DE10237199A1 - Storage-stable portioned liquid detergent or cleansing compositions packaged in water-soluble or -dispersible containers contain coated dispersed phosphates - Google Patents

Abstract

A liquid detergent or cleansing composition which is portioned in a water-soluble or -dispersible container and which comprises a low water-content matrix containing a dispersed phosphate is such that at least 10 wt.% of the dispersed phosphate is coated.

Description

The present invention resides the area of portioned liquid Detergents or cleaning agents, such as those for washing and cleaning active dosing Substances are used. In particular, the present relates Invention on low-water liquid Detergents or cleaning agents that contain phosphate.

Portioned and pre-dosed washing or detergents delight consumers their simple and safe handling is very popular. The packaging more fluid or more gel-shaped washing or cleaning active substances or substance mixtures in water-soluble or water-dispersible materials is accordingly in the booth technology described in a number of documents. It is between process applications for the production of water-soluble or water dispersible packaging on one side and Registrations regarding of the packaging materials and ingredients used on the differentiate.

Special designs of the thermoforming process disclose for the manufacture of deep-drawn packaging units, for example the international applications WO 00155044, WO 00144045, WO 00144046 and WO 00155415 (Hindustan Lever Limited). These deep-drawn bags included according to the description of these registrations fluid or gel-shaped Mixtures of substances, preferably from the field of active washing and cleaning Substances. The foil bag can be made of water-soluble materials such as polyvinyl alcohol consist. The registrations do not provide any details about the Composition of the liquid or gel-shaped Ingredients, their storage stability or water absorption behavior.

Subject of international registrations WO 02/16205 (Reckitt Benckiser Limited) is a manufacturing process water containers by thermoforming a water soluble PVA film with a water content below 5% by weight. The resulting containers are preferably with washing or cleaning active substances attacks, these preferably having a water content above 8% by weight. The detergents and cleaning agents can according to the disclosure of this application Contain alkali phosphates.

The application WO 02/16206 (Reckitt Benckiser Limited) describes a process for making inflated water container by adding gas-releasing salts to that in the containers Substances or mixtures of substances. With these means it can et al are washing or cleaning agents containing phosphate.

Liquid compositions with a water content above 3% by weight, which is packed in deep-drawn PVA containers international application WO 02/16222 (Reckitt Benckiser Limited). With the liquid Compositions can include to phosphate-containing textile or Trade dish detergent. None of the above registrations provides information about the packaging of liquid detergents or cleaning agents contained phosphates or the beneficial influence of a such packaging on storage stability and water absorption behavior of washing or cleaning agents containing phosphates.

Subject of WO 02/16541 (Reckitt Benckiser Limited) are water-soluble or liquid-filled water-dispersible containers. The liquids contained have and contain a water content of between 20 and 50% by weight at least one polyphosphate builder as well as potassium and sodium ions, being the molar ratio of potassium to sodium is between 0.55: 1 and 20: 1. As preferred polyphosphate is disclosed potassium tripolyphosphate. Details of the preferably used phosphates or their packaging not to be inferred from this registration.

The European patent EP 518 689 B1 (Rhone-Poulenc Agrochimie) claims container systems comprising a water-soluble or water-dispersible bag containing an agent which is a liquid or a gel, comprising a dangerous product, 5 to 55% by weight of water and an effective amount of an electrolyte which is an inorganic salt. According to the teaching of the addition of this electrolyte causes EP 518 689 B1 the reduction in the solubility of the bag material in the aqueous solution and in this way increases the stability of the bag. In addition to other inorganic salts, phosphates are also disclosed as effective electrolytes. This patent does not disclose the special nature of these phosphates or their packaging.

Liquid or gel forms of supply, as they are available pre-dosed in foil bags and in the aforementioned Applications have been described so far have a number of disadvantages on. Low-water liquids or gels in particular tend to for storage, Transport or use usual Temperatures and air humidity to form precipitates to the solidification of the entire gel. The formation of such precipitations is not just the external appearance of funds detrimental but also has an adverse impact on washing or cleaning performance of these funds as from the precipitation usually a reduced solubility the solidified detergent or cleaning agent ingredients result.

It was therefore the object of the present application low-water liquid or gel Ange to provide bot forms of detergents or cleaning agents which are suitable for packaging in water-soluble or water-dispersible films and which, even after storage for several weeks, have no precipitations or solidifications under the conditions customary for the production, storage and transport of these agents (temperature, air humidity).

It has now been found that in water soluble or water-dispersible containers packaged low-water, liquid Detergent or cleaning agent compositions then have a high storage stability, if at least 10% by weight of the phosphate contained in these agents have a coating.

A first subject of the present Registration is therefore a portioned, liquid, detergent or cleaning agent composition in a water soluble or water-dispersible container, comprising a low-water matrix and phosphate dispersed therein, characterized in that related based on the total weight of the dispersed phosphate at least 10 % By weight of the dispersed phosphate have a coating.

For further advantageous influencing storage stability as well as the solution properties and the appearance of the washing or cleaning agents claimed, in particular however, to further improve storage stability, it has proved to be advantageous that dispersed in the low-water matrix To coat phosphate to more than 10 wt .-%. It is therefore in the frame of the present invention preferred that the dispersed in the low water matrix Phosphate based on the total weight of the dispersed phosphate at least 30% by weight, particularly preferably at least 50% by weight and in particular has at least 70% by weight of a coating. In a particularly preferred embodiment of the present Invention, the entire phosphate has a coating.

As "low water" in the frame of the present application such liquid detergent or cleaning agent compositions referred to, the total water content, i.e. one Free water content and / or in the form of water of hydration and / or Constitution water present water below 18 wt .-%, each based on the total weight of the detergent and cleaning agent without consideration of water soluble or water-dispersible container, exhibit. The determination of the water content can, for example by titration according to Karl Fischer.

Preferred detergent or cleaning agent compositions have a total water content in the context of this application that is called a content of free water and / or in the form of water of hydration and / or constitutional water between 0.1 and 15% by weight, preferably between 0.5 and 12% by weight, particularly preferably between 1 and 9% by weight and in particular between 2 and 6% by weight, each based on the total weight of the detergent and cleaning agent without considering the water-soluble or water-dispersible container, on. Although the total water content (sum of free water and the constitutional water and the hydrated water) are more preferable means according to the invention is between 0.1 and 15% by weight, this is the proportion of free water in this total water content but preferably small. Within the scope of the present application therefore preferred detergent or cleaning agent compositions, which contains free water, that is, not in the form of water of hydration and / or constitutional water between 0.1 and 6 wt .-%, preferably between 0.1 and 5 wt .-%, particularly preferred between 0.1 and 4% by weight and in particular between 0.1 and 3% by weight, each based on the total weight of the detergent or cleaning agent composition, without consideration of water soluble or water-dispersible container, exhibit.

• a) wasserlöslichen nichtionischen Polymeren aus der Gruppe der
• a1) Polyvinylpyrrolidone,
• a2) Vinylpyrrolidon/Vinylester-Copolymere,
• a3) Celluloseether
• b) wasserlöslichen amphoteren Polymeren aus der Gruppe der
• b1) Alkylacrylamid/Acrylsäure-Copolymere
• b2) Alkylacrylamid/Methacrylsäure-Copolymere
• b3) Alkylacrylamid/Methylmethacrylsäure-Copolymere
• b4) Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure -Copolymere
• b5) Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)acrylsäure -Copolymere
• b6) Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere
• b7) Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat-Copolymere
• b8) Copolymere aus
• b8i) ungesättigten Carbonsäuren
• b8ii) kationisch derivatisierten ungesättigten Carbonsäuren
• b8iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren
• c) wasserlöslichen zwitterionischen Polymeren aus der Gruppe der
• c1) Acrylamidoalkyltrialkylammoniumchlorid/Acrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
• c2) Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
• c3) Methacroylethylbetain/Methacrylat-Copolymere
• d) wasserlöslichen anionischen Polymeren aus der Gruppe der
• d1) Vinylacetat/Crotonsäure-Copolymere
• d2) Vinylpyrrolidon/Vinylacrylat-Copolymere
• d3) Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere
• d4) Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen
• d5) gepfropften und vernetzten Copolymere aus der Copolymerisation von
• d5i) mindesten einem Monomeren vom nicht-ionischen Typ,
• d5ii) mindestens einem Monomeren vom ionischen Typ,
• d5iii) von Polyethylenglycol und
• d5iv) einem Vernetzter
• d6) durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltenen Copolymere:
• d6i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren,
• d6ii) ungesättigte Carbonsäuren,
• d6iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe d6ü) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols
• d7) Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester
• d8) Tetra- und Pentapolymere aus
• d8i) Crotonsäure oder Allyloxyessigsäure
• d8ii) Vinylacetat oder Vinylpropionat
• d8iii) verzweigten Allyl- oder Methallylestern
• d8iv) Vinylethern, Vinylestern oder geradkettigen Allyl- oder Methallylesterns
• d9) Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinylmethylether, Acrylamid und deren wasserlöslicher Salze
• d10) Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen in ☐-Stellung verzweigten Monocarbonsäure
• e) wasserlöslichen kationischen Polymeren aus der Gruppe der
• e1) quaternierten Cellulose-Derivate
• e2) Polysiloxane mit quaternären Gruppen
• e3) kationischen Guar-Derivate
• e4) polymeren Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure
• e5) Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylatss
• e6) Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere
• e7) quaternierter Polyvinylalkohol
• e8) unter den INCI-Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 und Polyquaternium 27 angegeben Polymere.

Polymers or polymer mixtures are particularly suitable as coating materials or as a component of the coating, for example as a binder in combination with salts, preferably inorganic salts, the polymer or at least 50% by weight of the polymer mixture being selected from

• a) water-soluble nonionic polymers from the group of
• a1) polyvinylpyrrolidones,
• a2) vinyl pyrrolidone / vinyl ester copolymers,
• a3) Cellulose ether
• b) water-soluble amphoteric polymers from the group of
• b1) Alkyl acrylamide / acrylic acid copolymers
• b2) alkyl acrylamide / methacrylic acid copolymers
• b3) alkyl acrylamide / methyl methacrylic acid copolymers
• b4) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
• b5) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
• b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
• b7) alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers
• b8) copolymers
• b8i) unsaturated carboxylic acids
• b8ii) cationically derivatized unsaturated carboxylic acids
• b8iii) optionally further ionic or nonionic monomers
• c) water-soluble zwitterionic polymers from the group of
• c1) Acrylamidoalkyltrialkylammoniumchlorid / acrylic acid copolymers and their alkali and ammonium salts
• c2) Acrylamidoalkyltrialkylammoniumchlorid / methacrylic acid copolymers and their alkali and ammonium salts
• c3) methacroylethylbetaine / methacrylate copolymers
• d) water-soluble anionic polymers from the group of
• d1) vinyl acetate / crotonic acid copolymers
• d2) vinyl pyrrolidone / vinyl acrylate copolymers
• d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
• d4) graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols
• d5) grafted and crosslinked copolymers from the copolymerization of
• d5i) at least one monomer of the non-ionic type,
• d5ii) at least one monomer of the ionic type,
• d5iii) of polyethylene glycol and
• d5iv) a networked person
• d6) copolymers obtained by copolymerization of at least one monomer from each of the following three groups:
• d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
• d6ii) unsaturated carboxylic acids,
• d6iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group d6ü) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol
• d7) terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester
• d8) tetra and pentapolymers
• d8i) crotonic acid or allyloxyacetic acid
• d8ii) vinyl acetate or vinyl propionate
• d8iii) branched allyl or methallyl esters
• d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
• d9) crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinylmethylether, acrylamide and their water-soluble salts
• d10) terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the ☐ position
• e) water-soluble cationic polymers from the group of
• e1) quaternized cellulose derivatives
• e2) polysiloxanes with quaternary groups
• e3) cationic guar derivatives
• e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid
• e5) copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate
• e6) vinyl pyrrolidone-methoimidazolinium chloride copolymers
• e7) quaternized polyvinyl alcohol
• e8) polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

Water-soluble polymers in the sense of Invention are those polymers that are at room temperature in water more than 2.5% by weight soluble are.

The in the liquid washing according to the invention and detergent dispersed phosphates are preferred coated with a polymer or polymer mixture, the polymer (and accordingly the entire coating) or at least 50 % By weight of the polymer mixture (and thus at least 50% of the coating) from certain polymers selected is. The coating consists entirely or at least 50% their weight from water soluble Polymers from the group of nonionic, amphoteric, zwitterionic, anionic and / or cationic polymers. In another preferred embodiment the coating of the phosphate consists of another inorganic Salt, which contains one of the polymers mentioned as a binder. preferred Polymers from these groups have been and are listed above below in more detail described.

• – Polyvinylpyrrolidone, wie sie beispielsweise unter der Bezeichnung Luviskol^® (BASF) vertrieben werden. Polyvinylpyrrolidone sind bevorzugte nichtionische Polymere im Rahmen der Erfindung. Polyvinylpyrrolidone [Poly(1-vinyl-2-pyrrolidinone)], Kurzzeichen PVP, sind Polymere der allg. Formel (I)
  
  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. 2500–50000 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.).
• – Vinylpyrrolidon/Vinylester-Copolymere, wie sie beispielsweise unter dem Warenzeichen Luviskol^® (BASF) vertrieben werden. Luviskol^® VA 64 und Luviskol^® VA 73, jeweils Vinylpyrrolidon/Vinylacetat-Copolymere, sind besonders bevorzugte nichtionische Polymere. Die Vinylester-Polymere sind aus Vinylestern zugängliche Polymere mit der Gruppierung der Formel (II)
  
  als charakteristischem Grundbaustein der Makromoleküle. Von diesen haben die Vinylacetat-Polymere (R = CN₃) mit Polyvinylacetaten als mit Abstand wichtigsten Vertretern die größte technische Bedeutung. Die Polymerisation der Vinylester erfolgt radikalisch nach unterschiedlichen Verfahren (Lösungspolymerisation, Suspensionspolymerisation, Emulsionspolymerisation, Substanzpolymerisation.). Copolymere von Vinylacetat mit Vinylpyrrolidon enthalten Monomereinheiten der Formeln (I) und (II)
• – Celluloseether, wie Hydroxypropylcellulose, Hydroxyethylcellulose und Methylhydroxypropylcellulose, wie sie beispielsweise unter den Warenzeichen Culminal^® und Benecel^® (AQUALON) vertrieben werden. Celluloseether lassen sich durch die allgemeine Formel (III) beschreiben,
  
  in R für N oder einen Alkyl-, Alkenyl-, Alkinyl-, Aryl- oder Alkylarylrest steht. In bevorzugten Produkten steht mindestens ein R in Formel (III) für -CH₂CH₂CH₂-OH oder -CH₂CH₂-OH. Celluloseether werden technisch durch Veretherung von Alkalicellulose (z.B. mit Ethylenoxid) hergestellt. Celluloseether werden charakterisiert über den durchschnittlichen Substitutionsgrad DS bzw. den molaren Substitutionsgrad MS, die angeben, wieviele Hydroxy-Gruppen einer Anhydroglucose-Einheit der Cellulose mit dem Veretherungsreagens reagiert haben bzw. wieviel mol des Veretherungsreagens im Durchschnitt an eine Anhydroglucose-Einheit angelagert wurden. Hydroxyethylcellulosen sind ab einem DS von ca. 0,6 bzw. einem MS von ca. 1 wasserlöslich. Handelsübliche Hydroxyethyl- bzw. Hydroxypropylcellulosen haben Substitutionsgrade im Bereich von 0,85-1,35 (DS) bzw. 1,5-3 (MS). Hydroxyethyl- und – propylcellulosen werden als gelblich-weiße, geruch- und geschmacklose Pulver in stark unterschiedlichen Polymerisationsgraden vermarktet. Hydroxyethyl- und -propylcellulosen sind in kaltem und heißem Wasser sowie in einigen (wasserhaltigen) organischen Lösungsmitteln löslich, in den meisten (wasserfreien) organischen Lösungsmitteln dagegen unlöslich; ihre wäßrigen Lösungen sind relativ unempfindlich gegenüber Änderungen des pH-Werts oder Elektrolyt-Zusatz.

