EP1287109B1 - Washing or cleaning agent shaped bodies - Google Patents

Abstract

A detergent tablet having at least one phase in the form of a solid foam having gas-filled cells delimited by solid partitions, and the tablet or the at least one phase comprises 40% to 90% by weight of one or more water-soluble polymers. A process for the production of detergent tablets by foaming a solution, melt, emulsion, or suspension comprising at least one active ingredient with a gaseous medium, and solidifying the resulting foam.

Description

The present invention relates to detergent tablets which have a novel structure.

Detergent or detergent tablets are widely described in the art and have prevailed because of their advantages in commerce and the consumer.

The customary production of detergent tablets comprises the preparation of particulate premixes which are compressed into tablets by tabletting methods known to those skilled in the art. However, this method of preparation has significant disadvantages, since pressure-sensitive ingredients can be damaged during manufacture. So far, these ingredients such as e.g. encapsulated enzymes, etc. can not be incorporated into tablets without loss of activity. In some cases, even instability or total inactivity could be expected.

In addition, the supply form of the compressed tablet implies that the ingredients are in direct physical proximity to each other, resulting in undesirable reactions, instabilities, inactivities or loss of active ingredient in incompatible substances.

Also, the strong densification in this offer form causes the solubility to decrease. Generally, there is a dichotomy between sufficient hardness (i.e., handling security in packaging, shipping and use) and sufficiently fast disintegration and dissolution rates.

To solve the above-mentioned problems, it has been proposed in the prior art to provide multi-phase tablets in which several layers are pressed on each other. Incompatibilities between ingredients should be excluded by separation. However, this has the disadvantage that the lower layers are subjected to a multiple pressure load, resulting in deteriorated solubility. In addition, the problems mentioned were not completely solved because more than three-layer tablets can not be produced with reasonable technical effort.

Another approach is the international patent applications WO99 / 06522 . WO99 / 27063 and WO99 / 27067 refer to. Here it is proposed to provide tablets of compressed and non-compressed portions and pressure-sensitive substances in the non-compressed To incorporate shares. However, the problem with simultaneous incorporation and separation of several pressure-sensitive ingredients is not solved here.

In addition, there is the problem that pressure-sensitive and temperature-sensitive ingredients can not be incorporated without loss of active substance even after the teaching of this document, since the non-compressed components are incorporated via the path of the melt in the moldings. Also, the optical originality of the tablets produced according to the teaching of these documents is low, which does not increase consumer acceptance over conventional tablets. Suggestions for improving the solubility of the individual phases in this prior art are limited to the conventional methods, such as the incorporation of disintegrants or the reduction of the hardness of the pressed components.

Foam-like detergents or cleaners represent an alternative to the above-described compressed forms of supply.

Thus, the European patent application discloses EP 711 826 A2 (Iscon Hygiene GmbH ) foamed dimensionally stable dishwashing detergent, which in addition to alkali metal silicates, alkali metal hydroxides, alkali metal carbonates, alkali phosphates and phosphoric acid partial esters.

The British patent GB 978 192 (G.Mazzoni SpA ) describes a process for producing floatable soap bars by plastic deformation of solid starting materials in the presence of a gas and subsequent extrusion. The starting substances used include fats, fatty acids, soaps or surfactants

In the European patent application EP 090 648 A1 (Unilever ) describes a process for producing foamed detergents by shearing washing or cleaning-active substances in the presence of a gas. As washing or cleaning-active substances, for example, fatty acids and fatty alcohols are used.

The postponed patent applications WO 01/25390 A1 (Procter & Gamble ) and WO 01/25323 A1 (Procter & Gamble ) single-phase detergent tablets based on foamed active ingredient mixtures.

The publication JP 59-179635 (Hitachi Chem. ) has foamed moldings based on water-insoluble polyolefins to the object.

There was therefore still a need to provide improved detergent tablets which combine the highest degree of mechanical stability with good solubility and also allow the economical production and the incorporation of pressure-sensitive ingredients in embodiments with more than three phases. In addition to the technical advantages, the form of supply to be developed should also bring about high consumer acceptance through optical originality.
It has now been found that laundry detergent or cleaning product tablets can be prepared which, wholly or partly, have structures of solid foams which combine the highest degree of mechanical stability with a dramatically improved dissolution rate and a completely new optical system.

A first embodiment of the present invention are multiphase detergent tablets in which at least one phase of the tablet comprises solid (s) and gas (s) and optionally other detergent or cleaning agent components, said phase consisting of gas-filled cells (pores) be bounded by solid partitions, and this phase contains 40 to 90 wt .-% water-soluble (s) polymer (s).

In the context of the present invention, therefore, the entire shaped body or at least one phase of multiphase shaped bodies consists of gas-filled cells (pores) which are delimited by fixed partitions. Such structures may also be referred to simply as "solid foams". In the context of the terms "foam" or "partitions of gas-filled cells", the term "solid" means the physical state of the partition at 25 ° C and 1013.25 mbar. This term expressly refers only to the fact that the partitions under the said physical conditions are no longer liquid and includes both rigid and flexible walls. Clearly, both the fall known as a cushioning foam polyurethane foams as well as the used for sealing purposes in the construction industry rigid polyurethane foams or polystyrene ^® in the category of gas-filled cells which are bounded by solid walls.

When the volume concentration of the foam-forming gas is less than 74% in homodisperse distribution, the gas bubbles are spherical due to the surface-area-decreasing effect of the interfacial tension. Above the boundary of the densest sphere packing, the bubbles are deformed into polyhedral fins, which are delimited by approximately 4-600 nm thin pellicles. The cell barriers, connected by so-called nodal points, form a coherent framework. The foam lamellae (closed-cell foam) stretch between the cell bridges. If the foam lamellae are destroyed or flow back into the cell ridges at the end of foaming, an open-celled foam is obtained. Foams are thermodynamically unstable because surface energy can be obtained by reducing the surface area. The stability and thus the existence of the foams according to the invention is thus dependent on the extent to which it is possible to prevent their self-destruction.
In order to produce the foams, the gaseous medium is blown into the liquids in preferred embodiments, or the foaming is achieved by vigorously beating, shaking, splashing or stirring the liquid in the relevant gas atmosphere. Due to the lighter and better controllable and feasible foaming is within the present invention, the foam generation by blowing the gaseous medium ("gassing") over the other variants clearly preferred. Depending on the desired process variant, the gassing takes place continuously or discontinuously via perforated plates, sintered disks, sieve inserts, venturi nozzles, inline mixers, homogenizers or other conventional systems. In the context of the present invention, self-foaming systems in which the intumescent gas is formed by chemical reaction of the components with one another are also preferred. Even before the foam collapses, the liquid, semi-liquid or highly viscous cell webs solidify to solids, stabilizing the foam and forming a "solid foam".

As a gaseous medium for foaming any gases or gas mixtures can be used. Examples of gases used in the art are nitrogen, oxygen, noble gases and noble gas mixtures such as helium, neon, argon and mixtures thereof, carbon dioxide, etc. For cost reasons, according to the invention preferably air is used as the gaseous medium. If the components to be foamed are resistant to oxidation, the gaseous medium can also consist wholly or partly of ozone, as a result of which oxidatively destructible impurities or discoloration in the foaming media eliminated or microbial attack of these components can be prevented.

The shaped bodies according to the invention or the respective phase (s) of the shaped bodies according to the invention can consist of relatively large gas-filled cells with solid cell stems, but it is also possible that the pore size is small. Shaped bodies (or parts thereof) which have a number of large cells in a "matrix" of many gas-filled cells with a small diameter, which at the edge regions of the shaped body (or phase) can be clearly distinguished from the matrix of the body as larger cavities, can also be optically attractive take off smaller cavities.

Irrespective of the pore size, detergent tablets or detergent tablets according to the invention are preferred in which the ratio of the average diameter of the gas-filled cells to the mean diameter of the solid intermediate walls is at least 1: 2, preferably at least 5: 1, more preferably at least 10: 1 and in particular more than 20 : 1 is.

Thus, relatively large pores and relatively thin solid partitions are preferred according to the invention. In absolute terms, with regard to the customary for washing or cleaning agent tablets molded body dimensions with diameters and heights of a few centimeters at most detergent or cleaning detergent tablets are preferred in which the average diameter of the gas-filled cells 0.005 to 5 mm, preferably 0.05 to 0.5 mm and in particular 0.1 to 0.3 mm.

Likewise preferred are detergent tablets in which the mean diameter of the solid partition walls is 0.001 to 2 mm, preferably 0.005 to 0.3 mm and in particular 0.01 to 0.1 mm.

Depending on the size of the gas-filled pores, on the thickness of the cell webs and on the amount of gas or wall material, the gas content of a given volume of a shaped body according to the invention or a phase of a shaped body according to the invention varies. Here, preference is given to detergent tablets which are characterized in that the volume of the gas-filled cells is at least 50% by volume, preferably at least 60% by volume and in particular at least 70% by volume of the total volume of the shaped body or phase.

In a further dependence on the density of the gas in the gas-filled pores and the density of the cell webs results for the detergent tablets according to the invention or for one or more phase (s) of the detergent tablets according to the invention a certain density, advantageously well below the Density conventional, produced by pressing technology molded body is. In the context of the present invention preferred Detergents or cleaning agent tablets are characterized in that the tablet or the phase has a density of 0.01 to 1.0 gcm ^-3 , preferably of 0.05 to 0.7 gcm ^-3 and in particular of 0.1 to 0, 3 gcm ^-3 .

As already mentioned above, air is preferably used here as the gaseous medium. But it is also possible to use other gases or gas mixtures as a filling of the gas-filled cells. For example, it may be preferable to pass pure oxygen or the air to be used as filling gas over an ozonizer before the gas is used to fill the pores. In this way, one can produce gas mixtures containing, for example, 0.1 to 4 wt .-% ozone. The ozone content of the gas then leads to the oxidative destruction of undesired constituents in the media to be foamed. In the context of the present invention, detergent tablets or detergent tablets are preferred in which the gas-filled cells contain one or more gases from the group of noble gases, carbon dioxide, nitrogen, nitrous oxide, oxygen, ozone, dimethyl ether and air.

The cell webs of the shaped bodies or shaped body phases according to the invention consist of substances or substance mixtures which are solid at 25 ° C. and 1013.25 mbar. In view of the large-scale and cost-effective manufacturability in this case solids are preferred as a material for the cell webs, which can be converted by dissolving, suspending, emulsifying, melting, etc. in a liquid or highly viscous mass, which then foamed by the addition of filler gas (see above) wherein the resulting foam is preferably carried out by cooling, evaporation of solvent, time-delayed solvent binding, crystallization, chemical reaction (in particular polymerization, polycondensation or polyaddition), changing the rheological properties or radiation curing.

Polymers which are either foamed in the form of concentrated solutions or suspensions or are formed from their monomers during foaming are therefore particularly suitable as material for the cell bridges. Moreover, in the case of the polyurethanes, the foaming gas is formed by reaction of the starting materials for the wall material.

Of course, as a wall material not only pure substances, but also mixtures of substances can be used. It is thus possible, for example, to prepare and foam from diisocyanates and diols a water-soluble polyurethane which serves as wall material. If the reaction mixture further substances (eg dyes, fragrances, enzymes, optical brighteners, silver protectants, surfactants, builders, bleach, bleach activators, etc.) are added, these are incorporated into the walls and released in the dissolution of the mold under use conditions.

In the context of the present invention, preferred detergent tablets are characterized in that the solid intermediate walls contain one or more detergent ingredients, preferably from the groups of surfactants, builders, co-builders, polymers, bleaches, bleach activators, enzymes, foam inhibitors, optical brighteners, Colorants and fragrances and / or disintegration aids.

The detergent tablets according to the invention consist in part (at least one phase of multiphase tablets) of water-soluble polymers which are present in admixture with ingredients of washing or cleaning agents and optionally auxiliaries and / or fillers. Such polymer foams can be used according to the invention as detergents or cleaning agents or as components thereof.

1. a) 40 bis 90 Gew.-% eines oder mehrerer wasserlöslicher Polymere,
2. b) 10 bis 60 Gew.-% eines oder mehrere Stoffe aus der Gruppe der Gerüststoffe, Acidifizierungsmittel, Chelatkomplexbildner, belagsinhibierenden Polymere oder nichtionischen Tenside,
3. c) 0 bis 50 Gew.-% eines oder mehrerer Hilfs- und/oder Füllstoffe

aufweisen.Another object of the present invention are therefore detergent tablets (solid foams) containing a content of

1. a) 40 to 90% by weight of one or more water-soluble polymers,
2. b) from 10 to 60% by weight of one or more substances from the group of builders, acidifiers, chelating agents, scale-inhibiting polymers or nonionic surfactants,
3. c) 0 to 50 wt .-% of one or more auxiliaries and / or fillers

exhibit.

The cell webs of the solid foams or molded body phases according to the invention consist of substances or substance mixtures which are solid at 25 ° C. and 1013.25 mbar. In view of the large-scale and cost-effective manufacturability in this case solids are preferred as a material for the cell webs, which can be converted by dissolving, suspending, emulsifying, melting, etc. in a liquid or highly viscous mass, which then foamed by the addition of filler gas (see above) is, wherein the resulting foam is preferably carried out by cooling, evaporation of solvent, time-delayed solvent binding, crystallization, chemical reaction (especially polymerization, polycondensation or polyaddition), change in the rheological properties or radiation curing.

Water-soluble polymers which are either foamed in the form of concentrated solutions or suspensions, or are formed from their monomers only during foaming, are therefore used according to the invention as material for the cell bridges. In the case of the polyurethanes, the foaming gas may additionally be formed by reaction of the starting materials for the wall material. Of course, foaming of molten mixtures is also possible from the water-soluble polymers and the other ingredients of the solid foams of the invention possible.

• i) Polyacrylsäuren und deren Salzen
• ii) Polymethacrylsäuren und deren Salzen
• iii) Polyvinylpyrrolidon,
• iv) Vinylpyrrolidon/Vinylester-Copolymeren,
• v) Celluloseethern
• vi) Polyvinylacetaten, Polyvinylalkoholen und ihren Copolymeren
• vii) Pfropfcopolymeren aus Polyethylenglykolen und Vinylacetat
• viii) Alkylacrylamid/Acrylsäure-Copolymeren und deren Salzen
• ix) Alkylacrylamid/Methacrylsäure-Copolymeren und deren Salzen
• x) Alkylacrylamid/Methylmethacrylsäure-Copolymeren und deren Salzen
• xi) Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure -Copolymeren und deren Salzen
• xii) Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)acrylsäure -Copolymeren und deren Salzen
• xiii) Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymeren und deren Salzen
• xiv) Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat-Copolymeren und deren Salzen
• xv) Copolymeren aus
  • xiii-i) ungesättigten Carbonsäuren und deren Salzen
  • xiii-ii) kationisch derivatisierten ungesättigten Carbonsäuren und deren Salzen
• xvi) Acrylamidoalkyltrialkylammoniumchlorid/Acrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
• xvii) Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
• xviii) Methacroylethylbetain/Methacrylat-Copolymere
• xix) Vinylacetat/Crotonsäure-Copolymere
• xx) Acrylsäure/Ethylacrylat/N-tert. Butylacrylamid-Terpolymere
• xxi) Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglykolen
• xxii) gepropften Copolymere aus der Copolymerisation von
  • xx-i) mindesten einem Monomeren vom nicht-ionischen Typ,
  • xx-ii) mindestens einem Monomeren vom ionischen Typ,
• xxiii) durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltenen Copolymere:
  • xxi-i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren,
  • xxi-i) ungesättigte Carbonsäuren,
  • xxi-iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe d6ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols.

