DE10338043A1 - Production of detergent or cleaning agent active preparations in cast shaped article form, including degassing stage in mold tool to increase breaking strength and improve optical appearance - Google Patents

Abstract

Production of a detergent or cleaning agent active preparation (I) in the form of a cast shaped article involves casting (I) into the receiving trough of a mold tool, then degassing (I).

Description

This Registration concerns detergents or cleaning agents. In particular concerns this application a process for the production of detergents or cleaning agents.

washing or cleaning agents are now available to consumers in a wide variety of forms available. In addition to washing powders and granules, this offer includes, for example also detergent 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 reduce the costs for packaging and transport. In particular, the detergent or cleaning agent tablets meet additionally the consumer's desire for simple dosing. The corresponding Means are extensively described in the prior art.

Except in the The fixed supply forms described can be detergents or cleaning agents continue to assemble as gels or pastes.

So the granted European patent reveals EP 331 370 (Unilever) a process for the preparation of stable, viscous liquid compositions for use in automatic dishwashers. Subject of the European patent EP 797 656 (Unilever) are non-aqueous liquid detergent compositions that contain polymeric hydrotropes.

For packaging solid or liquid Washing or cleaning agents are also particularly suitable for water-soluble or water dispersible films. The individual dosing units in this way packaged detergents can easily by inserting one or more bags directly in the washing machine or dishwasher or in their induction chamber, or by evaluating it in a predetermined amount of water, for example in a bucket or in the hand wash basin or sink. such Packaged detergents and cleaning agents are the subject of numerous Publications.

The granted European patent EP 700 989 B1 For example, claims 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 that is sticky on the outside.

The Application WO 02116222 (Reckitt-Benckiser) discloses water-soluble packaging for aqueous detergent compositions, the free water content of which is at least 3% by weight.

object WO 02116541 (Reckitt-Benckiser) are liquid detergent compositions with a water content between 20 and 50 wt .-%, which in one water-soluble or water-dispersible material are packaged, at least a polyphosphate builder have and by a certain ratio of those contained in the agent Potassium and sodium ions are labeled.

Despite of the numerous publications in the field of detergents or cleaning agents continues to exist a need after improving the cleaning performance of these agents, in particular while maintaining or reducing the per wash or wash cycle Amounts of substances active in washing or cleaning. There is also a need the amount of packaging and packaging of these funds non-active washing or cleaning materials (e.g. water-soluble or non-water soluble To reduce polymer films in the outer packaging).

task The present application was to provide a method for the production of quickly soluble High density detergents or cleaning agents. The procedure should with a high throughput of detergent tablets high breaking strength and novel optics. The resulting In particular, no or only detergents or cleaning agents should be used require a reduced additional outer packaging. Furthermore, one should novel form of assembly for Detergents or cleaning agents are provided, which are across from usual Ready-made shapes through improved washing or cleaning performance distinguished.

It has now been found that quickly soluble laundry detergent or cleaning product tablets with high Have the hardness and even, shiny surface produced using a casting process in which the washing or cleaning active preparation is degassed after casting and before solidification.

• a) Gießen einer wasch- oder reinigungsaktiven Zubereitung in die Aufnahmemulde eines Formwerkzeugs;
• b) Entgasen der wasch- oder reinigungsaktiven Aktivsubstanzmischung.

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 recess of a mold;
• b) degassing the washing or cleaning active mixture of active substances.

By the degassing of the washing or cleaning active preparation could not just an increase in average fracture hardness the cast body be achieved, in particular an improvement in optical effect of this body achieved. The process according to the invention manufactured body draw wise on their surface none due to gas inclusions caused bumps or holes on. Still have the body dependent on from that for the degassing process also used in comparison with after usual casting process Manufactured detergent tablets with smooth top.

to Degassing is suitable for various procedures. In addition to vibration these are in particular the action of a vacuum, of ultrasound or warmth on the pourable washable or active cleaning preparation. Within the scope of the present application degassing by vibration of the mold is preferred.

As "vibration" or "vibration" is within the scope of the present application denotes a periodic process, in which the mold is moved back and forth within certain limits. The vibration can be in both horizontal and vertical Direction. Methods in which horizontal ones are preferred and superimpose vertical vibrations. In preferred methods according to the invention the mold vibrates accordingly in a horizontal manner 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. The amplitude the vibration movement is in a preferred embodiment of the present invention in the horizontal direction less than 10 cm, preferably less than 7 cm, particularly preferably less than 4 cm and in particular less than 2 cm. The amplitude is in the vertical direction the vibration movement is preferably less than 4 cm, especially preferably less than 2 cm and in particular less than 1 cm.

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

In A preferred variant of the method according to the invention is amplitude and / or frequency of the vibration used is continuously adjustable. Through a stepless regulation of amplitude and / or frequency the vibration movement can easily meet the requirements the respective processed active washing or cleaning preparation customized become. The need for Such adjustments can occur, for example, when the recipe changes or changes in the process temperature (e.g .: temperature of the poured washing or cleaning active Preparation; outside temperature during production). Within the scope of the present application are the amplitude and frequency of those used for degassing Vibration during the degassing is preferably constant. However, it can also be advantageous, the amplitude and / or the frequency of the vibration while to change the degassing. Procedures in which the amplitude and / or frequency of vibration while the degassing change are preferred according to the invention. It is conceivable, for example, that at a constant frequency Vibration amplitude increases or increases. However, procedures can also be carried out where the frequency of the vibration increases at a constant amplitude or is reduced. Procedures in which during the degassing process constant amplitude the frequency of the vibration is increased are particularly preferred in the context of the present application.

Next the vibration described above are also suitable to create a Negative pressure, exposure to ultrasound or exposure of warmth for degassing the poured active washing or cleaning preparation.

In a preferred embodiment of the method according to the invention degassing takes place by applying a negative pressure. In this Process variants, pressures below 900 mbar are preferred maintenance 700 mbar, particularly preferably below 500 mbar, entirely particularly preferably below 300 mbar and in particular below 100 mbar used for degassing. The amount of vacuum used will, for example, depend on the viscosity of the washing or active cleaning preparation as well as at the boiling temperature contained in this active washing or cleaning preparation Active substances (e.g. non-aqueous Solvent) orientate. While it is generally preferred to degas the washing or active cleaning preparation the simultaneous evaporation easily volatile Avoiding ingredients, on the other hand, can cause such evaporation in special processes for degassing the washing or active cleaning preparations are used (drag effect). To generate the for the degassing of the washing or cleaning-active preparation required negative pressure are all suitable for the specialist pumps known for these purposes, in particular those for a rough vacuum above usable water jet, liquid steam, Water ring and Piston pumps. But can be used for example also rotary valve, gate valve, trochoid and Sorption pumps. as well as so-called roots blowers and cryopumps. For setting of a fine vacuum are, in particular, rotary vane pumps, diffusion pumps, Roots blower, positive displacement, Turbomolecular, sorption, ion getter pumps (getters) suitable.

In Another preferred process variant is the degassing by exposure to ultrasound. Ultrasound is within the scope the present application the name for sound, its frequencies above the human listening area (approx. 16 Hz – 20 kHz) and are below 109 Hz; Sound with frequencies greater than 109 Hz is called hypersonic. For the generation of ultrasound can mechanical or electrical vibrators are used. Because the strength the ultrasound is influenced by the transport medium, the absorption of sound generally increases with the number of vibrations at, the strength of ultrasound in the use according to the invention, preferably the selected Recipe adapted to the active washing or cleaning preparation. at degassing by ultrasound is particularly important to note that by the ultrasound absorption causes (local) heating of the medium, which to deactivate individual ingredients of the washing or cleaning active Carry out preparation can. In a preferred embodiment of the present invention contain the washing or cleaning active to be degassed Preparation therefore no enzymes and / or fragrances and / or dyes and / or bleaching agents and / or bleach activators.