Water-soluble polymers preferred according to the invention are nonionic. Suitable non-ionic Examples of polymers are:

• - polyvinylpyrrolidones, as, for example, sold under the name Luviskol ^® (BASF). Polyvinylpyrrolidones are preferred nonionic polymers 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. 2500-50000 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. 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 = CN 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, such as are for example sold under the trademark Culminal® ^® and Benecel ^® (AQUALON). Cellulose ethers can be described by the general formula (III)
  
  R represents N or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products at least one R in formula (III) is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of cellulose have reacted with the etherification reagent or how many moles of etherification reagent have been attached to an anhydroglucose unit on average. Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercial hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS). Hydroxyethyl and - propyl celluloses are yellowish white, Odorless and tasteless powders marketed in widely differing degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Further polymers preferred according to the invention are water-soluble amphopolymers. Ampho-polymers are amphoteric polymers, ie polymers that contain both free amino groups and free -OOOH or SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - Contain COO ^- or -SO ₃ ^- groups, and summarize those polymers which contain -OOOH or SO ₃ H groups and quaternary ammonium groups. An example of the present invention amphopolymer suitable is that available under the name Amphomer ^® acrylic resin which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Methacrylic acid and its simple esters. Also preferred amphopolymers are composed of unsaturated carboxylic acids (e.g. acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (e.g. acrylamidopropyl-trimethyl-ammonium chloride) and optionally other ionic or non-ionic monomers, such as in German Offenlegungsschrift 39 29 973 and the one cited therein State of the art can be seen. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat ^® 2001 N, are particularly preferred amphopolymers according to the invention. Other suitable amphoteric polymers are for example those available under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL) octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers.

Suitable zwitterionic polymers are, for example, acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts. Further suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are available under the name Amersette® ^® (AMERCHOL).

• – Vinylacetat/Crotonsäure-Copolymere, wie sie beispielsweise unter den Bezeichnungen Resyn® (NATIONAL STARCH), Luviset^® (BASF) und Gafset^® (GAF) im Handel sind. Diese Polymere weisen neben Monomereinheiten der vorstehend genannten Formel (II) auch Monomereinheiten der allgemeinen Formel (In auf: [-CH(CH₃)-CH(COOH)-]_n (IV)
• – Vinylpyrrolidon/Vinylacrylat-Copolymere, erhältlich beispielsweise unter dem Warenzeichen Luviflex^® (BASF). Ein bevorzugtes Polymer ist das unter der Bezeichnung Luviflex^® VBM-35 (BASF) erhältliche Vinylpyrrolidon/Acrylat-Terpolymere.
• – Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere, die beispielsweise unter der Bezeichnung Ultrahold^® strong (BASF) vertrieben werden.
• – Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen Solche gepfropften Polymere von Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch mit anderen copolymerisierbaren Verbindungen auf Polyalkylenglycolen werden durch Polymerisation in der Hitze in homogener Phase dadurch erhalten, daß man die Polyalkylenglycole in die Monomeren der Vinylester, Ester von Acrylsäure oder Methacrylsäure, in Gegenwart von Radikalbildner einrührt. Als geeignete Vinylester haben sich beispielsweise Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinylbenzoat und als Ester von Acrylsäure oder Methacrylsäure diejenigen, die mit aliphatischen Alkoholen mit niedrigem Molekulargewicht, also insbesondere Ethanol, Propanol, Isopropanol, 1-Butanol, 2-Butanol, 2-Methy-1-Propanol, 2-Methyl-2-Propanol, 1-Pentanol, 2-Pentanol, 3-Pentanol, 2,2-Dimethyl-1-Propanol, 3-Methyl-1-butanol; 3-Methyl-2-butanol, 2-Methyl-2-butanol, 2-Methyl-1-Butanol, 1-Hexanol, erhältlich sind, bewährt. Als Polyalkylenglycole kommen insbesondere Polyethylenglycole und Polypropylenglycole in Betracht. Polymere des Ethylenglycols, die der allgemeinen Formel V H-(O-CH₂-CH₂)_n-OH (V) genügen, wobei n Werte zwischen 1 (Ethylenglycol) und mehreren tausend annehmen kann. Für Polyethylenglycole existieren verschiedene Nomenklaturen, die zu Verwirrungen führen können. Technisch gebräuchlich ist die Angabe des mittleren relativen Molgewichts im Anschluß an die Angabe „PEG", so daß „PEG 200" ein Polyethylenglycol mit einer relativen Molmasse von ca. 190 bis ca. 210 charakterisiert. Für kosmetische Inhaltsstoffe wird eine andere Nomenklatur verwendet, in der das Kurzzeichen PEG mit einem Bindestrich versehen wird und direkt an den Bindestrich eine Zahl folgt, die der Zahl n in der oben genannten Formel V entspricht. Nach dieser Nomenklatur (sogenannte INCI-Nomenklatur, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) sind beispielsweise PEG-4, PEG-6, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14 und PEG-16 einsetzbar. Kommerziell erhältlich sind Polyethylenglycole beispielsweise unter den Handelsnamen Carbowax^® PEG 200 (Union Carbide), Emkapol^® 200 (ICI Americas), Lipoxol^® 200 MED (HÜLS America), Polyglycol® E-200 (Dow Chemical), Alkapol^® PEG 300 (Rhone-Poulenc), Lutrol^® E300 (BASF) sowie den entsprechenden Handelsnamen mit höheren Zahlen. Polypropylenglycole (Kurzzeichen PPG) sind Polymere des Propylenglycols, die der allgemeinen Formel VI
  
  genügen, wobei n Werte zwischen 1 (Propylenglycol) und mehreren tausend annehmen kann. Technisch bedeutsam sind hier insbesondere Di-, Tri- und Tetrapropylenglycol, d.h. die Vertreter mit n=2, 3 und 4 in Formel VI. Insbesondere können die auf Polyethylenglycole gepfropften Vinylacetatcopolymeren und die auf Polyethylenglycole gepfropften Polymeren von Vinylacetat und Crotonsäure eingesetzt werden.
• – gepfropfte und vernetzte Copolymere aus der Copolymerisation von
• i) mindesten einem Monomeren vom nicht-ionischen Typ,
• ii) mindestens einem Monomeren vom ionischen Typ,
• iii) von Polyethylenglycol und
• iv) einem Vernetzter Das verwendete Polyethylenglycol weist ein Molekulargewicht zwischen 200 und mehreren Millionen, vorzugsweise zwischen 300 und 30.000, auf. Die nicht-ionischen Monomeren können von sehr unterschiedlichem Typ sein und unter diesen sind folgende bevorzugt: Vinylacetat, Vinylstearat, Vinyllaurat, Vinylpropionat, Allylstearat, Allyllaurat, Diethylmaleat, Allylacetat, Methylmethacrylat, Cetylvinylether, Stearylvinylether und 1-Hexen. Die ionischen Monomeren können gleichermaßen von sehr unterschiedlichen Typen sein, wobei unter diesen besonders bevorzugt Crotonsäure, Allyloxyessigsäure, Vinylessigsäure, Maleinsäure, Acrylsäure und Methacrylsäure in den Pfropfpolameren enthalten sind. Als Vernetzer werden vorzugsweise Ethylenglycoldimethacrylat, Diallylphthalat, ortho-, meta- und para-Divinylbenzol, Tetraallyloxyethan und Polyallylsaccharosen mit 2 bis 5 Allylgruppen pro Molekül Saccharin. Die vorstehend beschriebenen gepfropften und vernetzten Copolymere werden vorzugsweise gebildet aus:
• i) 5 bis 85 Gew.-% mindesten eine Monomeren vom nicht-ionischen Typ,
• ii) 3 bis 80 Gew.-% mindestens eines Monomeren vom ionischen Typ,
• iii) 2 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-% Polyethylenglycol und
• iv) 0,1 bis 8 Gew.-% eines Vernetzers, wobei der Prozentsatz des Vernetzers durch das Verhältnis der Gesamtgewichte von i), ii) und iii) ausgebildet ist.
• – durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltene Copolymere:
• i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren,
• ii) ungesättigte Carbonsäuren,
• iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols Unter kurzkettigen Carbonsäuren bzw. Alkoholen sind dabei solche mit 1 bis 8 Kohlenstoffatomen zu verstehen, wobei die Kohlenstoffketten dieser Verbindungen gegebenenfalls durch zweibindige Heterogruppen wie -O-, -NH-, -S_ unterbrochen sein können.
• – Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester Diese Terpolymere enthalten Monomereinheiten der allgemeinen Formeln (II) und (IV) (siehe oben) sowie Monomereinheiten aus einem oder mehreren Allyl- oder Methallyestern der Formel VII:
  
  worin R³ für -H oder -CH₃, R² für -CH₃ oder -CH(CH₃)₂ und R¹ für -CH₃ oder einen gesättigten geradkettigen oder verzweigten C_1-6-Alkylrest steht und die Summe der Kohlenstoffatome in den Resten R¹ und R² vorzugsweise 7, 6, 5, 4, 3 oder 2 ist. Die vorstehend genannten Terpolymeren resultieren vorzugsweise aus der Copolymerisation von 7 bis 12 Gew.-% Crotonsäure, 65 bis 86 Gew.-%, vorzugsweise 71 bis 83 Gew.-% Vinylacetat und 8 bis 20 Gew.-%, vorzugsweise 10 bis 17 Gew.-% Allyl- oder Methallylestern der Formel VII.
• – Tetra- und Pentapolymere aus
• i) Crotonsäure oder Allyloxyessigsäure
• ii) Vinylacetat oder Vinylpropionat
• iii) verzweigten Allyl- oder Methallylestern
• iv) Vinylethern, Vinylestern oder geradkettigen Allyl- oder Methallylestern
• – Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinylmethylether, Acrylamid und deren wasserlöslicher Salze
• – Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen in ☐-Stellung verzweigten Monocarbonsäure.

Anionic polymers suitable according to the invention include:

• - vinyl acetate / crotonic acid copolymers, such as are commercially available for example under the names Resyn® (National Starch), Luviset ^® (BASF) and Gafset ^® (GAF). In addition to monomer units of the abovementioned formula (II), these polymers also have monomer units of the general formula (In: [-CH (CH ₃ ) -CH (COOH) -] _n (IV)
• - vinylpyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF). A preferred polymer is that available under the name Luviflex VBM-35 ^® (BASF) vinylpyrrolidone / acrylate terpolymers.
• - Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, which are sold, for example, under the name Ultrahold ^® strong (BASF).
• - Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols. Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or as a mixture with other copolymerizable compounds, can be used on polyalkylene glycols obtained by hot polymerization in a homogeneous phase by stirring the polyalkylene glycols into the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid, in the presence of free-radical formers. Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and as esters of acrylic acid or methacrylic acid, those which are used with low molecular weight aliphatic alcohols, in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl 1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are available. Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol which have the general formula V H- (O-CH ₂ -CH ₂ ) _n -OH (V) 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. Technically ge It is customary to state the average relative molecular weight following the "PEG", so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and directly after the hyphen is followed by a number which corresponds to the number n in the formula V 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. Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula VI
  
  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 VI. In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used.
• - grafted and crosslinked copolymers from the copolymerization of
• i) at least one monomer of the non-ionic type,
• ii) at least one monomer of the ionic type,
• iii) of polyethylene glycol and
• iv) a crosslinking agent The polyethylene glycol used has a molecular weight between 200 and several million, preferably between 300 and 30,000. The nonionic monomers can be of very different types and the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene. The ionic monomers can likewise be of very different types, of which crotonic acid, allyloxyacetic acid, vinyl acetic acid, maleic acid, acrylic acid and methacrylic acid are particularly preferably contained in the graft polymers. Ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallylsucrose with 2 to 5 allyl groups per molecule of saccharin are preferably used as crosslinkers. The grafted and crosslinked copolymers described above are preferably formed from:
• i) 5 to 85% by weight of at least one monomer of the nonionic type,
• ii) 3 to 80% by weight of at least one monomer of the ionic type,
• iii) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and
• iv) 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinking agent being formed by the ratio of the total weights of i), ii) and iii).
• Copolymers obtained by copolymerization of at least one monomer from each of the following three groups:
• i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
• ii) unsaturated carboxylic acids,
• iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol. Short-chain carboxylic acids or alcohols are understood to mean those with 1 to 8 carbon atoms, the carbon chains of these compounds may optionally be interrupted by double-bonded hetero groups such as -O-, -NH-, -S_.
• Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester These terpolymers contain monomer units of the general formulas (II) and (IV) (see above) and monomer units of one or more allyl or methallyesters of the formula VII:
  
  wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated straight-chain or branched C _1-6 alkyl radical and the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2. The above-mentioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight of vinyl acetate and 8 to 20% by weight, preferably 10 to 17% by weight .-% allyl or methallyl esters of the formula VII.
• - Tetra and pentapolymers
• i) crotonic acid or allyloxyacetic acid
• ii) vinyl acetate or vinyl propionate
• iii) branched allyl or methallyl esters
• iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
• - Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinylmethylether, acrylamide and their water-soluble salts
• - Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the ☐ position.

Further, preferably as a component Polymers that can be used in the coating are cationic polymers. Under The cationic polymers are the permanently cationic ones Polymers preferred. As "permanent According to the invention, cationic "are such Polymers referred to independently the pH of the agent (i.e. both the coating and the Molding) have a cationic group. These are usually polymers, which is a quaternary Contain nitrogen atom, for example in the form of an ammonium group.

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

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

• - Quaternized cellulose derivatives, as are commercially available under the names Celquat ^® and Polymer JR ^® . The compounds Celquat ^® L 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives.
• - polysiloxanes with quaternary groups, such as the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning ^® 929 Emulsion (containing a hydroxylamino-modified silicone which is also referred to as amodimethicone), SM 2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80),
• Cationic guar derivatives, such as in particular the products marketed under the trade names Cosmedia ^® Guar and Jaguar ^® ,
• - Polymers dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products commercially available under the names Merquat ^® 100 (poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers.
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755.
• - Vinylpyrrolidone-methoimidazolinium chloride copolymers, as are offered under the name Luviquat ^® .
• - Quaternized polyvinyl alcohol and those under the names
• - polyquaternium 2,
• - polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27

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

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

One in the context of the present application polyvinyl alcohol is a particularly preferred coating material for phosphates (PVA). In terms of the degree of hydrolysis and the molecular weight preferred for the coating The polyvinyl alcohols used apply below in the description in terms of the preferred container materials information provided, to which reference is made here to avoid repetitions becomes.

As already mentioned, the coating can be preferred according to the invention Phosphates also from a mixture of the aforementioned polymers with salts, preferably inorganic salts.

In summary, are in the frame the present application detergent or cleaning compositions preferred, in which the coating of the in the water-poor matrix dispersed phosphate selected from at least one substance the group of water-soluble organic polymers, preferably the water-soluble organic homo- and / or Copolymers, particularly preferably from the group of water-soluble Homopolymers, particularly preferably from the group of polyethylene glycols and / or Polypropylene glycols and in particular from the group of polyethylene glycols and / or polypropylene glycols with a molecular weight above 2000, contains where in the choice of the aforementioned coating materials in With regard to their processability and thermal resistance those substances which have a melting point are particularly preferred above 30 ° C, preferably above 60 ° C, particularly preferably above 90 ° C. and especially above 120 ° C exhibit.

• a) Einbringen eines oder mehrerer partikulärer Gerüststoffe(s) in eine Wirbelschicht;
• b) Aufsprühen der wäßrigen Lösung mindestens eines anorganischen Salzes, auf den/die partikuläre(n) Gerüststoft(e), wobei die in Schritt b) eingesetzte wäßrige Lösung weiterhin ein Bindemittel enthält.

Phosphate particles coated in this way can be produced, for example, by a granulation process in which particulate builders are brought into contact with aqueous solutions of inorganic salts containing binder in a fluidized bed. Such a method for producing coated phosphate particles comprises the steps:

• a) introducing one or more particulate builders (s) into a fluidized bed;
• b) spraying the aqueous solution of at least one inorganic salt onto the particulate framework (s), the aqueous solution used in step b) further containing a binder.

As particles or particulate builders granules separate particles are referred to in the context of the present application, such as by crystallization or agglomeration be preserved. The term particle is not tied to any particle size. The size of the in the inventive method Processed particles are processed exclusively by the technical possibilities of the fluidized bed used.