As ingredient a), the preferred detergent tablets according to the invention in the form of solid foams comprise water-soluble polymer (s). Water-soluble polymers in the context of the invention are those polymers which are soluble in water at room temperature in excess of 2.5% by weight. Particular preference is given to using certain water-soluble polymers in the context of the present invention. Foams according to the invention are preferred in which the water-soluble polymer (s) is / are selected from:

• i) polyacrylic acids and their salts
• ii) polymethacrylic acids and their salts
• iii) polyvinylpyrrolidone,
• iv) vinyl pyrrolidone / vinyl ester copolymers,
• v) cellulose ethers
• vi) polyvinyl acetates, polyvinyl alcohols and their copolymers
• vii) graft copolymers of polyethylene glycols and vinyl acetate
• viii) alkylacrylamide / acrylic acid copolymers and their salts
• ix) alkylacrylamide / methacrylic acid copolymers and their salts
• x) alkylacrylamide / methylmethacrylic acid copolymers and their salts
• xi) alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• xii) alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• xiii) alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• xiv) alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and their salts
• xv) copolymers
  • xiii-i) unsaturated carboxylic acids and their salts
  • xiii-ii) cationically derivatized unsaturated carboxylic acids and their salts
• xvi) Acrylamidoalkyltrialkylammoniumchlorid / acrylic acid copolymers and their alkali metal and ammonium salts
• xvii) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts
• xviii) Methacroylethylbetaine / methacrylate copolymers
• xix) vinyl acetate / crotonic acid copolymers
• xx) acrylic acid / ethyl acrylate / N-tert. Butylacrylamide terpolymers
• xxi) graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in admixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols
• xxii) grafted copolymers from the copolymerization of
  • xx-i) at least one non-ionic type monomer,
  • xx-ii) at least one monomer of the ionic type,
• xxiii) copolymers obtained by copolymerization of at least one monomer of each of the following three groups:
  • xxi-i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
  • xxi-i) unsaturated carboxylic acids,
  • xxi-iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-18 -alcohols.

The individual polymers mentioned above are described in more detail below:

Poly (meth) acrylic acids and their salts are described in detail below in the cobuilders.

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

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

als charakteristischem Grundbaustein der Makromoleküle. Von diesen haben die Vinylacetat-Polymere (R = CH₃) 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)Vinylpyrrolidone / Vinylester copolymers IV) are for example sold under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone-vinyl acetate copolymers, are particularly preferred polymers.
The vinyl ester polymers are vinyl ester-accessible polymers having the moiety of the formula (II)

as a characteristic building block of the macromolecules. Of these, the vinyl acetate polymers (R = CH ₃₎ with polyvinyl acetates, as by far the most important representatives of the greatest industrial importance.
The polymerization of the vinyl esters is carried out free-radically by different processes (solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization). Copolymers of vinyl acetate with vinylpyrrolidone contain monomer units of the formulas (I) and (II)

in R für H oder einen Alkyl-, Alkenyl-, Alkinyl-, Aryl- oder Alkylarylrest steht. In bevorzugten Produkten steht mindestens ein R in Formel (III) für -CH₂CH₂CH₂-OH oder -CH₂CH₂-OH. Celluloseether werden technisch durch Veretherung von Alkalicellulose (z.B. mit Ethylenoxid) hergestellt. Celluloseether werden charakterisiert über den durchschnittlichen Substitutionsgrad DS bzw. den molaren Substitutionsgrad MS, die angeben, wieviele Hydroxy-Gruppen einer Anhydroglucose-Einheit der Cellulose mit dem Veretherungsreagens reagiert haben bzw. 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.As cellulose ethers v) are particularly hydroxypropyl cellulose, hydroxyethyl cellulose and methyl, such as those sold under the trademarks Culminal.RTM ^® and Benecel ^® (AQUALON), into consideration.
Cellulose ethers can be described by the general formula (III)

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

Further particularly preferably usable water-soluble polymers are polyvinyl acetals, polyvinyl alcohols and their copolymers. Among these, preferred are homopolymers of vinyl alcohol, copolymers of vinyl alcohol with copolymerizable monomers or hydrolysis products of vinyl ester homopolymers or vinyl ester copolymers with copolymerizable monomers, so that foams of the invention in which the water-soluble polymer (s) is / are selected. are from homopolymers of vinyl alcohol, copolymers of vinyl alcohol with copolymerizable monomers or hydrolysis products of vinyl ester homopolymers or vinyl ester copolymers with copolymerizable monomers, preferred embodiments of the present invention. Homo- or copolymers of vinyl alcohol can not be obtained by polymerization of vinyl alcohol (H ₂ C = CH-OH), since its concentration in the tautomeric equilibrium with acetaldehyde (H ₃ C-CHO) is too low. These polymers are therefore prepared mainly from polyvinyl esters, in particular polyvinyl acetates via polymer-analogous reactions such as hydrolysis, but technically in particular by alkaline-catalyzed transesterification with alcohols (preferably methanol) in solution.

In the context of the present invention, polyvinyl alcohols are particularly preferred as water-soluble polymers. Polyvinyl alcohols, referred to as PVAL for short, are polymers of the general structure

[-CH ₂ -CH (OH) -] _n

in small proportions also structural units of the type

[-CH ₂ -CH (OH) -CH (OH) -CH ₂ ]

contain.

Commercially available polyvinyl alcohols, which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so still contain a residual content of acetyl groups. The polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

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

Foams preferred in the context of the present invention are characterized in that the water-soluble polymer is 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.

Preferably, polyvinyl alcohols of a certain molecular weight range are used, preference being given to foams according to the invention in which the water-soluble polymer is 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 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 about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.

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

Also suitable as water-soluble polymers a) are graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in admixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols. Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in admixture with other copolymerizable compounds on polyalkylene glycols are obtained by homogeneous-phase polymerization by subjecting the polyalkylene glycols to the monomers of vinyl esters, esters of acrylic acid or methacrylic acid, in The presence of free radical initiator stirs.
Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and esters of acrylic acid or methacrylic acid, those with aliphatic alcohols of low molecular weight, ie in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl 1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are proven.

Suitable polyalkylene glycols are, in particular, polyethylene glycols and polypropylene glycols. Polyethylene glycols are polymers of ethylene glycol which are of the general formula IV

H- (O-CH ₂ -CH ₂ ) _n -OH (IV)

satisfy, where n can assume values between 1 (ethylene glycol) and several thousand. For polyethylene glycols, there are various nomenclatures that can lead to confusion. Technically customary is the statement of the average relative molecular weight following the indication "PEG", so that "PEG 200" characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210. For cosmetic ingredients, a different nomenclature is used in which the abbreviation PEG is hyphenated and directly followed by the hyphen followed by a number corresponding to the number n in formula V 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. 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 (Propylenglykol) und mehreren tausend annehmen kann. Technisch bedeutsam sind hier insbesondere Di-, Tri- und Tetrapropylenglykol, d.h. die Vertreter mit n=2, 3 und 4 in Formel VI.
Insbesondere können die auf Polyethylenglykole gepfropften Vinylacetatcopolymeren und die auf Polyethylenglykole gepfropften Polymeren von Vinylacetat und Crotonsäure eingesetzt werden.

• gepropfte und vernetzte Copolymere aus der Copolymerisation von
  1. i) mindesten einem Monomeren vom nicht-ionischen Typ,
  2. ii) mindestens einem Monomeren vom ionischen Typ,
  3. iii) von Polyethylenglykol und
  4. iv) einem Vernetzter

Polypropylene glycols (abbreviated PPG) are polymers of propylene glycol which are of the general formula V

satisfy, where n can assume values between 1 (propylene glycol) and several thousand. Of particular 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
  1. i) at least one nonionic type monomer,
  2. ii) at least one ionic-type monomer,
  3. iii) of polyethylene glycol and
  4. iv) a networked person

The polyethylene glycol used has a molecular weight between 200 and several million, preferably between 300 and 30,000.

The monomers may be of very different types and among these, the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allylaurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene. The monomers of the second group may likewise be of very different types, of which, with particular preference, crotonic acid, allyloxyacetic acid, vinylacetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the graft polymers.

The crosslinking agents used are preferably ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallyl sucrose having 2 to 5 allyl groups per molecule of saccharin.

1. i) 5 bis 85 Gew.-% mindesten eine Monomeren vom nicht-ionischen Typ,
2. ii) 3 bis 80 Gew.-% mindestens eines Monomeren vom ionischen Typ,
3. iii) 2 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-% Polyethylenglykol und
4. 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.

The grafted and crosslinked copolymers described above are preferably formed from:

1. i) from 5 to 85% by weight of at least one nonionic type monomer,
2. ii) from 3 to 80% by weight of at least one ionic-type monomer,
3. iii) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and
4. iv) 0.1 to 8 wt% of a crosslinker, wherein the percentage of crosslinker is formed by the ratio of the total weights of i), ii) and iii).

Further suitable water-soluble polymers are copolymers of alkylacrylamide with acrylic acid, alkylacrylamide with methacrylic acid, alkylacrylamide with methylmethacrylic acid and also alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid -Copolymers, alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids optionally further ionic or nonionic monomers.

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

• 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 (VI) auf:
  
          [-CH(CH₃)-CH(COOH)-]_n     (VI)
  
  
• 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 Polykalkylenglykolen

According to the invention suitable anionic polymers include:

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

Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in admixture with other copolymerizable compounds on polyalkylene glycols are obtained by homogeneous-phase polymerization by subjecting the polyalkylene glycols to the monomers of vinyl esters, esters of acrylic acid or methacrylic acid, in The presence of free radical initiator stirs.

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

1. i) 5 bis 85 Gew.-% mindesten eine Monomeren vom nicht-ionischen Typ,
2. ii) 3 bis 80 Gew.-% mindestens eines Monomeren vom ionischen Typ,
3. iii) 2 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-% Polyethylenglykol und
4. 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.

The grafted and crosslinked copolymers described above are preferably formed from:

1. i) from 5 to 85% by weight of at least one nonionic type monomer,
2. ii) from 3 to 80% by weight of at least one ionic-type monomer,
3. iii) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and
4. iv) 0.1 to 8 wt% of a crosslinker, wherein the percentage of crosslinker is formed by the ratio of the total weights of i), ii) and iii).

1. i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren,
2. ii) ungesättigte Carbonsäuren,
3. 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

Copolymers obtained by copolymerization of at least one monomer of each of the three groups below are also suitable as ingredient a) according to the invention

1. i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
2. ii) unsaturated carboxylic acids,
3. iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C _8-18 -alcohols

Short-chain carboxylic acids or alcohols are to be understood as meaning those having 1 to 8 carbon atoms, it being possible for the carbon chains of these compounds to be interrupted, if appropriate, by divalent hetero groups such as -O-, -NH-, -S-.

Another particularly preferred class of polymers which may be included in the solid foams of the invention as ingredient a) are polyurethanes. Polyurethanes are water-soluble in the sense of the invention when they are soluble in water at room temperature to more than 2.5 wt .-%.

• einer Verbindung (A) mit mindestens 2 aktiven Wasserstoffatomen pro Molekül und
• einem Di- oder Polyisocyanat (B).

The polyurethanes consist of at least two different monomer types,

• a compound (A) having at least 2 active hydrogen atoms per molecule and
• a di- or polyisocyanate (B).

The compounds (A) may be, for example, diols, triols, diamines, triamines, polyetherols and polyesterols. The compounds having more than 2 active hydrogen atoms are usually used only in small amounts in combination with a large excess of compounds having 2 active hydrogen atoms.

Examples of compounds (A) are ethylene glycol, 1,2- and 1,3-propylene glycol, butylene glycols, di-, tri-, tetra- and poly-ethylene and -Propylenglykole, copolymers of lower alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, Ethylenediamine, propylenediamine, 1,4-diaminobutane, hexamethylenediamine and α, ω-diamines based on long-chain alkanes or polyalkylene oxides.

Polyurethanes in which the compounds (A) are diols, triols and polyetherols may be preferred according to the invention. In particular, polyethylene glycols and polypropylene glycols having molecular weights between 200 and 3000, in particular between 1600 and 2500, have proven to be particularly suitable in individual cases. Polyesterols are usually obtained by modifying the compound (A) with dicarboxylic acids such as phthalic acid, isophthalic acid and adipic acid.

As compounds (B) predominantly hexamethylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 4,4'-methylene di (phenyl isocyanate) and in particular isophorone diisocyanate are used. These compounds can be described by the general formula VII:

O = C = NR ¹ -N = C = O (VII),

wherein R ^{1 is} a linking moiety of carbon atoms, for example, a methylene-ethylene-propylene, butylene, pentylene, hexylene, etc. group. In the abovementioned, technically most widely used hexamethylene diisocyanate (HMDI), R ⁴ = (CH ₂ ) ₆ , in 2,4- or 2,6-toluene diisocyanate (TDI) R ^{4 is} C ₆ H ₃ -CH ₃ ) , in 4,4'-methylenedi (phenyl isocyanate) (MDI) for C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) and in isophorone diisocyanate R ^{4 is} the isophorone radical (3,5,5-trimethyl-2-cyclohexenone).

Furthermore, the polyurethanes used in the invention may contain other building blocks such as diamines as chain extenders and hydroxycarboxylic acids. Dialkylolcarboxylic acids such as dimethylolpropionic acid are particularly suitable hydroxycarboxylic acids. With regard to the further building blocks, there is no fundamental restriction as to whether they are nonionic, anionic or cationic building blocks.

For further information on the construction and production of polyurethanes, reference is expressly made to the articles in the relevant reviews such as Römpps Chemie-Lexikon and Ullmanns Enzyklopädie der technischen Chemie.

• ausschließlich aliphatische Gruppen im Molekül
• keine freien Isocyanatgruppen im Molekül
• Polyether- und Polyesterpolyurethane
• anionische Gruppen im Molekül.
  Besonders bevorzugte Polyurethane als Inhaltsstoff a) der erfindungsgemäßen festen Schäume enthalten mindestens anteilsweise Polyalkylenglykoleinheiten im Molekül. Hier sind erfindungsgemäße Schäume besonders bevorzugt, bei denen das bzw. die wasserlösliche(n) Polymer(e) ausgewählt ist/sind aus Polyurethanen aus Diisocyanaten (VII) und Diolen (VIII)
  
          O=C=N-R¹-N=C=O     (Vll),
  
          H-O-R²-O-H     (Vlll),
  
  

wobei die Diole mindestens anteilsweise ausgewählt sind aus Polyethylenglykolen (IV) und/oder Polypropylenglykolen (V)

        H-(O-CH₂-CH₂)_n-OH     (IV),

und R¹ sowie R² unabhängig voneinander für einen substituierten oder unsubstituierten, geradkettigen oder verzweigten Alkyl-, Aryl- oder Alkylarylrest mit 1 bis 24 Kohlstenstoffatomen und n jeweils für Zahlen von 5 bis 2000 stehen.Polyurethanes which have proved to be particularly suitable according to the invention in many cases have been able to be characterized as follows:

• exclusively aliphatic groups in the molecule
• no free isocyanate groups in the molecule
• Polyether and polyester polyurethanes
• anionic groups in the molecule.
  Particularly preferred polyurethanes as ingredient a) of the solid foams according to the invention contain at least partially polyalkylene glycol units in the molecule. Here, foams according to the invention are particularly preferred in which the water-soluble polymer (s) is / are selected from polyurethanes of diisocyanates (VII) and diols (VIII)
  
  O = C = NR ¹ -N = C = O (VII),
  
  HOR ² -OH (VIII),
  
  

wherein the diols are at least partially selected from polyethylene glycols (IV) and / or polypropylene glycols (V)

H- (O-CH ₂ -CH ₂ ) _n -OH (IV),

and R ¹ and R ² independently of one another represent a substituted or unsubstituted, straight-chain or branched alkyl, aryl or alkylaryl radical having 1 to 24 carbon atoms and n are each from 5 to 2,000.

In addition, the reaction mixtures may contain further polyisocyanates. A content of the reaction mixtures - and thus of the polyurethanes - on other diols, triols, diamines, triamines, polyetherols and polyesterols is possible. The compounds having more than 2 active hydrogen atoms are usually used only in small amounts in combination with a large excess of compounds having 2 active hydrogen atoms.

When adding further diols, etc., certain proportions to the present in polyurethane polyethylene and / or polypropylene glycol units are to be considered. Here, preference is given to polyurethanes in which at least 10% by weight, preferably at least 25% by weight, particularly preferably at least 50% by weight and in particular at least 75% by weight of the diols incorporated in the polyurethane are selected from polyethylene glycols (IV ) and / or polypropylene glycols (V).