Finally, can the degassing of the washing or cleaning active preparation in one another preferred method variant also by the action of Heat. Because of the heat can the viscosity of the active washing or cleaning preparation and thus reduced the escape of enclosed gas bubbles from this preparation be accelerated. Just like with the action of ultrasound can by warming the active washing or cleaning preparation also vaporizes easily volatile Ingredients favored during the course of this process, the preparation is also degassed is achieved. The temperatures reached during 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 especially in the range of 55 to 120 ° C. Heating the washing or cleaning active Preparation is preferably by heat radiation and / or hot air and / or realized by heating the molds.

The inventive method is suitable, for example, in the embodiments described so far for the production of compact cast detergent tablets. in the Connection to the Degassing or in the course of degassing, the cast washing or active cleaning preparation, however, also brought into shape become. The deformable, poured active washing or cleaning preparation in the mold forming a hollow shape.

The Manufacturing the hollow mold in step can be done using different techniques respectively. In the simplest case, a flowable mixture is transformed into an appropriate one Filled in the form, harden there left and then removed from the mold. The disadvantage here is the design of the shape, because the desired wall thickness the resulting hollow body a quick filling complicated geometries.

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 solidifies 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 be carried out before demolding respectively; filling during the solidification process is also possible.

• a) Gießen einer wasch- oder reinigungsaktiven Zubereitung in die Aufnahmemulde eines Formwerkzeugs;
• b) Entgasen der wasch- oder reinigungsaktiven Aktivsubstanzmischung;
• c) Wenden des Formwerkzeugs und Ausgießen überschüssiger wasch- oder reinigungsaktiver Zubereitung.

Preferred embodiments 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 recess of a mold;
• 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.

In dependence the mold is turned by the solidification mechanism preferably after a time t between 0 and 20 minutes, preferably after a time t between 1 and 17 minutes, particularly preferred after a time between 2 and 14 minutes, very particularly preferred between 3 and 11 minutes and in particular between 4 and 8 minutes.

• a) wasch- oder reinigungsaktiven Zubereitung in die Aufnahmemulde eines Formwerkzeugs gegossen wird;
• b) die wasch- oder reinigungsaktive Zubereitung entgast wird;
• c) die wasch- oder reinigungsaktive Zubereitung durch einen Stempel an die Wände der Aufnahmemulde gedrängt und so eine Hohlform hergestellt wird;

sind demnach ebenfalls bevorzugt. Besonders vorteilhaft bei dieser Verfahrensführung, die auch als "cold stamp-Methode" bezeichnet wird, ist die Möglichkeit, auch große Stückzahlen mit genau definierter Wandstärke der Hohlkörper herzustellen. Zudem ist das Verfahren weitgehend unempfindlich gegen schwankende Fließeigenschaften und auch bei höherviskosen Mischungen anwendbar. In einer bevorzugten Ausführungsform dieser bevorzugten Verfahrensvariante wird ein gekühlter Stempel eingesetzt. Die Temperatur dieses gekühlten Stempels beträgt vorzugsweise zwischen 5 und 20°C, besonders bevorzugt zwischen 8 und 19°C, ganz besonders bevorzugt zwischen 11 und 18°C und insbesondere zwischen 14 und 17°C.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 a kind of intermediate form between the "pouring technique" and the casting technique in negative forms of the hollow body. Corresponding processes in which for the production of a cast body from a washing or cleaning active preparation

• a) washing or cleaning-active preparation is poured into the receiving recess of a molding tool;
• 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 The methods described above are particularly suitable for hollow body to produce which have a shape without undercuts, thus have the shape of a "bowl". These "bowls" can be filled and optionally be closed. The resulting hollow bodies can have two, three, four or more individual recesses, which are preferably separated from one another by cast webs.

Regarding The shape of the shells is no limit for the expert in the selection set. From the hemisphere angular ("cardboard-like") shells up to to complex structures with a pronounced surface structure (e.g. in form of nutshells or animal forms) are all hollow body produced.

During or after solidification, in a preferred process variant according to the invention by turning or displacing them generated hollow bodies the one hanging out of the mold Noses or edges solidified washing or cleaning active preparation by knife cut or scraped and / or removed with a roller. In a particularly preferred embodiment of the method according to the invention are used for cutting or scrapers or rollers heated knives or Scraper or roller used. The temperature of this heated Knife, scraper or roller preferably at least 35 ° C, preferably at least 45 ° C and especially between 50 and 90 ° C.

• a) eine wasch- oder reinigungsaktiven Zubereitung in eine schließbare Doppelform gegossen wird; und
• b) die wasch- oder reinigungsaktive Zubereitung entgast wird.

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 washing or cleaning active preparation, in which

• a) a washing or cleaning active preparation is poured into a closable double mold; and
• b) the washing or cleaning active preparation is degassed.

The preparations that are active in washing or cleaning are preferred embodiment of the method according to the invention degassed and into a hollow body brought into shape. Subsequent solidification of the washing or cleaning active Preparations provides a stable shape after being brought into shape Mold. "Frozen" marks it any curing mechanism within the scope of the present invention which from a deformable, preferably flowable mixture or such Substance or such a mass solid at room temperature body delivers without pressing or Kompaktierkräfte are necessary. "Freeze" in the sense of the present The invention is therefore, for example, the curing of melts at Substances solid at room temperature by cooling. "Solidification processes" in the sense of the present application are also curing formable masses due to time-delayed water binding, by Evaporation of solvents, through chemical reaction, crystallization etc. as well as the reactive hardening of flowable powder mixtures to stable hollow bodies.

In summary are methods according to the invention preferred, in which the cast body, preferably the open one Hollow form, due to delayed Water retention, by cooling below the melting point, by evaporation of solvents, by crystallization, by chemical reaction (s), especially polymerization, by change the rheological properties e.g. by changing shear, by sintering or by radiation curing, especially produced by UV, alpha beta or gamma rays becomes.

in the Processes are preferred within the scope of the present application which the solidification of the cast body by cooling under the melting point occurs. The cooling below the melting point, for example, by heat emission to the environment, especially to the mold. Especially however, it is preferred to give off heat by using a cooling medium to support. Accordingly, such methods according to the invention are particularly preferred where the mold is cooled becomes. As a cooling medium (dried) cold air, dry ice or liquid nitrogen. With particular preference, however, circulating, preferably liquid coolant used. The cooling the mold is preferably carried out at 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 Another preferred process variant is used for cooling Temperatures between 5 and 20 ° C, particularly preferred at temperatures between 8 and 19 ° C, very particularly preferably at temperatures between 11 and 18 ° C and in particular at 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 detergent or cleaning agent ingredients or precursors thereof can also be introduced into the hollow body. The following substances or classes of substances may be mentioned 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, disintegration auxiliaries and Disintegrants, sulfates, phosphates, perborates, carboxymethyl cellulose (CMC), LAS powder (linear alkylbenzenesulfonates), 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 above-mentioned production stages in the physical states mentioned) can also be used, for example, to dry or to be absorbed on carriers.

in the Connection to the filling the open mold can be closed. This is with liquid or pasty fillings necessary to prevent the filling from leaking before use prevent. For fillings, which remain firmly in the mold, can be closed No form if desired is. A closing can also in such cases out of aesthetic establish be displayed.

The optional closing the hollow shape can be done in different ways. For molded articles with Bunghole can do this, for example, by inserting a suitable one Partially closed. Open hollow forms in the form of hollow bodies without Undercuts can closed with foils or after filling with other material for the Poured over the hollow form become. The optional closing with foils is described below.

The Foil covering the openings) of the hollow molds) gets to the surface the hollow form applied and firmly connected to what for example by gluing, partial melting or by chemical reaction can take place. It is possible to apply the film to all surfaces of the Hollow shape (not just over the opening) apply and bond firmly with it, so that the film a coating, a "coating" of the entire molded body. Preferred manufactured according to the invention Detergent and cleaning agent portions are, however, characterized by that the Do not film the entire molded body encloses.

Out establish process economics and the aesthetic It is impressively preferred that the Film is only applied in such a way that it fulfills a function, i.e. closing the hollow shape serves.