In the step b) of the procedure The coating agent used is an aqueous solution of a inorganic salt, which also contains binders. life laws Binder is not necessarily completely dissolved, for example even in the watery Phases are in suspension. Are preferred within the scope of the present Registration, however, coating compositions, which are both inorganic Salt, as well as the binder in dissolved form.

To carry out the coating process it has proven to be advantageous to control the supply air temperatures, to control the fluidized bed and the sprayed-on aqueous solution. Prefers are therefore methods according to the invention in the context of the present application, at which the temperature of the supply air used in step b) between 30 and 220 ° C, preferably between 60 and 210 ° C and in particular between 90 and 200 ° C and / or the fluidized bed while of spraying the aqueous solution in step b) a temperature above 30 ° C, preferably above 45 ° C and especially above 60 ° C and / or the aqueous solution sprayed on in step b) has a temperature above 30 ° C, preferably above 40 ° C and especially above 50 ° C having.

Are preferred in the context of the above Process aqueous solutions of inorganic Salts used, which at 20 ° C. a solubility have above 100 g / L. Inorganic which can be used advantageously Salts have been found in particular to be salts which form enabled by hydrates are. This group of the hydrate-forming salts in turn become Sodium sulfate, sodium carbonate, sodium phosphate or magnesium sulfate prefers. Granulation processes which are particularly preferred are characterized in that the sprayed in step b) solution at least one inorganic salt from the group used for formation enabled by hydrates are, in particular at least one inorganic salt from the group Sodium sulfate, sodium carbonate, sodium phosphate or magnesium sulfate contains.

The aforementioned inorganic salts are in the inventive method in the form of watery solutions used which additionally contain a binder. The use of this / these binders) in the method according to the invention elevated the bulk density and abrasion resistance the resulting granules and improves their flowability.

As a particularly suitable binder have become water soluble proven organic polymers, the polyalkylene glycols, in particular the polyethylene glycols and / or polypropylene glycols are particularly preferred become. A detailed one Description of preferred water-soluble Polymers for the coating can be found in the previous sections. On these designs is referred to here.

The coating of the invention in the liquid Detergent or cleaning agent compositions of dispersed phosphate, already leads significantly improved with small amounts of coating material Properties of these funds. It is within the scope of the present invention preferred that the amount of the coating substance (s), based on the total weight of the coated dispersed phosphate between 0.5 and 15% by weight, preferably between 1 and 12% by weight and in particular between 2 and 8 wt .-% is / are.

Low-water detergents or cleaning agents according to the invention contain phosphates which have at least 10% by weight of a coating. These phosphates are preferably selected from the group of the alkali metal phosphates. 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 and also contribute to cleaning performance.

Sodium tripolyphosphate (pentasodium phosphate, Na ₅ P ₃ O ₁₀ ) is an anhydrous or 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n =. 3 In the case of the anhydrous modifications, a distinction must be made between the crystalline phase I and phase II phosphates. About 17 g of the salt of water free of water of crystallization dissolve in 100 g of water at room temperature, about 20 g at 60 ° and around 32 g at 100 °; after heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.).

Washing machines according to the invention are particularly preferred or detergent compositions in which the dispersed Phosphate includes sodium tripolyphosphate and the phase I portion of the dispersed sodium tripolyphosphate based on the total weight of the dispersed sodium tripolyphosphate less than 25% by weight, preferably less than 20% by weight, particularly preferably less than 16% by weight, very particularly preferably less than 12% by weight and in particular less than 10 wt .-%, each based on the total weight of the dispersed sodium tripolyphosphate, since this is washing or Detergent compositions versus compositions with a higher Phase I portion of sodium tripolyphosphate is characterized by a higher storage stability.

Another bevovzugtes alkali metal phosphate is sodium dihydrogen phosphate, NaH ₂ PO _4, which (1.91 gcm density ^{- 3,} melting point 60 °) as the dihydrate exists and as the monohydrate (density 2.04 gcm ^-3). Both salts are white, water-soluble powders that lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KHP ₂ O ₄ , is a white salt with a density of 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^{- 3} , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , 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), becomes anhydrous at 100 ° and changes to the diphosphate Na ₄ P ₂ O ₇ when heated to a greater extent. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

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

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

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher molecular weight sodium and potassium phosphates, in which one can distinguish 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.

Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry.

All of the aforementioned phosphates are as preferred components in the context of the present invention liquid, to conceive of low-water detergent or cleaning agent compositions, in a particularly preferred embodiment of the present Invention the dispersed phosphate polyphosphate (s), preferably tripolyphosphate (s), particularly preferably sodium and / or potassium tripolyphosphate.

With the claimed means it is next to heavy duty detergents for Textiles or automatic dishwashing detergents, including special detergents act to care for fibers, glass, ceramics or metal. Prefers are in any case detergents and cleaning agents with a total phosphate content the detergent and cleaning agent composition between 30 and 70 % By weight, preferably between 35 and 65% by weight, particularly preferred between 40 and 60% by weight and in particular between 45 and 55% by weight, in each case based on the total weight of the liquid detergent and cleaning agent composition, without consideration of water soluble or water-dispersible container, exhibit.

A second method of improvement the shelf life means according to the invention in addition to the coating described above is hydration the phosphates dispersed in the low-water matrix, in particular of sodium tripolyphosphate. As mentioned at the beginning, sodium tripolyphosphate exists except in the two anhydrous modifications as crystalline Hexahydrate, its hydrate water content, based on the total weight, Is 28% by weight. In a further preferred embodiment, therefore Some dispersed sodium tripolyphosphate partly in the form of the hexahydrate. The dispersed sodium tripolyphosphate can however also completely are in the form of the hexahydrate. Washing machines are particularly preferred or detergent compositions in which the dispersed Sodium tripolyphosphate, based on its total weight, 10 to 70 % By weight, preferably 20 to 60% by weight and in particular 25 to 50 Wt .-% sodium tripolyphosphate contains hexahydrate. Instead of or in combination with the fully hydrated sodium tripolyphosphate hexahydrate partially hydrated sodium tripolyphosphate is also used become. Such partially hydrated phosphate has compared to that Hexahydrate has the advantage of being easier to process and allows the lower hydrate water content the production of washing or Detergent compositions of higher active ingredient concentration. The preparation of partially hydrated sodium tripolyphosphate can for example, by the action of hot steam or watery spray anhydrous phosphates. The degree of hydration of the phosphate can be doing about the amount of feed Determine water. Included in the scope of the present application preferred washing or cleaning agent compositions according to the invention the dispersed phosphate at least partially in the form of a hydrated phosphate, this hydrated phosphate being preferred a hydrate water content of 0.5 to 26 wt .-%, preferably of 1 to 24 wt .-% and in particular from 2 to 20 wt .-%, each based on the total weight of the dispersed hydrated phosphate, having.

The agents according to the invention are in the form of a solid suspension in a low-water matrix, which in addition to the water can also contain other non-aqueous solvents. In the context of the present application, the term “solid suspension” does not exclude that the solid substances contained in the agents according to the invention are at least partially in solution. Independently of these dissolved portions, however, the agents according to the invention have a portion of suspended solids. The above-mentioned non-aqueous solvents are derived, for example, from the groups of the monoalcohols, diols, triols or polyols, the ethers, esters and / or amides, with non-aqueous solvents being particularly preferred solvents that are water-soluble, wherein “water-soluble” solvents in the sense of the present application are solvents that are completely miscible with water at room temperature, ie without a miscibility gap.

Non-aqueous solvents in the agents according to the invention can be used preferably come from the group of mono- or polyhydric alcohols, Alkanolamines or glycol ethers, provided they are in the specified concentration range are miscible with water. The solvents are preferred selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerin, Diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, Ethylene glycol ethyl ether, ethylene glycol propyl ether, 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.

One within the scope of the present invention particularly preferred portioned detergent or cleaning agent composition is characterized in that it nonaqueous solvent (s) solvent in amounts from 0.1 to 70% by weight, preferably from 0.5 to 60% by weight, particularly preferably from 1 to 50% by weight, very particularly preferably from 2 to 40% by weight and in particular from 2.5 to 30% by weight, in each case based on the total composition, with preferred non-aqueous (s) solvent selected is / are from the group of non-ionic liquids which are liquid at room temperature Surfactants, the polyethylene glycols and polypropylene glycols, glycerin, Glycerol carbonate, triacetin, ethylene glycol, propylene glycol, propylene carbonate, Hexylene glycol, ethanol and n-propanol and / or iso-propanol.

The nonionic liquid at room temperature Surfactants continue to be active as washing or cleaning substances detailed below described.

Polyethylene glycols (abbreviation PEG) which can be used according to the invention are liquid at room temperature. PEG are polymers of ethylene glycol which have the general formula (VIII) H- (O-CH ₂ -CH ₂ ) _n -OH (VIII) are sufficient, where n values can be between 1 (ethylene glycol, see below) and approx. 16. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is so technically common, so that "PEG 200 ° characterizes a polyethylene glycol with a relative molecular weight of approx. 190 to approx. 210. According to this nomenclature, the Technically common polyethylene glycols PEG 200, PEG 300, PEG 400 and PEG 600 can be used.

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 above formula. 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) according to the invention, for example, PEG-4, PEG-6, PEG-8, PEG 9, PEG-10, PEG-12, PEG-14 and PEG-16 can be used according to the invention.

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.

genügen, wobei n Werte zwischen 1 (Propylenglycol, siehe unten) und ca. 12 annehmen kann. Technisch bedeutsam sind hier insbesondere Di-, Tri- und Tetrapropylenglycol, d.h. die Vertreter mit n=2, 3 und 4 in der vorstehenden Formel.Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the general formula (IX)

are sufficient, where n values can be between 1 (propylene glycol, see below) and approx. 12. Of particular technical importance here are di-, tri- and tetrapropylene glycol, ie the representatives with n = 2, 3 and 4 in the above formula.

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

Glycerol carbonate can be obtained by transesterification of ethylene carbonate or dimethyl carbonate with glycerin, ethylene glycol or methanol being obtained as by-products. Another synthetic route starts from glycidol (2,3-epoxy-1-propanol), which is converted under pressure in the presence of catalysts with CO ₂ to form glycerol carbonate. Glycerine carbonate is a clear, easily movable liquid with a density of 1.398 gcm ^-3 that boils at 125-130 ° C (0.15 mbar).

Ethylene glycol (1,2-ethanediol, "glycol") is a colorless, viscous, sweet tasting, strongly hygroscopic liquid, which is miscible with water, alcohols and acetone and has a density of 1.113. The freezing point of ethylene glycol is at –11.5 ° C, the liquid boils at 198 ° C. Technically, ethylene glycol is made from ethylene oxide by heating with Extracted water under pressure. Promising manufacturing processes can also be used on the acetoxylation of ethylene and beyond Hydrolysis or on synthesis gas reactions build up.

There are two of the propylene glycol Isomers, 1,3-propanediol and 1,2-propanediol. 1,3-propanediol (Trimethylene glycol) is a neutral, colorless and odorless, sweet tasting liquid density 1.0597 at -32 ° C solidified and at 214 ° C boils. 1,3-Propanediol can be produced from acrolein and Water under subsequent catalytic hydrogenation.

Technically far more important 1,2-propanediol (propylene glycol), which is an oily, colorless, almost odorless Liquid, represents the density 1.0381, which solidifies at -60 ° C and boils at 188 ° C. 1,2-propanediol is made from propylene oxide by adding water.

Propylene carbonate is a water-bright, easily moving liquid with a density of 1.21 gcm ^-3 , the melting point is -49 ° C, the boiling point is 242 ° C. Large quantities of propylene carbonate can also be obtained by reacting propylene oxide and CO ₂ at 200 ° C and 80 bar.

Except for the one described above Phosphate, preferred according to the invention Detergent or cleaning agent compositions more for these means usual Active substances, substances from the group of bleaching agents, Bleach activators, polymers, builders, Surfactants, enzymes, electrolytes, pN-setting agents, fragrances, perfume carriers, dyes Hydrotropes, foam inhibitors, anti-redeposition agents, optical Brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, Color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Corrosion inhibitors, antistatic agents, phobing and impregnating agents, Swelling and sliding solid, non-aqueous solvents, fabric softener, protein hydrolyzate, and UV absorbers are particularly preferred.

Bleaching agents and bleach activators can be included in the agents according to the invention as important components of washing or cleaning agents. Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaches which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Detergent tablets for automatic dishwashing can also contain bleaches from the group of organic bleaches. 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 arylpenoxy 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-phthalimidoperoxyaloacidoperoxycaproic acid (Pε) ) j, o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxydiacid-diperoxybutyldiacyldiperoxybutyldiacyldiperoxybutyldiacyldiperoxybutyldiacyldiperoxybutyldiacyldiperoxybutyldiacid, diperoxybutyldiacyldiperoxybutyldiacyldiperoxybutyldiacyldiperoxybutyldiacid, diperoxybutyldiacid, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Are the agents of the invention as automatic dishwashing detergent used so can these bleach activators contain to when cleaning at temperatures of 60 ° C and below to achieve an improved bleaching effect. As bleach activators can Compounds containing 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. Substances that are O- and / or are suitable N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

in der R¹ für -N, -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, 2– -(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 nitrile of the formula

in which R ^{1 is} -N, -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 , 2- - (CH ₂ CH ₂ -O) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion.

In particularly preferred agents according to the invention is a cationic nitrile of the formula

contain, in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , where R ^{4 can} additionally be -H and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ^{( +)} CH ₂ -CN X; (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH (CH ₃ )) ₃ N ^{( +)} CH ₂ -CN X ^- , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{- are} particularly preferred, the cationic nitrile of the formula (CH ₃ ) again being selected from the group of these substances ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , 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.

In addition to the conventional Bleach activators or in their place can also be so-called bleach catalysts be incorporated into the funds. These substances are 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 as well as Co, Fe, Cu and Ru amine complexes are used as bleaching catalysts usable.

In addition to the ingredients mentioned Bleaching agents and bleach activators are builders other important ingredients of detergents or cleaning agents. In the washing machines according to the invention or cleaning agents all usually builders used in these agents may be present, in particular Zeolites, silicates, carbonates, organic cobuilders and - where no ecological There are prejudices against their use - including 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 are. 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 delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well even lead to particularly good builders lead when 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.

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

Of course, there is also a stake of the well-known phosphates possible as builder substances, provided that such use is not avoided for ecological reasons should be. The sodium salts of the orthophosphates are particularly suitable, the pyrophosphates and especially the tripolyphosphates. To avoid of repetitions is for a detailed Description of these phosphates on the above statements directed.

Usable organic builders are, for example, those in the form of their alkali and especially sodium salts usable polycarboxylic acids, like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, Sugar acids, amino carboxylic acids, nitrilotriacetic (NTA), provided that such use is not 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.

Alkali carriers can be present as further constituents his. As an alkali carrier apply alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, Alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the aforementioned substances, wherein for the purposes of this invention preferably the alkali carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate can be used.

If the washing according to the invention or detergent for machine dishwashing used, so are water soluble Builder preferred as they work on dishes and hard surfaces tend to be less likely to form insoluble residues. Usual builder are the low molecular weight polycarboxylic acids and their salts, the homopolymers and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and silicates. Prefers are used to manufacture tablets for machine dishwashing trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or Sodium bicarbonate and / or gluconate and / or silicate builders used from the class of disilicates and / or metasilicates. A builder system containing a mixture is particularly preferred from tripolyphosphate and sodium carbonate.

It is also particularly preferred a builder system that is a mixture of tripolyphosphate and sodium carbonate and contains sodium disilicate.

As organic cobuilders, in the cleaning agents in the context of the present invention in particular Polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used become. These classes of substances are described below.

Usable 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, methylglycine, sugar acids and mixtures of these.

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

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

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

Suitable polymers are in particular Polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol exhibit. Because of their superior solubility can from this group, in turn, the short-chain polyacrylates, the molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1200 to 4000 g / mol, have, be preferred.

Are particularly preferred in the agents according to the invention both polyacrylates and copolymers of unsaturated Carboxylic acids, Containing sulfonic acid Monomers and optionally other ionic or nonionic Monomers used. The copolymers containing sulfonic acid groups will be detailed in the following described.

