitable complexing agents are, for example, citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.

The common definition in chemistry for "oxidation level" is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart New York, 9th edition, 1991, page 3168" reproduced.

Particularly preferred metal salts and / or metal complexes are selected from the group MnSOψ Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1-diphosphonate] .

V ₂ 0 ₅ , V ₂ 0 ₄ , V0 _2> TiOS0 ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoS0 ₄ , Co (N0 ₃ ) ₂ , Ce (N0 ₃ ) ₃ and mixtures thereof, so that preferred Machine dishwashing agents according to the invention are characterized in that the metal salts and / or metal complexes are selected from the group MnS0 ₄ , Mn (II) citrate,

Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1-diphosphonate], V ₂ Og, V ₂ 0 ₄ , V0 ₂ ,

TiOS0 ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoS0 ₄ , Co (N0 ₃ ) ₂ , Ce (N0 ₃ ) ₃ .

These metal salts or metal complexes are generally commercially available substances which can be used in the agents according to the invention for the purpose of protecting against silver corrosion without prior cleaning. For example, that's from S0 ₃ production

(Contact method) known mixture of pentavalent and tetravalent vanadium (V ₂ 0 ₅ , V0 ₂ , V ₂ 0 ₄ ) is suitable, as is the titanyl sulfate formed by diluting a Ti (S0 ₄ ) ₂ solution,

TiOS0 ₄ .

The inorganic redox-active substances, in particular metal salts or metal complexes, are preferably coated, ie completely coated with a waterproof material which is easily soluble at the cleaning temperatures, in order to prevent their premature decomposition or oxidation during storage. Preferred coating materials which are applied by known processes, for example melt coating processes according to Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher-melting alcohols such as hexadecanol, soaps or fatty acids. The coating material, which is solid at room temperature, is applied in a molten state to the material to be coated, for example by spinning finely divided material to be coated in a continuous stream through a spray zone of the molten coating material which is also continuously generated. The melting point must be selected so that the coating material easily dissolves or melts quickly during the silver treatment. The melting point should ideally be in the range between 45 ° C and 65 ° C and preferably in the range 50 ° C to 60 ° C. The metal salts and / or metal complexes mentioned are contained in cleaning agents, preferably in an amount of 0.05 to 6% by weight, preferably 0.2 to 2.5% by weight, in each case based on the total agent containing corrosion inhibitor.

enzymes

Enzymes can be used to increase the washing or cleaning performance of washing or cleaning agents. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents, which are accordingly preferred. Agents according to the invention preferably contain enzymes in total amounts of 1 × 10 ^"s to 5 percent by weight based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus ientus, subtilisin DY and the enzymes thermitase, proteinase K and the enzyme which can no longer be assigned to the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. The variants listed under the name BLAP ^{® are} derived from the protease from Bacillus Ientus DSM 5483.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, which is sold under the trade name Protosol ^® by Advanced Biochemicals Ltd., Thane, India, which is sold under the trade name Wuxi ^® by Wuxi Snyder Bioproducts Ltd., China, and in the trade name Proleather ^® and Protease P ^® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from β. amyloliquefaciens or from ß. stearothermophilus and its further developments for use in detergents and cleaning agents. The enzyme from ß. licheniformis is from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar ^® ST available. Development products of this α-amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase from ß. Amyloliquefaciens is sold by Novozymes under the name BAN ^® , and derived variants from the α-amylase from β. stearothermophilus under the names BSG ^® and Novamyl ^® , also from Novozymes.

Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from ß. to highlight agaradherens (DSM 9948).

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae. Another commercial product is the Amylase-LT ^® .

Lipases or cutinases can furthermore be used according to the invention, in particular because of their triglyceride-cleaving activities, but also to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ^® , Lipolase ^® Ultra, LipoPrime ^® , Lipozyme ^® and Lipex ^® . Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. Lipase ^® , Lipase AP ^® , Lipase M-AP ^® and Lipase AML ^® available. For example, the Genencor company can use the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products, the preparations originally sold by Gist-Brocades M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention, also the product Lumafast ^® from Genencor.