The closes Foil can of course also a laminate of several different compositions Slides be about different compositions of individual film layers can open the Hollow mold at certain times in the washing and cleaning cycle be released.

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

preferred Film materials are the polymers known from the prior art. In particular, films are preferred which are made of a polymer having 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, consist. With regard to the media, in the washing and cleaning agents usually detergent tablets are preferred, in which the film consists of a water-soluble polymer.

Such preferred polymers can synthetic or natural Be of origin. Are polymers on a native or part-native basis used as film material, film materials are made from one or several substances from the group Carrageenan, Guar, Pectin, Xanthan, cellulose and their derivatives, starch and their derivatives as well Gelatin preferred.

Further Polymers that can be used as film materials are synthetic polymers, which are preferably water-swellable and / or water-soluble. Such polymers on a synthetic basis for the desired Film permeability in storage and dissolution the film can be "tailor-made" when used. Especially preferred film materials are selected from a polymer or Polymer mixture, wherein the polymer or at least 50 wt .-% of Polymer mixture selected is made of polyvinyl alcohol.

• a) Gießen einer wasch- oder reinigungsaktiven Zubereitung in die Aufnahmemulde eines Formwerkzeugs;
• b) Entgasen der wasch- oder reinigungsaktiven Aktivsubstanzmischung;
• c) In Form bringen der wasch- oder reinigungsaktiven Zubereitung unter Ausbildung eines Hohlkörpers;
• d) Befüllen des Hohlkörpers mit einer weiteren wasch- oder reinigungsaktiven Zubereitung;
• e) Verschließen des Hohlkörpers.

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 recess of a mold;
• 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.

• i) 10 bis 85 Gew.-% Dispersionsmittel und
• ii) 15 bis 90 Gew.-% dispergierte Stoffe

enthalten, besonders bevorzugt werden.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 dispersing agent, dispersions being based on their total weight

• i) 10 to 85 wt .-% dispersant and
• ii) 15 to 90% by weight of dispersed substances

contain, are particularly preferred.

As In this application, dispersion becomes a system of several phases designated one of which is continuous (dispersant) and at least one other is finely divided (dispersed substances).

Especially preferred washing according to the invention or cleaning-active preparations are characterized in that that she the dispersant in amounts above 11% by weight, preferably above 13% by weight, particularly preferably above 15% by weight, entirely particularly preferably above 17% by weight and in particular above 19% by weight, based in each case on the total weight of the dispersion, contain. Dispersions which are also preferably used a dispersion with a weight fraction of dispersant above 20% by weight, preferably above 21% by weight and in particular above 22% by weight, based in each case on the total weight of the dispersion, exhibit. The maximum content of dispersants in preferred dispersions is, based on the total weight of the dispersion, preferably less than 63% by weight, preferably less than 57% by weight, particularly preferred less than 52% by weight, very particularly preferably less than 47% by weight and in particular less than 37% by weight. As part of the present In particular, such washing or cleaning active Preparations based on their total weight, dispersing agents in amounts from 12 to 62% by weight, preferably from 14 to 49% by weight and in particular contain from 16 to 38% by weight. Particularly preferred are dispersions containing dispersant between 16 and 30 wt .-%, preferably between 16 and 26 wt .-% and in particular between 16 and 22% by weight, based in each case on the total weight the dispersion.

The Dispersants used are preferably water-soluble or water-dispersible. The solubility this dispersant is at 25 ° C preferably more than 200 g / l, more 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.

As Dispersing agents are suitable in the context of the present invention preferably the water-soluble ones or water-dispersible polymers, especially the water-soluble ones or water-dispersible nonionic polymers. With the dispersant can be both a single polymer and mixtures different water soluble or water-dispersible polymers. In another preferred embodiment The present invention consists of the dispersant or at least 50% by weight of the polymer mixture of water-soluble or water-dispersible non-ionic polymers from the group of polyvinylpyrrolidones, Vinyl pyrrolidone / vinyl ester copolymers, cellulose ethers, polyvinyl alcohols, Polyalkylene glycols, especially polyethylene glycol and / or polypropylene glycol.

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

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

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

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

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

The vinyl esters are polymerized by free radicals using different 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).

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

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

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 approximately 500-2500 (corresponding to molar masses of approximately 20,000-100,000 g / mol) and have different degrees of hydrolysis from 98-99 and 87-89 mole%. 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- (O-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 immediately after the hyphen is followed by a number which corresponds to the number n in the formula VII mentioned above. 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.

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

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

Especially dispersions are preferably used as dispersing agents a nonionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol contain, the weight fraction of the poly (ethylene) glycol on Total weight of all dispersants preferably between 10 and 90% by weight, particularly preferably between 30 and 80% by weight and in particular is between 50 and 70% by weight. Dispersions in which the dispersant is particularly preferred more than 92% by weight, preferably more than 94% by weight, particularly preferably more than 96% by weight, very particularly preferably more as 98% by weight and in particular 100% by weight of a poly (alkylene) glycol, there is preferably poly (ethylene) glycol and / or poly (propylene) glycol, especially poly (ethylene) glycol. Dispersant, which in addition to poly (ethylene) glycol also contain poly (propylene) glycol, preferably have a ratio the parts by weight of poly (ethylene) glycol to poly (propylene) glycol 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 on.

Further preferred dispersants are the nonionic surfactants, which both alone, but particularly preferably in combination with one nonionic polymer can be used. Detailed designs on the usable nonionic surfactants can be found in the framework the description of washing or cleaning active substances below.

Prefers Dispersions used are characterized in that at least a dispersing agent has a melting point above 25 ° C, preferably above 35 ° C and especially above 40 ° C having. The use of dispersants is particularly preferred 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, these dispersants, based on the total weight of the dispersant 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.

As dispersed substances are suitable in the context of the present application all substances with active washing or cleaning activity at room temperature, in particular, however, washing or cleaning active substances the group of builders (Builder and Cobuilder), the wash- or cleaning-active polymers, bleaching agents, bleach activators, glass corrosion inhibitors, the silver protection agents and / or the enzymes. A more detailed description these ingredients can be found below in the text.

The Water content of preferably in the process according to the invention dispersions used, 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% by weight. Preferred according to the invention Disperisonen used are low in water or anhydrous. Especially Disperison used with preference are characterized by that she based on their total weight, a level of free water below 10 wt .-%, preferably below 7 wt .-%, particularly preferred below 3% by weight and in particular below 1% by weight.

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. Preferred methods 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 processes according to the invention are therefore characterized in that the dispersion has a density between 1,050 and 1,670 g / cm ³ , preferably between 1,120 and 1,610 g / cm3, particularly preferably between 1,210 and 1,570 g / cm ³ , very particularly preferably between 1,290 and 1,510 g / cm ³ , and in particular between 1.340 and 1.480 g / cm ^3. The information on the density relates in each case to the densities of the compositions 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 .

Preferred according to the invention Draw dispersions used as washing or cleaning active preparation is characterized by the fact that it in water (40 ° C) in less than 9 minutes, preferably less than 7 minutes in less than 6 minutes, particularly preferably in less than 5 minutes and especially dissolve in less than 4 minutes. To determine the solubility 20 g of the dispersion in the interior of a dishwasher (Rent G 646 PLUS). It becomes the main wash cycle of a standard wash program (45 ° C) started. The determination of solubility is done by measuring the conductivity, which is measured over a conductivity sensor is recorded. The release process is when the conductivity maximum is reached completed. In the conductivity diagram this maximum corresponds to a plateau. The conductivity measurement starts with the circulation pump in the main wash cycle. The amount of water used 5 liters.

The in the method according to the invention processed active washing or cleaning preparations and / or in a preferred process variant into those produced according to the invention hollow body filled Substances or mixtures of substances contain one or more common components of washing and cleaning agents, preferably from the group of builders, Surfactants, polymers, bleaches, 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 Active substances, germicides, fungicides, antioxidants, 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

To the builders counting in the context of the present application, in particular the zeolites, Silicates, carbonates, organic cobuilders and - where no ecological prejudices against their use persist - too the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. 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 O ₅ .yH ₂ O are preferred.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The dissolution delay compared to conventional amorphous sodium silicates can be done in various ways, for example by surface treatment; Compounding, compacting / compaction or caused 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 the sharp X-ray reflections that are typical of 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 deliver 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 In the context of the present invention, it is preferred that this 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% by weight, in each case based on the weight of the detergent or cleaning agent.