• i) ungesättigten Carbonsäuren
• ii) Sulfonsäuregruppen-haltigen Monomeren
• iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

enthalten.However, it is also possible to provide products according to the invention which, as so-called “3-in-1” products, combine the conventional cleaners, rinse aids and a salt replacement function. For this purpose, automatic dishwashing detergents according to the invention are preferred which additionally contain 0.1 to 70% by weight of copolymers out

• i) unsaturated carboxylic acids
• ii) Monomers containing sulfonic acid groups
• iii) optionally further ionic or nonionic monomers

contain.

These copolymers cause the Such items treated dishes in subsequent cleaning operations clearly become cleaner than dishes that have been washed using conventional means.

As an additional positive effect occurs a shortening the drying time of the dishes treated with the detergent on, i.e. the consumer can after the cleaning program the dishes earlier Take out of the machine and use again. Under drying time is part of the teaching of the invention in general the literal meaning understood, that is, the time that passes until one in a dishwasher treated dish surface has dried, but especially the time that passes until 90-% one with a detergent or rinse aid in concentrated or diluted form treated surface is dried.

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 ) OOOH (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 -COON 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 ¹ independently of one another are -N -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} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally available spacer group , which is selected from - (CH ₂ ) 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 IIa), 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-propenlsulfonic 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-sul fopropyl 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 another ionic or non-ionic Monomers are particularly suitable ethylenically unsaturated compounds. Preferably is the content of those used according to the invention Polymers on monomers of group iii) less than 20% by weight, based on the Polymer. Polymers to be used with particular preference only exist 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 -COOR⁴ 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(R¹)-X-SO₃H (XI), in der R⁵ bis R¹ 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 -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
• ii) Monomers of the formula XI containing sulfonic acid groups R ⁵ (R ⁶ ) C = C (R ¹ ) -X-SO ₃ H (XI) , in which R ⁵ to R ¹ 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 stands, 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.

Particularly preferred copolymers consist of

• i) one or more unsaturated carboxylic acids from the group consisting of acrylic acid, methacrylic acid and / or maleic
• 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} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally available 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, which are contained in the medium 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. Especially preferred polymers have certain structural units that are described below.

For example, agents according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula XII - [CH ₂ -CHCOOH) _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XII) , 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 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, are preferred.

These polymers are produced by copolymerization of acrylic acid with a sulfonic acid group-containing acrylic acid derivative. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the agents according to the invention is also preferred and is characterized in that the agents contain one or more copolymers which have 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 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, 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. Agents according to the invention which contain one or more copolymers 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) , 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 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 ) - is, are also preferred, a preferred embodiment of the present invention, just like agents are preferred, which are characterized in that they contain one or more copolymers having 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 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, are preferred.

Instead of or in addition to acrylic acid and / or methacrylic acid, maleic acid can also be used as a particularly preferred monomer from group i). In this way, preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers which have structural units of the formula XVI - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XVI) , 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 and to agents which are characterized in that they contain one or more copolymers which have structural units of the formula XVII - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (XVII) , 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.

In summary, automatic dishwashing agents according to the invention are preferred which contain, as ingredient b), one or more copolymers 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 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 ) with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In the polymers, the sulfonic acid 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. Appropriate means, which are characterized in that the sulfonic acid groups Partially or fully neutralized in the copolymer are preferred according to the invention.

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

Such are special with terpolymers preferred, the 20 to 85 wt .-% monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) included.

The molar mass of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the intended use. Preferred automatic dishwashing detergents 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 .

The content of one or more Copolymers in the agents according to the invention can vary depending on the application and the desired product performance, preferred machine according to the invention Dishwashing liquid are characterized in that they the copolymer (s) in amounts of 0.25 to 50% by weight, preferably from 0.5 to 35% by weight, particularly preferably from 0.75 to 20% by weight and in particular contain from 1 to 15% by weight.

As already mentioned further above, it is particularly preferred to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or nonionic monomers in the agents according to the invention. The polyacrylates were described in detail above. Combinations of the above-described copolymers containing sulfonic acid groups with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons, are particularly preferred. Such polyacrylates are commercially available under the trade names Sokalan ^® PA15 or Sokalan ^® PA25 (BASF).

Copolymers are also suitable Polycarboxylates, especially those of acrylic acid with methacrylic acid and of 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 100,000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 80,000 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 the 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.

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

Show other preferred copolymers as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and Vinyl acetate.

Are also preferred as others Builder substances polymeric aminodicarboxylic acids, their salts or their precursors to call. Polyaspartic acids or their salts and derivatives.

Other suitable builder substances are polyacetals, which by reacting dialdehydes with polyol carboxylic acids Have 5 to 7 carbon atoms and at least 3 hydroxyl groups can be. Preferred polyacetals are derived from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic and / or glucoheptonic acid receive.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The Hydrolysis can be carried out 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.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

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

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

Another class of substances with cobuilder properties represent the phosphonates. These are in particular around hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9) reacts. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (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 the Octa sodium salt of DTPMP. As a builder HEDP is preferably used from the class of the phosphonates. 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.

In addition, everyone can Compounds capable of forming complexes with alkaline earths, can be used as a cobuilder.

Preferred funds included in the frame the present application one or more surfactants) from the groups the anionic, nonionic, cationic and / or amphoteric Surfactants.

As anionic surfactants in acid form are preferred one or more substances from the group of carboxylic acids, the Schwefelsäurehalbester and the sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and of alkylarylsulfonic acids, used. In order to have sufficient surface-active properties, the compounds mentioned should have long-chain hydrocarbon residues feature, thus have at least 6 carbon atoms in the alkyl or alkenyl radical. Usually are the C chain distributions the anionic surfactants in the range from 6 to 40, preferably 8 to 30 and in particular 12 to 22 carbon atoms.

Carboxylic acids, which are used as soaps in detergents and cleaning agents in the form of their alkali metal salts, are technically largely obtained from native fats and oils by hydrolysis. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps), only water is used on an industrial scale to split the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage. Carboxylic acids which can be used as an anionic surfactant in acid form in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc. The preferred compound in the context of the present compound is Use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), triacidic acid (melotinic acid), triacidic acid (melotonic acid), and melonic acid unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-octadecenoic acid) (9c -Octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatreic acid ( Linolenic acid) For reasons of cost, it is preferred not to use the pure species, but rather technical mixtures of the individual acids, as can be obtained from fat cleavage. Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, 6 wt .-% C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% _C14, 10 wt .-% C _16, 2 wt .-% _C18, 8 wt .-% _{C18 ',} 1 wt .-% C _18''), palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt _12% C, 15 wt .-% C _14, 7 wt .-% C _16, 2 wt .-% C ₁₈ 15 wt .-% _{C18 ',} 1 wt .-% C _18''), tallow ( approx. 3% by weight C ₁₄ , 26% by weight C ₁₆ , 2% by weight C _{16 '} -, 2% by weight C ₁₇ , 17% by weight C ₁₈ , 44% by weight C _{18 '} , 3% by weight C _18'' , 1% by weight C _18''' ), hardened tallow fatty acid (approx. 2% by weight C ₁₄ , 28% by weight C ₁₆ , 2% by weight) % C ₁₇ 63 wt .-% C _18: 1 wt .-% C _{18 '),} technical grade oleic acid (about 1 wt .-% C _12, 3 wt .-% C _14, 5 wt .-% C ₁₆ , 6 wt% C _{16 '} , 1 wt% C ₁₇ , 2 wt% C ₁₈ , 70 wt% C _18' , 10 wt% C _{18 ''} , 0.5 wt. -% C _{18 '''} ), technical palmitin / stearic acid (approx. 1% by weight C ₁₂ , 2% by weight C ₁₄ , 45% by weight C ₁₆ , 2% by weight C ₁₇ , 47% by weight % C ₁₈ , 1% by weight C _{18 '} ) and soybean oil fatty acid (approx. 2% by weight C ₁₄ , 15% by weight of C ₁₆ , 5% by weight of C ₁₈ , 25% by weight of C _{18 '} , 45% by weight of C _18'' , 7% by weight of C _18''' ).

Sulfuric acid semiesters of longer-chain alcohols are also anionic surfactants in their acid form and can be used in the context of the present invention. Their alkali metal, in particular sodium salts, the fatty alcohol sulfates, are commercially available from fatty alcohols which are reacted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to give the alkyl sulfuric acids concerned and are subsequently neutralized. The fatty alcohols are obtained from the fatty acids or fatty acid mixtures concerned by high-pressure hydrogenation of the fatty acid methyl esters. The most significant in quantity The industrial process for the production of fatty alkyl sulfuric acids is the sulfonation of the alcohols with SO ₃ / air mixtures in special cascade, falling film or tube bundle reactors.

Another class of anionic surfactant acids that used according to the invention are the alkyl ether sulfuric acids, their salts, the alkyl ether sulfates, compared to the alkyl sulfates by a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts). Alkyl become like the alkyl sulfuric acids synthesized from fatty alcohols, which with ethylene oxide to the concerned Fatty alcohol ethoxylates are implemented. Instead of ethylene oxide propylene oxide can also be used. The subsequent sulfonation with gaseous Sulfur trioxide in short-term sulfonation reactors yields over 98% on the relevant alkyl ether sulfuric acids.

Alkanesulfonic acids and olefin sulfonic acids are also in the context of the present invention as anionic surfactants in acid form used. alkanesulfonic can the sulfonic acid group terminal bound (primary alkane sulfonic acids) or contain along the C chain (secondary alkanesulfonic acids), where only the secondary ones alkanesulfonic have commercial importance. These are by sulfochlorination or Sulfoxidation of linear hydrocarbons produced. In sulfochlorination according to Reed, n-paraffins with sulfur dioxide and chlorine under irradiation with UV light corresponding sulfochlorides implemented in the hydrolysis with alkalis directly deliver the alkanesulfonates, when reacting with water the alkanesulfonic acids. Because in the sulfochlorination, di- and polysulfochlorides as well as chlorinated hydrocarbons can occur as by-products of the radical reaction the reaction usually only carried out up to degrees of implementation of 30% and then canceled.

Another process for making alkanesulfonic acids is sulfoxidation, in the case of n-paraffins under irradiation with UV light with sulfur dioxide and oxygen be implemented. This radical reaction occurs successively Alkylsulfonyl radicals that add oxygen to the alkylpersulfonyl radicals continue to respond. The reaction with unreacted paraffin provides an alkyl radical and the alkyl persulfonic acid, which are converted into an alkyl peroxysulfonyl radical and a hydroxyl radical breaks down. The reaction of the two radicals with unreacted paraffin provides the alkyl sulfonic acids or water, which reacts with alkyl persulfonic acid and sulfur dioxide to form sulfuric acid. To the yield of the two end products alkyl sulfonic acid and Sulfuric acid if possible To keep high and suppress side reactions, this reaction is usually only carried out up to degrees of implementation of 1% and then terminated.

Olefin sulfonates are becoming technical by reaction of α-olefins made with sulfur trioxide. Intermediate hermaphrodites form which cyclize into so-called sultons. Under suitable conditions (alkaline or acidic hydrolysis) these sultones react to hydroxylalkanesulfonic acids or alkensulfonic acids both also as anionic surfactant acids can be used.

Alkylbenzenesulfonates as powerful Anionic surfactants have been around since the 1930s known. At that time, monochlorination of kogasin fractions and subsequent ones Friedel-Crafts alkylation alkylbenzenes made with oleum sulfonated and neutralized with sodium hydroxide solution. beginning of fifties Years have passed to the production of alkylbenzenesulfonates propylene branched α-dodecylene tetramerized and the product over a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride converted to tetrapropylene benzene, the following sulfonated and neutralized. This economic opportunity the production of tetrapropylene benzene sulfonates (TPS) led to Breakthrough of this class of surfactants, which subsequently the soaps as the main surfactant displaced in detergents and cleaning agents.

Because of the lack of biological Degradability of TPS resulted in the need for new alkylbenzenesulfonates to be presented, which are characterized by improved ecological behavior. These requirements are met by linear alkyl benzene sulfonates, which today almost exclusively alkylbenzenesulfonates produced and with the abbreviation ABS or LAS can be used.

Linear alkylbenzenesulfonates are made from linear alkylbenzenes, which in turn from linear Olefins accessible are. This will be on an industrial scale Petroleum fractions with molecular sieves into the n-paraffins of the desired Purity separated and dehydrated to the n-olefins, with both α- and i-olefins result. The resulting olefins then become more acidic in the presence Catalysts reacted with benzene to the alkylbenzenes, the Choice of the Friedel-Crafts catalyst has an impact on the Isomer distribution of the resulting linear alkylbenzenes has: The use of aluminum trichloride is the content of the 2-phenyl isomers in a mixture with the 3, 4, 5 and other isomers at approx. 30% by weight, however, if hydrogen fluoride is used as a catalyst, reduce the 2-phenyl isomer content to approx. 20% by weight. The sulfonation The linear alkylbenzenes finally succeed on an industrial scale with oleum, sulfuric acid or gaseous Sulfur tripxide, the latter being by far the most important. For sulfonation special film or tube bundle reactors are used, which deliver as a product a 97 wt .-% alkylbenzenesulfonic acid (ABSS), which in Can be used in the context of the present invention as anionic surfactant acid is.

in der die Summe aus x und y üblicherweise zwischen 5 und 13 liegt. Erfindungsgemäß bevorzugt als Aniontensid in Säureform sind C_8-16-, vorzugsweise C_9-13-Alkylbenzolsulfonsäuren. Es ist im Rahmen der vorliegenden Erfindung weiterhin bevorzugt, C_8-18-, vorzugsweise C_9-13-Alkybenzolsulfonsäuren einzusetzen, die sich von Alkylbenzolen ableiten, welche einen Tetralingehalt unter 5 Gew.-%, bezogen auf das Alkylbenzol, aufweisen. Weiterhin bevorzugt ist es, Alkylbenzolsulfonsäuren zu verwenden, deren Alkylbenzole nach dem HF-Verfahren hergestellt wurden, so daß die eingesetzten C_8-16-, vorzugsweise C_9-13-Alkybenzolsulfonsäuren einen Gehalt an 2-Phenyl-Isomer unter 22 Gew.-%, bezogen auf die Alkylbenzolsulfonsäure, aufweisen.By choosing the neutralizing agent, a wide variety of salts, ie alkylbenzenesulfonates, can be obtained from the ABSS. For reasons of economy, it is preferred to use the alkali metal salts and among these, the sodium salts of the ABSS are preferably produced and used. These can be described by the general formula XVIII:

in which the sum of x and y is usually between 5 and 13. According to the invention, preferred as the anionic surfactant in acid form are C _8-16 -, preferably C _9-13 -alkylbenzenesulfonic acids. In the context of the present invention, it is further preferred to use C _8-18 -, preferably C _9-13- alkylbenzenesulfonic acids which are derived from alkylbenzenes which have a tetralin content below 5% by weight, based on the alkylbenzene. It is further preferred to use alkylbenzenesulfonic acids whose alkylbenzenes have been prepared by the HF process, so that the C _8-16 -, preferably C _9-13- alkylbenzenesulfonic acids used have a 2-phenyl isomer content of less than 22% by weight. , based on the alkylbenzenesulfonic acid.

The anionic surfactants mentioned above in its acid form can used alone or in a mixture with one another. But it is also possible and preferred that the Anionic surfactant in acid form before adding to the substrate (s)) further, preferably acidic, ingredients of detergents and cleaning agents in amounts from 0.1 to 40% by weight, preferably from 1 to 15% by weight and in particular from 2 to 10% by weight, in each case based on the weight the mixture to be reacted.

Of course it is also possible that Use anionic surfactants partially or fully neutralized. These salts can then as a solution, Suspension or emulsion are present in the granulating liquid, but also as a solid be part of the solid bed. As cations for such Anionic surfactants are available in addition to the alkali metals (in particular here according to claim and K salts) ammonium and mono-, di- or triethanolalkonium ions on. Instead of mono-, di- or triethanolamine you can also the analog representatives of mono-, di- or trimethanolamine or those of the higher alkanolamines Alcohols quaternized and present as a cation.

