DE10107217A1 - Solid water-soluble polymeric foams use as detergent or cleaning articles, containing builders, acidifiers, chelate complex-formers, deposition-inhibiting polymers and/or nonionic surfactants - Google Patents

Abstract

Solid foams contain by weight: (A) water-soluble polymers (40-90%); (B) builders, acidifiers, chelate complex-formers, deposition-inhibiting polymers and/or nonionic surfactants (10-60%); and (C) auxiliaries and/or fillers (0-50%).

Description

The present invention relates to polymer foams used as washing or cleaning can be used as a medium or as a component.

Detergent tablets which contain solid (s) and gas (s) as well if necessary, contain other detergent or cleaning agent components, the molding per consists of gas-filled cells (pores) bounded by solid partitions are known from the older German patent application DE 100 24 261.8.

Here, detergent tablets are disclosed, all or in part Structures of solid foams have the highest degree of mechanical stability with a significantly improved release speed and a completely new look tie.

The task now was to create this new type of offer for washing or cleaning further improve to achieve additional success in washing or cleaning pro to achieve zeß. The functionality and production security should continue be improved. In particular, a simple and inexpensive solution should also be used Manufacturing processes for molded foam articles are provided.

It has now been found that mixtures of water-soluble polymers with In Contains substances from washing or cleaning agents to stable and advantageous foams Process, which as a detergent or cleaning tablets or part thereof can be used.

In a first embodiment, the present invention therefore relates to a solid foam which has 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 builders, Acidifying agents, chelating agents, deposit-inhibiting polymers or nonionic surfactants,
• c) 0 to 50% by weight of one or more auxiliaries and / or fillers

having.

In the context of the present invention, the term “solid foam” denotes structures from gas-filled cells (pores), which are bounded by solid partitions. in the Connection with the terms "foam" or "partitions of the gas-filled cell len "means the term" solid "the physical state of the partition at 25 ° C and 1013.25 mbar. This term expressly refers only to the partition walls are no longer liquid under the physical conditions mentioned and closes both rigid and flexible walls. Vividly, they both fall as upholstery known polyurethane flexible foams as well as for sealing purposes in the Construction industry uses rigid polyurethane foam or Styropor® in the category of gas-filled cells bounded by solid partitions.

If the volume concentration of the gas forming the foam at homodisperse Distribution is less than 74%, the gas bubbles are because of the small surface area the effect of the interfacial tension spherical. Above the limit of the densest Ball packing, the bubbles are deformed into polyhedral lamellae, which 4-600 nm thin cuticles can be limited. The cell webs, connected via so-called Nodes form a coherent framework. Span between the cell bars the foam lamellae (closed-cell foam). Become the foam lamella len destroyed or flow back into the cell webs at the end of foam formation you have an open cell foam. Foams are thermodynamically unstable because Ver reduction in surface area surface energy can be obtained. The stability and the existence of the foams according to the invention therefore depends on how far they manage to prevent their self-destruction.

A variety of methods can be used to produce the foams (see further below). In addition to the "classic" foaming using gaseous media, which in Solutions, melts or dispersions are also introduced, others are also available Processes such as extrusion followed by expansion. In the In "classic" gas foaming, the gaseous medium is absorbed into the liquids blow, or the foaming is achieved by violent beating, shaking, ver spray or stir the liquid in the gas atmosphere in question. Due to the easier and more controllable and feasible foaming is within the scope of present invention the foam generation by blowing the gaseous Me diums ("fumigation") clearly preferred over the other variants. The fumigation is carried out continuously or discontinuously depending on the desired process variant via perforated plates, sintered discs, sieve inserts, Venturi nozzles, inline mixers, homogenisers sensors or other common systems. Also within the scope of the present invention self-foaming systems in which the foaming gas is chemical Reaction of the components with one another is preferred. Even before the Foam collapses, the liquid, semi-liquid or highly viscous cell bars solidify Solids, which stabilize the foam and form a "solid foam".

Any gases or gas mixtures can be used as the gaseous medium for foaming be used. Examples of gases used in technology are nitrogen and acid substance, noble gases and noble gas mixtures such as helium, neon, argon and their Mixtures, carbon dioxide, etc. Is preferred according to the invention for reasons of cost Air used as a gaseous medium. If the components to be foamed are stable to oxidation, the gaseous medium can also be made entirely or partially from ozone exist, causing oxidatively destructible impurities or discoloration in the eliminates foaming media or prevents germ contamination of these components can be.

The solid foams according to the invention or the relevant phase (s) of the invention Moldings according to the invention can consist of relatively large gas-filled cells with fixed cell webs exist, but it is also possible that the pore size is small. Visually appealing NEN also be shaped bodies (or parts thereof), which are made up of many gas-filled in a "matrix" Small diameter cells have some large cells that are located on the edge range of the shaped body (or phase) as larger cavities clearly from the matrix of the smaller cavities.

Regardless of the pore size, solid foams according to the invention are preferred which is the ratio of the average diameter of the gas-filled cells to the average Diameter of the fixed partition walls at least 1: 2, preferably at least 5: 1, is particularly preferably at least 10: 1 and in particular more than 20: 1.

So there are relatively large pores and relatively thin solid partition walls in accordance with the invention moderately preferred. In absolute terms with regard to those for washing or cleaning Molding moldings usual mold dimensions with diameters and heights preferred of a maximum of a few centimeters of solid foams, in which the middle Diameter of the gas-filled cells 0.005 to 5 mm, preferably 0.05 to 0.5 mm and is in particular 0.1 to 0.3 mm.

Similarly, solid foams are preferred in which the mean diameter of the solid Partitions 0.001 to 2 mm, preferably 0.005 to 0.3 mm and in particular 0.01 is up to 0.1 mm.

Depending on the size of the gas-filled pores, the thickness of the cell webs and the gas content of a given gas varies from the amount of gas or wall material Volume of a foam according to the invention or a phase of a foam according to the invention outer molded body. Here, detergent tablets are preferred because there 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 Ge accounts for the total volume of the molded body or phase.

Depending on the density of the gas in the gas-filled pores and the density of the cell webs, a certain density results for the solid foams according to the invention or for one or more phase (s) of the detergent tablets according to the invention, which is advantageously well below the density conventionally cher, is made by pressing technology molded body. Solid foams preferred in the context of the present invention are characterized in that they or the phase have a density of 0.01 to 1.0 gcm ^-3, preferably 0.05 to 0.7 gcm ^-3 and in particular 0.1 up to 0.3 gcm ^-3 .