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 O _{2x + 1} .yH ₂ O, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, is preferably from 1: 9 to 4, and y is a number from 0 to 33. The crystalline layered silicates of the formula NaMSi _x O _{2x + 1} · yH ₂ O are sold, for example, by Clariant GmbH (Germany) under the trade name Na-SKS, for example Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ · xH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, Magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 ( Na ₂ Si ₄ O ₉ .xH ₂ O, makatite).

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 Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ ) are particularly suitable · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3H ₂ O, kanemite), Na-SKS-11 (t-Na ₂ Si ₂ O ₅₎ and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ).

If the silicates are used as a component of automatic dishwashing detergents, in the context of the present application these detergents contain a proportion by weight of the crystalline layered silicate of the formula NaMSi _x O _{2x + 1} .yH ₂ O of 0.1 to 20% by weight, preferably of 0 , 2 to 15 wt .-% and in particular from 0.4 to 10 wt .-%, each based on the total weight of these agents. 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 O _{2x + 1} · yH ₂ O.

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 within the scope of the present invention, for example, a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula n Na ₂ O · (1-n) K ₂ O · Al ₂ O ₃ · (2–2.5) SiO ₂ · (3.5–5.5) H ₂ O can be described. The zeolite can be used 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 goes without saying it is also possible to use the generally known phosphates as builder substances, provided that such use is not avoided for ecological reasons should be. This applies in particular to the use of agents according to the invention as automatic dishwashing detergent, which is particularly preferred in the context of the present application is. Among the large number of commercially available phosphates Alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) in the washing and Detergent industry the most important.

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

Suitable phosphates are, for example, sodium dihydrogen phosphate, NaH ₂ PO ₄ , in the form of the dihydrate (density 1.91 gcm ^-3 , melting point 60 °) or in the form of the monohydrate (density 2.04 gcm ^-3 ), the disodium hydrogen phosphate (secondary sodium phosphate) , Na ₂ HPO ₄ , which is anhydrous or with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm, melting point 48 ° with loss of 5 H ₂ O) and 12 mol Water (density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) can be used, but especially the trisodium phosphate (tertiary sodium phosphate) Na ₃ PO ₄ , which is used as dodecahydrate, as decahydrate (corresponding to 19-20 % P ₂ O ₅ ) and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) can be used.

Another preferred phosphate is tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ . Also preferred are the tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , which is given in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° under water loss) exists, as well as the corresponding potassium salt potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ .

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO 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 ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. The corresponding potassium salt, pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), comes for example in the form of a 50% by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

This are accurate according to the invention such as sodium tripolyphosphate, potassium tripolyphosphate or mixtures usable from these two; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and are potassium tripolyphosphate and sodium potassium tripolyphosphate usable according to the invention.

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

Prefers it is especially 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 to use. It is particularly preferred to use exclusively potassium tripolyphosphate without using other phosphates.

Further builders are the alkali carriers. As an alkali carrier apply, for example, alkali metal hydroxides, alkali metal carbonates, Alkali metal bicarbonates, alkali metal sesquicarbonates, the mentioned alkali silicates, alkali metasilicates, and mixtures of aforementioned substances, the preferred in the sense of this invention Alkali carbonates, especially sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate can be used. Particularly preferred is a builder system containing a mixture of tripolyphosphate and Sodium. A builder system is also particularly preferred containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate. Because of their comparison with other builder substances low chemical compatibility with the rest The ingredients of detergents or cleaning agents are the alkali metal hydroxides preferably 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 are based on their total weight are particularly preferred less than 0.5% by weight and especially no alkali metal hydroxides contain.

Especially preference is given to the use of 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. Be particularly preferred Means, which are based on the weight of the detergent or cleaning agent (i.e. the total weight of the combination product without packaging) less than 20% by weight, preferably less than 17% by weight, preferred less than 13% by weight and in particular less than 9% by weight carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonates, particularly preferably contain sodium carbonate.

As Organic cobuilders are in particular polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) as well as to name phosphonates. These classes of substances are as follows described.

useful organic builders are, for example, those that can be used in the form of their sodium salts polycarboxylic being under polycarboxylic acids such carboxylic acids can be understood that carry more than one acid function. For example these are citric acid, adipic acid, Succinic acid, Glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), unless such use for ecological reasons objectionable, and mixtures of these. Preferred salts are the salts of polycarboxylic acids like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, sugar acids and mixtures of these.

Also the acids can in itself be used. The acids In addition to their builder effect, they typically also have the property an acidifying component and thus also serve to set a lower and milder one pH value of detergents or cleaning agents. In particular, here are citric acid, Succinic acid, glutaric, adipic acid, gluconic and to name any mixtures of these.

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 molecule mass from 500 to 70000 g / mol.

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

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

Suitable are also copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid have been particularly suitable maleic proven to contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative molecular mass, 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 can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in washing or cleaning agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

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

In particular biodegradable polymers of more than two are also preferred various monomer units, for example those used as monomers Acrylic acid salts and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Acrylic acid salts and 2-alkylallylsulfonic acid as well as sugar derivatives.

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

As well are further preferred builder substances are polymeric aminodicarboxylic acids Salts or their precursors to call. Polyaspartic acids or their salts and.

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

Further Suitable organic builder substances are dextrins, for example Oligomers or polymers of carbohydrates by partial Hydrolysis of starches can be obtained. The hydrolysis can be carried out according to the usual for example acid or enzyme-catalyzed processes. Preferably acts are hydrolysis products with average molecular weights in the range from 400 to 500000 g / mol. There is a polysaccharide with one Dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, are preferred, where DE is a common one Measure of the reducing Effect of a polysaccharide compared to dextrose, which a DE of 100 has. Both maltodextrins can be used 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.

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

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

Further Organic cobuilders that can be used are, for example, acetylated ones hydroxy or: their salts, which may also be in lactone form can and which have at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups contain.

A phosphonates represent another class of substances with cobuilder properties It is particularly hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder. It is preferred used as the sodium salt, the disodium salt being neutral and the tetrasodium salt is alkaline (pH 9). As aminoalkane phosphonates come preferably ethylenediaminetetramethylene phosphonate (EDTMP), Diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reactions Sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta- and octa sodium salt the DTPMP. As a builder, the class becomes the Phosphonates preferably used HEDP. The aminoalkane phosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the agent also bleach contain, be preferred, aminoalkanephosphonates, in particular DTPMP, to use, or to use mixtures of the phosphonates mentioned.

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

surfactants

to In addition to the nonionic surfactants, the group of surfactants will continue to be used the anionic, cationic and amphoteric surfactants counted.

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 fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical 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.

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

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, Ndimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The 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.

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

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C₁–₄-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder Propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula

in 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 is or an oxyalkyl group having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl groups being preferred, and [Z] is a linear polyhydroxyalkyl residue, whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this remainder.

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

Low-foaming nonionic surfactants are used as preferred surfactants. The cleaning agents according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical 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 particular nonionic surfactants which have a melting point above are preferred Have room temperature, with nonionic surfactants with a Melting point above 20 ° C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, 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 are solid at room temperature or can be highly viscous. 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.

Prefers nonionic surfactants to be used as solid at room temperature originate from the groups of alkoxylated nonionic surfactants, especially ethoxylated ones primary Alcohols and mixtures of these surfactants with structurally complicated built-up surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants stand out beyond that through good foam control.

In a preferred embodiment The present invention is the nonionic surfactant with a Melting point above room temperature an ethoxylated nonionic surfactant, that from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferred at least 15 moles, especially at least 20 moles of ethylene oxide per Mol alcohol or alkylphenol has emerged.