Cationic surfactants can also be used Use advantage as active substance. The cationic surfactant can be in be delivered directly to the mixer in its delivery form, or in Form of a liquid to pasty Cationic surfactant preparation form are sprayed onto the solid carrier. Let such cationic surfactant preparation forms by mixing commercially available cationic surfactants with auxiliaries such as nonionic surfactants, polyethylene glycols or polyols. Lower alcohols such as ethanol and isopropanol can also be used the amount of such lower alcohols in the liquid cationic surfactant formulation for the reasons mentioned above should be below 10% by weight.

Suitable cationic surfactants for the agents according to the invention all usual Substances are considered, cationic surfactants with fabric softening Effect are clearly preferred.

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.The agents according to the invention can contain one or more cationic, fabric softening agents of the formulas XIX, XX or XXI as cationic active substances with fabric softening effect:

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 preferred embodiments of the present invention the detergent or cleaning agent composition additionally nonionic surfactant (s) as an active substance.

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

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

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

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 XXII,

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 C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula XXIII,

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

[Z] is preferably by reductive Obtained amination of a reduced sugar, for example glucose, Fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy substituted compounds can then 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.

It is special for many applications preferred if the ratio from anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably is between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2. Prefers are containers according to the invention which Surfactant (s), preferably anionic (s) and / or nonionic (s) Surfactant (s), in amounts from 5 to 80% by weight, preferably from 7.5 to 70% by weight, particularly preferably from 10 to 60% by weight and in particular from 12.5 to 50% by weight, based in each case on the weight of the enclosed Solids.

As already mentioned, the use of surfactants in cleaning agents for automatic dishwashing is preferably limited to the use of nonionic surfactants in small amounts. Agents for automatic dishwashing according to the invention therefore preferably contain only certain nonionic surfactants, which are described below. Usually only weakly foaming nonionic surfactants are used as surfactants in automatic dishwashing detergents. By contrast, representatives from the groups of anionic, cationic or amphoteric surfactants are of lesser importance. 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.

Especially with cleaning agents for the machine dishwashing it is preferred that this one contain nonionic surfactant that has a melting point above Has room temperature, preferably a nonionic surfactant a melting point above 20 ° C. Nonionic surfactants to be used with preference have melting points above 25 ° C, particularly preferably to be used nonionic surfactants have melting points between 25 and 60 ° C, in particular between 26.6 and 43.3 ° C.

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

Preferred than at room temperature fixed nonionic surfactants come from the groups of alkoxylated Nonionic surfactants, especially ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control out.

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.

The nonionic surfactant that 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.

Further particularly preferably to be used Contains nonionic surfactants with melting points above room temperature 40 to 70% of 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 trimethylol propane.

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

Another preferred surfactant can be represented by the formula R ¹ O (CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ] describe in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1, 5 and y represents 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} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula can be different if ≥ 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 stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 represents} H and x assumes values from 6 to 15.

Agents according to the invention can contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all the enzymes established in the prior art for these purposes. 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 (bicinchoninic acid; 2,2'-bichinolyl-4,4'-dicarboxylic acid) 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, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase, or Savinase ^® from Novozymes. The variants listed under the name BLAP ^{® are} derived from the protease from Bacillus lentus DSM 5483.

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

Examples of amylases which can be used according to the invention are the a-amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B. stearothermophilus and their further developments for use in detergents and cleaning agents. The enzyme from B. licheniformis is available from Novozymes 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, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the Cyclo highlight dextrin-glucanotransferase (CGTase) from B. agaradherens (DSM 9948); fusion products of the molecules mentioned can also be used.

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 ^® .

Agents according to the invention can contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order 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.

Agents according to the invention can, especially if they for the Treatment of textiles are thought to contain cellulases, each by purpose as pure enzymes, as enzyme preparations or in the form of Mixtures in which the individual components are advantageously complement in terms of their various performance aspects. To count these performance aspects especially contributions for primary washing performance, for secondary washing performance of the agent (anti-redeposition effect or graying inhibition) and finish (tissue effect), up to the exertion of a "stone washed" effect.

A useful fungal, endoglucanase (EG) -rich cellulase preparation or its further developments are offered by the Novozymes company under the trade name Celluzyme ^® . The products Endolase ^® and Carezyme ^® , also available from Novozymes, are based on the 50 kD-EG and the 43 kD-EG from H. insolens DSM 1800. Other possible commercial products from this company are Cellusoft ^® and Renozyme ^® . The 20 kD EG cellulase from Melanocarpus, which is available from AB Enzymes, Finland, under the trade names Ecostone ^® and Biotouch®, can also be used. Other commercial products from AB Enzymes are Econase® and Ecopulp ^® . Another suitable cellulase from Bacillus sp. CBS 670.93 is available from Genencor under the trade name Puradax ^® . Other commercial products from Genencor are "Genencor detergent cellulase L" and IndiAge ^® Neutra.

Agents according to the invention can contain further enzymes, 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 Rohapec ^® B1L is available from AB Enzymes and Pyrolase ^® from Diversa Corp., San Diego, CA. The β-glucanase obtained from B. subtilis is available under the name Cereflo ^® from Novozymes ,

To increase the bleaching effect, washing or cleaning agents according to the invention can use oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) contain. 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 agents according to the invention the enzymes used 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.

Purification of the concerned Enzymes are conveniently made by themselves 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.

Agents according to the invention can be added to the enzymes in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel form agents, solutions of the enzymes, advantageously concentrated, low in water and / or mixed with stabilizers.

Alternatively, the enzymes can be used for both the solid for as well 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 enclosed in a solidified or in the core-shell type, in which an enzyme-containing core with a water, air and / or Chemical-impermeable Protective layer covered 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.

It is also possible to have two or assemble several enzymes so that a single Granulate multiple enzyme activities having.

One in an agent according to the invention contained protein and / or enzyme can be particularly during the Storage against damage 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. Benzamidine hydrochloride, Borax, boric acids, boronic acids or their salts or esters are used, especially derivatives with aromatic groups, such as ortho, meta or para substituted phenylboronic, or their salts or esters. Furthermore, peptide aldehydes, this means Suitable oligopeptides with reduced C-terminus. As a peptide Protease inhibitors include ovomucoid and leupeptin mention; an additional Option is the formation of fusion proteins from proteases and peptide inhibitors.

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

Lower aliphatic alcohols but above all polyols, such as glycerol, ethylene glycol, Propylene glycol or sorbitol are other frequently used enzyme stabilizers. Furthermore protects also di-glycerol phosphate against denaturation by physical Influences. Calcium salts, such as calcium acetate, are also used or calcium formate and magnesium salts.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or, such as cellulose ethers, acrylic polymers and / or polyamides, stabilize the enzyme preparation, inter alia, against physical influences or pH = fluctuations. Polymers containing polyamine-N-oxide act simultaneously as enzyme stabilizers and as color transfer inhibitors. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkyl polyglycosides can also stabilize the enzymatic components of the agent according to the invention and even increase their performance. Crosslinked N-containing compounds fulfill a double function as soil release agents and as enzyme stabilizers.

Reducing agents and antioxidants such as sodium sulfite or reducing sugars increase the stability of the enzymes across from oxidative decay.

Combinations of are preferred Stabilizers 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 can by the combination with boric acid and / or boric acid derivatives and polyols increased and according to the additional use of divalent cations, such as calcium ions reinforced become.

Is particularly preferred in the frame of the present invention the use of liquid enzyme formulations. Here are agents according to the invention preferred that in addition Enzymes and / or enzyme preparations, preferably solid and / or liquid Protease preparations and / or amylase preparations, in amounts of 1 to 5% by weight, preferably from 1.5 to 4.5 and in particular from 2 to 4% by weight, in each case based on the entire average.

A wide number of different salts can be used as electrolytes from the group of inorganic salts. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl ₂ in the granules according to the invention is preferred.

In order to bring the pH of solutions of the washing or cleaning agents according to the invention into the desired range, the use of pN adjusting agents can be indicated. All of them can be used here Liche known acids or alkalis, provided that their use is not prohibited for technical or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 1% by weight of the total formulation.

As perfume oils or fragrances can in Individual fragrance compounds within the scope of the present invention, e.g. synthetic products of the ester, ether, aldehyde type, Ketones, alcohols and hydrocarbons can be used. fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Count among the ethers e.g. benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, among the Ketones e.g. the Jonone, ∞-isomethylionon 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 Contain fragrance mixtures as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Likewise suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as Orange blossom oil, neroliol, Orange peel oil and Sandalwood oil.

The general description of the usable perfumes (see above) generally represents the different classes of substances of fragrances. In order to be perceptible, a fragrance must be volatile, being in addition to the nature of the functional groups and the structure the molecular weight also plays an important role in the chemical compound plays. Most fragrance substances have molecular weights of up to around 200 Dalton while Molar masses of 300 daltons and above rather an exception. Because of the different volatility changed by fragrances the smell of one composed of several fragrances perfumes or fragrance during of evaporation, whereby the odor impressions in "top note", "Heart or middle note" and "base note" (end note or dry out) divided. Because the smell perception too a big one The top note is partly based on the intensity of the smell of a perfume or fragrance not only from volatile compounds, while the Base note for the most part from less volatile, i.e. non-stick fragrances. When composing perfumes can be easier volatile Fragrances are bound to certain fixatives, for example, which prevents it from evaporating too quickly. The following Classification of the fragrances into "more volatile" or "adhesive" fragrances is over the smell impression and above, whether the corresponding fragrance is perceived as a top or heart note nothing is said.

Through a suitable selection of the fragrances or perfume oils mentioned, both the smell of the water-soluble or water-dispersible container and the smell of the liquid enclosed by this container (product fragrance); and, after the cleaning and care process has ended, the laundry scent can also be influenced, for example. In order to ensure an unmistakable product fragrance, more volatile fragrances are used in particular, while the use of more adhesive fragrances is advantageous in order to achieve a sufficient laundry fragrance. Adhesive odoriferous substances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, bergamot oil, champagne flower oil, noble fir oil, noble pine cone oil, elemi oil, eucalyptus oil, fennel oil, geranium oil, spruce oil, spruce oil, spruce oil, spruce oil, oil spruce oil, spruce oil, spruce oil, spruce oil, spruce oil guaiac wood oil, gurjun balsam oil, Helichrysumöl, Ho oil, ginger oil, iris oil, cajeput oil, calamus oil, camomile oil, camphor oil, Kanagaöl, cardamom oil, cassia oil, pine needle oil, Kopaïvabalsamöl, coriander oil, spearmint oil, caraway oil, Kuminöl, lavender oil, lemongrass oil, lime oil, mandarin oil, melissa oil, Musk grain oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, orange oil, origanum oil, palmarosa oil, patchouli oil, Peru balsam oil, petitgrain oil, pepper oil, peppermint oil, allspice oil, pine oil, rose oil, rosemary oil, sandalwood oil, starja oil, celery oil, celery oil, celery oil, celery oil Thyme oil, ver bena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, lemon oil, lemon oil and cypress oil. However, the higher-boiling or solid odorants of natural or synthetic origin can also be used in the context of the present invention as adherent odorants or odorant mixtures, that is to say fragrances. These compounds include the compounds mentioned below and mixtures of these: ambrettolide, α-amyl cinnamaldehyde, anethole, anisaldehyde, anise alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzylacetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzyl benzate, boryl formate benzyl benzyl benzate, benzyl formate benzyl benzyl benzate, benzyl formate benzyl benzyl benzate, benzyl benzate benzyl benzyl benzate benzyl benzyl benzate benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzoate , Bornyl acetate, α-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchylacetate, geranyl acetate, geranyl formate, heliotropine, heptinocarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroquinone dimethyl ether, hydroquinone dimethyl ether, hydroquinone dimethyl ether, hydroquinone dimethyl ether , Isoeugenolmethylether, Isosafrol, Jasmon, Camphor, Karvakrol, Karvon, p-Cresolmethylether, Coumarin, p-Methoxyacetophenon, Methyl-n-amylketone, Methylan methyl thranilic acid, p-methylacetophenone, methylchavicol, p-methylquinoline, methyl-β-naphthyl ketone, methyl-n-nonylacetaldehyde, methyl-n-nonyl ketone, muscon, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, nitrobenzene alcohol, n-nonlayl alcohol, n-nonlayl alcohol n-octylaldehyde, p-oxy-acetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegon, safrole, salicylic acid isoamyl ester, salicylic acid methyl ester, salicyl acid hexyl ester, oleic acid, cyclolhexyl enolylolate, sylololylololate, sylololylololate, sylololylolol, olicylic acid Veratrum aldehyde, cinnamaldehyde, cimate alcohol, cinnamic acid, ethyl cinnamate, benzyl cinnamate. The more volatile fragrances include, in particular, the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures. Examples of more volatile fragrances are alkyisothiocyanates (alkyl mustards), butanedione, limonene, linalool, linaylacetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinylacetate, citral, citronellal.

To the aesthetic impression of the enclosed liquid or the water-soluble container can improve they are dyed with suitable dyes. Preferred dyes, the selection of which is of no difficulty for the person skilled in the art high storage stability and insensitivity to the rest Ingredients of the agents and against light. Are the agents of the invention used for textile cleaning, the dyes used not a distinct one substantivity across from Have textile fibers so as not to stain them.

As a hydrotrope or solubilizer are substances that are present in others because of their presence a certain solvent practically insoluble Compounds in this solvent soluble or make emulsifiable (solubilization). There are solution mediators with the slightly soluble Substance is a molecular compound and those that work through micell formation. One can also say that only solution brokers a so-called latent solvent lend its solvency. With water as (latent) solvent one speaks instead of solution brokers mostly from hydrotropes, in certain cases better from emulsifiers.

Foam inhibitors which can be used in the agents according to the invention include soaps, oils, fats, paraffins or silicone oils, which can optionally be applied to carrier materials. Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the aforementioned materials. Agents preferred in the context of the present application contain paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are structured according to the scheme (R ₂ SiO) x and are also referred to as silicone oils. These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids with a molecular weight between 1000-150,000, and viscosities between 10 u. 1,000,000 mPas.

Suitable anti-redeposition agents, which are also referred to as soil repellents are, for example, nonionic Cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30 wt .-% and of 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 nonionic modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.

Optical brighteners (so-called "whiteners") can agents according to the invention can be added to the graying and yellowing of the treated Eliminate textiles. These substances pull on the fiber and cause a brightening and feigned bleaching effect by they invisible ultraviolet radiation into visible longer-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-biphenylene, Methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid, Benzoxazole, Benzisoxazole and Benzimidazole systems and the pyrene derivatives substituted by heterocycles.

Graying inhibitors have that Task, the detached from the fiber Keep dirt suspended in the fleet and keep it moving to prevent the 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 cellulose ethers such as carboxymethyl cellulose (sodium salt) can also be used, Methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures.

Because textile fabrics, especially from Rayon, rayon, cotton and their blends, for wrinkling can, because the individual fibers prevent bending, kinking. Pressing and squeezing The agents according to the invention can be sensitive across the grain contain synthetic anti-crease agents. These include, for example synthetic products based on fatty acids, fatty acid esters. fatty acid amides, -alkyl esters, -alkylolamides or fatty alcohols, mostly with Ethylene oxide are implemented, or products based on lecithin or modified phosphoric acid ester. One in particular textile finishing Suitable care and substance is the cottonseed oil, which for example by pressing out the brown, cleaned cotton seeds and refining with about 10% sodium hydroxide or by extraction made with hexane at 60-70 ° C can be. Such cotton oils contain 40 to 55 wt .-% linoleic acid, 16 to 26 wt .-% oleic acid and 20 to 26% by weight palmitic acid. More on fiber smoothing and fiber care particularly preferred agents are the glycerides, in particular the monoglycerides of fatty acids such as glycerol monooleate or glycerol monostearate.

To fight microorganisms can the agents according to the invention contain antimicrobial agents. A distinction is made here depending on the antimicrobial spectrum and mechanism of action between Bacteriostatics and bactericides, fungistats and fungicides etc. Important substances from these groups are, for example, benzalkonium chlorides, Alkylarlyl sulfonates, halophenols and phenol mercuric acetate, wherein in the inventive means also entirely these connections can be dispensed with.