Both in the case of compounds of the formula (IV) and of compounds of the formula (V), such representatives are preferred monomer building blocks in which the number n is between 6 and 1500, preferably between 7 and 1200, more preferably between 8 and 1000 , more preferably between 9 and 500 and in particular between 10 and 200 stands. For certain applications, polyethylene and polypropylene glycols of the formula (IV) and / or (V) may be preferred in which n is a number between 15 and 150, preferably between 20 and 100, more preferably between 25 and 75 and in particular between 30 and 60 stands.

Examples of compounds which are optionally further present in the reaction mixtures for preparing the polyurethanes are ethylene glycol, 1,2- and 1,3-propylene glycol, butylene glycols, ethylenediamine, propylenediamine, 1,4-diaminobutane, hexamethylenediamine and α, ω-diamines based on long-chain Alkanes or polyalkylene oxides. Solid foams according to the invention in which the polyurethanes contain additional diamines, preferably hexamethylenediamine and / or hydroxycarboxylic acids, preferably dimethylolpropionic acid, are preferred.

Summarizing these statements, in the context of the present invention, particularly preferred foams are characterized in that the water-soluble polymer is a polyurethane of diisocyanates (I) and diols (II)

O = C = NR ¹ -N = C = O (VII),

HOR ² -OH (VIII),

where R ^{1 is} a methylene-ethylene-propylene, butylene, pentylene group or - (CH ₂ ) ₆ - or 2,4- or 2,6-C ₆ H ₃ -CH ₃ , or C ₆ H _{4 is} -CH ₂ -C ₆ H ₄ or isophorone radical (3,5,5-trimethyl-2-cyclohexenone) and R ^{2 is} selected from -CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n - or -CH ₂ -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n - where n = 4 to 1999.

Depending on which reaction partners are reacted with one another to give the polyurethanes, polymers having different structural units are obtained. Here are foams according to the invention, in which the water-soluble polymer is a polyurethane which has structural units of the formula (IX)

- [OC (O) -NH-R ¹ -NH-C (O) -OR ² ] _k - (IX),

in which R ^{1 is} - (CH ₂ ) ₆ - or for 2,4- or 2,6-C ₆ H ₃ -CH ₃ , or for C ₆ H ₄ -CH ₂ -C ₆ H ₄ and R ² is selected from -CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n - or - CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n -, where n is a Number is from 5 to 199 and k is a number from 1 to 2000.

In this case, the diisocyanates described as being preferred are convertible to polyurethanes with all diols described as being preferred, so that preferred foams according to the invention comprise polyurethanes which have one or more of the structural units (IX a) to (IX h):

- [OC (O) -NH- (CH ₂ ) ₆ -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n ] _k - (IX a),

- [OC (O) -NH- (2,4-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n ] _k - (IX b),

- [OC (O) -NH- (2,6-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n ] _k - (IXc),

- [OC (O) -NH- (C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n ] _k - (IX d),

- [OC (O) -NH- (CH ₂ ) ₆ -NH-C (O) -O-CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n ] _k - ( IX e),

- [OC (O) -NH- (2,4-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) - CH ₂ ) _n ] _k - (IX f),

- [OC (O) -NH- (2,6-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) - CH ₂ ) _n ] _k - (IX g),

- [OC (O) -NH- (C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) -NH-C (O) -O-CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n ] _k - (IX h),

where n is a number from 5 to 199 and k is a number from 1 to 2000.

As already mentioned above, the reaction mixtures in addition to diisocyanates (VII) and diols (VIII) may also contain other compounds from the group of polyisocyanates (in particular triisocyanates and tetraisocyanates) and from the group of polyols and / or di- or polymains. In particular, triols, tetrols, pentols and hexols as well as di- and triamines can be present in the reaction mixtures. A content of compounds with more than two "active" H atoms (all classes except the diamines) leads to a partial crosslinking of the polyurethane reaction products and can advantageous properties such as control of the dissolution behavior, abrasion stability or flexibility of the foams of the invention, Process advantages in the production, etc. cause. The content of such compounds having more than two "active" H atoms in the reaction mixture is usually less than 20% by weight of the total reaction partners used for the diisocyanates, preferably less than 15% by weight and in particular less than 5% by weight. %.

In preferred embodiments of the present invention, the polyurethanes in the foams according to the invention have molecular weights of from 5000 to 150,000 gmol ^-1 , preferably from 10,000 to 100,000 gmol ^-1 and in particular from 20,000 to 50,000 gmol ^-1 .

The amounts in which the water-soluble polymer (s) are contained in the solid foams according to the invention, amount to 40 to 90 wt .-%, each based on the solid foam. Preferred foams are characterized in that they contain the water-soluble polymer (s) in amounts of from 45 to 87.5% by weight, preferably from 50 to 85% by weight, particularly preferably from 55 to 82, 5 wt .-% and in particular from 60 to 80 wt .-%, contained.

As a second ingredient, the solid foams of the invention contain 10 to 60 wt .-% of one or more substances from the group of builders, Acidifizierungsmittel, chelating agents, scale-inhibiting polymers or nonionic surfactants. Regardless of the type of ingredient b) are preferred foams containing the ingredient b) in amounts of from 12.5 to 55 wt .-%, preferably from 15 to 50 wt .-%, particularly preferably from 17.5 to 45 wt .-% and in particular from 20 to 40 wt .-%. The classes of substances mentioned as well as preferred representatives of these are described below.

The most important ingredients of laundry detergents or dishwashing detergents are builders. Ingredients b) in the foams according to the invention may include all builders customarily employed in detergents or cleaners, in particular zeolites, silicates, carbonates, organic cobuilders and 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 sheet silicates of given formula are those in which M is sodium and x takes the value 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed are. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of 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 dissolution delay compared with the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

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

nNa ₂ O • (1-n) K ₂ O • Al ₂ O ₃ • (2 - 2.5) SiO ₂ • (3.5-5.5) H ₂ O

can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

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

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid 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), pass. 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 (potassium phosphate primary or monobasic potassium phosphate, KDP), KH ₂ PO ₄ , is a white salt of 2.33 gcm ^-3 density, 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 slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of 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 readily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate 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 ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals. Na ₄ P ₂ O ₇ is formed on heating of 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 agents 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 being 1% Solution at 25 ° 10.4.

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: melting or annealing phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The industrially important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is a water-free or with 6 H ₂ O crystallizing a non-hygroscopic white water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are used according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

Further suitable builders are carbonates, bicarbonates and the salts of oligocarboxylic acids, for example gluconates, succinates and in particular citrates. Foams according to the invention which contain as ingredient b) one or more builders from the group of sodium carbonate, sodium hydrogencarbonate and trisodium citrate are preferred according to the invention.

Acidifying agents are also suitable as ingredient b) in the context of the present invention. Substances from this group can be used, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. However, it is also possible in particular to use the other solid mono-, oligo- and polycarboxylic acids. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred from this group. Organic sulfonic acids such as sulfamic acid are also usable. A commercially available as an acidifier in the context of the present invention is also preferably usable Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) (and adipic acid at most 33% by weight). Particularly preferred invention

Another possible group of ingredients b) are the chelating agents. Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". In this case, usually stretched verbs are closed by complex formation via an ion into rings. The number of bound ligands depends on the coordination number of the central ion.

Typical and preferred chelating agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Also, complexing polymers, ie polymers that carry either in the main chain itself or side by side to this functional groups that can act as ligands and react with suitable metal atoms usually to form chelate complexes. are used according to the invention. The polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.

Complexing groups (ligands) of conventional complexing polymers are iminodiacetic, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cyclic) polyamino, mercapto, 1,3-dicarbonyl and Crown ether residues with z. T. very specific. Activities towards ions of different metals. Base polymers of many also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided by polymer-analogous transformations with other ligand functionalities.

1. (i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
2. (ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,
3. (iii) geminalen Diphosphonsäuren,
4. (iv) Aminophosphonsäuren,
5. (v) Phosphonopolycarbonsäuren,
6. (vi) Cyclodextrine

enthalten.In the context of the present invention, foams which contain as ingredient b) one or more chelate complexing agents from the groups of the group are particularly preferred

1. (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
2. (ii) nitrogen-containing mono- or polycarboxylic acids,
3. (iii) geminal diphosphonic acids,
4. (iv) aminophosphonic acids,
5. (v) phosphonopolycarboxylic acids,
6. (vi) cyclodextrins

contain.

1. a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt wie Gluconsäure,
2. b) stickstoffhaltige Mono- oder Polycarbonsäuren wie Ethylendiamintetraessigsäure (EDTA), N-Hydroxyethylethylendiamintriessigsäure, Diethylentriaminpentaessigsäure, Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N,N-Di-(β-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-asparaginsäure oder Nitrilotriessigsäure (NTA),
3. c) geminale Diphosphonsäuren wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon und 1-Aminoethan-1,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon,
4. d) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure), Diethylentriaminpenta(methylenphosphonsäure) oder Nitrilotri(methylenphosphonsäure),
5. e) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure sowie
6. f) Cyclodextrine.

In the context of the present invention, all complexing agents of the prior art can be used. These can belong to different chemical groups. Preferably, used individually or in admixture with each other:

1. a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid,
2. b) nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N, N-di- (β-hydroxyethyl) -glycine, N- (1,2- Dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA),
3. c) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), their higher homologues having up to 8 carbon atoms and hydroxy- or amino-containing derivatives thereof and 1-aminoethane-1,1-diphosphonic acid whose higher homologues with up to 8 carbon atoms and hydroxyl- or amino-containing derivatives thereof,
4. d) aminophosphonic acids, such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or nitrilotri (methylenephosphonic acid),
5. e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and
6. f) cyclodextrins.

For the purposes of this patent application, polycarboxylic acids a) are understood as meaning carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl and the hydroxyl groups contained in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. In the case of the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

In the case of the scale-inhibiting polymers as ingredient b) are, in particular, one or more scale-inhibiting polymers from the group of cationic homopolymers or copolymers, in particular hydroxypropyltrimethylammonium guar; Copolymers of aminoethyl methacrylate and acrylamide, copolymers of dimethyldiallylammonium chloride and acrylamide, polymers having imino groups, polymers having quaternized ammonium alkyl methacrylate groups as monomer units, cationic polymers of monomers such as trialkylammonium alkyl (meth) acrylate and acrylamide, respectively; Dialkyldiallyldiammoniumsalze; polymer-analogous reaction products of ethers or esters of polysaccharides with pendant ammonium groups, in particular guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium groups; quaternary ethyleneimine polymers and polyesters and polyamides having quaternary side groups are preferred.

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

enthalten, bevorzugte Ausführungsformen der vorliegenden Erfindung.Another preferred ingredient b) are certain sulfonic acid group-containing copolymers. Thus, foams which contain one or more copolymers as ingredient b) are also preferred

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

contain, preferred embodiments of the present invention.

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

R ¹ (R ² ) C = C (R ³ ) COOH (X),

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

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

In the sulfonic acid group-containing monomers, those of the formula XI are preferred,

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

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

Preferred among these monomers are those of the formulas 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 is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred sulfonic acid-containing monomers are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₂ CH ₃ ) in formula X1a), 2-acrylamido-2-propane-sulfonic acid (X = - C (O) NH-C (CH ₃ ) ₂ in formula Xla), 2-acrylamido-2-methyl-1-propane-sulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula Xla), 2-methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula XIb), 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C (O) NH-CH ₂ CH (OH) CH ₂ - in formula XIb), allylsulfonic acid (X = CH ₂ in formula XIa), 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-propenol-sulfonic acid (X = CH ₂ in formula XIb), styrenesulfonic acid (X = C ₆ H ₄ in formula XIa), vinylsulfonic acid (X not present in formula XIa), 3-sulfopropyl acrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula XIa), 3-sulfopropyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula XIb), sulfomethacrylamide (X = -C (O) NH- in formula XIb), sulfomethylmethacrylamide (X = - C (O) NH-CH ₂ - in formula XIb) and water-soluble salts of said acids.

Suitable further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds. The content of the monomers used according to the invention to monomers of group iii) is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers consist only of monomers of groups i) and ii).

1. i) einer oder mehrerer ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
2. ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln Xla, Xlb und/oder Xlc:
   
           H₂C=CH-X-SO₃H     (XIa),
   
           H₂C=C(CH₃)-X-SO₃H     (Xlb),
   
           HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H     (Xlc),
   
   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)-
3. iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren.

Particularly preferred foams contain as ingredient b) one or more copolymers

1. i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid
2. ii) one or more sulfonic acid group-containing monomers of the formulas Xla, Xlb and / or Xlc:
   
   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 (Xlc),
   
   in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , - CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -
3. iii) optionally further ionic or nonionic monomers.

The copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii). Particularly preferred polymers have certain structural units, which are described below.

For example, a foam according to the invention which contains one or more copolymers which contain structural units of the formula XII is preferred

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

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

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. Copolymerizing the sulfonic acid-containing acrylic acid derivative with methacrylic acid, one arrives at another polymer whose use as ingredient b) of the foams of the invention is also preferred and characterized in that one or more copolymers are used, the structural units of the formula XIII

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XIII)

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

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, preference is given to foams according to the invention which contain as ingredient b) one or more copolymers having 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 are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or - NH-CH (CH ₂ CH ₃ ) - are, preferably, also a preferred embodiment of the present invention, just as foams are preferred, which are characterized in that they contain as ingredient b) one or more copolymers, the 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 are in each case an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula XVI

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

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or - NH-CH (CH ₂ CH ₃ ) -, and to foams, which are characterized in that they contain as ingredient b) one or more copolymers, the 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 are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or - NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. Corresponding solid foams, which are characterized in that the sulfonic acid groups are partially or fully neutralized in the copolymer, are preferred according to the invention.

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

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

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

Another class of substances which is suitable as ingredient b) in the solid foams according to the invention are nonionic surfactants. Foams according to the invention are preferred here which contain as ingredient b) 12.5 to 55% by weight, preferably 15 to 50% by weight, more preferably 17.5 to 45% by weight and in particular 20 to 40% by weight. containing one or more nonionic surfactants.

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

As further nonionic surfactants, preference may be given to using propoxylated and / or butoxylated nonionic surfactants, particular importance being attached to the mixed alkoxylated, advantageously propoxylated and ethoxylated nonionic surfactants. Also in these nonionic surfactants, the C chain length in the alkyl radical is preferably 8 to 18 C atoms, with C _9-11 alkyl radicals, C _12-13 alkyl radicals and C _16-18 alkyl radicals having particular significance. In particular, nonionic surfactants are preferred which have been obtained from C _9-11 or C _12-13 oxo alcohols. In the preferred nonionic surfactants on average 1 to 20 moles of alkylene oxide (AO) are used per mole of alcohol, wherein AO is the sum of EO and PO. Particularly preferred nonionic surfactants of this group contain 1 to 5 moles of PO and 5 to 15 moles of EO. An especially preferred representative of this group is an alkoxylated with 2 PO and EO 15 C _12-20 oxo alcohol, the (BASF) 300 is available under the trade name Plurafac ^® LF.

Instead of PO groups or in addition thereto, preferred nonionic surfactants may also have butylene oxide groups. Here, the abovementioned alkyl radicals, in particular the oxoalcohol radicals, are again preferred. The number of BO groups in preferred nonionic surfactants is 1, 2, 3, 4 or 5, wherein the total number of alkylene oxide groups is preferably in the range of 10 to 25. An especially preferred representative of this group is (BASF) available under the trade name Plurafac ^® LF 221 and can be represented by the formula C _13-15 -O- (EO) _9-10 (BO) describe _1-2

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

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

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

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.Further suitable surfactants are polyhydroxy fatty acid amides of the formula (XVIII),

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

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder 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-Alkytrest 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 (XIX),

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

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

It is particularly preferred in the foams of the invention to contain a nonionic surfactant which has a melting point above room temperature. Here, foams are preferred, the nonionic (s) surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, in amounts of 10 to 55 wt .-%, preferably from 15 to 50 wt .-%, particularly preferably from 20 to 45 and in particular from 25 to 40 wt .-%, each based on the total agent included.