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

Accordingly, particularly preferred ethoxylated nonionic surfactants obtained from C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol, of ethylene oxide per mol of alcohol were.

The Nonionic surfactant which is solid at room temperature preferably has additional propylene oxide units in the molecule. Such PO units preferably make 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 additionally Have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules makes preferably more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight such non-ionic surfactants. Preferred dishwashing detergents are characterized in that that she 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 make up 15% by weight of the total molecular weight of the nonionic surfactant, contain.

Further nonionic surfactants with melting points to be used with particular preference above 40 to 70% contain a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants 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 ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _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 O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} N 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 for throws 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 O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 represents} H and x assumes values from 6 to 15.

If the latter statements are summarized, the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 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, preferably with surfactants of the type R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² in which x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃; -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.In the context of the present 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)

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 being from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol are preferred. Alcohols accessible from synthetic sources are, for example, Guerbet alcohols or residues which are methyl-branched in the 2-position or linear and methyl-branched residues in a mixture, as are usually present in oxo alcohol residues. 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 O [CH ₂ CH (R ³ ) O] _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 O [CH ₂ CH ₂ O] _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.

In particular, those end group-capped poly (oxyalkylated) nonionic surfactants which are of the formula (VI) R ¹ O [CH ₂ CH ₂ O] _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 (O) CH ₂ with an ethoxylated alcohol of the formula R ¹ O [CH ₂ CH ₂ O] _x-1 CH ₂ CH ₂ OH obtained.

The specified C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the aforementioned Nonionic surfactants represent statistical mean values that are required for a specific Product can be an integer or a fractional number. by virtue of The manufacturing process consists of commercial products of the formulas mentioned mostly not from an individual representative, but from mixtures, whereby both for the C chain lengths for as well the degrees of ethoxylation or degrees of alkoxylation mean values and resulting in fractional numbers.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. 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.

Further suitable anionic surfactants are sulfonated fatty acid glycerol esters. Among fatty acid glycerol esters are the mono-, di- and triesters and their mixtures to understand how they in the manufacture by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerin be preserved. Preferred sulfonated fatty acid glycerol esters are included the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or Behenic acid.

As alk (en) yl sulfates are the alkali and especially 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 ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 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 of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of 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 alk (en) yl chain or salts thereof.

As other anionic surfactants are particularly suitable for soaps. Saturated fatty acid soaps are suitable, like the salts of lauric acid, myristic, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and especially from natural ones fatty acids, e.g. Coconut, palm kernel or tallow derived soap mixtures.

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

are the anionic surfactants a component of automatic dishwashing detergents, so is their content, based on the total weight of the compositions, is preferred less than 4% by weight, preferably less than 2% by weight and very particularly preferably less than 1% by weight. Machine dishwashing liquid, which do not contain anionic surfactants are particularly preferred.

On Site of the surfactants mentioned or in connection with them can also cationic and / or amphoteric surfactants are used.

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

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

In automatic dishwashing detergent, is the content of cationic and / or amphoteric surfactants is preferred 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. Machine dishwashing liquid, which do not contain cationic or amphoteric surfactants particularly preferred.

polymers

to Count group of polymers in particular the washing or cleaning active polymers, for example the rinse aid polymers and / or as a softener effective polymers. Generally are in washing or cleaning agents in addition to nonionic polymers also cationic, anionic and amphoteric polymers can be used.

As softeners effective polymers are, for example, those containing sulfonic acid groups Polymers, which are used with particular preference.

Especially preferred as containing sulphonic acid groups Copolymers of unsaturated carboxylic acids containing sulfonic acid groups can be used as polymers Monomers and optionally other ionic or nonionic Monomers.

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-SO 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 (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas XIa, XIb and / or XIc, H ₂ C = CH-X-SO ₃ H (XIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (XIb), HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XIc), in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) 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 (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₂ CH ₃ ) in formula XIa), 2-acrylamido-2-propanesulfonic acid (X = -C ( O) NH-C (CH ₃ ) ₂ in formula XIa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula XIa), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula XIb), 3-methacrylamido-2-hydroxy-propanesulfonic acid (X = -C (O) NH-CH ₂ CH (OH) CH ₂ - in formula XIb), allylsulfonic acid (X = CH ₂ in formula XIIa), methallylsulfonic acid (X = CH ₂ in formula XIb), allyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula XIa), methallyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula XIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid (X = CH ₂ in formula XIb), styrene sulfonic acid (X = C ₆ H ₄ in formula XIa), vinyl sulfonic acid (X not present in formula XIa), 3-sulfopropylacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in Formula XIa), 3-su Isopropyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula XIb), sulfomethacrylamide (X = -C (O) NH- in formula XIb), sulfomethyl methacrylamide (X = -C (O) NH- CH ₂ - in formula XIb) and water-soluble salts of the acids mentioned.

As other ionic or nonionic monomers come in particular ethylenically unsaturated compounds into consideration. Preferably is the content of those used according to the invention Polymers to monomers of group iii) less than 20 wt .-%, based on the polymer. Polymers to be used with particular preference only from monomers of groups i) and ii).

• i) ungesättigten Carbonsäuren der Formel X. R¹(R²)C=C(R³)COOH (X),in der R¹ bis R³ unabhängig voneinander für -H-CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOH⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,
• ii) Sulfonsäuregruppen-haltigen Monomeren der Formel XI R⁵(R⁶)C=C(R⁷)-X-SO₃H (XI), in der R⁵ bis R⁷ unabhängig voneinander für -H-CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)
• iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

besonders bevorzugt.In summary, copolymers are made of

• i) unsaturated carboxylic acids of 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 -COOH 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-SO 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 (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ )
• iii) optionally further ionic or nonionic monomers

particularly preferred.

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

Other 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 XIa, XIb and / or XIc containing sulfonic acid groups: H ₂ C = CH-X-SO ₃ H (XIa), H ₂ C = C (CH ₃ ) -X-SO ₃ H (XIb), HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XIc), in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) 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 (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -
• iii) optionally further ionic or nonionic monomers.

The Copolymers can the monomers from groups i) and ii) and, if appropriate, iii) Contained in varying amounts, with all representatives from the group i) with all Representatives from group ii) and all representatives from the Group iii) can be combined. 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 (O) -Y-SO ₃ H] _p - (XII), contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) with n = 0 to 4, represents -O- (C ₆ H ₄ ) -, represents -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , 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 (O) -Y-SO 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, spacer groups in which Y represents -O - (CH ₂ ) _n - with n = 0 to 4, represents -O- (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 (O) -Y-SO 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, spacer groups in which Y represents -O- (CH ₂ ) with n = 0 to 4, represents -O- (C ₆ H ₄ ) -, represents -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , just as preferred as copolymers, of structural units of the formula XV - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO 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 hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O - (CH ₂ ) _n - with n = 0 to 4, represents -O- (C ₆ H ₄ ) -, represents -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - ,

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

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 (O) -Y-SO ₃ H] _p - (XII), - [CH ₂ -C (CH ₃ ) COOH) _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XIII), - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XIV), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XV), - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XVI), - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO 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 -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands.

In the polymers can the sulfonic acid groups are wholly or partly in neutralized form, i.e. that the acid Hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups against metal ions, preferably alkali metal ions and in particular can be exchanged for sodium ions. The use of partially or fully neutralized sulfonic acid groups Copolymers are preferred according to the invention.

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

at Terpolymers are particularly preferred those that 20 to 85 wt .-% Monomer from group i), 10 to 60% by weight monomer from the group ii) and 5 to 30% by weight of monomer from group iii).

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

With amphoteric or cationic polymers continue to be particularly preferred used. These particularly preferred polymers are characterized in that that she have at least one positive charge. Such polymers are preferably water soluble or water dispersible, that is, they exhibit in water 25 ° C one solubility 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 (O) NH (CH ₂ ) ₂ N ⁺ ( CH ₃ ) ₃ X ^- ), methacrylamidopropyl (trimethyl) ammonium salts (R ¹ and R ² = H, R ³ = CH ₃ H, R ⁴ = C (O) 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.