Furthermore, enzymes can be used, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and ß-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 L from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, USA , The from ß. subtilis .beta.-glucanase obtained is available under the name Cereflo ^® from Novozymes. To increase the bleaching effect, oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenoloxidases, polyphenol oxidases) can be used according to the invention. Suitable commercial products are Denilite ^® 1 and 2 from Novozymes. Advantageously, organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of greatly different redox potentials between the oxidizing enzymes and the soiling.

The enzymes originate, for example, either originally from microorganisms, for example of the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological processes known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi.

The enzymes in question are preferably purified by methods which are established per se, for example by means of precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.

The enzymes can be used in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural, polymer or in the form of capsules, for example those in which the enzyme is enclosed in a solidified gel are or in those of the core-shell type in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers. Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating. Furthermore, it is possible to assemble two or more enzymes together, so that a single granulate has several enzyme activities.

A protein and / or enzyme can be protected against damage, such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage, especially during storage. When the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Agents according to the invention can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.

A group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used, including above all derivatives with aromatic groups, for example ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their salts or esters. Ovomucoid and leupeptin may be mentioned as peptide protease inhibitors; an additional option is the formation of fusion proteins from proteases and peptide inhibitors.

Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and their mixtures, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders can additionally stabilize an enzyme contained.

Lower aliphatic alcohols, but above all polyols, such as, for example, glycerol, ethylene glycol, propylene glycol or sorbitol are further frequently used enzyme stabilizers. Calcium salts, such as calcium acetate or calcium formate, and magnesium salts are also used.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, among other things, against physical influences or pH fluctuations. Polymers containing polyamine N-oxide act as enzyme stabilizers. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkyl polyglycosides can stabilize the enzymatic components of the agent according to the invention and even increase their performance. Cross-linked N-containing compounds also act as enzyme stabilizers.

Reducing agents and antioxidants increase the stability of the enzymes against oxidative decay. A sulfur-containing reducing agent is, for example, sodium sulfite. Combinations of stabilizers are preferably used, for example made of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The effect of peptide-aldehyde stabilizers is increased by the combination with boric acid and / or boric acid derivatives and polyols and is further enhanced by the additional use of divalent cations, such as calcium ions.

One or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, are preferred in amounts of 0.1 to 5% by weight, preferably of 0.2 to 4.5 and in particular of 0, 4 to 4 wt .-%, each based on the total enzyme-containing agent used.

disintegration aid

In order to facilitate the disintegration of prefabricated moldings, disintegration aids, so-called tablet disintegrants, can be incorporated into these agents in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184), tablet disintegrants or disintegration accelerators are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in resorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling) and on the other hand a pressure can be generated by the release of gases, which breaks the tablet into smaller particles disintegrates. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.

Disintegration aids are preferably used in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight, based in each case on the total weight of the agent containing disintegration aids.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred washing and cleaning agent compositions contain such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ Hιo0 ₅ ) _n and is considered formally a ß-1, 4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.

The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be pressed. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier available in the present invention.

Microcrystalline cellulose can be used as another cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. Subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, into granules with an average particle size of 200 μm.

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

According to the invention, gas-developing effervescent systems can also preferably be used as tablet disintegration aids. The gas-developing shower system can consist of a single substance which releases a gas when it comes into contact with water. Among these compounds, magnesium peroxide should be mentioned in particular, which releases oxygen on contact with water. Usually, however, the gas-releasing bubble system itself consists of at least two components that react with one another to form gas. While a large number of systems which release nitrogen, oxygen or hydrogen, for example, are conceivable and executable here, the sprinkling system used in the detergent and cleaning agent compositions according to the invention can be selected on the basis of both economic and ecological aspects. Preferred effervescent systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium salts are clearly preferred over the other salts for reasons of cost. Of course, the pure alkali metal carbonates or bicarbonates in question do not have to be used; rather, mixtures of different carbonates and hydrogen carbonates may be preferred.