As already mentioned above, air is the preferred gaseous medium used. But it is also possible to fill other gases or gas mixtures  use gas-filled cells. For example, it may be preferred to use pure oxygen or to pass the air to be used as the filling gas over an ozonizer before the gas is used to fill the pores. In this way you can produce gas mixtures len, which contain, for example 0.1 to 4 wt .-% ozone. The ozone content of the gas leads then for the oxidative destruction of undesirable constituents in those to be foamed Media. In the context of the present invention are detergent or cleaning agent form body preferred, in which the gas-filled cells one or more gases from the Group of noble gases, carbon dioxide, nitrogen, nitrous oxide, oxygen, ozone, dime contain ethyl ether and air.

The cell webs of the solid foams or molded body phases according to the invention exist from substances or substance mixtures which are solid at 25 ° C and 1013.25 mbar. With regard to the large-scale and cost-effective producibility are fixed here substances preferred as material for the cell webs, which are characterized by dissolution, suspension Transfer, emulsify, melt etc. into a liquid or highly viscous mass leave, which is then foamed by adding filling gas (see above), whereby the resulting foam preferably by cooling, evaporation of solvent, time-delayed solvent binding, crystallization, chemical reaction (in particular polymerization, polycondensation or polyaddition), change in rheological Properties or radiation curing takes place.

According to the invention, water-soluble polymers are therefore used as the material for the cell webs used either in the form of concentrated solutions or suspensions be foamed, or formed from their monomers only during foaming will. In the case of polyurethanes, the foaming gas is also generated by reak tion of the raw materials for the wall material. Of course, an investigation is also possible of molten mixtures of the water-soluble polymers and the wide Ren ingredients of the solid foams according to the invention possible.

The solid foams according to the invention contain water-soluble polymer (s) as ingredient a). Water-soluble polymers for the purposes of the invention are those polymers which are more than 2.5% by weight soluble in water at room temperature. Especially before given certain water-soluble polymers are used 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:

• a) Polyacrylic acids and their salts
• b) polymethacrylic acids and their salts
• c) polyvinylpyrrolidone,
• d) vinyl pyrrolidone / vinyl ester copolymers,
• e) cellulose ethers
• f) polyvinyl acetates, polyvinyl alcohols and their copolymers,
• g) graft copolymers of polyethylene glycols and vinyl acetate
• h) alkyl acrylamide / acrylic acid copolymers and their salts
• i) alkyl acrylamide / methacrylic acid copolymers and their salts
• j) alkyl acrylamide / methyl methacrylic acid copolymers and their salts
• k) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• l) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• m) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid Copolymers and their salts
• n) alkyl acrylamide / alkyl methacrylate / alkylaminoethyl methacrylate / alkyl methacrylate Copolymers and their salts
• o) copolymers
  • 1. xiii-i) unsaturated carboxylic acids and their salts
  • 2. xiii-ii) cationically derivatized unsaturated carboxylic acids and their salts
• p) Acrylamidoalkyltrialkylammoniumchlorid / acrylic acid copolymers and their Alkali and ammonium salts
• q) Acrylamidoalkyltrialkylammoniumchlorid / methacrylic acid copolymers and their alkali and ammonium salts
• r) Methacroylethylbetaine / methacrylate copolymers
• s) vinyl acetate / crotonic acid copolymers
• t) Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
• u) 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
• v) grafted copolymers from the copolymerization of
  • 1. xx-i) at least one monomer of the non-ionic type,
  • 2. at least one monomer of the ionic type,
• w) each of the three follow by copolymerization of at least one monomer copolymers obtained in the groups:
• x)
  • 1. xxi-i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
  • 2. xxi-i) unsaturated carboxylic acids,
  • 3. xxi-iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol.

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

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

Polyvinylpyrrolidones iii) are sold, for example, under the name Luviskol® (BASF). Polyvinylpyrrolidones are preferred polymers in the context of the present invention. Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (I)

by the radical polymerization of 1-vinylpyrrolidone by the process of or suspension polymerization using radical formers (peroxides, azo Compounds) are prepared as initiators. The ionic polymerization of the mono meren only supplies products with low molecular weights. Commercial polyvinylpyrrolidones have molar masses in the range of approx. 2500-750 000 g / mol, which can be Values are characterized and - depending on the K value - glass transition temperatures of Own 130-175 °. They are presented as white, hygroscopic powders or as aqueous ones. Lö  offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, Phe nole u. a.).

Vinylpyrrolidone / vinyl ester copolymers IV) are, for example, under the product Chen Luviskol® (BASF) sold. Luviskol® VA 64 and Luviskol® VA 73, each vinylpyr rolidone / vinyl acetate copolymers are particularly preferred polymers.

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

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

The vinyl esters are polymerized by free radicals using various processes (Solution polymerization, suspension polymerization, emulsion polymerization, sub punch polymerization.). Copolymers of vinyl acetate with vinyl pyrrolidone contain mono mer units of formulas (I) and (II).

Particularly suitable cellulose ethers v) are hydroxypropyl cellulose and hydroxyethyl cellulose se and methylhydroxypropyl cellulose, such as, for example, under the trademark Culminal® and Benecel® (AQUALON) are marketed.

Cellulose ethers can be described by the general formula (III)

in R represents 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 manufactured industrially by etherification of alkali cellulose (e.g. with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of cellulose have reacted with the etherification reagent or how many moles of etherification reagent on average to an anhydroglucose unit were added. Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercial Hy droxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish white, odorless and tasteless powders in widely differing degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Other particularly preferred water-soluble polymers are polyvinyl acetals, polyvinyl alcohols and their copolymers. Among these, 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 are preferred, so that foams according to the invention in which the water-soluble polymer (s) are selected is / are composed of 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, are preferred embodiments of the present invention. Homopolymers or copolymers of vinyl alcohol cannot be obtained by polymerizing vinyl alcohol (H ₂ C = CH-OH) since its concentration in tautomer equilibrium with acetaldehyde (H ₃ C-CHO) is too low. These polymers are therefore 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, abbreviated as PVAL, are polymers of the general structure

[-CH ₂ -CH (OH) -] _n

which in small proportions also structural units of the type

[-CH ₂ -CH (OH) -CH (OH) -CH ₂ ]

contain.