Especially preferred amphoteric polymers contain derivatives as monomer units of diallylamine, especially dimethyldiallylammonium salt and / or Methacrylamidopropyl (trimethyl) ammonium salt, preferably in the form of chloride, bromide, iodide, hydroxide, phosphate, sulfate, hydrosulfate, Ethyl sulffasts, methyl sulfates, mesylates, tosylates, formates or Acetates in combination with monomer units from the group of the ethylenic unsaturated Carboxylic acids.

Bleaching agent Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water. Further usable bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, dipeiazelaic 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) the 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-phthalimidthanoic acid paproacidaproacidoxyhexanoic acid , o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebacinsäure, diperoxybrassylic acid, diperoxyphthalic acids, the 2-decyldiperoxybutane-1,4- diacid, N, N-terephthaloyl-di (6-aminopeicapronic acid) can be used.

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

Bleach activators

Bleach activators are used, for example, in detergents or cleaning agents, to improve cleaning at temperatures of 60 ° C and below To achieve bleaching effect. As bleach activators, compounds the aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid result can be used. Suitable substances are the O- and / or N-acyl groups of the above Number of carbon atoms and / or optionally substituted benzoyl groups wear. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 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 anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

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

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 _1-24 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 -O) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion.

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

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 -CNX ^- , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CNX ^- , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CNX ^- , (CH ₃ CH (CH ₃ ) ) ₃ N ⁽⁺⁾ CH ₂ -CNX ^- , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CNX ^{- are} particularly preferred, the cationic nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CNX ^- , in which X ^{- stands} for an anion which is selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate ,

As Bleach activators can continue compounds that are aliphatic under perhydrolysis conditions peroxycarboxylic with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid result can be used. Suitable substances are the O- and / or N-acyl groups of the above C number of carbon atoms and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine, are preferred (TAED), acylated triazine derivatives, in particular 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 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) and acetylated sorbitol and mannitol or their Mixtures (SORMAN), acylated sugar derivatives, especially pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. hydrophilic Substituted acylacetals and acyl lactams are also preferred used. Combinations of conventional bleach activators can also be used become.

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

Provided in addition to the nitrile quats, other bleach activators can be used are preferred, bleach activators from the group of multiple acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (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 up to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 up to 6% by weight, in each case based on the total weight of the bleach activator-containing Means 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 of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate in usual Amounts, preferably in an amount up to 5 wt .-%, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01 % By weight to 0.25% by weight, in each case based on the total weight of the agents containing bleach activator. But in special cases more bleach activator can also be used.

Glass corrosion inhibitors

Glass corrosion inhibitors prevent the appearance of cloudiness, Streaks and scratches but also the iridescence of the glass surface 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 used to prevent glass corrosion can be used 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 particularly insoluble zinc salts preferred according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn ₂ (OH) ₂ CO ₃ ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn ₃ (PO ₄ ) ₂ ), and zinc pyrophosphate (Zn ₂ (P ₂ O ₇ )).

The 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 wt .-%, each based on the total glass corrosion inhibitor-containing Means, effect. The exact content of the agent in the zinc salt or the zinc salts are naturally dependent on the type of zinc salts - each less soluble the zinc salt used, the higher its concentration should be to be in the middle.

There the insoluble Zinc salts during of the dishes cleaning process for the most part unchanged remain is the particle size of the salts a criterion to be observed so that the salts are not on glassware or machine parts stick. Means are preferred here in which the insoluble Zinc salts one particle size below Have 1.7 millimeters.

If the maximum particle size of the insoluble Zinc salts below 1.7 mm are insoluble residues in the dishwasher not to fear. Preferably the insoluble zinc salt an average particle size that is well below this value to make the hazard more insoluble Residues continue to increase minimize, for example an average particle size smaller 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. at very poorly soluble Zinc salts, the average particle size is preferably below 100 μm. For yet less soluble Salts can be even lower; for example, are very for that poorly soluble Zinc oxide mean particle sizes below of 100 μm prefers.

A further preferred class of compounds are magnesium and / or Zinc salts) of at least one monomeric and / or polymeric organic Acid. These also cause with repeated use, the surfaces of the glassware do not change corrosively, especially no cloudiness, Streaks or scratches but also no iridescence on the glass surfaces become.

Even though all magnesium and / or zinc salts) monomeric and / or polymeric organic acids used can be are, as described above, the magnesium and / or Zinc salts of monomeric and / or polymeric organic acids the groups of unbranched saturated or unsaturated Monocarboxylic acids, the branched saturated or unsaturated Monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, of sugar acids, of hydroxy acids, of oxo acids, of amino acids and / or the polymeric carboxylic acids prefers.

The Spectrum of the preferred according to the invention Zinc salts of organic acids, preferably organic carboxylic acids, ranges from salts that are difficult or insoluble in water, a solubility below 100 mg / L, preferably below 10 mg / L, in particular no solubility have up to such salts that are soluble in water above 100 mg / L, preferably above 500 mg / L, particularly preferred above 1 g / L and especially above 5 g / L (all solubilities at 20 ° C Water temperature). The first group of zinc salts include, for example the zinc citrate, zinc oleate and zinc stearate, to the group the soluble Zinc salts belong for example zinc formate, zinc acetate, zinc lactate and the 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 betaate and zinc oxalate are also coming Trains t.

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 dishes or the machine, especially in the area of automatic dishwashing Silver protection agents have a special meaning. Can be used the known substances of the prior art. Generally can before selected all silver protection from the group of triazoles, benzotriazoles, bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. To be used particularly preferably are benzotriazole and / or alkylaminotriazole. As examples of the preferred according to the invention 3-Amino-5-alkyl-1,2,4-triazoles to be used can be named: 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. In dishwashing detergents are the alkyl-amino-1,2,4-triazoles or their physiologically compatible Salts in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2 wt .-%, particularly preferably 0.01 to 0.04 wt .-% used. Preferred acids for the Salt formation is hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous Acid, organic carboxylic acids like vinegar, glycolic, citric, succinic acid. Very effective are 5-pentyl-, 5-heptyl-, 5-nonyl-, 5-undecyl-, 5-isononyl-, 5-versatic-10-acid-alkyl-3-amino-1,2,4-triazoles as well as mixtures of these substances.

you often finds active chlorine in cleaner formulations Means that can significantly reduce the corroding of the silver surface. In chlorine-free cleaners are especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, z. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Prefers here are the transition metal salts, that are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used for prevention corrosion on the wash ware be used.

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

The Metal salts or metal complexes used should at least partially soluble in water his. The counterions suitable for salt formation include all the usual ones one, two or three times negatively charged inorganic anions, z. B. oxide, sulfate, nitrate, fluoride, but also organic anions such as B. stearate.

metal complexes in the sense of the invention are compounds which have a central atom and one or more ligands and optionally additionally one or more of the above Anions exist. The central atom is one the above Metals in one of the above Oxidation states. The ligands are neutral molecules or anions that are monodentate or multidentate; the term "ligand" in the sense of the invention is e.g. in "Römpp Chemie Lexicon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, Page 2507 "explained in more detail. Complement each other the charge of the central atom and the charge in a metal complex of the ligand (s) is not zero, depending on whether a or there is an anionic excess charge, either one or more of the above Anions or one or more Cations, e.g. B. sodium, potassium, ammonium ions for charge balance. Suitable complexing agents are e.g. Citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.

The common in chemistry Definition 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 MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ and mixtures thereof. Preferred dishwasher detergents according to the invention are characterized in that the metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-Hydroxyethane-1,1-diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ .

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, the mixture of pentavalent and tetravalent vanadium (V ₂ O ₅ , VO ₂ , V ₂ O ₄ ) known from SO ₃ production (contact process) is suitable, as is that by diluting a Ti (SO ₄ ) ₂ - Solution of titanyl sulfate, TiOSO ₄ .