The preferred shower system is 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10% by weight. -% of an acidifying agent, based in each case on the total weight of the agent.

Acidifying agents which release carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, organic acidifying agents are preferably used, citric acid being a particularly preferred acidifying agent. However, the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are preferred from this group. Organic suifonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight). In the context of the present invention, preference is given to acidifying agents in the effervescent system from the group of the organic di-, tri- and oligocarboxylic acids or mixtures.

fragrances

As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallyl propionate and benzylsalpionate. The ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, α-isomethylionon and methylcedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be processed directly, but it can also be advantageous to apply the fragrances to carriers which ensure a long-lasting fragrance due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

dyes

Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the agents and to light, and no pronounced substantivity to the substrates to be treated with the dye-containing agents, such as, for example, glass, ceramics, plastic dishes or textiles not to stain them.

solvent

The solvents include, in particular, the non-aqueous organic solvents, with particular preference given to using non-aqueous solvents from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerin, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether,

Ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propyl -3- methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents.

foam inhibitors

Suitable foam inhibitors are, for example, soaps, paraffins or silicone oils, which can, if appropriate, be applied to carrier materials. Suitable anti-redeposition agents, which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methylhydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether and the polymers of phthalic acid and / or terephthalic acid or of their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of the phthalic acid and terephthalic acid polymers are particularly preferred.

Optical brighteners

Optical brighteners (so-called "white toners") can be added to detergents or cleaning agents in order to eliminate graying and yellowing of textiles treated with these agents. These substances absorb on the fiber and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and pure with the yellow tone of the grayed or yellowed laundry White results. Suitable compounds for example, originate from the substance classes of the 4,4 ^'- diamino-2,2'-stilbenedisulfonic (flavonic), 4,4'-distyryl-biphenylene, Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems and the pyrene derivatives substituted by heterocycles.

graying

Graying inhibitors in textile cleaning agents have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. Cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof can also be used as graying inhibitors in the particulate compositions.

Antimicrobial agents

Antimicrobial agents are used to combat microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halophenols and phenol mercuric acetate, although the use of these agents can also be dispensed with entirely.

softener

The formulations can also have fabric-softening clay minerals, which can be selected from a large number of minerals, in particular the layered silicates. The smectite group has proven to be advantageous. The term smectite includes both clays in which aluminum oxide is present in a silicate grid and clays in which magnesium oxide occur in a silicate grid. Typical smectites have the following general formula: Al ₂ (Si ₂ 0 ₅ ) ₂ (OH) ₂ ^" nH ₂ 0 and compounds with the following formula Mg ₃ (Si ₂ 0 ₅ ) ₂ (OH) ₂ ^" nH ₂ 0. Smectites are usually in an extensive three-layer structure. Specific examples of suitable smectites include those selected from the class of montmorillonites, hectorites, volchonskites, nontronites, saponites and sauconites, especially those with alkali or alkaline earth metal ions in the crystal lattice structure. Preferred is a three-layer, expandable aluminum silicate, which is characterized by a dioctahedral crystal lattice, whereas the extensive three-layer magnesium silicate structure has a trioctahedral crystal lattice. As previously mentioned, the clay minerals contain cationic counterions such as protons, sodium ions, potassium ions, calcium ions, magnesium ions and the like. The clay minerals are usually distinguished on the basis of the cations that are predominantly or exclusively absorbed. For example, a sodium bentonot is such a clay mineral in which sodium is predominantly present as the absorbed cation. Such absorbed cations can carry out exchange reactions with other cations in aqueous solutions. A typical exchange reaction involving a smectite type is as follows:>