Commercial polyvinyl alcohols, which are used as white-yellowish powder or granules with poly degrees of merization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol) are offered, have degrees of hydrolysis of 98-99 or 87-89 mol%, contain a residual content of acetyl groups. The buttocks are characterized Lyvinyl alcohols on the part of the manufacturer by indicating the degree of polymerization of the Starting polymers, the degree of hydrolysis, the saponification number or the solution viscosity sity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and few strong polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not consumed by (chlorinated) hydrocarbons, esters, fats and oils grabbed. Polyvinyl alcohols are classified as toxicologically safe and are organic at least partially biodegradable. The water solubility can be checked by Nachbe treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or reduce by treatment with dichromates, boric acid or borax. The Beschich Polyvinyl alcohol solutions are largely impervious to gases such as oxygen, Nitrogen, helium, hydrogen, carbon dioxide, however, allow water vapor to pass through.

Foams preferred in the context of the present invention are characterized thereby net that the water-soluble polymer is a polyvinyl alcohol, the degree of hydrolysis 70th to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and is in particular 82 to 88 mol%.

Polyvinyl alcohols of a certain molecular weight range are preferably used, foams according to the invention are preferred in which the water-soluble polymer is a polyvinyl alcohol, the molecular weight of which is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , particularly is 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 approximately 200 to about 2100, preferably between about 220 to about 1890 preferably between about 240 to about 1680 and especially between about 260 to about 1500.

The polyvinyl alcohols described above are widely available commercially at for example under the trademark Erkol® (from Erkol). As part of the present Polyvinyl alcohols particularly suitable according to the invention are, for example, Erkol® 3-83, Erkol® 4-88, Erkol® 5-88 and Erkol® 8-88.

Also suitable as water-soluble polymers a) are graft polymers from 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 polyalky lenglycols. Such grafted polymers of vinyl esters, esters of acrylic acid or Methacrylic acid alone or in a mixture with other copolymerizable compounds on polyalkylene glycols by heat polymerization in a homogeneous phase obtained in that the polyalkylene glycols in the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid, stirred in the presence of radical formers.

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

Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols. Polyethylene glycols are polymers of ethylene glycol which have the general formula IV

H- (O-CH ₂ -CH ₂ ) _n -OH (IV)

are sufficient, where n can have values between 1 (ethylene glycol) and several thousand. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is technically customary, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the formula V mentioned above. According to this nomenclature (so-called INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Editi on, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), for example, PEG-4, PEG-6, PEG-8, PEG -9, PEG-10, PEG-12, PEG-14 and PEG-16 can be used. Polyethylene glycols are commercially available, for example, under the trade names Carbowax® PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HÜLS America), Polyglykol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rhone -Poulenc), Lutrol® E300 (BASF) and the corresponding trade names with higher numbers.

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

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

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

Grafted and crosslinked copolymers from the copolymerization of

• a) at least one monomer of the non-ionic type,
• b) at least one monomer of the ionic type,
• c) of polyethylene glycol and
• d) a networked person.

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

The monomers can be of very different types and among these are fol preferred preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl thec, stearyl vinyl ether and 1-witches. The monomers of the second group can equally from very low be different types, among them particularly preferred ccotonic acid, Ally loxyacetic acid, vinyl acetic acid, maleic acid, acrylic acid and methacrylic acid in the Graft polymers are included.

Ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallylsucrose with 2 to 5 Allyl groups per molecule of saccharin.

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

• a) 5 to 85% by weight of at least one monomer of the non-ionic type,
• b) 3 to 80% by weight of at least one monomer of the ionic type,
• c) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and
• d) 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinking agent is formed by the ratio of the total weights of i), ii) and iii).

Other suitable water-soluble polymers are copolymers of alkyl acrylamide with Acrylic acid, alkyl acrylamide with methacrylic acid, alkyl acrylamide with methyl methacrylic acid as well as alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, alkyl acryl amide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, alkyl acryl amide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers as well Copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated Carboxylic acids optionally other ionic or nonionic monomers.

Other polymers suitable according to the invention are water-soluble amphopolymers. Under the generic term amphoteric polymers are amphoteric polymers, ie polymers that contain free amino groups as well as free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and -COO ^- - or -SO ₃ ^- contain groups, and summarized such polymers that contain -COOH or SO ₃ H groups and quaternary ammonium groups. An example of an amphopolymer that can be used according to the invention is the acrylic resin available under the name Amphomer®, which is a copoly mer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group Acrylic acid, methacrylic acid and their simple esters. Also preferred amphopolymers are composed of unsaturated carboxylic acids (e.g. acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (e.g. acrylamidopropyl-trimethyl-ammonium chloride) and optionally other ionic or nonionic monomers. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat®2001 N, are particularly preferred amphopolymers according to the invention. Other suitable amphoteric polymers are, for example, the octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers available under the names Amphomer® and Amphomer® LV-71 (DELFT NATIONAL).

Suitable zwitterionic polymers are, for example, acrylamidopropyltrimethyl ammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali and ammonium salts. Suitable zwitterionic polymers are methacroyl ethylbetainl methacrylate copolymers sold under the name Amersette® (AMERCHOL) are commercially available.

Anionic polymers suitable according to the invention include:

• - Vinyl acetate / crotonic acid copolymers, as are commercially available, for example, under the names Resyn® (NATIONAL STARCH), Luviset® (BASF) and Gafset® (GAF).
  In addition to monomer units of the abovementioned formula (II), these polymers also have monomer units of the general formula (VI)
  [-CH (CH ₃ ) -CH (COOH) -] _n (VI)
• - Vinyl pyrrolidone / vinyl acrylate copolymers, available for example under the goods logo Luviflex® (BASF). A preferred polymer is under the designation Luviflex® VBM-35 (BASF) available vinyl pyrrolidone / acrylate terpolymers.
• - AcrylsäurelEthylacrylat / N-tert.Butylacrylamid terpolymers, for example, under the name Ultrahold® strong (BASF).
• - Graft polymers from 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 polykalkylene glycols.

Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in a mixture with other copolymerizable compounds on polyalky Lenglykolen are by polymerization in the heat in a homogeneous phase keep that the polyalkylene glycols in the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid, stirred in the presence of radical formers.

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

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

• a) 5 to 85% by weight of at least one monomer of the non-ionic type,
• b) 3 to 80% by weight of at least one monomer of the ionic type,
• c) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and
• d) 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinking agent is formed by the ratio of the total weights of i), ii) and iii).

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

• a) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids ren,
• b) unsaturated carboxylic acids,
• c) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group ii) with saturated or unsaturated, ge-chain or branched C _8-18 alcohol.

Short-chain carboxylic acids or alcohols include those with 1 to 8 carbons To understand atoms of matter, given the carbon chains of these compounds if can be interrupted by double-bonded hetero groups such as -O-, -NH-, -S-.

Another particularly preferred class of polymers which in the invention ß solid foams can be contained as ingredient a) are polyurethanes. Polyu rethanes are water-soluble in the sense of the invention if they are at room temperature in water are more than 2.5% by weight soluble.

The polyurethanes consist of at least two different types of monomers,

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

The compounds (A) can be, for example, diols, triols, diamines, Triami ne, act polyetherols and polyesterols. The connections with more than 2 active hydrogen atoms usually only in small amounts in combination with a large excess of compounds with 2 active hydrogen atoms.

Examples of compounds (A) are ethylene glycol, 1,2- and 1,3-propylene glycol, buty Lenglycols, di, tri, tetra and poly ethylene and propylene glycols, copolymers of never whose alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, ethylenediamine, Pro pylendiamine, 1,4-diaminobutane, hexamethylenediamine and α, ω-diamines based on long chain alkanes or polysylene oxides.

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

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

O = C = NR ¹ -N = C = O (VII),

in which R ^{1 represents} a connecting group of carbon atoms, for example a methylene-ethylene-propylene, butylene, pentylene, hexylene, etc. group. In the above-mentioned, most widely used hexamethylene diisocyanate (HMDI), R ⁴ = (CH ₂ ) ₆ , in 2,4- or 2,6-toluenediisocyanate (TDI) R ⁴ stands for 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 represents} the isophorone residue (3,5,5-trimethyl-2-cyclohexenone) .

Furthermore, the polyurethanes used according to the invention can also contain building blocks such as for example, diamines as chain extenders and hydroxycarboxylic acids. Dial Cyclic carboxylic acids such as dimethylol propionic acid are particularly suitable Hydroxy carboxylic acids. With regard to the other building blocks, there is no fundamental one Restriction on whether it is non-ionic, anionic or cationic Building blocks.

For more information on the structure and manufacture of the polyurethanes is explicitly referred to the articles in the relevant overviews such as Römpps Chemical encyclopedia and Ullmann's encyclopedia of technical chemistry referenced.

Polyurethanes which can be characterized as follows have proven particularly suitable according to the invention in many cases:

• - only 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. Foams according to the invention are particularly preferred here in which the water-soluble polymer (s) is / are selected from polyurethanes from diisocyanates (VII) and diols (VIII).

O = C = NR ¹ -N = C = O (VII),

HOR ² -OH (VIII),

the diols being selected at least in part 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 each number from 5 to 2000.

The reaction mixtures can additionally contain further polyisocyanates. Also a Content of the reaction mixtures - and thus the polyurethanes - in other diols, trio len, diamines, triamines, polyetherols and polyesterols is possible. The Compounds with more than 2 active hydrogen atoms usually only in small Amounts in combination with a large excess of 2 active compounds Hydrogen atoms used.

If other diols etc. are added, there are certain quantitative ratios to those in the polyurethane existing polyethylene and / or polypropylene glycol units. Here are Polyurethanes preferred 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 reacted in the polyurethane are selected from polyethylene glycol kofen (IV) and / or polypropylene glycols (V).

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

Examples of optional further in the reaction mixtures for the production of the polyurethane ne contained compounds are ethylene glycol, 1,2- and 1,3-propylene glycol, butylene glycol kole, ethylenediamine, propylenediamine, 1,4-diaminobutane, hexamethylenediamine and α, ω- Diamines based on long-chain alkanes or polyalkylene oxides. According to the invention solid foams in which the polyurethanes contain additional diamines, preferably hexa methylenediamine and / or hydroxycarboxylic acids, preferably dimethylolpropionic acid, are preferred.

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

O = C = NR ¹ -N = C = O (VII),

HOR ² -OH (VIII),

where R ¹ for a methylene-ethylene-propylene, butylene, pentylene group or for - (CH ₂ ) ₆ - or for 2,4- or 2,6-C ₆ H ₃ -CH ₃ , or for C ₆ H ₄ -CH ₇ -C ₆ H ₄ or for an isopho ronrest (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 - with n = 4 to 1999.

Depending on which reactants are reacted with each other to form the polyurethanes, the result is polymers with different structural units. 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 stands} for - (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 from 5 to 199 and k is a number from 1 to 2000.

The diisocyanates described as preferred can be reacted with all the diols described as preferred to give polyurethanes, so that preferred foams according to the invention contain 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 - (IX c),

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

- [OC (C) -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 can be used in addition to diisocyanates (VII) and diols (VIII) also other compounds from the group of polyisocyanates (in particular tri-isocyanates and tetra-isocyanates) and from the group of polyols and / or di or polymaine included. In particular triols, tetrols, pentoles and hexols as well as di- and triamines can be contained in the reaction mixtures. A salary on compounds with more than two "active" H atoms (all of the above substances  classes with the exception of diamines) leads to partial crosslinking of the polyurethane Reaction products and can have advantageous properties such as control of the Dissolution behavior, abrasion stability or flexibility of the foams according to the invention, Process advantages in manufacturing, etc. cause. The salary is usually such compounds with more than two "active" H atoms on the reaction mixture less than 20% by weight of the total reactants used for the diisocyanate te, preferably less than 15 wt .-% and in particular less than 5 wt .-%.

In preferred embodiments of the present invention, the polyurethanes in the foams according to the invention have molecular weights from 5,000 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) in the invention ß solid foams are contained, are 40 to 90 wt .-%, each based on the firm foam. Preferred foams are characterized in that they the water-soluble polymer (s) in amounts of 45 to 87.5% by weight, preferably from 50 to 85% by weight, particularly preferably from 55 to 82.5% by weight and in particular from 60 to 80% by weight.