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

Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the 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.

In a preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged. Corresponding foams are characterized in that the / the nonionic surfactant (s) ethoxylated (s) nonionic surfactant (s) is / are that / from C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 Fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol were obtained (n), are therefore preferred.

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

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particulate automatic dishwashing compositions containing ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably Up to 20% by weight and especially up to 15% by weight of the total molecular weight of the nonionic surfactant are preferred embodiments of the present invention. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.

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

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

A further preferred surfactant can be defined 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 ]

in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1, 5 and y is a value of at least 15. Particulate automatic dishwashing detergents, characterized in that they contain nonionic surfactants of the formula

R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ]

in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and x is values between 0.5 and 1, 5 and y is a value of at least 15, are therefore preferred.

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

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

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

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

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

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

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

In summary, preference is given to foams which contain as ingredient b) end-capped poly (oxyalkylated) nonionic surfactants of the formula

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

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

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

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

1. a) nichtionischen Tensiden aus der Gruppe der alkoxylierten Alkohole,
2. b) nichtionische Tensiden aus der Gruppe der hydroxylgruppenhaltigen alkoxylierten Alkohole ("Hydroxymischether").

With particular preference, mixtures of different nonionic surfactants are used in the foams of the invention. Particular preference is given here as ingredient b) mixtures of

1. a) nonionic surfactants from the group of alkoxylated alcohols,
2. b) nonionic surfactants from the group of hydroxyl-containing alkoxylated alcohols ("hydroxy mixed ethers").

The nonionic surfactants from group a) have already been described in detail above, with particular C _12-14 fatty alcohols with 5EO and 4PO and C _12-18 fatty alcohols having an average of 9 EO have been found to be outstanding. With similar preference end-capped nonionic surfactants, in particular C _12-18 fatty alcohol-9 EO-butyl ether, can be used.

Surfactants from group b) show e.g. outstanding clear rinse effects and reduce the stress corrosion cracking on plastics. Furthermore, they have the advantageous property that their network behavior over the entire usual temperature range is constant. The surfactants from group b) are particularly preferably alkoxylated alcohols containing hydroxyl groups.

In the context of the present invention, surfactant-capped surfactants and nonionic surfactants with butoxy groups are preferably also usable as nonionic surfactants. The first group includes in particular representatives of the formula

R ¹ O [CH ₂ CH (R ³⁾ O] _x R ^2,

in the R ¹ for a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 C atoms, R ^{2 is} a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 C atoms, which is optionally substituted with 1, 2, 3, 4 or 5 hydroxy groups and optionally with further ether groups, R ^{3 is} -H or methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or tert -butyl and x can assume values between 1 and 40. R ² may optionally be alkoxylated, wherein the alkoxy group is preferably selected from ethoxy, propoxy, butoxy groups and mixtures thereof.

In this case, preference is given to surfactants of the abovementioned formula in which R ^{1 is} a C _9-11 or C _11-15 -alkyl radical, R ³ = H and x assumes a value of 8 to 15, while R ² preferably represents a straight-chain or branched saturated Alkrest stands. Particularly preferred surfactants can be defined by the formulas C _9-11 (EO) ₈ -C (CH ₃ ) ₂ CH ₂ CH ₃ , C _11-15 (EO) ₁₅ (PO) ₆ -C _12-14 , C _9-11 (EO) ₈ (CH ₂ ) ₄ CH ₃ .

Also suitable are mixed-alkoxylated surfactants, preference being given to those having butoxy groups. Such surfactants can be defined by the formula

R ¹ (EO) _a (PO) _b (BO) _c

in which R ^{1 is} a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30, preferably 6 to 20 C atoms, a for values between 2 and 30, b for values between 0 and 30 and c is between 1 and 30, preferably between 1 and 20.

Alternatively, the EO and PO groups in the above formula may also be reversed so that surfactants of the general formula

R ¹ (PO) _b (EO) _a (BO) _c ,

in the R ¹ for a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30, preferably 6 to 20 C atoms, a for values between 2 and 30, b for values between 0 and 30 and c for values between 1 and 30, preferably between 1 and 20, is also usable with preference.

Particularly preferred representatives of this group of surfactants can be distinguished by the formulas C _9-11 (PO) ₃ (EO) ₁₃ (BO) ₁₅ , C _9-11 (PO) ₃ (EO) ₁₃ (BO) ₆ , C _{9- 11} (PO) ₃ (EO) ₁₃ (BO) _3, C _9-11 (EO) ₁₃ (BO) _6, C _9-11 (EO) ₁₃ (BO) _3, C _9-11 (PO) (EO) ₁₃ (BO) _3, C _9-11 (EO) ₈ (BO) _3, C _9-11 (EO) ₈ (BO) _2, C _12-15 (EO) ₇ (BO) _2, C _9-11 ( EO) ₈ (BO) ₂ , C _9-11 (EO) ₈ (BO). A particularly preferred surfactant of formula C _13-15 (EO) _9-10 (BO) _1-2 is commercially available under the name Plurafac LF ^® 221st Another especially preferred surfactant with 10 EO and BO 2 is available under the tradename Genapol ^® 25 EB 102nd It is also possible to use a surfactant of the formula C _12-13 (EO) ₁₀ (BO) ₂ .

In addition to the abovementioned ingredients a) (water-soluble polymer) and b) (substance from the group of builders, Acidifizierungsmittel, chelating agents, deposit-inhibiting polymers or nonionic surfactants), the solid foams of the invention may also contain other auxiliaries and / or fillers. In preferred foams according to the invention, these come from the groups of dyes and fragrances, adjusting agents, binders, humectants and / or salts.

In order to improve the aesthetic impression of the agents according to the invention, they can be wholly or partly dyed with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the treated substrates such as dishes to not stain them.

When choosing the colorant, it should be noted that the colorants do not have too high an affinity for the surfaces. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents varies. For highly soluble dyes, for example, Basacid Green ^® or Sandolan Blue ^®, dye concentrations in the range of a few 10 ^-2 to 10 ^-3 wt .-% are typically chosen. In the due to their brilliance, particularly preferred, but are less readily water-soluble pigment dyes, for example the Pigmosol ^® ATTO-dyes, the appropriate concentration of the colorant is in washing or cleaning agents, however, typically a few 10 ^-3 to 10 ^-4 wt .-%.

Fragrances are added to the compositions according to the invention in order to improve the aesthetic impression of the products and to provide the consumer, in addition to the performance of the product, a visually and sensory "typical and unmistakable" product. As perfume oils or fragrances, individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, α-isomethylionone and methyl cedrylketone , among the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes like Limes and pinas. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.

The content of the foams according to the invention of fragrances is usually up to 2% by weight of the total formulation. The fragrances can be incorporated directly into the compositions of the invention, but it can also be advantageous to apply the fragrances on carriers, which enhance the adhesion of the perfume on the laundry or other treated substrates and provide a long-lasting fragrance by a slower release of fragrance. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.

Binders and humectants may also be included as ingredient c) in the foams of the invention. Here, the contents are usually in amounts between 0.5 and 10 wt .-%, preferably between 0.75 and 7.5 wt .-% and in particular between 1 and 5 wt .-%, each based on the total solid foam.

Suitable salts are, in particular, readily soluble salts. Particularly preferred salts have solubilities above 200 grams of salt in one liter of deionized water at 20 ° C. As such preferred salts for incorporation into the foams of the invention are in the context of the present invention, a whole series of compounds. It is preferred if the salts have even higher solubilities, so that salts are preferred which have a solubility of more than 250 g per liter of water at 20 ° C, preferably more than 300 g per liter of water at 20 ° C and in particular of more than 350 g per liter of water at 20 ° C.

It is possible according to the invention to formulate the solid foams as part of a washing or cleaning agent and then to combine them with further constituents to form a finished washing or cleaning agent. Detergent tablets or detergent tablets, ie detergent tablets, detergent tablets or special forms such as bleach tablets or patch salt tablets, are particularly suitable for this purpose. Here, conventional, ie produced by pressing technology tablets can be combined with solid foams according to the invention, which then represent a visually differentiated molded body phase. Of course, it is also possible to formulate the solid foams according to the invention in such a way that they are in themselves a ready-to-use washing or cleaning agent. For this, as ingredient c) selected the ingredients that perform important functions in the washing or cleaning process, so mainly surfactants from other classes of surfactants (especially anionic and / or cationic surfactants), co-builders, bleach, bleach activators, enzymes, optical brighteners, silver protectants, etc., which hereinafter be briefly described.

As organic cobuilders it is possible in particular to use polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates in the foams. These classes of substances are described below.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

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

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

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

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

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

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

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

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 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. Also suitable is an oxidized oligosaccharide. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

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

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds capable of forming complexes with alkaline earth ions can be used as co-builders.

As anionic surfactants can be used as ingredient c) of the foams of the invention, for example, those of the sulfonate type and sulfates. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which, for example, according to the U.S. Patents 3,234,258 or 5,075,041 are manufactured and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

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

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated Erucic acid and behenic acid and in particular from natural fatty acids, such as coconut, palm kernel or tallow, derived soap mixtures derived.

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

In addition to the constituents mentioned, the foams according to the invention may contain further ingredients customary in detergents and cleaners from the group of bleaches, bleach activators, optical brighteners, enzymes, foam inhibitors, silicone oils, anti-redeposition agents, grayness inhibitors, dye transfer inhibitors and corrosion inhibitors.

To develop the desired bleaching performance, the foams of the present invention may contain bleaching agents. In this case, in particular the usual bleaching agents from the group of sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate have proven useful, the latter being clearly preferred.

"Sodium percarbonate" is a term used in unspecified form for sodium carbonate peroxohydrates, which strictly speaking are not "percarbonates" (ie salts of percarbonic acid) but hydrogen peroxide adducts of sodium carbonate. The commercial product has the average composition 2 Na ₂ CO ₃ · 3 H ₂ O ₂ and is therefore no peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm ^-3 , which readily decomposes into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first obtained in 1899 by precipitation with ethanol from a solution of sodium carbonate in hydrogen peroxide, but mistakenly regarded as peroxycarbonate. It was not until 1909 that the compound was recognized as a hydrogen peroxide addition compound, yet the historical name "sodium percarbonate" has prevailed in practice.

The industrial production of sodium percarbonate is predominantly produced by precipitation from aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium by salting-out agent (mainly sodium chloride), Kristallisierhilfsmittel (for example, polyphosphates, polyacrylates) and stabilizers (for example, Mg ²⁺ ions). The precipitated salt, which still contains 5 to 12 wt .-% mother liquor, is then removed by centrifugation and dried in fluid bed dryers at 90 ° C. The bulk density of the finished product may vary between 800 and 1200 g / l, depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating methods and substances used for coating are in the patent literature broadly described. In principle, all commercially available percarbonate types can be used according to the invention, as offered for example by the companies Solvay Interox, Degussa, Kemira or Akzo.

For the bleaching agents used, the content of the foams on these substances depends on the intended use. While conventional universal detergents contain between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular between 12.5 and 22.5% by weight of bleach, the levels in bleach or bleach booster formulations are between 15 and 50% by weight, preferably between 22.5 and 45% by weight and in particular between 30 and 40% by weight.

In addition to the bleaching agents used, the foams according to the invention may contain bleach activator (s), which is preferred in the context of the present invention. Bleach activators are incorporated into detergents to achieve improved bleaching performance when washed at temperatures of 60 ° C and below. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSl), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.

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

When the foams according to the invention comprise bleach activators, they contain, in each case based on the total foam, between 0.5 and 30% by weight, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight of one or more Bleach activators or bleach catalysts. Depending on the intended use of the foams produced, these quantities may vary. Thus, in typical universal detergents, bleach activator levels are between 0.5 and 10% by weight, preferably between 2 and 8% by weight and in particular between 4 and 6% by weight, while bleach preparations certainly have higher contents, for example between 5 and 30% by weight, preferably between 7.5 and 25 wt .-% and in particular between 10 and 20 wt .-% may have. The person skilled in the art is not limited in terms of freedom from formulation and can thus produce stronger or weaker bleaching detergents, cleaners or bleach preparations by varying the levels of bleach activator and bleach.

A particularly preferred bleach activator is N, N, N ', N'-tetraacetylethylenediamine, which is widely used in detergents and cleaners. Accordingly, preferred foams are characterized in that tetraacetylethylenediamine is used in the abovementioned amounts as bleach activator.

The foams may contain optical brighteners of the diaminostilbene disulfonic acid type or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed compounds which, instead of the morpholino group, a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl). Mixtures of the aforementioned brightener can be used. The optical brighteners are in the foams according to the invention as ingredient c) in concentrations between 0.01 and 1 wt .-%, preferably between 0.05 and 0.5 wt .-% and in particular between 0.1 and 0.25 wt. -%, in each case based on the total foam used.

Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens, as well as enzymatically-derived variants derived from their genetically modified variants. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. These are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from Protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases. Cellulases used are preferably cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures of these. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation. The proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-%.

In addition, the foams as ingredient c) may also contain components which positively influence the oil and Fettauswaschbarkeit from textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component. The preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxy-propylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, as well as the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

Further preferred foams characterized in that they contain as ingredient c) silver protectants from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes, more preferably benzotriazole and / or alkylaminotriazole, in amounts of 0, 01 to 5 wt .-%, preferably from 0.05 to 4 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the weight of the foam containing.

The corrosion inhibitors mentioned can be used to protect the items to be washed or the machine, with silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. Generally In particular, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

Instead of water-soluble polymers or in addition thereto, the solid between partition walls of the detergent tablets according to the invention may also consist of other substances. Ideally, the solid partitions in preferred detergent or cleaning product tablets or phases thereof according to the invention consist entirely of detergent or cleaning agent ingredients. In the case of some classes of substances, this can be easily realized (high-melting nonionic surfactants, organic polymers as co-builder), other substances are difficult to convert into a state that allows the formation of solid foam structures. In such cases, it is preferable to use a matrix substance as an assistant, which is converted into a foamable state together with the active substance in question and foamed. In addition to the already mentioned polymers (see also below), meltable substances, which are described below, are suitable as matrix substance.

Under the influence of temperature softenable masses can be easily assembled by the desired other ingredients (preferably detergents or cleaning ingredients) with a meltable or softenable substance (referred to above as matrix material) and the mixture heated to temperatures in the softening range of this substance and shaping at these temperatures is processed, whereby a foam is formed, which is converted by cooling in a solid foam. In this case, waxes, paraffins, polyalkylene glycols, etc. are particularly preferably used as meltable or softenable substances. These are described below.

The meltable or softenable substances should have a melting range (solidification range) in such a temperature range, in which the other ingredients of the masses to be processed matrix substance and other ingredients not too high thermal stress get abandoned. On the other hand, however, the melting range must be sufficiently high in order to still provide a handleable molded body (or molded body phase) at at least slightly elevated temperature. In preferred compositions according to the invention, the meltable or softenable substances have a melting point above 30 ° C.

It has proved to be advantageous if the meltable or softenable substances do not show a sharply defined melting point, as usually occurs in the case of pure, crystalline substances, but instead have a melting range which may be several degrees Celsius. The meltable or softenable substances preferably have a melting range of between about 45 ° C and about 75 ° C. That is, in the present case, the melting range occurs within the specified temperature interval and does not indicate the width of the melting range. Preferably, the width of the melting range is at least 1 ° C, preferably from about 2 to about 3 ° C.

The above properties are usually met by so-called waxes. "Waxing" is understood to mean a series of naturally or artificially produced substances which generally melt above 40 ° C. without decomposition and are already relatively low-viscosity and non-stringy just above the melting point. They have a strong temperature-dependent consistency and solubility.

According to their origin, the waxes are divided into three groups, the natural waxes, chemically modified waxes and the synthetic waxes.

The natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japan wax, Espartograswachs, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, spermaceti, lanolin (wool wax), or crepe fat, mineral waxes such as ceresin or ozokerite (groundwax), or petrochemical waxes such as petrolatum, paraffin waxes or microwaxes.

The chemically modified waxes include, for example, hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes. It is also possible to use as meltable or softenable substances compounds from other substance classes which fulfill the stated requirements with regard to the softening point. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, commercially available under the name Unimoll 66 ^® (Bayer AG) is available, proven. Also suitable are synthetically produced waxes from lower Carboxylic acids and fatty alcohols, for example dimyristyl tartrate, which is available under the name Cosmacol ^® ETLP (Condea). Conversely, synthetic or partially synthetic esters of lower alcohols can be used with fatty acids from natural sources. This class of substances includes, for example, ^Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Shellac, for example shellac KPS three-ring SP (Kalkhoff GmbH) can also be used according to the invention as meltable or softenable substances.

Likewise to the waxes in the context of the present invention, for example, the so-called wax alcohols are calculated. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols having generally about 22 to 40 carbon atoms. The wax alcohols are, for example, in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating of the present invention the solid particles coated can optionally also contain wool wax alcohols which are understood to be understood triterpenoid and steroid alcohols, for example lanolin, for example, under the trade designation Argowax ^® (Pamentier & Co) is available also at least partly as a constituent of the meltable or softenable substances in the context of the present invention, fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.

Particularly preferred meltable or softenable substances in the masses to be processed include those from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG), with polyethylene glycols having molecular weights of from 1500 to 36,000 being preferred, and those having molecular weights of from 2000 to 12,000 being particularly preferred and those having molecular weights of 3,000 to 5,000 are particularly preferred. Corresponding washing or cleaning agent shaped articles which are characterized in that the cell webs contain at least one substance from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) are preferred. Shaped bodies according to the invention which contain propylene glycols (PPG) and / or polyethylene glycols (PEG) as the only meltable or softenable substances in the cell webs are particularly preferred. These substances have been described in detail above.

In a further preferred embodiment, the cell stems contain predominantly paraffin wax. This means that at least 50% by weight of the total meltable or softenable substances contained in the cell webs, preferably more, consist of paraffin wax. Particularly suitable are paraffin wax contents (based on the total amount of meltable or softenable substances) of about 60% by weight, about 70% by weight or about 80% by weight, with even higher proportions of, for example, more than 90% by weight. are particularly preferred. In a particular embodiment of the invention, the total amount of the meltable or softenable substances used in the cell webs consists exclusively of paraffin wax.

In the context of the present invention, paraffin waxes have the advantage over the other natural waxes mentioned that no hydrolysis of the waxes takes place in an alkaline detergent environment (as is to be expected, for example, in the case of wax esters), since paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of alkanes, as well as low levels of iso and cycloalkanes. The paraffin to be used according to the invention preferably has substantially no constituents with a melting point of more than 70 ° C., more preferably of more than 60 ° C. Shares of high-melting alkanes in the paraffin can fall below this melting temperature in the detergent leaving unwanted wax residue on the surfaces to be cleaned or the property to be cleaned. Such wax residues usually lead to an unsightly appearance of the cleaned surface and should therefore be avoided.

Preferred detergent tablets contain as meltable or softenable substances at least one paraffin wax having a melting range of 50 ° C. to 60 ° C., preferred methods being characterized in that the cell bars comprise a paraffin wax having a melting range of 50 ° C. to 55 ° C included.

Preferably, the content of the paraffin wax used at ambient temperature (usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible. The more solid wax constituents in a wax at room temperature, the more useful it is within the scope of the present invention. As the proportion of solid wax constituents increases, the load-bearing capacity of the detergent tablets according to the invention increases against impacts or friction on other surfaces, which leads to longer-lasting protection. High levels of oils or liquid wax components can weaken the moldings or moldings, thereby opening pores and breaking the macroscopic structure.

The meltable or softenable substances may contain, in addition to paraffin as the main constituent, one or more of the abovementioned waxes or waxy substances. In a further preferred embodiment of the present invention, the mixture forming the meltable or softenable substances should be such that the foamable composition and the molded article or molded article constituent formed therefrom are at least substantially water-insoluble. The solubility in water should not exceed about 10 mg / l at a temperature of about 30 ° C and preferably be below 5 mg / l.

In such cases, however, the meltable or softenable substances should have the lowest possible water solubility, even in water at elevated temperature, in order to avoid as much as possible a temperature-independent release of the active substances.

The principle described above is the delayed release of ingredients at a certain time in the cleaning cycle and can be particularly advantageous when rinsing in the main rinse at a lower temperature (for example 55 ° C), so that the active substance from the rinse aid particles only in the rinse cycle at higher Temperatures (about 70 ° C) is released.

Preferred shaped bodies according to the invention are characterized in that they contain, as meltable or softenable substances in the cell webs, one or more substances having a melting range from 40 ° C. to 75 ° C. in amounts of from 6 to 30% by weight, preferably from 7.5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the weight of the mass.

As matrix material for the cell webs, the shaped bodies or phases according to the invention may contain one or more fatty substances, preferred cell bridges being characterized in that they have 12.5 to 85, preferably 15 to 80, particularly preferably 17.5 to 75 and in particular 20 to 70,% by weight .-% fat (s) included.

For the purposes of this application, fatty substances are understood to mean liquid to solid substances from the group of the fatty alcohols, the fatty acids and the fatty acid derivatives, in particular the fatty acid esters, at normal temperature (20 ° C.). Reaction products of fatty alcohols with alkylene oxides and the salts of fatty acids count in the present application to the surfactants (see above) and are not fatty substances in the context of the invention. Fatty substances which can be used according to the invention are preferably fatty alcohols and fatty alcohol mixtures, fatty acids and fatty acid mixtures, fatty acid esters with alkanols or diols or polyols, fatty acid amides, fatty amines, etc.

Preferred detergent tablets or phases thereof contain as matrix material in the cell walls one or more substances from the groups of fatty alcohols, fatty acids and fatty acid esters.

Examples of fatty alcohols which are obtainable from native fats and oils are 1-hexanol (caproic alcohol), 1-heptanol (oenanthalcohol), 1-octanol (caprylic alcohol), 1-nonanol (pelargon alcohol), 1-decanol (capric alcohol), 1-undecanol , 10-undecene-1-ol, 1-dodecanol (lauryl alcohol), 1-tridecanol, 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexadecanol (cetyl alcohol), 1-heptadecanol, 1-octadecanol (stearyl alcohol), 9 -cis-octadecen-1-ol (oleyl alcohol), 9-trans-octadecen-1-ol (erucyl alcohol), 9-cis-octadecene-1,12-diol (ricinoleic alcohol), all-cis-9,12-octadecadiene 1-ol (Linoleyl alcohol), all-cis-9,12,15-octadecatrien-1-ol (linolenyl alcohol), 1-nonadecanol, 1-eicosanol (arachidyl alcohol), 9-cis-eicosen-1-ol (gadoleyl alcohol), 5.8 , 11,14-eicosatetraen-1-ol, 1-heneicosanol, 1-docosanol (behenyl), 1-3-cis-docosen-1-ol (erucyl alcohol), 1-3-trans-docosen-1-ol (brassidyl alcohol ) and mixtures of these alcohols. According to the invention, Guerbet alcohols and oxo alcohols, for example C _13-15 oxo alcohols or mixtures of C _12-18 alcohols with C _12-14 alcohols, can also be used without problems as fatty substances. Of course, however, it is also possible to use alcohol mixtures, for example those such as C _16-18 -alcohols produced by ethylene polymerization according to Ziegler. Specific examples of alcohols which can be used as component b) are the abovementioned alcohols as well as lauryl alcohol, palmityl and stearyl alcohol and mixtures thereof.

Particularly preferred detergent tablets according to the invention comprise as matrix material in the cell stacks one or more C _10-30 fatty alcohols, preferably C _12-24 fatty alcohols with particular preference to 1-hexadecanol, 1-octadecanol, 9-cis-octadecene-1 ol, all-cis-9,12-octadecadien-1-ol, all-cis-9,12,15-octadecatrien-1-ol, 1-docosanol and mixtures thereof.

Fatty acids can also be used as matrix material for the cell bridges. These are largely derived from native fats and oils by hydrolysis. While the alkaline saponification already carried out in the past century led directly to the alkali salts (soaps), today only large amounts of water are used for cleavage, which cleaves the fats into glycerol and the free fatty acids. Examples of industrially applied processes are the autoclave cleavage or continuous high pressure cleavage. 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. are preferred in the context of the present invention. The use of Fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotinic acid (melissic acid) and the unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid ( Linolaidic acid) and 9c, 12c, 15c-octadecatenic acid (linolenic acid). Of course, tridecanoic acid, pentadecanoic acid, margaric acid, nonadecanoic acid, erucic acid, elaeostearic acid and arachidonic acid can be used. For cost reasons, it is preferred not to use the pure species, but technical mixtures of the individual acids, as they are accessible from lipolysis. Such mixtures are for example coconut oil (about 6 wt .-% C ₈ , 6 wt .-% C ₁₀ , 48 wt .-% C ₁₂ , 18 wt .-% C ₁₄ , 10 wt .-% C ₁₆ , 2 wt % C ₁₈ , 8% by weight C ₁₈ , 1% by weight C _{18 "} ), palm kernel oil fatty acid (about 4% by weight C ₈ , 5% by weight C ₁₀ , 50 wt .-% C ₁₂ , 15 wt .-% C ₁₄ , 7 wt .-% C ₁₆ , 2 wt .-% C ₁₈ , 15 wt .-% C ₁₈ , 1 wt .-% C _{18 "} ), Tallow fatty acid (about 3% 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 (about 2% by weight C ₁₄ , 28% by weight C ₁₆ , 2% by weight). -% C ₁₇ , 63 wt .-% C ₁₈ , 1 wt .-% C ₁₈ ), technical oleic acid (about 1 wt .-% C ₁₂ , 3 wt .-% C ₁₄ , 5 wt .-% C ₁₆ , 6% by weight C _{16 '} , 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C _18' , 10% by weight C ₁₈ ", 0.5% by weight % C _{18 "'} ), technical palmitic / stearic acid (about 1 wt .-% C ₁₂ , 2 wt .-% C ₁₄ , 45 wt .-% C ₁₆ , 2 wt .-% C ₁₇ , 47 wt. % C ₁₈ , 1% by weight C _{18 '} ) and soybean oil fatty acid (about 2% by weight C ₁₄ , 15% by weight C ₁₆ , 5% by weight C ₁₈ , 25% by weight C ₁₈ , 45% by weight C _{18 "} , 7% by weight C _18"' ).

The fatty acid esters which can be used are the esters of fatty acids with alkanols, diols or polyols, with fatty acid polyol esters being preferred. Suitable fatty acid polyol esters are mono- or diesters of fatty acids with certain polyols. The fatty acids which are esterified with the polyols are preferably saturated or unsaturated fatty acids having 12 to 18 carbon atoms, for example lauric acid, myristic acid, palmitic acid or stearic acid, preferably using the technically occurring mixtures of the fatty acids, for example those of coconut, Palm kernel or tallow derived acid mixtures. In particular, acids or mixtures of acids having 16 to 18 carbon atoms such as tallow fatty acid are suitable for esterification with the polyhydric alcohols. Suitable polyols which are esterified with the abovementioned fatty acids are, for the purposes of the present invention, sorbitol, trimethylolpropane, neopentyl glycol, ethylene glycol, polyethylene glycols, glycerol and polyglycerols.

Preferred embodiments of the present invention provide that glycerine is used as the polyol esterified with fatty acid (s). Accordingly, detergent tablets or detergent tablets according to the invention are preferred, the matrix material for the cell webs containing one or more fatty substances from the group of fatty alcohols and fatty acid glycerides. Particularly preferred detergent tablets contain a fatty substance from the group of fatty alcohols and fatty acid monoglycerides in the cell stems. Examples of such preferred fatty substances used are glycerol monostearic acid esters or glycerol monopalmitic acid esters.

In the context of the present invention preferred detergent tablets are characterized in that the solid partition walls one or more substances having a melting point above 50 ° C, preferably from the group of paraffins, polyethylene glycols and fatty substances containing.

Further preferred materials for the cell webs of the detergent tablets or ranges thereof are in particular polymers. These can be used either alone or in mixture with other ingredients (that is, as a matrix material). In general, completely water-soluble polymers in terms of the scope of the Moldings according to the invention are preferred. For this purpose, reference may be made to the above statements.

Biopolymers such as gelatin, starch, pectin, alginates, etc. can also be used as materials for the solid cell webs.

Gelatin is a polypeptide (molecular weight: about 15,000-> 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 gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as water-soluble coating material is extremely widespread, especially in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin has little use because of its high price compared to the polymers mentioned above.

Also preferred within the scope of the present invention are detergent tablets whose cell webs (or parts thereof) consist of at least one polymer from the group of starch and starch derivatives, cellulose and cellulose derivatives, in particular methylcellulose, and mixtures thereof.

Starch is a homoglycan, wherein the glucose units are linked α-glycosidically. Starch is composed of two components of different molecular weight: about 20-30% straight-chain amylose (MW 50,000-150,000) and 70-80% branched-chain amylopectin (MW 300,000-2,000,000); Amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, entangled chains with about 300-1200 glucose molecules as a result of the binding in the 1,4-position, the chain branched in amylopectin after an average of 25 glucose building blocks by 1,6-bond to a branch-like structure with about 1500-12000 molecules of glucose. In addition to pure starch, the production of solid foam structures in the context of the present invention also includes starch derivatives which are obtainable from starch by polymer-analogous reactions. Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and have therefore average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.

The shaped bodies according to the invention can be manufactured in a predetermined spatial form and predetermined size. As a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section. This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.

The shaped bodies according to the invention can in each case be designed as individual elements which are separate from each other and which corresponds to the predetermined dosage amount of the washing and / or cleaning agents. Likewise, it is possible to form moldings which connect a plurality of such mass units in a body, wherein in particular by predetermined predetermined breaking points, the easy separability portioned smaller units is provided. For the use of laundry detergents in machines of the type commonly used in Europe with horizontally arranged mechanics, the formation of the portioned shaped bodies as tablets, in cylindrical or cuboidal form may be expedient, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred.

The spatial form of another embodiment of the moldings is adapted in their dimensions of the dispenser of commercial household washing machines, so that the moldings can be metered without dosing directly into the dispenser, where it dissolves during the dispensing process. Of course, however, a use of the detergent tablets via a dosing is easily possible and preferred in the context of the present invention.

Another preferred molded article which can be produced has a plate-like or tabular structure with alternately thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, which are the short thin segments, broken and in the Machine can be entered. This principle of the "bar-shaped" shaped body wash can also be used in other geometric shapes, for example vertically standing triangles, which are connected together only on one of their sides alongside, are realized.

But it is also possible that the various components are not combined into a single tablet, but that moldings are obtained which have multiple layers, ie at least two layers. It is also possible that these different layers have different dissolution rates. This can result in advantageous performance properties of the molded body. If, for example, components are contained in the moldings which interact negatively, it is possible to integrate one component in the faster soluble layer and to incorporate the other component into a slower soluble layer, so that the first component has already reacted, when the second goes into solution. The layer structure of the moldings can be carried out both in a staggered manner, wherein a dissolution process of the inner layer (s) takes place at the edges of the molded body already when the outer layers are not completely dissolved, but it can also be a complete coating of the inner layer (s ) are reached through the respective outer layer (s), which leads to a prevention of premature dissolution of constituents of the inner layer (s).

In a further preferred embodiment of the invention, a shaped body consists of at least three layers, ie two outer and at least one inner layer, at least in one of the inner layers containing a peroxy bleach, while the stacked shaped body, the two outer layers and the envelope-shaped body However, outermost layers are free of peroxy bleach. Furthermore, it is also possible to separate peroxy bleach and optionally present bleach activators and / or enzymes spatially in a molding from each other. Such multilayer moldings have the advantage that they can be used not only via a dispensing compartment or via a metering device, which is placed in the wash liquor; Rather, it is also possible in such cases, to give the molding in direct contact with the textiles in the machine without stains caused by bleach and the like to be feared.