Smectite (Na) + NH ₄ OH -> smectite (NH ₄ ) + NaOH

In the aforementioned equilibrium reaction, one equivalent of ammonium ion is replaced by one equivalent of sodium ion. It is common to increase the cation exchange capacity in milliequivalents / 100 g measure (meq / 100 g). The cation exchange capacity of the clays can be determined in a number of ways, for example by electrodialysis or by exchange with ammonium ions, followed by titration, as described, for example, in the book by Grimshaw, "The chemistry and physics of clays", pages 264-265, Interscience 1971. Smectites such as, for example, nontonite have an ion exchange capacity of approximately 70 meq / 100 g, and montmorillonites, which have an exchange capacity of above 70 meq / 100 g, have proven to be extremely preferred in the context of the present invention, since they are particularly effective towards them pull on the treating textiles and give them the desired soft feel. Particularly preferred clay minerals in the context of the present invention are therefore expanded three-layer smectite types with an ion exchange capacity of at least 50 meq / 100 g.

Organophilic clay minerals can also be used in the present invention. Such hydrophobically modified clay minerals in which inorganic metal ions are exchanged for organic ions by the previously described exchange process are also preferred. The modified clay minerals are very miscible with organic solvents and have the property of storing organic solvents between the layers. Suitable examples of organophilic clay minerals are Benton SD-1, SD-2 and SD-3 from Rheox. .

From the group of smectites, bentonites have proven to be particularly preferred. Bentonites are contaminated clays that are formed by weathering volcanic tuffs. Due to their high montmorillonite content, bentonites have valuable properties such as swellability, ion exchange capacity and thixotropy. It is possible to modify the properties of the bentonites according to the intended use. Bentonites are a common clay component in tropical soils and are used as sodium bentonite e.g. mined in Wyoming / USA. Sodium bentonite has the most favorable application properties (swellability), so that its use is preferred in the context of the present invention. Naturally occurring calcium bentonites originate, for example, from Mississippi / USA or Texas / USA or from Landshut / D. The naturally obtained Ca bentonites are artificially converted into the more swellable Na bentonites by exchanging Ca for Na.

The main constituents of the bentonites are so-called montmorillonites, which can also be used in pure form in the context of the present invention. Montmorillonites are clay minerals belonging to the phyllosilicates and here to the dioctahedral smectites, which crystallize monoclinic-pseudohexagonal. Montmorillonite predominantly form white, gray-white to yellowish, completely amorphous appearing, easily friable, swelling in the water, but not plastic, by the general formulas

AI ₂ [(OH) ₂ / Si ₄ O ₁₀ ] -nH ₂ O or AI ₂ 0 ₃ -4Si0 ₂ -H ₂ 0-nH ₂ 0 or AI ₂ [(OH) ₂ / Si ₄ O ₁₀ ] (dried at 150 °)

can be described.

Montmorillonites have a three-layer structure, which consists of two tetrahedral layers that are electrostatically cross-linked via the cations of an intermediate octahedral layer. The layers are not rigidly connected, but can swell by reversible incorporation of water (in 2-7 times the amount) and other substances such as alcohols, glycols, pyridine, ammonium compounds, hydroxyaluminosilicate ions, etc. The above. Formulas are only approximate formulas since montmorillonites have a large ion exchange capacity. So AI can be exchanged for Mg, Fe ²⁺ , Fe ³⁺ , Zn, Cr, Cu and other ions. As a result of such a substitution, the layers are negatively charged, which is balanced by other cations, especially Na ⁺ and Ca ²⁺ .

Calcium or magnesium bentonites are usually non-swellable and usually less effective plasticizers. However, it is advantageous to combine non-swellable bentonites with carrier materials, such as, for example, polyethylene glycol, in order to achieve a considerably improved soft feel of the textiles treated with them. Calcium or magnesium bentonites, which are used in the presence of a sodium source, such as NaOH or NaC0 ₃ , are also advantageous.