The inorganic redox-active substances, especially metal salts or metal complexes are preferably coated, i.e. completely with a waterproof but easily soluble at cleaning temperatures Material covered, to prevent their premature decomposition or oxidation during storage prevent. Preferred coating materials, which are produced by known processes, such as Sandwik melt coating processes from the food industry, are applied, paraffins, micro waxes, waxes are natural Origin such as carnauba wax, candella wax, beeswax, higher melting Alcohols such as hexadecanol, soaps or fatty acids. there the coating material, which is solid at room temperature, is melted State applied to the material to be coated, e.g. by fine-grained material to be coated in a continuous stream through a likewise continuously generated spray zone of the molten coating material is thrown. The melting point must be like this chosen be that yourself the coating material during the Silver treatment easily dissolves or melts quickly. The melting point should ideally be in the Range between 45 ° C and 65 ° C and preferably in the range of 50 ° C up to 60 ° C lie.

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

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 ^-6 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 lentus, subtilisin DY and the enzymes thermitase, proteinase K and that 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, Bagsværd, 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 lentus DSM 5483.

Further usable proteases are, for example, those under the trade names Durazym ^® , Relase ^® , Everlase ^® , Nafizym, Natalase ^® , Kannase ^® and Ovozymes ^® from Novozymes, those under the trade names, Purafect ^® , Purafect ^® OxP and Properase ^® from 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, which is sold under the trade names 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 B. amyloliquefaciens or from B. stearothermophilus and their further developments which are improved for use in detergents and cleaning agents. The enzyme from B. licheniformis is from Novozymes available under the name Termamyl ^® and from Genencor under the name Purastar ^® ST. 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 B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and variants derived from the α-amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes.

Furthermore are for for this purpose the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. 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 (3-glucanases. Suitable mannanases are, for example, under the names Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 L available from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, United States. the obtained from B. subtilis R-glucanase under the name Cereflo ^® from Novozymes available.

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 For example, enzymes are either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or according to known biotechnological processes produced by suitable microorganisms, such as transgenic Expression hosts of the genera Bacillus or filamentous fungi.

The Purification of the relevant enzymes is preferably carried out per se established processes, for example via precipitation, sedimentation, concentration, Filtration of the liquid Phases, microfiltration, ultrafiltration, exposure to chemicals, Deodorization or suitable combinations of these steps.

The Enzymes can used in any form established according to the state of the art become. This includes for example by granulation, extrusion or lyophilization obtained solid preparations or, especially with liquid or gel-shaped Means, solutions the enzymes, advantageously as concentrated as possible, low in water and / or mixed with stabilizers.

alternative can the enzymes for both the fixed as well for the liquid Dosage form are encapsulated, 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 enzymes as in a solidified gel or in a core-shell type in which a Enzyme-containing core coated with a protective layer impermeable to water, air and / or chemicals is. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or Dyes are applied. Such capsules are after known methods, for example by shaking or Roll granulation or applied in fluid-bed processes. Are advantageous granules of this type, for example by applying polymeric film formers, low dust and storage stable due to the coating.

Farther Is it possible, to assemble two or more enzymes so that a single Granulate multiple enzyme activities having.

On Protein and / or enzyme can protect against damage especially during storage such as inactivation, denaturation or decay, for example through physical influences, Oxidation or proteolytic cleavage are protected. With microbial Obtaining the proteins and / or enzymes is an inhibition of Proteolysis is particularly preferred, especially if the agents Proteases included. Agents according to the invention can stabilizers for this purpose contain; the provision of such means is preferred embodiment of the present invention.

A Group of stabilizers are reversible protease inhibitors. Become frequent Benzamidine hydrochloride, Borax, boric acids, boronic acids or their salts or esters are used, especially derivatives with aromatic groups, such as ortho-substituted, meta-substituted and para-substituted phenylboronic, or their salts or esters. As peptidic protease inhibitors include ovomucoid and leupeptin; a 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.

low aliphatic alcohols, but especially polyols, such as Glycerin, ethylene glycol, propylene glycol or sorbitol are further frequently Enzyme stabilizers used. Calcium salts are also used, such as calcium acetate or calcium formate, and magnesium salts.

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 agent and increase antioxidants the stability of the enzymes oxidative decay. A sulfur-containing reducing agent is, for example Sodium sulfite.

Prefers combinations of stabilizers are used, for example from 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 Salt. The effect of peptide-aldehyde stabilizers is due to the combination with boric acid and / or boric acid derivatives and polyols increased and by the additional use of divalent Cations, such as calcium ions further enhanced.

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

disintegration aid

Around the disintegration of prefabricated moldings to facilitate it is possible Disintegration aids, so-called tablet disintegrants, in incorporate these agents to reduce disintegration times. Under Tablet disintegrants and disintegrants are used according to Römpp (9. Edition, Vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, Pp. 182-184) Excipients understood that for the rapid disintegration of tablets in water or gastric juice and for release of the pharmaceuticals in a resorbable form.

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

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

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 H ₁₀ O ₅ ) _n and, viewed formally, is a β-1,4-polyacetal of cellobiose, which in turn is made up 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.

As further disintegrant based on cellulose or as a component this component can use microcrystalline cellulose. This microcrystalline cellulose is obtained by partial hydrolysis of Celluloses obtained under such conditions that only the amorphous Attack areas (approx. 30% of the total cellulose mass) of the celluloses and complete dissolve, leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the hydrolysis microfine celluloses provide the microcrystalline celluloses, the primary particle sizes of approx. 5 μm have and compactible for example to granules with an average particle size of 200 microns are.

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

Preferred according to the invention can about that furthermore, gas developing effervescent systems as tablet disintegration aids be used. The gas-developing shower system can be made from one only substance that releases a gas when in contact with water. Among these compounds is magnesium peroxide in particular to be mentioned, which releases oxygen on contact with water. Usually However, the gas-releasing bubble system consists of itself at least two components that form gas together react. While a variety of systems is conceivable and executable here, for example It will release nitrogen, oxygen or hydrogen in the washing machine according to the invention and bubble system used detergent compositions both based on economic as also based on ecological Select points of view to let. Preferred shower systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent that is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.

at the alkali metal carbonates or bicarbonates are the sodium and potassium salts for cost reasons across from clearly preferred to the other salts. Of course you don't have to the relevant pure alkali metal carbonates or bicarbonates be used; rather can Mixtures of different carbonates and hydrogen carbonates are preferred his.

Prefers are used as a shower system 2 to 20 wt .-%, preferably 3 to 15 wt .-% 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 wt .-% of an acidifying agent, each based on Total weight of the agent used.

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 sulfonic 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).

Prefers are acidifying agents in the context of the present invention in the shower system from the group of organic di-, tri- and oligocarboxylic acids or Mixtures.

fragrances

As Perfume oils or Fragrances can individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type be used. Fragrance compounds are of the ester type e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, Dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, Benzyl formate, ethyl methylphenylglycinate, allylcyclohexylpropionate, Styrallyl propionate and benzyl salicylate. The ethers include, for example Benzyl ethyl ether, to 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-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons belong mainly the terpenes like limes and pinene. However, mixtures are preferred different fragrances, which together make an appealing Generate fragrance. Such perfume oils can also natural fragrance mixtures included as they are available from plant sources, e.g. Pine, Citrus, Jasmine, patchouly, rose or ylang-ylang oil. Are also suitable 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 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 successful as such carrier materials, the cyclodextrin-perfume complexes can also be coated with other auxiliaries.

dyes

preferred Dyes, the selection of which is not difficult for the expert, have a high storage stability and insensitivity to the rest Ingredients of the agents and against light and no pronounced substantivity towards the substrates to be treated with the dye-containing agents, such as for example glass, ceramics, plastic tableware or textiles, so as not to stain them.

solvent

To the solvents counting especially the non-aqueous ones organic solvents, with particular preference non-aqueous solvents from the group monohydric or polyhydric alcohols, alkariolamines or glycol ethers, provided they are miscible with water in the specified concentration range are used. The solvents are preferred selected from ethanol, n- or i-propanol, butanols, glycol, propane or Butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, Etheylene 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 butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, Propylene glycol t-butyl ether and mixtures of these solvents.