The solid foams according to the invention contain 10 to as a second ingredient 60% by weight of one or more substances from the group of builders, acidifying agents, Chelating agents, scale-inhibiting polymers or nonionic surfactants. Independent Depending on the type of ingredient b), foams are preferred which contain the ingredient b) in amounts of 12.5 to 55% by weight. preferably from 15 to 50% by weight, particularly preferably contain from 17.5 to 45% by weight and in particular from 20 to 40% by weight. The substance classes mentioned as well as preferred representatives from these are shown below described.

The most important ingredients of textile detergents or automatic dishwashing are builders. As ingredient b) in the foams of the invention all builders commonly used in detergents or cleaning agents hold, especially so 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. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .y H ₂ O are preferred.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used are delayed. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray genamorphic”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried 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. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used within the scope of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight zeolite X), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula

n Na ₂ O. (1-n) K ₂ O.Al ₂ O _3. (2-2.5) SiO _2. (3.5-5.5) H ₂ O

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

It goes without saying that the generally known phosphates are also used as builders Substances possible, provided that such use is not ver should be avoided. Have among the variety of commercially available phosphates the alkali metal phosphates with particular preference for pentasodium or penta Potassium triphosphate (sodium or potassium tripolyphosphate) in washing and cleaning medium-sized industry the greatest importance.

Alkali metal phosphates is the general term for the alkali metal (in particular special sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and limescale encrustations in tissues and also contribute to 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, water-soluble powders that lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₄ , at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below), NaH ₂ PO ₄ reacts acidic; it forms when phosphoric acid is adjusted to pH 4.5 with sodium hydroxide solution and the mash is sprayed in. Potassium dihydrogen phosphate (primary or monobasic Potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is readily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water (density 1.52 gcm ^-3 melting point 35 ° with loss of 5 H ₂ O), becomes water-free at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

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

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 melting point 94 ° with loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to <200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4. Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt.

All higher sodium and potassium phosphates are collectively called condensed phos called phate.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] that crystallizes with 6 H ₂ O. _n -Na with n = 3. In 100 g of water, about 17 g of the salt of water free of water of crystallization dissolve at room temperature, about 20 g at 60 ° and around 32 g at 100 °; after heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium tri phosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (<23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

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

According to the invention, these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of sodium tripoly phosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium Umtripoiyphosphat and sodium potassium tripolyphosphate can be used according to the invention.

Other suitable builders are carbonates, hydrogen carbonates and the salts of Oligocarboxylic acids, for example gluconates, succinates and especially citrates. Erfin Foams according to the invention which contain one or more builders from the ingredient b) Group contain sodium carbonate, sodium hydrogen carbonate and trisodium citrate preferred according to the invention.  

Acidifying agents are also included in the scope of the present invention b) suitable. Substances from this group are, for example, boric acid and alkali metal hy drug sulfates, alkali metal dihydrogen phosphates and other inorganic salts bar. However, organic acidifying agents are preferably used, the Citric acid is a particularly preferred acidifying agent. But can be used also in particular the other solid mono-, oligo- and polycarboxylic acids. From this Tartaric acid, succinic acid, malonic acid, adipic acid, Maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as Amidosulfonic acid can also be used. Commercially available and as acidification is also preferably used in the context of the present invention kalan® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), Glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight). Especially before pulled according to the invention.

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

Common chelate complex bil preferred in the context of the present invention which are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Even complex-forming polymers, i.e. polymers, either in the main chain itself or laterally to these functional groups wear that can act as ligands and usually with suitable metal atoms react to form chelate complexes can be used according to the invention. The Polymer-bound ligands of the resulting metal complexes can only consist of originate from a macromolecule or belong to different polymer chains.

The latter leads to the crosslinking of the material, provided the complex-forming polymers do not were previously linked via covalent bonds.

Complexing groups (ligands) of conventional complex-forming polymers are iminodi acetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid re, amidoxime, aminophosphoric acid, (cycl.) polyamino, mercapto, 1,3-dicarbonyl and  Crown ether residues with z. T. very specific Activities towards ions of different Metals. Basic polymers of many commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and Po lyethyleneimine. Natural polymers such as cellulose, starch or chitin are also complex forming polymers. In addition, these can be achieved through polymer-analogous conversions can be provided with further ligand functionalities.

In the context of the present invention, particular preference is given to foams which contain one or more chelate complexing agents from the groups of

• a) polycarboxylic acids in which the sum of the carboxyl and optionally Hy droxyl groups is at least 5,
• b) nitrogen-containing mono- or polycarboxylic acids,
• c) geminal diphosphonic acids,
• d) aminophosphonic acids,
• e) phosphonopolycarboxylic acids,
• f) cyclodextrins

contain.

All complexing agents of the prior art can be used in the context of the present invention. These can be heard in different chemical groups. The following are preferably used individually or in a mixture:

• a) polycarboxylic acids in which the sum of the carboxyl and optionally Hy droxyl groups is at least 5 like gluconic acid,
• b) nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediamine triacetic acid, Diethy lentriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3- propionic acid, isoserine diacetic 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),
• c) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), their higher homologues with up to 8 carbon atoms as well as hydroxy or ami Derivatives thereof containing nogroups and 1-aminoethane-1,1-diphosphonic acid, the  higher homologues with up to 8 carbon atoms as well as hydroxy or amino groups pen-containing derivatives thereof,
• d) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), Di ethylenetriaminepenta (methylenephosphonic acid) or nitrilotri (methylene phosphonic acid),
• e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and
• f) cyclodextrins.

As polycarboxylic acids a), carboxylic acids - also monocarboxylic acids - understood in which the sum of carboxylic and in Molecule contained hydroxyl groups is at least 5. Complexing agent from the Group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. At 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 immaterial whether they are introduced in the form of acids or in the form of salts. In the case of the one sentence as salts are alkali, ammonium or alkylammonium salts, especially natri salts, preferred.