Similar effects can also be achieved by coating ("coating") individual constituents of the washing and cleaning agent composition to be tabletted or of the entire shaped body. For this purpose, the bodies to be coated can be sprayed, for example, with aqueous solutions or emulsions, or obtained by the process of melt coating a coating.

As an optical differentiation, in addition to the shape and a multi-layered structure, incorporation of colored particles, so-called speckles, into the shaped bodies can also take place. In this case, for example, a white body homogeneous with colored, such as blue, red, greens, yellows, etc., speckles are colored. In order to provide a homogeneous distribution of the colored speckles throughout the tablet and thus a visually attractive shaped article, the amount of color speckles and their particle size should be adapted to the remainder of the premix forming the shaped article matrix from which the speckles are visually apparent. If a tableting mixture has, for example, a particle size range of 200 to 1800 μm, speckles which move in the same or coarser particle spectrum achieve a homogeneous distribution only above a threshold value of ≥ 6% by weight, based on the tableting mixture. Smaller amounts then lead to optically unsightly accumulation of speckles in some molding areas, while other areas remain almost unpainted. In order to obtain a homogenous impression even at lower use levels of colored particles, it is advisable to reduce the particle size of the color-speckle particles. Thus, in the above example, the tableting mixture in the particle size range of 200 to 1800 μm already achieved a homogeneous distribution of the speckles with 2 to 3% by weight of colored speckle particles if these particle sizes are between 200 and 800 μm.

By a homogeneous mottling, which can be achieved in the manner described above by adjusting the speckle particle size and amount of the premix, also a layer structure of the shaped body can be visualized. In this way, two- or multi-layer moldings can be produced, one layer of which is uncoloured, while a second layer is optically highlighted by speckles. For example, this concept can also be applied to three-layered tablets in which one layer is undyed, the second is speckled and the third is through-dyed. In addition to the coloring of layers, it is also possible, for example, to dye or sprinkle cores or other subregions in core coated tablets, ring-core tablets or point tablets. In the variation of these implementation possibilities for optical differentiation the expert has no limits.

In the case of multiphase moldings, detergent tablets or detergent tablets according to the invention are preferred, which are characterized in that the phases have the form of layers.

In addition to the "classic" layer structure, various other forms can be realized according to the invention, which is an advantage of the present invention. For example, laundry detergent or cleaning product tablets according to the invention are also preferred in which at least one phase comprises a cavity in which another phase is at least partially embedded.

The cavity of the shaped body can have any shape. It can pass through the shaped body, ie have an opening at the top and bottom of the shaped body, but it can also be a cavity which does not pass through the entire shaped body and whose opening can only be seen on a shaped body side.

The shaped bodies according to the invention can assume any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylindrical segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, hexagonal and octagonal prismatic and rhombohedral forms are preferred. Even completely irregular surfaces such as arrow or animal shapes, trees, clouds, etc. can be realized. If the shaped bodies according to the invention have corners and edges, these are preferably rounded off. As additional optical differentiation, an embodiment with rounded corners and chamfered edges is preferred.

The shape of the cavity can be freely selected within wide limits. For reasons of process economy, through holes whose openings are located on opposite surfaces of the moldings, and wells with an opening on a molded body side have proven. In preferred detergent tablets, the cavity has the shape of a through hole, the openings of which are located on two opposite mold body surfaces. The shape of such a through hole can be chosen freely, wherein moldings are preferred in which the through hole has circular, elliptical, dreiekkige, rectangular, square, pentagonal, hexagonal, heptagon or octagonal horizontal sections. Even completely irregular hole shapes such as arrow or animal shapes, trees, clouds, etc. can be realized. As with the moldings, in the case of square holes, those with rounded corners and edges or with rounded corners and chamfered edges are preferred.

The aforementioned geometric realization forms can be combined with each other as desired. Thus, moldings with a rectangular or square base and circular holes can be made as well as round moldings with octagonal holes, the variety of possible combinations are no limits. For reasons of process economy and aesthetic consumer sentiment, moldings with a hole are particularly preferred in which the mold body base area and the hole cross section have the same geometric shape, for example shaped bodies with a square base area and a centrally machined square hole. Particularly preferred are ring shaped bodies, i. circular shaped bodies with a circular hole.

If the above-mentioned principle of the hole open on two opposite molded body sides is reduced to an opening, hollow body moldings are obtained. Detergent tablets according to the invention in which the cavity has the shape of a trough are also preferred. As in the case of the "shaped perforated bodies", the shaped bodies according to the invention can also assume any geometric form in this embodiment, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, octagonal, octagonal prismatic and rhombohedral shapes are preferred. Even completely irregular surfaces such as arrow or animal shapes, trees, clouds, etc. can be realized. If the shaped body has corners and edges, these are preferably rounded off. As additional optical differentiation, an embodiment with rounded corners and chamfered edges is preferred.

The shape of the trough can be chosen freely, wherein moldings are preferred in which at least one trough is a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal , five-, seven- and octagonal-prismatic as well as rhombohedral form. Completely irregular shapes such as arrow or animal shapes, trees, clouds etc. can also be realized. As with the moldings, wells with rounded corners and edges or with rounded corners and chamfered edges are preferred.

The size of the trough or the through hole compared to the entire shaped body depends on the desired use of the shaped body. Depending on whether the cavity is to contain a further molding phase and whether a smaller or larger amount of further phase is desired, the size of the cavity may vary. Regardless of the intended use, detergent tablets are preferred in which the volume ratio of tablet to cavity is 2: 1 to 100: 1, preferably 3: 1 to 80: 1, particularly preferably 4: 1 to 50: 1 and in particular 5: 1 to 30: 1, is.

Similar statements can be made to the surface portions that make up the molded body with the cavity ("shaped body") or the opening area of the cavity on the entire surface of the Fornkörpers. Here, detergent tablets are preferred in which the area of the opening (s) of the cavity (s) constitutes 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the total surface of the shaped body ,

In the case of multi-phase moldings with cavity, any of the conceivable possibilities can be realized according to the invention, ie biphasic moldings according to the invention can be produced in which the phase with the cavity consists of gas-filled cells (pores) bounded by fixed partitions, while the cavity is filled originated by another manufacturing technology. Furthermore, the exact opposite case is possible, a shaped body in which the phase with the cavity was produced by pressing, casting, sintering, etc., and the filling of the cavity consists of gas-filled cells (pores) which are bounded by solid partitions. Last but not least, it is of course also possible to produce shaped bodies according to the invention in which both the phase with the cavity and the filling of the cavity consist of gas-filled cells (pores) which are delimited by fixed intermediate walls.

According to the invention, multiphase moldings can also be realized by virtue of the fact that the phase, which consists of gas-filled cells (pores) bounded by solid partitions, serves as a type of "matrix" in which particles which form the other phase are suspended. Here it is optically particularly attractive if the embedded particles have a size in the range of several millimeters, for example in the range of 1 to 10 mm, preferably from 2 to 7 mm and in particular from 2.5 to 5 mm. Such detergent tablets, in which one phase consists of gas-filled cells surrounded by solid partitions, in which the other phase (s) are embedded, are preferred according to the invention.

Particular preference is given to washing or cleaning agent tablets which are characterized in that the phase embedded in the phase consisting of gas-filled cells surrounded by solid intermediate walls consists of particulate solids.

In the case of the multiphase shaped bodies, a shaped body phase according to the invention can be combined with other non-inventive shaped body phases which have been produced by conventional technologies. For example, detergent tablets or detergent tablets according to the invention are preferred in which the non-foamed phase is a compressed part.

However, washing or cleaning agent shaped bodies in which the non-foamed layer is a non-compressed part are also preferred. Among these, particular preference is given to washing or cleaning agent shaped bodies according to the invention in which the non-foamed layer is a sintered part, or even more preferably, washing or cleaning agent shaped bodies in which the non-foamed layer is a cast part.

In all combinations of inventive phase with non-inventive phase detergent or detergent tablets are generally preferred, which are characterized in that the weight ratio between the foamed and non-foamed phase in the range of 30: 1 to 1:50, preferably from 5: 1 to 1:30 and especially from 1: 1 to 1:10.

Similarly, washing or cleaning agent shaped bodies are preferred in which the volume ratio between foamed and non-foamed phase in the range of 50: 1 to 1:20, preferably from 10: 1 to 1:10, particularly preferably from 5: 1 to 1: 5 and in particular from 4: 1 to 1: 2.

Depending on the choice of ingredients, a controlled release of ingredients can be achieved in multiphase moldings by controlling the rate of dissolution of individual phases. Here, detergent tablets or detergent tablets according to the invention are preferred in which the foamed phase (s) dissolves / dissolves faster than the non-foamed phase (s).

It is particularly preferred in this case if at least 50 wt .-% of the foamed phase (s) are dissolved when not more than 10 wt .-% of the non-foamed phase (s) are dissolved.

Alternatively, the foamed phase can also be delayed release. Here, detergent tablets or detergent tablets are preferred in which the foamed phase (s) dissolves / dissolve more slowly than the non-foamed phase (s), with particularly preferred detergent tablets being characterized in that at least 50 Wt .-% of the non-foamed phase (s) are dissolved when a maximum of 10 wt .-% of the foamed phase (s) are dissolved.

Further details on physical parameters of the detergent tablets according to the invention and information on the preparation can be found below. The following is an illustration of the preferred ingredients of the moldings which may be included in both the foamed phase and optionally non-foamed phases.

In the detergent tablets according to the invention, all builders commonly used in detergents and cleaners may be present, in particular zeolites, silicates, carbonates, organic co-builders and, where there are no ecological prejudices against their use, also the phosphates. In general, laundry detergent or detergent tablets according to the invention are preferred, the builders in amounts of 1 to 95 wt .-%, preferably from 5 to 90 wt .-%, particularly preferably from 10 to 85 wt .-% and in particular from 20 to 75 wt .-%, in each case based on the weight of the entire molding.

The builders were described in detail above.

In the context of the present invention, preferred detergent tablets are characterized in that they contain silicate (s), preferably alkali metal silicates, more preferably crystalline or amorphous alkali disilicates, in amounts of from 10 to 60% by weight, preferably from 15 to 50% by weight. % and in particular from 20 to 40 wt .-%, each based on the weight of the total molding. In the context of the present invention also preferred detergent tablets are characterized in that they phosphate (e), preferably alkali metal phosphate (s), more preferably pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate), in amounts of 20 to 80 wt .-%, preferably from 25 to 75 wt .-%, in particular from 30 to 70 wt .-%, each based on the weight of the entire molded article, included.

As further constituents alkali carriers may be present. Examples of alkali carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the alkali metal silicates mentioned, alkali metal silicates, and mixtures of the abovementioned Substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium hydrogencarbonate or sodium sesquicarbonate, for the purposes of this invention. Particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate. Also particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate. In particularly preferred detergent tablets or detergent tablets are carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonates, particularly preferably sodium carbonate, in amounts of from 5 to 50 wt .-%, preferably from 7.5 to 40 wt .-% and in particular from 10 to 30% by weight, based in each case on the weight of the entire molding.

Preferred detergent tablets also contain one or more surfactants. In the detergent tablets according to the invention anionic, nonionic, cationic and / or amphoteric surfactants or mixtures thereof may be used. From an application point of view, laundry detergent tablets are preferably mixtures of anionic and nonionic surfactants and detergents tablets nonionic surfactants. The total surfactant content of the tablets in the case of detergent tablets is 5 to 60% by weight, based on the tablet weight, with surfactant contents above 15% by weight being preferred, whereas automatic dishwashing detergent tablets preferably contain less than 5% by weight of surfactant (e ) contain. The surfactants have also been described in detail above.

In the context of the present invention detergent tablets and detergent tablets which contain anionic and nonionic surfactant (s) are preferred as laundry detergent tablets, technical advantages resulting from certain quantitative ratios in which the individual classes of surfactants are used.

For example, washing and cleaning agent tablets are particularly preferred in which the ratio of anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2. Preference is also given to washing and cleaning agent tablets containing surfactant (s), preferably anionic (s) and / or nonionic surfactant (s), in amounts of from 5 to 40% by weight, preferably from 7.5 to 35% by weight .-%, particularly preferably from 10 to 30 wt .-% and in particular from 12.5 to 25 wt .-%, in each case based on the weight of the molded article.

From an application point of view, it can have advantages if certain types of surfactant are not present in some phases of the detergent tablets or in the entire tablet, ie in all phases. Another important embodiment of the present invention provides, therefore, that at least one phase of the shaped body is free of nonionic surfactants.

Conversely, however, the content of individual phases or of the entire molding, i. all phases, on certain surfactants a positive effect can be achieved. The incorporation of the above-described alkylpolyglycosides has proved to be advantageous, so that detergent tablets are preferred in which at least one phase of the tablets contains alkylpolyglycosides.

Similar to the nonionic surfactants, the omission of anionic surfactants from individual or all phases may result in washing and cleaning agent tablets which are more suitable for certain fields of application. It is therefore within the scope of the present invention also possible to use detergent tablets in which at least one phase of the tablets is free of anionic surfactants.

In the case of automatic dishwashing detergent tablets, detergent tablets or detergent tablets according to the invention are preferred, the total surfactant contents being below 5% by weight, preferably below 4% by weight, more preferably below 3% by weight and in particular below 2% by weight .-%, in each case based on the weight of the entire molding.

Conversely, laundry detergents or detergent tablets which contain anionic and / or nonionic surfactant (s) and total surfactant contents of more than 5% by weight, preferably more than 10% by weight and in particular of above, are preferred in the case of textile detergents 15 wt .-%, each based on the molding weight, have.

As already mentioned, the use of surfactants in automatic dishwashing detergent tablets is preferably restricted to the use of small amounts of nonionic surfactants. Detergent tablets preferably to be used as detergent tablets are characterized in that the tablet has total surfactant contents below 5% by weight, preferably below 4% by weight, more preferably below 3% by weight and in particular below of 2 wt .-%, each based on the weight of the molding having. As surfactants, only low-foaming nonionic surfactants are usually used in automatic dishwashing detergents. Representatives of the groups of anionic, cationic or amphoteric surfactants, however, have less importance. With particular preference, the machine dishwashing detergent tablets according to the invention contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. These have been described in detail above.

In order to facilitate the disintegration of moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into the moldings in order to shorten the disintegration times. By tablet disintegrants or disintegrants are meant auxiliaries which ensure the rapid disintegration of tablets into water or gastric juice and for the release of the drugs in resorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume upon ingress of water, on the one hand increasing the intrinsic volume (swelling), and on the other hand creating a pressure via the release of gases which can break the tablet into smaller particles decays. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
Preferred detergent tablets contain from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, of one or more disintegration aids, in each case based on the weight of the tablet. If only the shaped body contains disintegration aids, then the details given relate only to the weight of the shaped body.

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

The cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. Detergents and cleaning product tablets containing disintegrators in granular or optionally cogranulated form are incorporated into the German patent applications DE 197 09 991 (Stefan Herzog ) and DE 197 10 254 (Henkel ) as well as the international patent application WO98 / 40463 (Henkel ). Further details of the production of granulated, compacted or cogranulated cellulose explosives can be found in these publications. The particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns. The above and described in more detail in the documents cited coarser disintegration aids, are preferred in the present invention as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier.

As a further disintegrating agent based on cellulose or as a component of this component, microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact. Subsequent deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 μm and can be compacted, for example, into granules having an average particle size of 200 μm.

In the context of the present invention, preferred detergent tablets also contain a disintegration aid, preferably a cellulose-based disintegration assistant, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight. -% and in particular from 4 to 6 wt .-%, each based on the molding weight.

In addition, the detergent tablets according to the invention may contain a gas-evolving effervescent system both in the tablet and in the cavity. The gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water. Among these compounds, mention should be made in particular of magnesium peroxide, which liberates oxygen on contact with water. Usually, however, the gas-releasing effervescent system in turn consists of at least two components which together with gas formation react. While here a variety of systems is thinkable and executable that release, for example, nitrogen, oxygen or hydrogen, the bubble system used in the detergent tablets according to the invention can be selected both on the basis of economic as well as ecological aspects. Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.