In a particularly preferred embodiment, the clay is a treated montmorillonite-containing clay which has the following properties:

I) Montmorillonite content of at least 85% and

II) When the clay activated with sodium ions is dried and ground into particles, the ground particles do not swell more than two and a half times within a period of 24 hours when deionized water is added at room temperature.

A clay containing montmorillonite is particularly preferred, which is obtained by the following process steps: a) drying the clay to a water content of 25-35% by weight, b) extruding the dried material into a paste; c) drying the paste to a moisture content of 10-14% by weight and d) calcining at a temperature between 120 and 250 ° C.

The chemical composition of the bentonite to be used as the starting material is preferably the following:

Si0 ₂ : 55.0-61.0% by weight

Al ₂ 0 ₃ : 14.5-17.6% by weight Fe ₂ 0 ₃ : 1.45-1.7% by weight

CaO: 2.8 - 7.0% by weight

MgO: 5.0 - 6.3% by weight

K ₂ 0: 0.5-0.58% by weight

Na ₂ 0: 0.25-0.3% by weight

Mn ₃ 0 ₄ : 0.04-0.25% by weight

A detailed description of the process for the treatment of bentonite can be found in WO 00/03959, the disclosure of which is fully incorporated in this application.

The crystalline structure of montmohllonite is more or less resistant to acid treatment. Acid treatment in the context of the invention means that a sample of the clay (for example 1 g / l) in an IN HCI solution is exposed to a temperature of 80 ° C. for 15 hours. It must be mentioned that most clays can be destroyed by acid treatment with, for example, fluoride. In the context of the present invention, however, acid treatment means HCI treatment. Montmorillonites (magnesium saturated / air dried) usually have a maximum diffraction distance of 14-15 in the 001 plane when treated with X-rays. This maximum diffraction distance usually does not change by treating the clay with HCI.

In the context of the present invention, however, acid-sensitive montmorillonites are preferred, for example montmorillonites, the crystalline structure of which is destroyed when they are treated with HCl. The use of such clay minerals has a softening effect and also ensures better dispersibility in the aqueous wash liquor or the aqueous textile treatment liquid. The destruction of the crystalline structure can be determined by measuring the diffraction distance, so that the maximum diffraction distance to be expected for crystalline montmorilonites in the 001 plane of 14-15 does not appear for the destroyed montmorillonites.

Without being bound by theory, it is believed that acid sensitivity is related to an increased exchange of aluminum for magnesium in the octahedral layer of the montmorillonite clay. A ratio of Al ₂ O ₂ / MgO of less than 4, particularly preferably less than 3, is preferred. The above-mentioned acid-sensitive montmorillonites have the advantage that they enable a reduced tendency to gel and an improved dispersibility in the wash liquor. In addition, it has been observed that such clay minerals produce an improved soft feel.

Claims

claims

1. A method for producing a cast body from a washing or cleaning active preparation, comprising the steps: a) pouring a washing or cleaning active preparation into the receiving trough of a molding tool; b) degassing the active washing or cleaning preparation;

2. The method according to claim 1, characterized in that the degassing is achieved by vibration of the mold.

3. The method according to any one of claims 1 or 2, characterized in that the amplitude of the vibration is continuously adjustable.

4. The method according to any one of claims 1 to 3, characterized in that the frequency of the vibration is continuously adjustable.

5. The method according to any one of claims 1 to 4, characterized in that the vibration takes place in the horizontal and / or vertical spatial direction.

6. The method according to any one of claims 1 to 5, characterized in that the amplitude and the frequency of the vibration during the degassing are constant.

7. The method according to any one of claims 1 to 6, characterized in that the amplitude and / or the frequency of the vibration change during the degassing.

8. The method according to any one of claims 1 to 7, characterized in that the degassing is carried out by applying a negative pressure.

9. The method according to any one of claims 1 to 8, characterized in that the degassing is carried out by the action of ultrasound.

10. The method according to any one of claims 1 to 9, characterized in that the degassing is carried out by the action of heat.