To unwanted, due to exposure to oxygen and other oxidative processes caused changes in the washing and To prevent cleaning agents and / or the treated textiles, can the agents according to the invention Contain antioxidants. This connection class includes, for example substituted phenols, hydroquinones, pyrocatechols and aromatic Amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

An increased wearing comfort can the additional Use of antistatic agents result, the agents according to the invention additionally enclosed become. Antistatic agents increase the Surface conductivity and enable thus an improved drainage formed charges. External antistatic agents are usually substances with at least one hydrophilic molecular ligand and give on the surfaces a more or less hygroscopic film. These are mostly surface-active Antistatic agents can be broken down into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphoric (phosphoric acid esters) and divide sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable also as antistatic for Textiles or as an additive to detergents, with an additional Finishing effect is achieved.

Phobing and impregnation processes are used to finish Textiles with substances that prevent the deposition of dirt or make it easier to wash out. Preferred phobic and impregnating are perfluorinated fatty acids, also in the form of their aluminum u. Zirconium salts, organic silicates, silicones, polyacrylate with perfluorinated alcohol component or with perfluorinated acyl or sulfonyl radical-coupled, polymerizable compounds. Also Antistatic agents can be included. The dirt-repellent finish with phobing and impregnating agents is often classified as an easy-care kit. The intrusion the impregnating agent in the form of solutions or emulsions of the active substances concerned can be added by adding Wetting agents that reduce the surface tension are facilitated. On Another area of application of phobing and impregnating agents is water-repellent equipment of textile goods, tents, tarpaulins, leather etc., in contrast to that the tissue pores are not closed to make them waterproof, the fabric therefore remains breathable (hydrophobic). The one for waterproofing coat the water repellant used Textiles, leather, paper, wood etc. with a very thin layer hydrophobic groups, such as longer ones Alkyl chains or siloxane groups. Suitable water repellents are z. B. paraffins, waxes, metal soaps, etc. with additives Aluminum or zirconium salts, quaternary ammonium compounds with long-chain Alkyl residues, urea derivatives, fatty acid-modified melamine resins, Chromium complex salts, silicones, tin organic compounds and glutardialdehyde as well as perfluorinated compounds. The hydrophobic materials feel does not look greasy; nevertheless - similar to greased substances - water drops pearl on them without wetting. So z. B. silicone-impregnated Textiles a soft touch u. are water u. stain-resistant; Stains from ink, wine, fruit juices and the like are easier to remove.

The agents according to the invention can contain fabric softeners to care for the textiles and to improve the textile properties such as a softer "handle" (softening) and reduced electrostatic charging (increased wearing comfort). The active ingredients in fabric softener formulations are "esterquats", quaternary ammonium compounds with two hydrophobic residues, such as for example, disteraryldimethylammonium chloride, which, however, due to its insufficient biodegradability, is increasingly being replaced by quaternary ammonium compounds which contain ester groups in their hydrophobic residues as predetermined breaking points for biodegradation. Such "esterquats" with improved biodegradability can be obtained, for example, by mixing mixtures of methyldiethanolamine and / or triethanolamine esterified with fatty acids and the reaction products subsequently in a manner known per se with alkylating agents terniert. Dimethylolethylene urea is also suitable as a finish.

To improve water absorption, the Rewettability of the treated textiles and for relief of ironing of the treated textiles can in the agents according to the invention, for example Silicone derivatives are used. These also improve that rinse behavior of the agents according to the invention due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups one to five Have carbon atoms and are partially or completely fluorinated. preferred Silicones are polydimethylsiloxanes, which may be derivatized could be and then are amino-functional or quaternized or Si-OH-, Si-H- and / or have Si-Cl bonds. Other preferred silicones are the polyalkylene oxide modified polysiloxanes, i.e. polysiloxanes, which have, for example, polyethylene glycols and the polyalkylene oxide-modified Dimethylpolysiloxanes.

Protein hydrolyzates are on the ground their fiber care effect further within the scope of the present Invention preferred active substances in the field of washing and Cleaning supplies. Protein hydrolyzates are product mixtures that are created by acidic, basic or enzymatically catalyzed breakdown of proteins (proteins) become. According to the invention, protein hydrolyzates both vegetable and animal origin can be used. Animal protein hydrolyzates are, for example, elastin, collagen, Keratin, silk and milk protein protein hydrolyzates, too may be in the form of salts. Preferred according to the invention is the use of protein hydrolyzates of plant origin, z. B. soy, almond, rice, pea, potato and wheat protein hydrolyzates. Although the use of the protein hydrolyzates as such is preferred where appropriate, amino acid mixtures obtained otherwise or single amino acids such as arginine, lysine, histidine or pyrroglutamic acid become. Also possible is the use of derivatives of protein hydrolyzates, for example in the form of their fatty acid condensation products.

Finally, the agents according to the invention also contain UV absorbers that attach to the treated textiles and lightfastness of the fibers improve. Connections that you want Have properties are, for example, those due to non-radiation Deactivating active compounds and derivatives of benzophenone with substituents in the 2- and / or 4-position. Furthermore, too substituted benzotriazoles, in the 3-position phenyl substituted acrylates (Cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes as well as natural substances such as umbelliferone and the body's own urocanic suitable.

Detergents for automatic dishwashing can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents and glass corrosion inhibitors being particularly important in the field of automatic dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, active chlorine-containing agents are often found in detergent formulations, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate and the manganese complexes [Me-TACN) Mn ^{I V} (m-0) ₃ Mn ^{I V} (Me-TACN)] ²⁺ (PF ₆ ^- ) ₂ , [Me-McTACN) Mn ^IV (m-0) ₃ Mn ^IV (Me-McTACN)] ²⁺ (PF ₆ ^- ) ₂ , [Me-TACN) Mn ^III (m-0) (m-0Ac) ₂ Mn ^III (Me-TACN) ] ²⁺ (PF ₆ ^- ) ₂ and [Me-McTACN) Mn ^{I I I} (m-0) (m-OAc) ₂ Mn ^III (Me-McTACN)] ²⁺ (PF ₆ ^- ) ₂ , where Me- TACN stands for 1,4,7-trimethyl-1,4,7-triazacyclononane and Me-McTACN stands for 1,2,4,7-tetramethyl-1,4,7-triazacyclononane. Zinc compounds can also be used to prevent corrosion on the wash ware.

Within the scope of the present invention it is preferred, in addition at least one silver protection agent selected from the group of triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the Alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole, in amounts from 0.001 to 1% by weight, preferably from 0.01 to 0.5 % By weight and in particular from 0.05 to 0.25% by weight, in each case based the total weight of the solids enclosed in the water-soluble containers according to the invention, use.

In addition to the aforementioned silver protection agents, agents according to the invention can also contain one or more substances for reducing glass corrosion. In the context of the present application, in particular additives of zinc and / or inorganic and / or organic zinc salts and / or silicates, for example the layered crystalline sodium disilicate SKS 6 from Clariant GmbH, and / or Water-soluble glasses, for example glasses which have a mass loss of at least 0.5 mg under the conditions specified in DIN ISO 719, are preferred for reducing glass corrosion.

A preferred class of compounds the agents according to the invention for preventing glass corrosion can be added, are insoluble Zinc salts. these can yourself during the dishwashing process on the glass surface accumulate and prevent metal ions from dissolving there from the glass network as well as the hydrolysis of the silicates. Prevent additionally these insoluble Zinc salts also the deposit of silicate on the glass surface, so that this Glass is protected from the consequences described above.

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 zinc compounds mentioned are in the agents according to the invention used in amounts that contain zinc ions between the agents 0.02 and 10 wt .-%, preferably between 0.1 and 5.0 wt .-% and in particular between 0.2 and 1.0 wt .-%, each based on the agent without the container. The exact content of the agents in the zinc salt or zinc salts is naturally dependent on the type of zinc salts - each less soluble the zinc salt used, the higher its concentration should be in the agents according to the invention his.

Another preferred class of Compounds are magnesium and / or zinc salts) at least one monomeric and / or polymeric organic acid. These also cause repeated use does not change the surfaces of glassware, especially no cloudiness, Streaks or scratches but also no iridescence on the glass surfaces become.

Although according to the invention all magnesium and / or zinc salts) of monomeric and / or polymeric organic acids can be contained in the claimed agents, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the groups of unbranched saturated or unsaturated monocarboxylic acids, branched saturated or unsaturated monocarboxylic acids, saturated and unsaturated dicarboxylic acids, aromatic mono-, di- and tricarboxylic acids, sugar acids, hydroxy acids, oxo acids, amino acids and / or polymeric carboxylic acids are preferred. Within the scope of the present invention, the acids mentioned below are again preferred within these groups:
The spectrum of the zinc salts of organic acids, preferably organic carboxylic acids preferred according to the invention, extends from salts which are sparingly or not soluble in water, ie have a solubility below 100 mg / L, preferably below 10 mg / L, in particular no solubility, up to such salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, particularly preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C. water temperature). The first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

In a further preferred embodiment of the present invention contain the agents according to the invention at least one zinc salt, but no magnesium salt of an organic one Acid, which is preferably at least one zinc salt of an organic Carboxylic acid, particularly preferably a zinc salt from the group of zinc stearate, Zinc oleate, zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate is. Zinc ricinoleate, zinc betaate and zinc oxalate are also preferred.

A preferred agent in the context of the present invention contains zinc salt in amounts of 0.1 to 5% by weight, preferably 0.2 to 4% by weight and in particular 0.4 to 3% by weight, or zinc in oxidized form (calculated as Zn ²⁺ ) in amounts from 0.01 to 1% by weight, preferably from 0.02 to 0.5% by weight and in particular from 0.04 to 0.2% by weight , each based on the agent without the container.

Contain particularly preferred agents at least one zinc salt of an organic acid, preferably selected from from the group zinc oleate, zinc stearate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate.

Within the scope of the present invention particularly preferred detergent or cleaning agent compositions can be determined using a modified Olten test. According to this modified tests are 300 g of the liquid detergent or cleaning agent composition to 20 ° C tempered, with stirring (Stirrers 3-blade propeller, 800 rpm) at 80 ° C tempered solution of 50 g sodium sulfate in 200 mL water in a 1 L cylinder Dewar (Half-life: 10 hours) and then the temperature change dependent on determined by time. Preferred liquid detergent or cleaning agent composition are distinguished in this test by the fact that five minutes after the entry of 300 g one at 20 ° C tempered sample of liquid Detergent or cleaning agent composition in a temperature controlled to 80 ° C solution of 50 g sodium sulfate in 200 mL water the temperature of this solution less than 72 ° C, preferably less than 70 ° C, particularly preferably less than 68 ° C. and in particular less than Is 65 ° C.

The liquid detergent and cleaning agent compositions according to the invention are packed in water-dispersible or water-soluble containers. The corresponding Packaging materials are known from the prior art and come, for example, from the group (acetalized) polyvinyl alcohol, Polyvinyl pyrrolidone, polyethylene oxide, gelatin and mixtures thereof.

Particularly preferred portioned according to the invention Detergent or cleaning agent compositions are characterized in that that the water-soluble or water-dispersible containers one or more water-soluble) Polymer (s), preferably a material from the group (if appropriate acetalized) polyvinyl alcohol (PVAL), polyvinyl pyrrolidone, polyethylene oxide, Gelatin, cellulose, and their derivatives and mixtures thereof.

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

enthalten."Polyvinyl alcohols" (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure

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

contain.

Commercial polyvinyl alcohols, the as white-yellowish Powder or granules with degrees of polymerization in the range of approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol) are offered have degrees of hydrolysis of 98-99 and 87-89 mol%, respectively, so they still contain a residual content of acetyl groups. The polyvinyl alcohols are characterized on the part of the manufacturer by specifying the degree of polymerization the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

Polyvinyl alcohols are dependent on Degree of hydrolysis soluble in water and a few strongly polar organic solvents (Formamide, dimethylformamide, dimethyl sulfoxide); from (chlorinated) They do not attack hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. The water solubility can be achieved by post-treatment with aldehydes (acetalization) Complexing with Ni or Cu salts or by treatment with dichromates, boric acid or reduce borax. The coatings are made of polyvinyl alcohol largely impenetrable for Gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but let water vapor pass through.

Within the scope of the present invention it is preferred that the water-soluble or water-dispersible containers comprises a polyvinyl alcohol, whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol% is.

Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the containers, it being preferred according to the invention that the water-soluble or water-dispersible container comprises a polyvinyl alcohol, the molecular weight of which is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , particularly preferably from 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 .

The degree of polymerization of such preferred Polyvinyl alcohols is between about 200 to about 2100, preferably between approximately 220 to about 1890, more preferably between about 240 to about 1680 and especially between about 260 to about 1500th

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88 and Mowiol ^® 8-88.

Further polyvinyl alcohols that are particularly suitable as material for the container can be found in the table below:

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

The water solubility of PVAL can be due to Aftertreatment with aldehydes (acetalization) or ketones (ketalization) changed become. As particularly preferred and pronounced on the basis of it good solubility in cold water Polyvinyl alcohols have been found to be particularly advantageous, those with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof can be acetalized or ketalized. As extremely beneficial The reaction products made of PVAL and starch are to be used.

Furthermore, the water solubility by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, Change borax and so targeted to desired Set values. PVAL films are largely impenetrable for gases like oxygen, nitrogen, helium, hydrogen, carbon dioxide however water vapor will pass through.

Examples of suitable water-soluble PVAL films are the PVAL films available from Syntana Handelsgesellschaft E. Harke GmbH & Co. under the name "SOLUBLON ^® ". Their solubility in water can be adjusted to the degree, and films of this product range are available which are soluble in the aqueous phase in all temperature ranges relevant to the application.

Polyvinylpyrrolidones, abbreviated as PVP, can be described by the following general formula:

PVP are through radical polymerization made from 1-vinylpyrrolidone. Commercial PVP have molecular weights in the range of approx. 2,500 to 750,000 g / mol and are called white, hygroscopic Powder or offered as aqueous solutions.

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula H- [O-CH ₂ -CH ₂ ] _n -OH which are produced industrially by base-catalyzed polyaddition of ethylene oxide (oxirane) in systems containing mostly small amounts of water with ethylene glycol as the starting molecule. They have molar masses in the range from approx. 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n from approx. 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.

Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as a water-soluble coating material is particularly in the pharmaceutical industry in the form of hard or soft gelati necapsules extremely widespread. In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.

Are preferred within the scope of the present Invention also means according to the invention, the packaging of at least partially water-soluble film of at least a polymer from the group starch and Starch derivatives, Cellulose and cellulose derivatives, in particular methyl cellulose and Mixtures of this consists.

Starch is a homoglycan, being the glucose units are α-glycosidic connected are. Strength is made up of two components of different molecular weights: from approx. 20 to 30% straight-chain amylose (MW. approx. 50,000 to 150,000) and 70 to 80% branched chain amylopectin (MW approx. 300,000 to 2,000,000). There are also small amounts of lipids, phosphoric acid and Cations included. While the amylose due to the binding in the 1,4-position long, helical, intertwined Forms chains with about 300 to 1,200 glucose molecules the chain for amylopectin after an average of 25 glucose units through 1,6-binding to a knot-like Formations with about 1,500 to 12,000 molecules of glucose. In addition to pure starch to make water soluble wrappings the detergent, detergent and detergent portions within the scope of the present invention also starch derivatives suitable, which can be obtained by polymer-analogous reactions from starch. Such chemically modified starches include, for example, products from esterifications or etherifications, in which hydroxy hydrogen atoms have been substituted. But also Strengthen, in which the hydroxy groups against functional groups that do not have a Oxygen atoms are replaced, can be used as starch derivatives deploy. The starch derivatives group, for example Alkali strengths, carboxymethyl (CMS), starch ester and - ether as well as amino strengths.

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 approx. 500 to 5,000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions can also be used in the context of the present invention. 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. A cellulose derivative used with particular preference as a water-soluble or water-dispersible packaging material in the context of the present invention is hydroxypropylmethyl cellulose (HPMC).

The water-soluble or water-dispersible Container, which are the agents according to the invention can contain produced by any of the methods described in the prior art become. In preferred embodiments In the present invention, these containers are Foil bags (so-called pouches) or around injection molding, deep-drawing or blow molded body. Preferred laundry detergents according to the invention or detergent compositions are therefore characterized in that that the water-soluble or water-dispersible containers a film and / or an injection molded part and / or a blow molded part and / or includes a deep-drawn part.