In the case of the deposit-inhibiting polymers as ingredient b), one or several deposit-inhibiting polymers from the group of the cationic homo- or Co polymeric, especially hydroxypropyltrimethylammonium guar; Copolymers from Ami noethyl methacrylate and acrylamide, copolymers of dimethyldiallylammonium chloride and Acrylamide, polymers with imino groups, polymers that quaterni as monomer units have ammonium alkyl methacrylate groups, cationic polymers of Mo. nomers such as trialkylammonium alkyl (meth) acrylate or acrylic acid; Dialkyldiallyldiam monium salts; polymer-analogous reaction products of ethers or esters of poly saccharides with ammonium side groups, especially guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium groups; quaternary ethylene imine polymers and polyesters and polyamides with quaternary side groups are preferred.

Another preferred ingredient b) are certain copolymers containing sulfonic acid groups. Foams are also preferred which contain one or more copolymers as ingredient b)

• a) unsaturated carboxylic acids
• b) monomers containing sulfonic acid groups
• c) optionally further ionic or nonionic monomers

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

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

Preferred monomers containing sulfonic acid groups are those of the formula Xl

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

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

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₂ OH ₃ ) in formula XIa), 2-acrylamido-2-propane sulfonic acid (X = -C (O) NH-C (CH ₃ ) ₂ in formula XIa), 2-acrylamido-2-methyl-1-propane sulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula XIa) , 2-methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula XIb), 3-methacrylamido-2-hy droxy-propanesulfonic 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), allyloxybenzene sulfonic acid (X = -CH ₂ - OC ₆ H ₄ - in formula XIa), methallyloxybenzenesulfonic acid (X = -CH ₂ - OC ₆ H ₄ - in formula XIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid (X = CH ₂ in formula XIb), styrene sulfonic acid (X = C ₆ H ₄ in formula XIa), vinyl sulfonic acid (X not present in formula XIa), 3-sulfopropyl acrylate (X = -C (O) NH- CH ₂ OH ₂ CH ₂ - in formula XIa), 3-sulfopro pyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula XIb), sulfomethacrylamide (X = -C (O) NH- in formula XIb), sulfomethyl methacrylamide (X = -C (O) NH -CH ₂ - in formula XIb) and water-soluble salts of the acids mentioned.

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

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

• a) one or more unsaturated carboxylic acids from the group Acrylic acid, methacrylic acid and / or maleic acid
• b) one or more monomers of the formulas XIa, XIb and / or XIc containing sulfonic acid groups:
  H ₂ C = CH-X-SO ₃ H (XIa),
  H ₂ C = C (CH ₃ ) -X-SO ₃ H (XIb),
  HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XIc),
  in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally available spacer group, which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -,
• c) optionally further ionic or nonionic monomers.

The copolymers can be the monomers from groups i) and ii) and, if appropriate iii) contained in varying amounts, with all representatives from group i) with all representatives from group ii) and all representatives from group iii) can be combined. Particularly preferred polymers have a certain structure units that are described below.

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

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

contain, in which m and p each represent an integer between 1 and 2000 as well as Y for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -O- (CH ₂ ) _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 copolymerizing acrylic acid with a sulfonic acid group-containing acrylic acid derivative. If the sulfonic acid group-containing acrylic acid derivative is copolymerized with methacrylic acid, another polymer is obtained whose use as ingredient b) of the foams according to the invention is also preferred and is 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),

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

Completely analogously, acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Foams according to the invention are preferred which contain one or more copolymers with structural units of the formula XIV as the ingredient b)

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

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

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

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

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

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

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

In the polymers, the sulfonic acid groups can be neutralized in whole or in part Form, d. H. that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups against metal ions, preferably alkali metal ions and can be exchanged in particular for sodium ions. Appropriate fixed Foams which are characterized in that the sulfonic acid groups in the copolymer partially or fully neutralized are preferred according to the invention.  

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

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

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

Another class of substances that can be found as ingredient b) in the invention solid foams are non-ionic surfactants. Here are inventive Foams preferred which contain as ingredient b) 12.5 to 55% by weight, preferably 15 to 50 % By weight, particularly preferably 17.5 to 45% by weight and in particular 20 to 40% by weight contain one or more nonionic surfactants.

In particularly preferred embodiments of the present invention, the foam according to the invention contains non-ionic surfactants from the group of the alkoxylated alcohols as ingredient b). As such nonionic surfactants, alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol are used, in which the alcohol radical is linear or preferably in the 2-position can be methyl-branched or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C. _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The given degrees of ethoxylation represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol holoxylates have a narrow homolog distribution (narrow range ethoxyla tes, 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.

Propoxylated and / or butoxylated nonionic surfactants can preferably be used as further nonionic surfactants, the mixed alkoxylated, advantageously propoxylated and ethoxylated nonionic surfactants being of particular importance. In the case of these nonionic surfactants, too, the C chain length in the alkyl radical is preferably 8 to 18 C atoms, C _9-11 alkyl radicals, C _12-13 alkyl radicals and C _16-18 alkyl radicals being particularly important. Nonionic surfactants obtained from C _9-11 or C _12-13 oxo alcohols are particularly preferred. In the preferred nonionic surfactants, on average 1 to 20 moles of alkylene oxide (AO) are used per mole of alcohol, where AO stands for the sum of EO and PO. Particularly preferred nonionic surfactants in this group contain 1 to 5 moles of PO and 5 to 15 moles of EO. A particularly preferred representative of this group is a C _12-20 oxo alcohol alkoxylated with 2 PO and 15 EO, which is available under the trade name Plurafac® LF 300 (BASF).

Instead of or in addition to PO groups, preferred nonionic surfactants can also have butylene oxide groups. Here, the above-mentioned alkyl radicals, in particular the oxo alcohol radicals, are again preferred. The number of BO groups in preferred nonionic surfactants is 1, 2, 3, 4 or 5, the total number of alkylene oxide groups preferably being in the range from 10 to 25. A particularly preferred representative of this group is available under the trade name Plurafac® LF 221 (BASF) and can be described by the formula C _13-15 -O- (EO) _9-10 (BO) _1-2 .

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

Another class of preferred nonionic surfactants used, either as an allei some nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and pro poxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkano lamides can be suitable. The amount of these nonionic surfactants is preferred not more than that of ethoxylated fatty alcohols, especially not more than that Half of it.

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

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

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

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

[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 tongue with methyl fetates in the presence of an alkoxide as a catalyst in the ge desired polyhydroxy fatty acid amides.