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

In preferred detergent tablets, the effervescent system is 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10 wt .-% of an Acidifizierungsmittels, in each case based on the entire molded body used.

Acidifying agents which release carbon dioxide from the alkali metal salts in aqueous solution include, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. However, it is also possible in particular to use the other solid mono-, oligo- and polycarboxylic acids. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred from this group. Organic sulfonic acids such as sulfamic acid are also usable. A commercially available as an acidifier in the context of the present invention is also preferably usable Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) (and adipic acid at most 33% by weight).

In the context of the present invention, preference is given to washing and cleaning agent tablets in which a substance from the group of organic di-, tri- and oligocarboxylic acids or mixtures thereof is used as the acidifying agent in the effervescent system.

Bleaching agents and bleach activators, which are important ingredients of detergents or cleaners, have been described above. Detergent tablets characterized in that the tablet contains bleaching agents selected from the group consisting of oxygen or halogen bleaches, in particular chlorine bleaches, with particular preference to sodium perborate and sodium percarbonate, in amounts of from 2 to 25% by weight, preferably 5 to 20 wt .-% and in particular from 10 to 15 wt .-%, each based on the weight of the molding Mass, are an inventively preferred embodiment of the present invention. It is likewise preferred for the shaped bodies according to the invention to contain bleach activators. Detergent tablets in which the tablet contains bleach activators from the groups of polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n or iso-NOBS) and n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), in amounts of 0.25 to 15 wt .-%, preferably from 0.5 to 10 wt .-% and in particular from 1 to 8 wt .-%, each based on the weight of the entire molded body, are also preferred.

The detergent tablets according to the invention may contain, in particular in the foamed phase for the protection of the items to be washed or the machine corrosion inhibitors, which have already been described above. In preferred detergent tablets according to the invention, the tablet contains silver protectants from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes, more preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.01 to 5 wt .-%, preferably from 0.05 to 4 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the weight of the molding.

In addition to the ingredients mentioned above, further classes of substances are suitable for incorporation into detergents and cleaners. Thus, washing and cleaning agent tablets are preferred in which the shaped body further comprises one or more substances from the groups of enzymes, corrosion inhibitors, coating inhibitors, cobuilders, dyes and / or fragrances in total amounts of 6 to 30 wt .-%, preferably of 7, 5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the weight of the molding containing.

In addition to the constituents builder, surfactant, disintegration aid bleach and bleach activator, the detergent tablets according to the invention may contain further ingredients customary in detergents and cleaners from the group of dyes, perfumes, optical brighteners, enzymes, foam inhibitors, silicone oils, antiredeposition agents, grayness inhibitors, dye transfer inhibitors and Contain corrosion inhibitors. Enzymes, dyes and fragrances have been described in detail above.

The detergent tablets according to the invention may contain one or more optical brighteners. These fabrics, also known as "whiteners", are used in modern laundry detergents because even freshly washed and bleached white laundry has a slight yellowish tinge. Optical brighteners are organic dyes that convert part of the invisible UV radiation of sunlight into longer-wavelength blue light. The emission This blue light complements the "gap" in the light reflected by the textile, so that a fabric treated with optical brightener appears whiter and brighter to the eye. Since the mechanism of action of brighteners requires their application to the fibers, a distinction is made depending on the "fibers to be dyed", for example, brighteners for cotton, polyamide or polyester fibers. The commercially available brighteners suitable for incorporation in detergents essentially comprise five structural groups on the stilbene, the diphenylstilbene, the coumarin-quinoline, the diphenylpyrazoline group and the group of the combination of benzoxazole or benzimidazole with conjugated systems. An overview of common brighteners is, for example, in G. Jakobi, A. Lohr "Detergents and Textile Washing", VCH-Verlag, Weinheim, 1987, pages 94 to 100 Find. For example, salts of 4,4'-bis [(4-anilino-6-morpholino-6-triazin-2-yl) -amino] -stilbene-2,2'-disulphonic acid or compounds of similar construction which are used in place of the morpholino Group a Diethanolaminogruppe, a methylamino group, an anilino group or a 2-Methoxyethylaminogruppe carry. Furthermore, brighteners of the substituted diphenylstyrene type may be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brightener can be used.

In addition, the detergent tablets may also contain components which positively influence the oil and grease washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component. The preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxy-propylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, as well as the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

Suitable foam inhibitors which can be used in the compositions according to the invention are, for example, soaps, paraffins or silicone oils, which may optionally be applied to support materials.

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. For this purpose, water-soluble colloids are usually suitable organic nature, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or the Cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches etc. Polyvinylpyrrolidone is also useful. However, preference is given to using cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the compositions

Since textile fabrics, in particular of rayon, rayon, cotton and their mixtures, can crumple because the individual fibers against bending, kinking. Pressing and squeezing transverse to the fiber direction are sensitive, the compositions of the invention may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

For controlling microorganisms, the compositions of the invention may contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungiostats and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, although it is entirely possible to do without these compounds.

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

An increased wearing comfort can result from the additional use of antistatic agents which are additionally added to the agents according to the invention. Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges. External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. The lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable themselves as antistatic agents for textiles or as an additive to detergents, wherein additionally a softening effect is achieved.

To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, for example, silicone derivatives can be used in the compositions according to the invention. These additionally improve the rinsing behavior of the agents by their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones are in the range between 100 and 100,000 centistokes at 25 ° C, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total agent can be used

Finally, the compositions according to the invention may also contain UV absorbers which are absorbed by the treated textiles and improve the light resistance of the fibers. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.

In multi-phase moldings according to the invention, which consist of several phases, the ingredients can be divided into the individual phases and thereby separated from one another. If these shaped bodies have a foamed part and a non-foamed part, preference is given to detergent tablets in which the foamed part comprises at least one enzyme from the group of enzymes, surfactants, soil-release polymers, disintegration aids, bleaches, bleach activators, bleach catalysts, Silver protectants and mixtures thereof.

As already mentioned, multiphase moldings can be used for separating active substances. In particular, in certain drug combinations, the separation is advantageous. The following remarks are made for verbal separation half for multi-phase moldings of foamed and non-foamed phase, but mutatis mutandis apply to moldings of several foamed phases.

Particular preference is given to detergent tablets or detergent tablets according to the invention, which are characterized in that the foamed part or non-foamed part contains bleach, while the other area of the tablet contains bleach activators.

Washing or cleaning agent tablets in which the foamed part or the non-foamed part contains bleach while the other region of the tablet contains enzymes are inventively preferred embodiments, as well as detergent tablets, which are characterized in that the foamed part or the non-foamed part contains bleach, while the other part of the molded part contains deformable mass corrosion inhibitor.

Last but not least, detergent tablets or detergent tablets in which the foamed part or non-foamed part contains bleach, while the other region of the tablet surfactants, preferably nonionic surfactants, with particular preference alkoxylated alcohols having 10 to 24 carbon atoms and 1 to 5 alkylene oxide , As well as detergent tablets, characterized in that the foamed part or the non-foamed part contain the same active ingredient in different amounts, preferred embodiments of the present invention.

1. a) Herstellung von Formkörpern durch an sich bekannte Verfahren,
2. b) Beaufschlagung einer Lösung, Suspension, Emulsion oder Schmelze, die mindestens eine Aktivsubstanz enthält, mit einem gasförmigen Medium, wobei Formkörper gebildet werden, die aus gasgefüllten Zellen (Poren) bestehen, welche von festen Zwischenwänden begrenzt werden,
3. c) Vereinigen der in den Schritten a) und b) hergestellten Formkörper

gekennzeichnet ist.Another object of the present invention is also a method for producing multiphase shaped bodies, by the steps

1. a) production of moldings by methods known per se,
2. b) applying to a solution, suspension, emulsion or melt containing at least one active substance, with a gaseous medium, wherein shaped bodies are formed, which consist of gas-filled cells (pores), which are bounded by fixed partitions,
3. c) combining the shaped bodies produced in steps a) and b)

is marked.

In these processes, the shaped bodies according to the invention are provided as a phase of multiphase shaped bodies. The production of the shaped bodies in step a) takes place in preferred variants of this process by extrusion, pelleting, pressing, sintering, casting. Injection molding, thermoforming, extrusion or rolling. These methods and moldings obtained by these methods are known in the art.

The compound of the shaped bodies according to the invention with the conventional shaped bodies in step c) of the method according to the invention is preferably carried out by joining and / or joining into one another, wherein optionally adhesion promoters are applied to the contact surfaces between the parts.

Of course, the inventive method is not limited to biphasic moldings, but also three, four and five-phase up to even higher-phase moldings can be produced. Methods according to the invention, which are characterized in that a plurality of non-foamed moldings are combined with one or more foamed moldings, are therefore likewise preferred.

1. a) Beaufschlagung einer Lösung, Suspension, Emulsion oder Schmelze, die mindestens eine Aktivsubstanz enthält, mit einem gasförmigen Medium, wobei Formkörper gebildet werden, die aus gasgefüllten Zellen (Poren) bestehen, welche von festen Zwischenwänden begrenzt werden,
2. b) Beaufschlagung einer weiteren Lösung oder Schmelze, die mindestens eine Aktivsubstanz enthält, mit einem gasförmigen Medium, wobei Formkörper gebildet werden, die aus gasgefüllten Zellen (Poren) bestehen, welche von festen Zwischenwänden begrenzt werden,
3. c) Vereinigen der in den Schritten a) und b) hergestellten Formkörper

gekennzeichnet ist, ein weitere Ausführungsform der vorliegenden Erfindung.Not least is also a process for the production of multiphase moldings, by the steps

1. a) applying a gaseous medium to a solution, suspension, emulsion or melt containing at least one active substance, forming shaped bodies consisting of gas-filled cells (pores) delimited by fixed partitions,
2. b) charging a further solution or melt, which contains at least one active substance, with a gaseous medium, wherein shaped bodies are formed, which consist of gas-filled cells (pores) which are delimited by fixed partitions,
3. c) combining the shaped bodies produced in steps a) and b)

is another embodiment of the present invention.

As already explained in detail above, the ingredients of the multiphase moldings according to the invention are preferably not homogeneously distributed over the entire mold body, but concentrated predominantly or exclusively in certain phases. Methods in which the composition of the shaped bodies produced in steps a) and b) are different are therefore particularly preferred embodiments of the present invention, wherein it is particularly preferred that the shaped bodies produced in steps a) and b) contain different active substance (s) ) contain.

However, it is also possible to choose the composition of the molded body parts identically so as to be able to exploit controlled release effects on account of the packaging. Processes in which the composition of the shaped bodies produced in steps a) and b) are identical are therefore also feasible according to the invention.

This embodiment is particularly attractive if two (or more) shaped bodies according to the invention are combined to give a shaped body having two (or more) phases which consist of gas-filled cells (pores) bounded by solid partitions and in which the particulate solids are distributed. In such moldings special optical effects are achieved by different pore sizes. Therefore, processes in which the shaped bodies produced in steps a) and b) differ in their average pore sizes are also preferred.

1. a) Beaufschlagung einer Lösung, Suspension, Emulsion oder Schmelze, die mindestens eine Aktivsubstanz enthält, mit einem gasförmigen Medium,
2. b) Einarbeiten von partikelförmigen Feststoffen in den im Schritt a) gebildeten Schaum,
3. c) Abkühlung und/oder Aushärtung, wobei eine Formkörpermatrix gebildet wird, die aus gasgefüllten Zellen (Poren) besteht, welche von festen Zwischenwänden begrenzt werden und in der die partikelförmigen Feststoffe verteilt sind

gekennzeichnet ist.Another object of the present invention is a process for producing multiphase shaped bodies, which by the steps

1. a) applying a gaseous medium to a solution, suspension, emulsion or melt containing at least one active substance,
2. b) incorporation of particulate solids into the foam formed in step a),
3. c) cooling and / or curing, wherein a shaped body matrix is formed, which consists of gas-filled cells (pores), which are bounded by solid partitions and in which the particulate solids are distributed

is marked.

In turn, processes are preferred in which the solids incorporated in step b) originate from the group of granules, agglomerates, extrudates, compacts or pellets and particle sizes of 400 to 3000 .mu.m, preferably from 600 to 2500 .mu.m and in particular from 800 to 2000 microns exhibit.

Alternatively, an optically inconspicuous incorporation of particles may be desired so that the particles do not optically protrude within the foam structure. Here, preference is given to processes which are characterized in that the solids incorporated in step b) have particle sizes of from 50 to 600 .mu.m, preferably from 100 to 500 .mu.m and in particular from 200 to 400 .mu.m.

For foaming any gases or gas mixtures can be used. Examples of gases used in the art are nitrogen, oxygen, noble gases and noble gas mixtures such as helium, neon, argon and mixtures thereof, carbon dioxide, etc. For reasons of cost, air is preferably used according to the invention as a foaming gas. When the frothing up Components are stable to oxidation, the gaseous medium may also consist entirely or partially of ozone, which eliminates oxidatively destructible impurities or discoloration in the foaming media or microbial attack of these components can be prevented.

Even volatile compounds can be used as foaming gases. Here, for example, lower ethers such as dimethyl ether and diethyl ether into consideration. The blowing agents known from spray cans such as propane or butane are suitable in the context of the present invention as a foaming gas. It is crucial in the suitability as an ingredient d) only that the substance in the processing conditions produce cavities and thus can form foam structures from the mixture of ingredients.

In preferred processes, gaseous substances from the group consisting of carbon dioxide, nitrogen, nitrous oxide, propane, butane, dimethyl ether and mixtures thereof are used as blowing agents at room temperature in amounts of from 0.01 to 20% by weight, preferably from 0.05 to 15% by weight. -%, particularly preferably from 0.1 to 10 wt .-% and in particular from 0.25 to 5 wt .-%, each based on the mass of the solution, melt, emulsion or suspension used.

Of course, substances can be used which release gases under the working conditions of the manufacturing process. Here, for example, sodium bicarbonate, paa-Toluolsulfonylhydrazid, 4,4'-oxybis (benzenesulfonyhydrazid) or mixtures of acids and bicarbonates offer. Here, preference is given to processes according to the invention in which solids which are solid at room temperature and which release gases at the extrusion temperature are used as blowing agents in amounts of 0.5-10% by weight, preferably 1-7.5% by weight, based in each case on the mass of the Polymer or of the polymer mixture can be used.

In order to produce the foams, the gaseous medium is blown into liquids in preferred embodiments, or the foaming is achieved by vigorously beating, shaking, splashing or stirring liquid in the relevant gas atmosphere. Due to the lighter and better controllable and feasible foaming is within the present invention, the foam generation by blowing the gaseous medium ("gassing") over the other variants clearly preferred. Depending on the desired process variant, the gassing takes place continuously or discontinuously via perforated plates, sintered disks, sieve inserts, venturi nozzles, inline mixers, homogenizers or other conventional systems. In the context of the present invention, self-foaming systems in which the intumescent gas is formed by chemical reaction of the components with one another are also preferred. Even before the foam collapses, the liquid, semi-liquid or highly viscous cell webs solidify to solids, stabilizing the foam and forming a "solid foam".

Solutions to be foamed are solutions, dispersions, emulsions or melts, the latter being preferred in the context of the present invention.

Alternatively, higher-viscous systems can be foamed, which can go up to the formation of foam from plastic masses. In the latter case, it is recommended to plasticize the mixture of ingredients a) to c) in an extruder and feed it to the extruder outlet under the action of propellant. This process provides stable foams and does not require the raw material mixture to be melted, dissolved or dispersed.

The use of foamed moldings or molded body components as detergents or cleaning agents has manifold advantages over conventional detergent tablets. Thus, the dissolution rate can be made almost arbitrary, which is difficult for moldings that are produced by conventional pressing technology. Also, any geometric shapes can be realized, whereby completely new shapes are possible, which can also have overlaps, which also prohibits the method of pressing technology. Last but not least, the process advantages are significant as the processability of foams is better because of their lower viscosities over gels or liquids. Last but not least, elastic reversibly compressible structures can be produced through the choice of materials for the cell bridges, which enable a high degree of differentiation compared to competitor products.