Are the invention as packaging selected container formed in the form of foil bags, it is preferred that the water-soluble foil, which forms the bag, a thickness of 1 to 150 microns, preferably from 2 to 100 microns, particularly preferably from 5 to 75 μm and in particular from 10 to 50 μm.

Are considered water soluble or water-dispersible containers however, injection molding or deep-drawn body used, the wall of preferred containers has a thickness of 50 to 300 μm, preferably from 70 to 200 μm and in particular from 80 to 150 μm on.

A method which is particularly suitable for the production of water-soluble or water-dispersible containers according to the invention is injection molding. Injection molding refers to the shaping of a molding compound in such a way that the mass contained in a mass cylinder for more than one injection molding process plastically softens under the action of heat and flows under pressure through a nozzle into the cavity of a previously closed tool. The process is mainly used for non-hardenable molding compounds that solidify in the mold by cooling. Injection molding is a very economical, modern process for the production of non-cutting shaped objects and is particularly suitable for automated mass production. In practical operation, the thermoplastic molding materials (powder, granules, cubes, pastes, etc.) are heated to liquefaction (up to 180 ° C) and then injected under high pressure (up to 140 MPa) into closed, two-part, that is, from dies (formerly Die) and core (formerly patrix), preferably water-cooled hollow molds, where they cool and solidify. Piston and screw injection molding machines can be used. Suitable molding compounds (injection molding compounds) are water-soluble polymers such as, for example, the cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyr mentioned above rolidone, alginates, gelatin or starch.

• a) Spritzgießen eines Behälters aus einem wasserlöslichen oder wasserdispergierbaren Material,
• b) Befüllen des Basisformkörpers mit einer flüssigen Wasch- oder Reinigungsmittelzusammensetzung, umfassend eine wasserarme Matrix und darin dispergierte Phosphate,
• c) Verschließen des befüllten Behälters mit einer wasserlöslichen oder wasserdispergierbaren Verschlußeinheit,

dadurch gekennzeichnet, daß das dispergierte Phosphat Natriumtripolyphosphat umfaßt und der Phase-I Anteil des dispergierten Natriumtripolyphosphats bezogen auf das Gesamtgewicht des dispergierten Natrimtripolyphosphat weniger als 25 Gew.-% beträgt.The subject of the present application is therefore also a method for producing a filled water-soluble container comprising the steps:

• a) injection molding a container from a water-soluble or water-dispersible material,
• b) filling the base molding with a liquid detergent or cleaning agent composition, comprising a low-water matrix and phosphates dispersed therein,
• c) closing the filled container with a water-soluble or water-dispersible closure unit,

characterized in that the dispersed phosphate comprises sodium tripolyphosphate and the phase I proportion of the dispersed sodium tripolyphosphate based on the total weight of the dispersed sodium tripolyphosphate is less than 25% by weight.

In the case of water-soluble or water-dispersible Shutter unit, which is used in step c) to close the filled container it is preferably an injection molded body, this body preferably which has the same spatial shape as the basic molded body. Is preferred in the frame the present invention consequently in particular a method in which the closure unit the has the same spatial shape as the container produced in step a).

In a further preferred embodiment of the described method according to the invention as a locking unit a film is used, this film, for example, by Thermoforming process can be processed shaping. Another preferred subject of the present application is accordingly a The aforementioned method, characterized in that it is in the water-soluble introduced in step c) shutter unit to be a water soluble or water-dispersible film.

From the previous information yourself that the Thickness of water soluble outer wall inventive container not is necessarily homogeneous, but depending on the manufacturing process chosen can fluctuate. It is part of the present application prefers these fluctuations within the above preferred ranges for wall thickness move container according to the invention.

Also closing Basic tablet with the locking unit can be done in different ways. Preferred within the present invention will use closure methods which are based on partial Solvation of the surface of the container and / or the locking unit and / or on heating the container and / or the closure unit based on a temperature at which they are plastically deformable. Both partial solvation and warming will preferably not on the entire surface of the container and / or the entire surface surface the locking unit take place, but only in the areas in which the following Sealing should take place with the formation of a sealed seam. The warming the surface of the container and / or the closure unit is preferably done through the use of hot air, hot plates, heated Rolling or heat radiation, preferably laser radiation or other IR sources such as glass fiber (optical fiber). Preferred subject of the present application is therefore a previously described method in which the sealing in step c) is carried out by means of fusion bonding.

In addition to the injection molding process described is the rotary die process for manufacturing in a special way means according to the invention suitable, with the term of the rotary die process in the context the present application also process variants such as the Accogel process, the Reciprocating-Die process using a Norton encapsulation machine, the Colton and Upjohn methods are summarized. The The concept of the rotary die method is therefore not restrictive understand, but embraces all process variants known to the person skilled in the art, which are used of form rollers are suitable for the production of filled containers.

• a) Zuführen zweier unter Lösungsmitteleinfluß und/oder Temperatureinfluß plastisch deformierbarer wasserlösllicher oder wasserdispergbierbar Folien auf zwei sich gegensinnig drehende Formwalzen, wobei mindestens eine dieser Formwalzen in ihrer Oberfläche Vertiefungen zur Aufnahme des herzustellenden Behälters aufweist, welche durch Stege begrenzt sind,
• b) Auftragen eines Lösungsmittels auf mindestens eine dieser Folien unter mindestens anteilsweiser Solvatisierung der Oberfläche dieser Folie und/oder Erwärmen mindestens einer dieser Folien auf eine Temperatur bei welcher diese Folie plastisch deformierbar ist,
• c) optionales Tiefziehen und/oder Eindrücken und/oder Einsinken lassen mindestens einer dieser Folien in die Vertiefungen der Formwalze,
• d) Einfüllen, einer flüssigen Wasch- oder Reinigungsmittelzusammensetzung, umfassend eine wasserarme Matrix und darin dispergiertes Phosphat,
• d) optionales Auftragen eines Klebemittels,
• e) Zusammenführen der zwei unter Lösungsmitteleinfluß und/oder Temperatureinfluß plastisch deformierbarer wasserlösllicher Folien im Zwischenraum der zwei sich gegensinnig drehenden Formwalzen,
• f) Verkleben und/oder Abquetschen der Folien durch Krafteinwirkung der Stege auf die Folien unter Heraustrennung des Behälters,

dadurch gekennzeichnet, daß das dispergierte Phosphat Natriumtripolyphosphat umfaßt und der Phase-I Anteil des dispergierten Natriumtripolyphosphats bezogen auf das Gesamtgewicht des dispergierten Natrimtripolyphosphat weniger als 25 Gew.-% beträgt.In the context of the present application, however, an automatic rotary die process using two rotating shaping rollers is particularly preferred, comprising the steps:

• a) supplying two plastically deformable, water-soluble or water-dispersible foils which are plastically deformable under the influence of solvent and / or temperature, onto two mold rolls rotating in opposite directions, at least one of these mold rolls having depressions in their surface for receiving the container to be produced, which are delimited by webs,
• b) applying a solvent to at least one of these films with at least partial solvation of the surface of this film and / or heating at least one of these films to a temperature at which this film is plastically deformable,
• c) optional deep drawing and / or pressing in and / or sinking in at least one of these foils into the depressions of the forming roll,
• d) filling, a liquid detergent or cleaning composition comprising a low-water matrix and phosphate dispersed therein,
• d) optional application of an adhesive,
• e) bringing together the two water-soluble foils which are plastically deformable under the influence of solvent and / or temperature in the space between the two shaping rollers which rotate in opposite directions,
• f) the foils are glued and / or squeezed off by the force of the webs on the foils, with the container being separated,

characterized in that the dispersed phosphate comprises sodium tripolyphosphate and the phase I proportion of the dispersed sodium tripolyphosphate based on the total weight of the dispersed sodium tripolyphosphate is less than 25% by weight.

When performing this procedure is to note that the temperatures for the plastic deformation in step b) and the heat seal can clearly distinguish. The general rule is that the temperature selected in steps b) and c) below that for The fusion bonding described above as part of the injection molding process necessary temperatures. For example, HPMC films used, is the temperature for the plastic deformation preferably 85 to 90 ° C, while the fusion bonding in the temperature range from 150 to 170 ° C. For PVA films, the temperatures are for plastic Deformation at about 150 ° C, while the fusion bonding takes place in the range from 160 to 200 ° C. As in the aforementioned make can the warming of the container materials by hot air, thermal radiation or direct contact with suitable heating plates or heated ones Rolling done.

• a) Zuführen einer unter Lösungsmitteleinfluß und/oder Temperatureinfluß plastisch deformierbaren wasserlösllichen oder wasserdispergierbaren Folie auf eine Matrize, welche Vertiefungen zur Aufnahme des herzustellenden Behälters aufweist,
• b) Auftragen eines Lösungsmittels auf diese Folie unter mindestens anteilsweiser Solvatisierung der Oberfläche dieser Folie und/oder Erwärmen dieser Folie bis zu einer Temperatur, bei welche diese plastisch deformierbar ist,
• c) Tiefziehen und/oder Eindrücken und/oder Einsinken lassen dieser Folie in die Vertiefungen der Matrize,
• d) Beaufschlagen der Folie mit einer flüssigen Wasch- oder Reinigungsmittelzusammensetzung, umfassend eine wasserarme Matrix und darin dispergiertes Phosphat,
• e) Zuführen einer weiteren wasserlöslichen oder wasserdispergierbaren Folie und Verschließen der tiefgezogenen Form mit dieser Folie,

dadurch gekennzeichnet, daß das dispergierte Phosphat Natriumtripolyphosphat umfaßt und der Phase-I Anteil des dispergierten Natriumtripolyphosphats bezogen auf das Gesamtgewicht des dispergierten Natrimtripolyphosphat weniger als 25 Gew.-% beträgt.Another method suitable for the production of water-soluble or water-dispersible containers is the so-called deep-drawing method, in particular the thermoforming method, the heating used in typical thermoforming methods optionally supplementing / replacing the at least partial solvation of these foils in the context of the present application can be. The present application therefore also relates to a method for producing a water-soluble container, comprising the steps:

• a) supplying a water-soluble or water-dispersible film which is plastically deformable under the influence of solvent and / or temperature, to a die which has depressions for receiving the container to be produced,
• b) applying a solvent to this film while at least partially solvating the surface of this film and / or heating this film to a temperature at which it is plastically deformable,
• c) deep drawing and / or indenting and / or sinking this film into the recesses of the die,
• d) applying a liquid detergent or cleaning agent composition to the film, comprising a low-water matrix and phosphate dispersed therein,
• e) supplying a further water-soluble or water-dispersible film and sealing the deep-drawn mold with this film,

characterized in that the dispersed phosphate comprises sodium tripolyphosphate and the phase I proportion of the dispersed sodium tripolyphosphate based on the total weight of the dispersed sodium tripolyphosphate is less than 25% by weight.

While sink in or indent the plastically deformable film in step c) of the claimed Appropriate procedures for the deformation of these foils represent, is nevertheless within the scope of the present application A particularly preferred method in which the film in step c) under the action of a vacuum on the plastically deformable film is deep-drawn, which is preferably until after the completion of the process remains in step e) and the film is retained in the recess.

Closing a container according to the invention in Step e) of the aforementioned deep-drawing process, as in the rest described methods by gluing or melt gluing take place, both methods optionally in combination with one additional Pressure can. Depending on the composition, suitable adhesives are suitable the films, in addition to the adhesives known to the person skilled in the art, also solvents, such as water. The application of the adhesive to the Foil is made in a preferred process variant of the latter Method preferably after step b) and / or step c) and / or Step d).

However, the seal can also by melt sealing or pressure. Repetitions should be avoided regarding the sealing at this point on the detailed descriptions as part of the injection molding and rotary die processes directed. In a preferred process variant of the thermoforming process accordingly, the closure takes place in step e) by temperature and / or due to pressure.

• (a) Urformen eines Vorformlings aus einer Blasformmasse basierend auf einem wasserlöslichen polymeren Thermoplasten;
• (b) Blasformen des Vorformlings zu einem Hohlkörper;
• (c) Füllen des Hohlkörpers mit dem erfindungsgemäßen Wasch- oder Reinigungsmittel; und
• (d) flüssigkeitsdichtes Verschließen des blasgeformten Hohlkörpers;

A fourth method which is particularly suitable for producing the water-soluble or water-dispersible containers is blow molding. Such a method comprises the steps:

• (a) master shaping of a preform from a blow molding compound based on a water-soluble polymer thermoplastic;
• (b) blow molding the preform into a hollow body;
• (c) filling the hollow body with the washing or cleaning agent according to the invention; and
• (d) liquid-tight sealing of the blow-molded hollow body;

In a particularly preferred embodiment has the manufactured according to one of the methods described above water-soluble or water-dispersible containers one or more embossing (s) and / or one or more imprints). Those enclosed in the container can also be used Solids of this type or have imprints. The embossing or de print can, in addition to lettering, also patterns, shapes, etc. include. That way you can for example, universal detergent with a T-shirt symbol, color detergent with a wool symbol, detergent for automatic dishwashing Symbols like glasses, Plates, pots, Pans etc. to be identified. The creativity of product managers there are no limits. For example, are suitable as lettering still the name of the product or the manufacturer.

These water-soluble films can after different manufacturing processes can be produced. Here are principally Blowing, calendering and casting processes to call. In a preferred method, the foils are used starting from a melt with air over a blow mandrel to one Blown hose. The calendering process, too belongs to the preferred manufacturing process, are by suitable additions plasticized raw materials atomized to form the foils. Here it may be necessary, in particular, to inject a Connect drying. In the casting process, which is also one of the preferred manufacturing processes an aqueous polymer preparation placed on a heatable drying roller, after evaporation of the Water is optionally cooled and peeled off the film as a film. If necessary, this film before or during of peeling additionally powdered.

Basically, all come as container materials Materials in question under the given conditions of a Washing, rinsing or cleaning process (temperature, pH, concentration of detergent Components) in the aqueous phase Completely or partially solve can. The polymer materials can particularly preferably the groups (optionally partially acetalized) Polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, Cellulose and its derivatives, starch and their derivatives, especially modified starches, and mixtures (polymer blends, associations, Coextrudates etc.) of the materials mentioned - see above. Gelatin and polyvinyl alcohols are particularly preferred the two materials mentioned in combination with starch or modified starch. Inorganic salts and mixtures thereof also come as materials for the at least partially water-soluble coating in question.

An embodiment is preferred according to the invention, according to the container as a whole water soluble is, d. H. if used as intended when washing or machine cleaning, completely dissolves when the for the loosening provided conditions are met. Major advantage of this embodiment is that itself the container within a practically relevant short time - as a non-limiting example can be a few seconds to 5 minutes - under precisely defined conditions solve at least partially in the cleaning liquor and thus accordingly the requirements the enveloped Content, d. H. the cleaning active material or several materials, into the fleet.

In another, also due advantageous features of preferred embodiment of the invention, the water-soluble container comprises less good or not water soluble or only at a higher temperature water-soluble Areas and well water soluble or areas soluble in water at low temperature. With others Words: the container does not consist of a uniform water solubility in all areas showing material, but from materials of different Water solubility. Areas of good water solubility must be distinguished on the one hand from areas with less good water solubility, with poor or lack of water solubility or from areas where water solubility is only at a higher temperature or only at a different pH value or only at a changed one Electrolyte concentration the desired Value reached, on the other hand. This can lead to improper use under adjustable conditions release certain areas of the container while others Areas remain intact. This creates a pore or hole Container, penetrate into the water and / or liquor, wash-active, rinse-active or detach active ingredients and discharge them from the container can. In the same way you can also systems in the form of multi-chamber containers or in the form of one another arranged containers ("Onion system") can be provided. This is how systems can be used controlled release of washing-active, rinsing-active or cleaning-active Manufacture ingredients.

The invention is not subject to any restrictions on the formation of such systems. Thus, containers can be provided in which a uniform polymer material comprises small areas of incorporated compounds (for example salts) which are more water-soluble than the polymer material. On the other hand, several polymer materials with different water solubility can also be mixed (polymer blend), so that the more rapidly soluble polymer material is caused by water under defined conditions or the fleet is disintegrated faster than the slower soluble one.