It is particularly preferred for the foams according to the invention that they are non-ionic contain surfactant that has a melting point above room temperature. Foams are preferred here, the nonionic surfactant (s) with a melting point above 20 ° C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, in amounts of 10 to 55% by weight, preferably from 15 to 50% by weight, particularly preferably from 20 to 45 and in particular re from 25 to 40 wt .-%, each based on the total agent.

Suitable nonionic surfactants, the melting or softening points in the above Temperature range are, for example, low-foaming nonionic Surfactants that can be solid or highly viscous at room temperature. Be at room temperature-viscous nonionic surfactants used, it is preferred that these have a viscosity above 20 Pa.s, preferably above 35 Pa.s and in particular above Have 40 Pa.s. Also non-ionic surfactants, which have a waxy consistency at room temperature zen are preferred.

Preferred nonionic surfactants to be used as solid at room temperature originate from the Groups of alkoxylated nonionic surfactants, especially ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as Polyoxypropylene / Polyoxyethylene / Polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has been produced. Corresponding foams, which are characterized in that the nonionic surfactant (s) is / are ethoxylated nonionic surfactant (s), which / which consist of 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, are accordingly preferred.

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

The nonionic surfactant, which is solid at room temperature, preferably additionally has propylene oxide units in the molecule. Such PO units preferably make up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total ten molar mass of the nonionic surfactant. Particulate machine dishes detergents containing ethoxylated and propoxylated nonionic surfactants, in which the Propy lenoxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and esp special up to 15 wt .-% of the total molecular weight of the nonionic surfactant Chen are preferred embodiments of the present invention. Especially before 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 does more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70 wt .-% of the total molecular weight of such nonionic surfactants.

Other nonionic surfactants to be used with particular preference with melting points above Room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene len / polyoxypropylene block polymer blends containing 75% by weight of an inverted block Copol 51341 00070 552 001000280000000200012000285915123000040 0002010107217 00004 51222 polymers of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles Propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxy propylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles Propylene oxide per mole of trimethylol propane.

Nonionic surfactants, which can be used with particular preference, are from for example under the name Poly Tergent® SLF-18 from Olin Chemicals true.

Another preferred surfactant can be represented by the formula

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

describe in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1 , 5 and y stands for a value of at least 15. Particulate dishwasher detergents, which are characterized in that they are 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 ]

contain, in which R ^{1 stands} for a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1 , 5 and y stands for a value of at least 15 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 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ≧ 2, each R ³ in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

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

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

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

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

In summary, foams are preferred 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

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

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

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

Mixtures of different nonionic surfactants are used with particular preference in the foams according to the invention. Mixtures of are particularly preferred as ingredient b)

• a) nonionic surfactants from the group of the alkoxylated alcohols,
• 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, C _12-14 fatty alcohols with 5 EO and 4 PO and C _12-18 fatty alcohols with an average of 9 EO having proven particularly outstanding. End group-sealed nonionic surfactants, in particular C _12-18 fatty alcohol 9 EO-butyl ether, can also be used with a similar preference.

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

In the context of the present invention, non-ionic surfactants and non-ionic surfactants with butyloxy groups can also preferably be used as nonionic surfactants. The first group includes representatives of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x R ² ,

in which R ^{1 is} 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 are optionally substituted with 1, 2, 3, 4 or 5 hydroxyl groups and optionally with further ether groups, R ³ for -H or methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or is tert-butyl and x can assume values between 1 and 40. R ² can optionally be alkoxylated, the alkoxy group preferably being selected from ethoxy, propoxy, butyloxy groups and mixtures thereof.

Preferred surfactants are those of the above-mentioned formula in which R ^{1 is} a C _9-11 or C _11-15 alkyl radical, R ³ = H and x assumes a value from 8 to 15, while R2 is preferably one straight-chain or branched saturated alkyl residue. Particularly preferred surfactants can be summarized 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 Describe (EO) ₈ (CH ₂ ) ₄ CH ₃ .

Mixed alkoxylated surfactants are also suitable, preference being given to those which have butyloxy groups. Such surfactants can be represented by the formula

R ¹ (EO) _a (PO) _b (BO) _c

describe in the R ¹ for a linear or branched, saturated or unsaturated th, aliphatic or aromatic hydrocarbon radical having 1 to 30, preferably 6 to 20 carbon atoms, a for values between 2 and 30, b for values between 0 and 30 and c stands for values between 1 and 30, preferably between 1 and 20.

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

R ¹ (PO) _b (EO) _a (BO) _c ,

in 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, can also preferably be used.

Particularly preferred representatives from this group of surfactants can be represented 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 the formulas C _13-15 (EO) _9-10 (BO) ₁₂ is commercially available under the name Plurafac® LF 221. Another particularly preferred surfactant with 10 EO and 2 BO is available under the trade name Genapol® 25 EB 102. A surfactant of the formula C _12-13 (EO) ₁₀ (BO) ₂ can also be used with preference.

In addition to the ingredients a) (water-soluble polymer) and b) (Substance from the group of builders, acidifying agents, chelating agents, be Laginhibitory polymers or nonionic surfactants) can the invention solid foams also contain other auxiliaries and / or fillers. In preferred inventions foams according to the invention come from the groups of dyes and fragrances, Setting agents, binders, humectants and / or salts.

In order to improve the aesthetic impression of the agents according to the invention, they can fully or partially colored with suitable dyes. Preferred dyes, the selection of which is no problem for the expert has a high stock stability and insensitivity to the other ingredients of the agent and ge  light and no pronounced substantivity towards the treated substrates such as dishes so as not to stain them.

When choosing the colorant, care must be taken that the colorants do not have too strong 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 compared 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 dye in the detergents varies. In the case of readily water-soluble colorants, e.g. B. Basacid® Green or Sandolan® Blue, colorant concentrations in the range from a few 10 ^-2 to 10 ^-3 wt .-% are typically selected. In the preferred because of their brilliance, but less water-soluble pigment dyes, for. B. the Pigmosol® dyes, the suitable concentration of the colorant in washing or cleaning agents, however, is typically around 10 ^-3 to 10 ^-4 wt .-%.