foam inhibitors

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

Optical brighteners

optical Brighteners (so-called "whiteners") can wash or cleaning agents can be added to graying and yellowing from textiles treated with these agents. These substances draw on the fiber and cause a lightening and feigned bleaching effect, by turning invisible ultraviolet radiation into visible long-wave Convert light, being the ultraviolet absorbed from sunlight Light as a slightly bluish Fluorescence is emitted and with the yellow tone of the grayed or yellowed laundry pure white results. Suitable compounds come from the substance classes, for example 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyryl-biphenyls, methylumbelliferones, Coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic imides, Benzoxazole, Benzisoxazole and Benzimidazole systems and those substituted by heterocycles Pyrene derivatives.

graying

graying in textile cleaning agents do the job of the fiber loosened dirt to keep suspended in the fleet and so the rewinding of the To prevent dirt. For this purpose, water-soluble colloids are usually more organic Suitable in nature, for example the water-soluble salts of polymeric carboxylic acids, glue, Gelatin, salts of ether sulfonic acids of strength or the cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water soluble, polyamides containing acidic groups are suitable for this purpose. Farther can be soluble Starch preparations and other than the above starch products use, e.g. degraded starch, aldehyde etc. Polyvinyl pyrrolidone is also useful. As graying inhibitors in the particulate Agents can also be used cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as Methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures.

Antimicrobial agents

antimicrobial Active substances are used to combat them of microorganisms. A distinction is made here depending on the antimicrobial Spectrum and mechanism of action between bacteriostatics and bactericides, fungistatics and fungicides etc. Important substances from these groups are, for example Benzalkonium chlorides, alkylarlyl sulfonates, halophenols and phenol mercuric acetate, 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 O ₅ ) ₂ (OH) ₂ .nH ₂ O and compounds with the following formula Mg ₃ (Si ₂ O ₅ ) ₂ (OH) ₂ .nH ₂ O. 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 the following: Smectite (Na) + NH ₄ OH → smectite (NH ₄ ) + NaOH

In the above equilibrium reaction becomes an equivalent Ammonium ion replaced by an equivalent Sodium ion. It is usual, the cation exchange capacity in milliequivalents / 100 g to be measured (meq / 100 g). The cation exchange capacity of the clays can be determined in different ways, for example by Electrodialysis or by exchange with ammonium ions, followed by a titration, such as in the book by Grimshaw, "The chemistry and physics of clays ", Pages 264-265, Interscience 1971. Smectites such as Nontonite have an ion exchange capacity of approx. 70 meq / 100 g, and Montmorillonite, which has an exchange capacity of above 70 meq / 100 g have been found to be extremely preferred proven in the context of the present invention because they are special effectively on the textiles to be treated and give them the desired Give soft handle. Particularly preferred clay minerals in the frame The present invention is therefore three-layer expanded Smectite types with an ion exchange capacity of at least 50 meq / 100 g.

organophilic Clay minerals can can also be used in the context of the present invention. Such hydrophobically modified clay minerals, in which inorganic Metal ions are exchanged for organic ions through the Exchange processes previously described are also preferred. The modified clay minerals are very miscible with organic solvents and have the property of organic solvents between the layers store. Suitable examples are organophilic clay minerals Benton SD-1, SD-2 and SD-3 from Rheox.

Out Among the group of smectites, bentonites have been particularly preferred exposed. Bentonites are contaminated clays caused by weathering volcanic tuffs have arisen. Because of their high salary On montmorillonite, bentonites have valuable properties such as Swelling capacity, Ion exchange capacity and thixotropy. It is possible the properties of the bentonites according to the intended use to modify. Bentonites are found in tropical clay Floors often and are used as sodium bentonite e.g. mined in Wyoming / USA. Sodium bentonite exhibits the best application properties (swellability), so that its Use in the context of the present invention is preferred. Naturally occurring Calcium bentonites originate, for example, from Mississippi / USA or Texas / USA or from Landshut / D. Of course Ca bentonites obtained become artificial by exchanging Ca for Na into the swellable Na bentonites.

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 belong to the phyllosilicates and here to the dioctahedral smectites clay minerals that crystallize monoclinic-pseudohexagonal. Montmorillonite predominantly form white, gray-white to yellowish, completely amorphous appearing, easily friable, swelling in the water, but not becoming plastic, by the general formulas Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] .nH ₂ O or Al ₂ O ₃ · 4SiO ₂ · H ₂ O · nH ₂ O or Al 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, hydroxy-aluminosilicate ions, etc. The above. Formulas are only approximate formulas because montmorillonites have a large ion exchange capacity. Al 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 NaCO ₃ , are also advantageous.

• I) Montmorillonit-Gehalt von mindestens 85% und
• II) wenn der mit Natriumionen aktivierte Ton, getrocknet und zu Partikeln gemahlen wird, dann quellen die gemahlenen Partikel nicht mehr als das zweieinhalbfache an innerhalb einer Zeit von 24 Stunden, wenn entionisiertes Wasser bei Raumtemperatur hinzugefügt wird.

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) Trocknen des Tons auf einen Wassergehalt von 25–35 Gew.-%,
• b) Extrudieren des getrockneten Materials zu einer Paste;
• c) Trocknen der Paste auf einen Feuchtigkeitsgehalt von 10–14 Gew.-% und
• d) Kalzinieren bei einer Temperatur zwischen 120 und 250°C.

A clay containing montmorillonite, which is obtained by the following process steps, is particularly preferred:

• 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:
SiO ₂ : 55.0-61.0% by weight
Al ₂ O ₃ : 14.5-17.6% by weight
Fe ₂ O ₃ : 1.45-1.7% by weight
CaO: 2.8-7.0% by weight
MgO: 5.0-6.3% by weight
K ₂ O: 0.5-0.58% by weight
Na ₂ O: 0.25-0.3% by weight
Mn ₃ O ₄ : 0.04-0.25 wt%

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

The crystalline structure of montmorillonite 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 a 1N HCl solution is exposed to a temperature of 80 ° C. for 15 hours. It has to be there 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 HCl treatment. Montmorillonites (magnesium saturated / air dried) usually have a maximum diffraction distance of 14-15 Å in the 001 plane when treated with X-rays. This maximum diffraction distance usually does not change by treating the clay with HCl.

in the However, acid-sensitive montmorillonites are within the scope of the present invention preferred, for example montmorillonites, their crystalline Structure destroyed when treated with HCl. The use of such clay minerals has a softening effect and also ensures a better one Dispersibility in the aqueous wash liquor or the aqueous textile treatment liquid. The destruction the crystalline structure can be measured by measuring the diffraction distance be determined so that at the destroyed one Montmorillonites the one to be expected from crystalline Montmorilonites maximum diffraction distance in the 001 plane of 14–15 Å does not appear.

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 (10)

Process for making a cast body a washing or cleaning active preparation, comprising the steps: a) to water a washing or cleaning active preparation in the receiving trough a molding tool; b) degassing the active washing or cleaning Preparation; A method according to claim 1, characterized in that the Degassing is achieved by vibration of the mold. Method according to one of claims 1 or 2, characterized in that that the The amplitude of the vibration is continuously adjustable. Method according to one of claims 1 to 3, characterized in that that the Frequency of vibration is continuously adjustable. Method according to one of claims 1 to 4, characterized in that that the Vibration occurs in the horizontal and / or vertical spatial direction. Method according to one of claims 1 to 5, characterized in that that the Amplitude and frequency of vibration during degassing constant are. Method according to one of claims 1 to 6, characterized in that that itself the amplitude and / or frequency of vibration during the Change degassing. Method according to one of claims 1 to 7, characterized in that that the Degassing takes place by applying a negative pressure. Method according to one of claims 1 to 8, characterized in that that the Degassing takes place through the action of ultrasound. Method according to one of claims 1 to 9, characterized in that that the Degassing by exposure to heat he follows.