It corresponds to a particularly preferred one embodiment the invention that the less water soluble Areas or not water soluble at all Areas or only at higher Temperature water soluble Areas of the containers Areas are made of a material that is chemically essentially one the water-soluble Areas or water-soluble areas at a lower temperature, however, a higher one Has layer thickness and / or a changed degree of polymerization of the same polymer and / or a higher degree of crosslinking thereof Has polymer structure and / or a higher degree of acetalization (at PVAL, for example with saccharides, polysaccharides, such as starch) and / or a content of water-insoluble Has salt components and / or a content of a water-insoluble Has polymers. Even considering the fact that itself the containers not completely to solve, can detergent or cleaning agent compositions so portioned according to the invention are provided, the beneficial properties in the release the detergent or cleaning agent composition into the respective Have fleet.

It has been shown that at the one in water soluble or water-dispersible containers packaged detergent and cleaning agent compositions due to manufacturing Problems arise. When packaging the detergent and cleaning agent compositions in the water-soluble container fine particles stick to the container and get into the sealing of the container in the formed seams. By these particles in the seal are against the seams in question the atmosphere not completely tight, leading to stability problems the detergent or cleaning agent composition as well as leaks the appropriate seams to lead can.

With liquid detergent or cleaning agent compositions can additionally happen that Drops or threads of product, which are included in the seam to be formed when in use a heat sealing process are so thermally stressed that the composition boils and thereby to further leaks, discoloration or even in an emergency accidents can result from thermal decomposition.

Interestingly, there is a change the viscosity the liquid Detergent or cleaning agent composition not successful; she rather must through appropriate further measures be supported in product assembly, taking these measures also independently on the viscosity of funds lead to improved results.

To avoid these problems and for the Provision of a portioned liquid, i.e. pourable washing or detergent composition in which the seams of the container made of water-dispersible or water-soluble film compared to the the atmosphere are tight, it has proven to be advantageous if the portions to be portioned hydrated liquid Detergent or cleaning agent compositions certain criteria regarding the particle size of the in the low-water, liquid Matrix suspended particles.

Preferred detergent or cleaning agent compositions in the context of the present invention are therefore characterized in that that at least 70% by weight, preferably at least 80% by weight, preferably at least 85% by weight, particularly preferably at least 90% by weight and in particular at least 95% by weight of the dispersed phosphate particle sizes below 200 μm, preferably below 160 μm, particularly preferably below 120 μm and in particular below 100 μm, exhibit.

In the particle size range mentioned occur the above problems of sealing in the Seam of remaining drops or fluid threads, no longer open. there are the at least 70% by weight of the particles and the 200 μm as upper limits to understand, for example, that result from technical establish Solids used also contain small amounts of coarse fractions can. In the context of the present invention, however, it is preferred to use one preferably high and well above 70 wt .-% proportion of particles with sizes below 200 microns in the Have detergent and cleaning agent composition available. On Proportion of particularly fine particles whose particle sizes are clear less than 200 μm lie can also be advantageous.

The water-soluble or water-dispersible container material is preferably transparent. Under transparency is in the sense of this Invention to understand that the permeability within the visible spectrum of light (410 to 800 nm) greater than 20%, preferably greater than 30%, extremely preferred larger than 40% and especially larger than Is 50%. As soon as a wavelength of the visible spectrum of the Light a permeability larger than 20%, it is to be regarded as transparent in the sense of the invention.

Portioned washing or Detergent compositions packaged in transparent containers are, can contain a stabilizing agent as an essential component. Stabilizing agents in the sense of the invention are materials that the detergent components in their water-soluble, transparent containers Protect against decomposition or deactivation by light. As special Antioxidants, UV absorbers and fluorescent dyes are suitable here proved.

Particularly suitable stabilizers in the sense of the invention are the antioxidants. To un Desired to prevent changes to the formulations caused by light exposure and thus radical decomposition, the formulations may contain antioxidants. Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants. Further examples are propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long-chain (C8-C22) esters of gallic acid, such as dodecyl gallate. Other substance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives, such as isopropyl citrate, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic acid palmitate, organosulfur compounds, such as the esters of 3,3'-thiodipropionic acid with C _1-18 alkanols, in particular C _10-18 alkanols, metal ion deactivators which are capable of metal ions, such as copper, which catalyze the autooxidation. to complex, such as nitrilotriacetic acid and its derivatives and their mixtures. Antioxidants can be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight.

Another class of stabilizers that can preferably be used are the UV absorbers. UV absorbers can improve the lightfastness of the formulation components. These include organic substances (light protection filters) that are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, eg heat. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Substituted benzotriazoles, such as, for example, the water-soluble benzenesulfonic acid 3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Cibafast ^® H), are also phenyl-substituted acrylates in the 3-position ( Cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid. Of particular importance are biphenyl and especially stilbene derivatives, which are commercially available as Tinosorb ^® FD or Tinosorb ^® FR ex Ciba. 3-Benzylidene camphor or 3-benzylidene norcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor, may be mentioned as UV-B absorbers; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate; Propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene); Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropyl benzyl ester, salicylic acid homomethyl ester; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives, such as 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and Octyl Triazone or Dioctyl Butamido Triazone (Uvasorb HEB ^®); Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'methoxy-phenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-benzylidene camphor, such as 4- (2-oxo-3-bornylidene methyl) benzene sulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl, are particularly suitable as typical UV-A filters -4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds. The UV-A and UV-B filters can of course also be used in mixtures. In addition to the soluble substances mentioned, insoluble light-protection pigments, namely finely dispersed, preferably nanoized metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. Silicates (talc), barium sulfate or zinc stearate can be used as salts. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or a shape which differs in some other way from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobicized. Typical examples are coated titanium dioxide, such as titanium dioxide T 805 (Degussa) or Eusolex ^® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Micronized zinc oxide is preferably used.

UV absorbers can be present in the detergent or cleaning agent compositions in amounts of up to 5% by weight, preferably up to 3% by weight, particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1 % By weight may be included.

Another preferred one The class of stabilizers are the fluorescent dyes. Count among them the 4,4'-diamino-2,2'-stilbene disulfonic acids (flavonic acids), 4,4'-distyrylbiphenylene, Methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid, Benzoxazole, Benzisoxazole and Benzimidazole systems and those substituted by heterocycles Pyrene derivatives. The sulfonic acid salts are of particular importance of the diaminostilbene derivatives, as well as polymeric fluorescent substances.

Fluorescent substances can be found in the formulations in amounts of up to 5% by weight, preferably up to 1% by weight, particularly preferably from 0.01 to 0.5 and in particular from 0.03 to 0.1 wt .-% be included.

In a preferred embodiment the aforementioned stabilizers in any mixtures used. The stabilizers are used in amounts of up to 40% by weight, preferably up to 30% by weight, particularly preferably from 0.01 to 20 % By weight, in particular from 0.02 to 5% by weight.

As already mentioned further above, portioned detergent or cleaning agent compositions according to the invention can be provided in such a way that the packaging is water-soluble on the one hand and tightly closing on the other hand, ie sealed off from the environment. Two embodiments can be implemented according to the invention:
Thus, it corresponds to a preferred embodiment of the invention that the container (s) is / are and contain at least one gas which does not react with the detergent or cleaning agent composition, more preferably in an amount that the total pressure within the or the closed container) is above the external pressure, more preferably is at least 1 mbar above the external pressure. Very particularly preferred embodiments of these portions according to the invention contain at least one gas which does not react with the detergent or cleaning agent composition in such an amount that the total pressure inside the sealed container is at least 5 mbar, more preferably at least 10 mbar, very particularly preferably in Range from 10 mbar to 50 mbar above the external pressure. Particularly in the case of the preferred embodiments with a total pressure inside the container which is significantly above the external pressure, the visual appearance, in particular of film bags, can be significantly improved. The correspondingly packaged compositions have an increased inherent stability and give the impression of a bulging, “powerful” agent. In connection with the present invention, “external pressure” is understood to mean the pressure that prevails on the surrounding side of the containers and on the exterior of the containers acts, at the time of filling the container with the respective at least one gas.

According to the invention, the containers can contain either one or more gases. In practice, it is preferred to apply a gas to the containers due to the associated lower costs. Preferred detergent or cleaning agent portions according to the invention comprise as gases) at least one gas which is selected from the group N ₂ , noble gas (s), CO ₂ , N ₂ O, O ₂ , H ₂ , air, gaseous hydrocarbons, especially N ₂ , which is cheaply available everywhere. The gases mentioned are advantageously inert to the components of the wash-active preparation and are therefore sometimes referred to as "inert gases" in the context of the present invention.

According to another, likewise preferred embodiment is / are the container (s) completed and contain at least one substance that reacts with water, one that does not react with the wash-active preparations) Gas releases in an amount that the total pressure is within the closed container increases. Portions in which are particularly advantageous the contained in the container (s) at least one substance when reacting with water at least one that releases in an amount that the total pressure is within the closed, container by at least 1 mbar the external pressure increases, preferably by at least 5 mbar, particularly preferably by a value in the range of 5 to 50 mbar higher than the external pressure. This embodiment is particularly advantageous in that its manufacture over that embodiment, in which the gas is contained in the closed container, greatly simplified is because only the at least one substance has to be added, which at At least contact with moisture / water in the closed container generates a gas. Any moisture that has penetrated into the container continues immediately absorbed by the substance capable of reacting with water and implemented and therefore stands for a deterioration in quality the components of the detergent or cleaning agent composition no longer available. Mixed forms of portions are also conceivable, from the beginning There is at least one gas in the container and one with Water enabled reaction Substance is included.

According to a preferred embodiment of the invention, the substance which releases a gas with water is a constituent of the detergent or cleaning agent composition and, more preferably, is a hygroscopic substance which is compatible with the components of the detergent or cleaning agent composition. Such a substance is preferably metered separately from the liquid detergent or cleaning agent composition according to the invention into the water-soluble or water-dispersible container, this container preferably already within a few seconds, in particular within 10 seconds which is sealed after the gas-releasing substance comes into contact with the detergent composition. The release of the gas then increases the internal pressure inside the container to a value above atmospheric pressure and thus achieves the advantages mentioned above.

Examples of such substances are, without being understood as limiting, substances which are selected from the group consisting of bound hydrogen peroxide-containing substances, substances containing -OO groups, substances containing OCO groups, hydrides and carbides, more preferably a substance, which is selected from the group of percarbonates (particularly preferably sodium percarbonate), persulfates, perborates, peracids, M _A M _B H ₄ , where M _{A is} an alkali metal (particularly preferably Li or Na) (for example LiAlH ₄ , NaBH ₄ , NaAlH ₄ ) and M _{B is} B or Al, or M ^I ₂ C ₂ or M ^II C ₂ , where M ^{I is} a monovalent metal and M ^{II is} a divalent metal (for example CaC ₂ ).

Claims (19)

Portioned, liquid, detergent or cleaning agent composition in a water-soluble or water-dispersible container, comprising a low-water matrix and phosphate dispersed therein, characterized in that, based on the total weight of the dispersed phosphate, at least 10% by weight of the dispersed phosphate has a coating. Detergent or cleaning agent composition according to claim 1, characterized in that related to the total weight of the dispersed phosphate at least 30 % By weight, preferably at least 50% by weight, particularly preferably at least 70% by weight and in particular at least 90% by weight of a coating exhibit. Detergent or cleaning composition according to one of claims 1 or 2, characterized in that the Coating at least one substance selected from the group of water-soluble organic Polymers, preferably the water-soluble organic homo- and / or copolymers, particularly preferably from Group of water soluble Homopolymers, particularly preferably from the group of polyethylene glycols and / or polypropylene glycols and in particular from the group of Polyethylene glycols and / or poly propylene glycols with a molecular weight above 2000. Detergent or cleaning composition according to claims 3, characterized characterized that the Substance has a melting point above 30 ° C, preferably above 60 ° C, particularly preferably above 90 ° C and especially above 120 ° C having. Detergent or cleaning composition according to one of claims 1 to 4, characterized in that the Weight share of the coating substance (s) in the total weight of the coated dispersed phosphate between 0.5 and 15% by weight, preferably between 1 and 12% by weight and in particular between Is 2 and 8 wt .-% be. Detergent and cleaning composition according to one of claims 1 to 5, characterized in that the Total phosphate content of the detergent and cleaning agent composition between 30 and 70% by weight, preferably between 35 and 65% by weight, particularly preferably between 40 and 60% by weight and in particular between 45 and 55 wt .-%, each based on the total weight of the liquid washing and Detergent composition, without taking into account the water-soluble or water-dispersible container, is. Detergent and cleaning agent according to one of claims 1 to 6, characterized in that the dispersed phosphate polyphosphate (s), preferably tripolyphosphate (s), particularly preferably sodium and / or potassium tripolyphosphate. Detergent or cleaning composition according to one of claims 1 to 7, characterized in that the dispersed phosphate comprises sodium tripolyphosphate and the Phase-I proportion of the dispersed sodium tripolyphosphate based on the total weight of the dispersed sodium tripolyphosphate less than 25% by weight, preferably less than 20% by weight, particularly preferably less than 16% by weight, very particularly preferably less than 12 wt .-% and in particular less than 10 wt .-%, each based on the total weight of the dispersed sodium tripolyphosphate, is. Detergent or cleaning agent composition according to one of Claims 1 to 8, characterized in that the dispersed phosphate has a hydrate water content of 0.5 to 26% by weight, preferably 1 to 24% by weight and in particular 2 to 20% by weight. %, each based on the total weight of the disper gated hydrated phosphate. Detergent or cleaning composition according to one of claims 1 to 9, characterized in that at least 70% by weight, preferably at least 80% by weight, preferably at least 85% by weight, particularly preferably at least 90% by weight and in particular at least 95% by weight of the dispersed phosphate particle sizes below 200 μm, preferably below 160 μm, particularly preferably below 120 μm and in particular below 100 μm, exhibit. Detergent or cleaning composition according to one of claims 1 to 10, characterized in that the Detergent or cleaning agent composition containing free, i.e. not in the form of water of hydration and / or constitutional water water present between 0.1 and 6 wt .-%, preferably between 0.1 and 5% by weight, particularly preferably between 0.1 and 4% by weight and in particular between 0.1 and 3 wt .-%, each based on the total weight of the detergent and cleaning agent, without consideration of water soluble or water-dispersible container, having. Detergent or cleaning composition according to one of claims 1 to 11, characterized in that it non-aqueous (s) solvent contains where the solvent (s) preferably selected is / are from the group of non-ionic liquids which are liquid at room temperature Surfactants, polyethylene glycols, polypropylene glycols, glycerin, Glycerol carbonate, triacetin, ethylene glycol, propylene glycol, propylene carbonate, Hexylene glycol, ethanol and n-propanol and / or iso-propanol. Detergent or cleaning agent composition according to claim 12, characterized in that the Non-aqueous content of the detergent or cleaning agent composition Solvent (s) 0.1 to 70% by weight, preferably from 0.5 to 60% by weight, particularly preferably from 1 to 50% by weight, very particularly preferably from 2 to 40 wt .-% and in particular from 2.5 to 30 wt .-%, each based on the entire composition. Detergent or cleaning composition according to one of claims 1 to 13, characterized in that the water-soluble or water-dispersible containers a film and / or an injection molded part and / or a blow molded part and / or a deep-drawn part. Detergent or cleaning composition according to one of claims 1 to 14, characterized in that the water-soluble or water-dispersible containers one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) Polyvinyl alcohol (PVAL), polyvinyl pyrrolidone, polyethylene oxide, gelatin, Cellulose, and their derivatives and mixtures thereof. Detergent or cleaning composition according to one of claims 1 to 15, characterized in that the water-soluble or water-dispersible containers comprises a polyvinyl alcohol, whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, is particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%. Detergent or cleaning agent composition according to one of claims 1 to 16, characterized in that the water-soluble or water-dispersible container comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , particularly preferably from 12,000 up to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 . Detergent or cleaning composition according to one of claims 1 to 17, characterized in that the water-soluble or water-dispersible containers is a film bag and the film has a thickness of 1 to 150 μm, preferably from 2 to 100 μm, particularly preferably from 5 to 75 μm and in particular from 10 to 50 μm, having. Detergent or cleaning composition according to one of claims 1 to 18, characterized in that the water-soluble or water-dispersible containers an injection molding or blow-molded or deep-drawn body comprises the wall of which has a thickness of 50 to 300 μm, preferably 70 to 200 μm and in particular from 80 to 150 μm having.