Examples:

The mixtures given below were processed in a Brabender twin-screw kneader (DSC) 42/7. The DSK works with counter-rotating screws, which ensures extremely good mixing. The temperatures for processing the mixtures were 140 ° C and 147 ° C in the exit nozzle in the three existing zones along the screw. The mixtures were extruded through a strand die at 50 rpm. The diameter of the nozzle was 4 mm, the corresponding foamed strands had a diameter of more than 5 mm (foam 1, and 2).

Foam 1:

Mowiol ^® 4/88 61.3% glycerin 5.1% sorbitol 5.0% Aerosil ^® R972 0.4% stearic acid 0.2% PEG 400 5.0% sodium sulphate 23.0%

Foam 2:

Mowiol ^® 8/88 42.5% Mowiol ^® 4/88 42.5% glycerin 4.3% sorbitol 2.6% Dest. Water 0.5% Aerosil ^® R972 0.5% stearic acid 0.3% sodium 6.8%

Foam 3

The processing temperatures must be higher depending on the selected blowing agent, in the case of the foam 3 temperatures of 180-190 ° C at the outlet nozzle of the extruder are required. The foamed polymer must then be rapidly cooled at these temperatures otherwise the foam collapses. This can be done for example by cooling with liquid nitrogen or other coolants in which the polyvinyl alcohol is not soluble or poorly soluble, such as solid carbon dioxide cooled ethanol, cyclohexanol, diethyl ether, ethylene glycol, etc (mixing ratio: 30% carbon dioxide: 70% solvent) , Mowiol ^® 4/88 (PVA) 78.5% glycerin 6.9% sorbitol 5.6% foaming agent 9.0% (equimolar mixture of citric acid + sodium bicarbonate)

Claims (47)

1. Multiphase washing or cleaning composition shaped body, characterized in that at least one phase of the shaped body comprises solid(s) and gas(es) and optionally other washing or cleaning composition constituents, said phase consisting of gas-filled cells (pores) bordered by solid intermediate walls and said phase containing 40 to 90% by weight of water-soluble polymer(s).
2. Washing or cleaning composition shaped body according to Claim 1, characterized in that the ratio of the mean diameter of the gas-filled cells to the mean diameter of the solid intermediate walls is at least 1:2, preferably at least 5:1, more preferably at least 10:1 and in particular more than 20:1.
3. Washing or cleaning composition shaped body according to one of Claims 1 and 2, characterized in that the mean diameter of the gas-filled cells is 0.005 to 5 mm, preferably 0.05 to 0.5 mm and in particular 0.1 to 0.3 mm.
4. Washing or cleaning composition shaped body according to one of Claims 1 to 3, characterized in that the mean diameter of the solid intermediate walls is 0.001 to 2 mm, preferably 0.005 to 0.3 mm and in particular 0.01 to 0.1 mm.
5. Washing or cleaning composition shaped body according to one of Claims 1 to 4, characterized in that the volume of the gas-filled cells makes up at least 50% by volume, preferably at least 60% by volume and in particular at least 70% by volume of the total volume of the shaped body or of the phase.
6. Washing or cleaning composition shaped body according to one of Claims 1 to 5, characterized in that the shaped body or the phase has a density of 0.01 to 1.0 gcm^-3, preferably of 0.05 to 0.7 gcm^-3 and in particular of 0.1 to 0.3 gcm^-3.
7. Washing or cleaning composition shaped body according to one of Claims 1 to 6, characterized in that the gas-filled cells comprise one or more gases from the group of the noble gases, carbon dioxide, nitrogen, dinitrogen oxide, oxygen, ozone, dimethyl ether and air.
8. Washing or cleaning composition shaped body according to one of Claims 1 to 7, characterized in that the solid intermediate walls comprise one or more washing or cleaning composition constituents, preferably from the group of the surfactants, builders, cobuilders, polymers, bleaches; bleach activators, enzymes, foam inhibitors, optical brighteners, dyes and fragrances and/or disintegration assistants.
9. Washing or cleaning composition shaped body (solid foam) according to one of Claims 1 to 8, characterized by a content of

   a) 40 to 90% by weight of one or more water-soluble polymers,

   b) 10 to 60% by weight of one or more substances from the group of the builders, acidifiers, chelate complexing agents, film-inhibiting polymers or nonionic surfactants,

   c) 0 to 50% by weight of one or more assistants and/or fillers.
10. Washing or cleaning composition shaped body according to Claim 9, characterized in that the water-soluble polymer(s) is/are selected from:

    i) polyacrylic acids and salts thereof

    ii) polymethacrylic acids and salts thereof

    iii) polyvinylpyrrolidone

    iv) vinylpyrrolidone/vinyl ester copolymers

    v) cellulose ethers

    vi) polyvinyl acetates, polyvinyl alcohols and copolymers thereof

    vii) graft copolymers of polyethylene glycols and vinyl acetate

    viii) alkylacrylamide/acrylic acid copolymers and salts thereof

    ix) alkylacrylamide/methacrylic acid copolymers and salts thereof

    x) alkylacrylamide/methyl methacrylate copolymers and salts thereof

    xi) alkylacrylamide/acrylic acid/alkylaminoalkyl (meth)acrylate copolymers and salts thereof

    xii) alkylacrylamide/methacrylic acid/alkylaminoalkyl (meth)acrylate copolymers and salts thereof

    xiii) alkylacrylamide/methyl methacrylate/alkylaminoalkyl (meth)acrylate copolymers and salts thereof

    xiv) alkylacrylamide/alkyl methacrylate/alkylaminoethyl methacrylate/alkyl methacrylate copolymers and salts thereof

    xv) copolymers of

    xv-i) unsaturated carboxylic acids and salts thereof

    xv-ii) cationically derivatized unsaturated carboxylic acids and salts thereof

    xvi) acrylamidoalkyltrialkylammonium chloride/acrylic acid copolymers and the alkali metal and ammonium salts thereof

    xvii) acrylamidoalkyltrialkylammonium chloride/methacrylic acid copolymers and the alkali metal and ammonium salts thereof

    xviii) methacryloylethylbetaine/methacrylate copolymers

    xix) vinyl acetate/crotonic acid copolymers

    xx) acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymers

    xxi) 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

    xxii) grafted copolymers from the copolymerization of

    xxii-i) at least one monomer of the nonionic type

    xxii-ii) at least one monomer of the ionic type

    xxiii) copolymers obtained by copolymerization of at least one monomer of each of the three following groups:

    xxiii-i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and/or esters of short-chain saturated alcohols and unsaturated carboxylic acids

    xxxiii-ii) unsaturated carboxylic acids

    xxiii-iii) esters of long-chain carboxylic acids and unsaturated alcohols and/or esters of the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C_8-18 alcohols.
11. Washing or cleaning composition shaped body according to one of Claims 9 and 10, characterized in that the water-soluble polymer(s) is/are selected from homopolymers of vinyl alcohol, copolymers of vinyl alcohol with copolymerizable monomers or hydrolysis products of vinyl ester homopolymers or vinyl ester copolymers with copolymerizable monomers.
12. Washing or cleaning composition shaped body according to Claim 11, characterized in that the water-soluble polymer is a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, more preferably 81 to 89 mol% and in particular 82 to 88 mol%.
13. Washing or cleaning composition shaped body according to Claim 11 or 12, characterized in that the water-soluble polymer is a polyvinyl alcohol whose molecular weight is in the range of 10 000 to 100 000 g/mol^-1, preferably of 11 000 to 90 000 g/mol^-1, more preferably of 12 000 to 80 000 g/mol-¹ and in particular of 13 000 to 70 000 g/mol^-1.
14. Washing or cleaning composition shaped body according to one of Claims 9 and 10, characterized in that the water-soluble polymer(s) is/are selected from polyurethanes formed from diisocyanates (VII) and diols (VIII)
    
            O=C=N-R¹-N=C=O     (VII)
    
            H-O-R²O-H     (VIII)
    
    where the diols are at least partly selected from polyethylene glycols (IV) and/or polypropylene glycols (V)
    
            H-(O-CH₂-CH₂)_n-OH     (IV)
    
    

    

    and R¹ and R² are each independently a substituted or unsubstituted, straight-chain or branched alkyl, aryl or alkylaryl radical having 1 to 24 carbon atoms, and n is in each case 5 to 2000.
15. Washing or cleaning composition shaped body according to Claim 14, characterized in that the water-soluble polymer is a polyurethane formed from diisocyanates (VII) and diols (VIII)
    
            O=C=N-R¹-N=C=O     (VII)
    
            H-O-R²-O-H     (VIII)
    
    where R¹ is a methylene, ethylene, propylene, butylene, pentylene group or is -(CH₂)₆- or is 2,4- or 2, 6-C₆H₃-CH₃ or is C₆H₄-CH₂-C₆H₄ or is an isophorone radical (3,5,5-trimethyl-2-cyclohexenone), and R² is selected from -CH₂-CH₂-(O-CH₂-CH₂)_n- or -CH₂-CH₂-(O-CH(CH₃)-CH₂)_n- where n = 4 to 1999.
16. Washing or cleaning composition shaped body according to one of Claims 14 and 15, characterized in that the water-soluble polymer is a polyurethane which has structural units of the formula (IX)
    
            -[O-C(O)-NH-R¹-NH-C(O)-O-R²]_k-     (IX)
    
    in which R¹ is -(CH₂)₆- or is 2,4- or 2, 6-C₆H₃-CH₃ or is C₆H₄-CH₂-C₆H₄, and R² is selected from -CH₂-CH₂-(O-CH₂-CH₂)_n- or -CH (CH₃) -CH₂- (O-CH (CH₃) - CH₂)_n- where n is 5 to 199 and k is 1 to 2000.
17. Washing or cleaning composition shaped body according to one of Claims 9 to 16, characterized in that it comprises the water-soluble polymer (s) in amounts of 45 to 87.5% by weight, preferably of 50 to 85% by weight, more preferably of 55 to 82.5% by weight and in particular of 60 to 80% by weight.
18. Washing or cleaning composition shaped body according to one of Claims 9 to 17, characterized in that it comprises, as constituent b), 12.5 to 55% by weight, preferably 15 to 50% by weight, more preferably 17.5 to 45% by weight and in particular 20 to 40% by weight of one or more nonionic surfactants.
19. Washing or cleaning composition shaped body according to one of Claims 9 to 18, characterized in that it comprises, as constituent c), one or more substances from the group of the dyes and fragrances, standardizers, binders, humectants and/or salts.
20. Washing or cleaning composition according to one of Claims 1 to 8, characterized in that the solid intermediate walls comprise one or more substances having a melting point above 50°C, preferably from the group of the paraffins, the polyethylene glycols and the fatty substances.
21. Washing or cleaning composition shaped body according to one of Claims 1 to 20, characterized in that the phases have the form of layers.
22. Washing or cleaning composition shaped body according to one of Claims 1 to 20, characterized in that at least one phase comprises a cavity in which another phase is embedded at least partly.
23. Washing or cleaning composition shaped body according to one of Claims 1 to 20, characterized in that a phase composed of gas-filled cells surrounded by solid intermediate walls is embedded into the other phase(s).
24. Washing or cleaning composition shaped body according to Claim 23, characterized in that the phase embedded in the phase consisting of gas-filled cells surrounded by solid intermediate walls consists of particulate solids.
25. Washing or cleaning composition shaped body according to one of Claims 21 to 24, characterized in that the unfoamed phase is a compressed part.
26. Washing or cleaning composition shaped body according to one of Claims 21 to 24, characterized in that the unfoamed layer is an uncompressed part.
27. Washing or cleaning composition shaped body according to one of Claims 21 to 24, characterized in that the unfoamed layer is a sintered part.
28. Washing or cleaning composition shaped body according to one of Claims 21 to 24, characterized in that the unfoamed layer is a cast part.
29. Washing or cleaning composition shaped body according to one of Claims 1 to 28, characterized in that the weight ratio between foamed and unfoamed phase is in the range of 30:1 to 1:50, preferably of 5:1 to 1:30 and in particular of 1:1 to 1:10.
30. Washing or cleaning composition shaped body according to one of Claims 1 to 28, characterized in that the weight ratio between foamed and unfoamed phase is in the range of 50:1 to 1:20, preferably of 10:1 to 1:10, more preferably of 5:1 to 1:5 and in particular of 4:1 to 1:2.
31. Washing or cleaning composition shaped body according to one of Claims 1 to 30, characterized in that the foamed phase(s) dissolve(s) more rapidly than the unfoamed phase(s).
32. Washing or cleaning composition shaped body according to Claim 31, characterized in that at least 50% by weight of the foamed phase (s) has dissolved when not more than 10% by weight of the unfoamed phase(s) has dissolved.
33. Washing or cleaning composition shaped body according to one of Claims 1 to 30, characterized in that the foamed phase(s) dissolve(s) more slowly than the unfoamed phase(s).
34. The washing or cleaning composition shaped body according to Claim 33, characterized in that at least 50% by weight of the unfoamed phase (s) has dissolved when not more than 10% by weight of the foamed phase(s) has dissolved.
35. Washing or cleaning composition shaped body according to one of Claims 1 to 34, characterized in that the foamed part comprises at least one active substance from the group of the enzymes, surfactants, soil-release polymers, disintegration assistants, bleaches, bleach activators, bleach catalysts, silver protectants and mixtures thereof.
36. Process for producing multiphase washing or cleaning composition shaped bodies, characterized by the steps of

    a) producing shaped bodies by processes known per se,

    b) contacting a solution, suspension, emulsion or melt which comprises at least one active substance with a gaseous medium to form shaped bodies which consist of gas-filled cells (pores) bordered by solid intermediate walls,

    c) combining the shaped bodies produced in steps a) and b).
37. Process according to Claim 36, characterized in that the shaped bodies are produced in step a) by extrusion, pelletization, compression, sintering, casting, injection moulding, thermoforming, strand pressing or rolling.
38. Process according to one of Claims 36 and 37, characterized in that step c) comprises joining and/or interlocking, for which adhesion promoters may be applied to the contact areas between the parts.
39. Process according to one of Claims 36 to 38, characterized in that a plurality of unfoamed shaped bodies are bonded to one or more foamed shaped bodies.
40. Process for producing multiphase washing or cleaning composition shaped bodies, characterized by the steps of

    a) contacting a solution, suspension, emulsion or melt which comprises at least one active substance with a gaseous medium to form shaped bodies which consist of gas-filled cells (pores) bordered by solid intermediate walls,

    b) contacting a further solution or melt which comprises at least one active substance with a gaseous medium to form shaped bodies which consist of gas-filled cells (pores) which are bordered by solid intermediate walls,

    c) combining the shaped bodies produced in steps a) and b).
41. Process according to Claim 40, characterized in that the composition of the shaped bodies produced in steps a) and b) is different.
42. Process according to one of Claims 40 and 41, characterized in that the shaped bodies produced in steps a) and b) comprise different active substance(s).
43. Process according to Claim 40, characterized in that the composition of the shaped bodies produced in steps a) and b) is identical.
44. Process according to Claim 43, characterized in that the shaped bodies produced in steps a) and b) differ in their mean pore sizes.
45. Process for producing multiphase washing or cleaning composition shaped bodies, characterized by the steps of

    a) contacting a solution, suspension, emulsion or melt which comprises at least one active substance with a gaseous medium,

    b) incorporating particulate solids into the foam formed in step a),

    c) cooling and/or curing to form a shaped body matrix which consists of gas-filled cells (pores) which are bordered by solid intermediate walls and in which the particulate solids are distributed.
46. Process according to Claim 45, characterized in that the solids incorporated in step b) stem from the group of the granules, agglomerates, extrudates, compactates or pellets, and have particle sizes of 400 to 3000 µm, preferably of 600 to 2500 µm and in particular of 800 to 2000 µm.
47. Process according to Claim 45, characterized in that the solids incorporated in step b) have particle sizes of 50 to 600 µm, preferably of 100 to 500 µm and in particular of 200 to 400 µm.