Fragrances are added to the agents according to the invention in order to maintain an aesthetic appearance to improve product pressure and consumer in addition to product performance a visually and sensorially "typical and distinctive" product is available put. As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and Koh type Hydrogen oils are used. Fragrance compounds of the ester type are e.g. B. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dime thylbenzyl-carbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. To the Ethers include, for example, benzyl ethyl ether, the aldehydes e.g. B. the linear Alka nale with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, ∝- Isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, are hydrocarbons mainly the terpenes such as limes and pinene. However, Wed are preferred uses different fragrances, which together make an appealing Generate fragrance. Such perfume oils can also ent natural fragrance mixtures ent keep as accessible from plant sources, e.g. B. Pine, Citrus, Jasmine, Pat chouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Ka  millen oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, Vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, Orange peel oil and sandalwood oil.

The fragrance content of the foams according to the invention is usually up to 2% by weight of the total formulation. The fragrances can directly in the invention ß agents are incorporated, but it can also be advantageous to the fragrances Apply carriers that adhere the perfume to laundry or other be reinforced substrates and through a slower fragrance release for langan keeping scent. Cyclodex, for example, has proven to be such carrier materials trine has proven itself, the cyclodextrin-perfume complexes additionally with others Auxiliaries can be coated.

Binders and humectants can also be part of the inventions as ingredient c) foams according to the invention. Here the contents are usually between two 0.5 and 10 wt .-%, preferably between 0.75 and 7.5 wt .-% and in particular re between 1 and 5 wt .-%, each based on the total solid foam.

Easily soluble salts are particularly suitable as 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 Invention According to the invention, a whole range of foams are suitable of connections. It is preferred if the salts have even higher solubilities have, so that salts are preferred which have a solubility of more than 250 g per liter Water at 20 ° C, preferably more than 300 g per liter of water at 20 ° C and esp have more than 350 g per liter of water at 20 ° C.

It is possible according to the invention to use the solid foams as part of a washing or cleaning confectioning agent and then with other components to a ferti to connect detergents or cleaning agents. This is particularly useful Detergent tablets on, d. H. Detergent tablets, cleaning agents tablet or special offer forms such as bleach tablets or stain remover tablets. Conventional, i.e. H. Tablet manufactured using press technology ten are connected with solid foams according to the invention, which then also represent optically differentiated shaped body phase.  

Of course, it is also possible to use the solid foams according to the invention in this way formulate that they represent a finished detergent or cleaning agent in themselves. For this purpose, the ingredients are selected as ingredient c), the important functions in Take over washing or cleaning process, i.e. primarily surfactants from others Classes of surfactants (especially anionic and / or cationic surfactants), cobuilders, Bleaching agents, bleach activators, enzymes, optical brighteners, silver protection agents, etc., wel che are briefly described below.

Polycarboxylates / poly. In particular can be used as organic cobuilders in the foams carboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, others organic cobuilders (see below) and phosphonates are used. This stuff classes are described below.

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

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. 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 figures deviate significantly from the molecular weight figures for which polystyrene sulfonic acids are used as the standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight have from 2000 to 20,000 g / mol. Because of their superior solubility, can this group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10,000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably be.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special  copolymers of acrylic acid with maleic acid, 50 contain up to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative Molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

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

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

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

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Po are particularly preferred lyaspartic acids or their salts and derivatives, in addition to cobuilder properties also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are obtained by converting Dialdehydes with polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 Hy have droxyl groups, can be obtained. Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches  can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme catalyzed processes are carried out. It is preferably hydrolyz Se products with average molecular weights in the range of 400 to 500,000 g / mol. There is a Polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular preferred from 2 to 30, DE being a common measure of the reducing we kung a polysaccharide compared to dextrose, which has a DE of 100, is. Both maltodextrins with a DE between 3 and 20 and dry glu can be used cosesirupe with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molar masses in the range from 2000 to 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. An oxidized oligosaccharide is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenedia mindisuccinate, are other suitable cobuilders. Here, ethylenediamine-N, N'- disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and Gly are also preferred in this context cerintrisuccinate. Suitable amounts are in zeolite and / or silicate salts gene formulations at 3 to 15 wt .-%.

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder. It is preferably used as the sodium salt sets, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reactions Sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta- and octa- Sodium salt of DTPMP, used. As a builder, the class becomes the phospho nate prefers HEDP. The aminoalkanephosphonates also have a embossed heavy metal binding capacity. Accordingly, it can, especially if the agents also contain bleach, preferably aminoalkane phosphonates, in particular DTPMP to use, or to use mixtures of the phosphonates mentioned the.

In addition, all compounds that are capable of complexes with alkaline earth train ions as cobuilders.

Anionic surfactants which can be used as ingredient c) of the foams according to the invention are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins having an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkane sulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under fatty acid gly Cerinestern are to be understood as the mono-, di- and triesters and their mixtures as they are in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated Fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Capric acid. Myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ -Oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. From the washing, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ are - C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates of preferably. Also 2,3-alkyl sulfates, which are produced for example according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Qil Company under the name DAN®, are suitable anionic surfactants.

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

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

Soaps are particularly suitable as further anionic surfactants. Are suitable 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, e.g. B. coconut, palm kernel or tallow fatty acids, derived soap mixtures.

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

In addition to the constituents mentioned, the foams according to the invention can also include Detergents and cleaning agents usual ingredients from the group of bleaching agents, Bleach activators, optical brighteners, enzymes, foam inhibitors, silicone oils, antirede positioning agents, graying inhibitors, color transfer inhibitors and corrosion inhibitors bitters included.

The foams of the present can be used to develop the desired bleaching performance Invention contain bleach. Here, the most common ones Bleaching agent from the group sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate has proven itself, the latter being clearly preferred.

"Sodium percarbonate" is a non-specific term for sodium carbonate peroxohydrates which, strictly speaking, are not "percarbonates" (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate. The merchandise has the average composition 2 Na ₂ CO ₃ .3 H ₂ O ₂ and is therefore not peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm ^-3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first made in 1899 by precipitation with ethanol from a Obtained solution of sodium carbonate in hydrogen peroxide, but mistakenly as peroxy viewed carbonate. It was not until 1909 that the compound was Addition compound recognized, nevertheless the historical designation "sodium per carbonate "prevailed in practice.

The industrial production of sodium percarbonate is predominantly produced by precipitation from an aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg ²⁺ ions). The precipitated salt, which still contains 5 to 12% by weight of mother liquor, is then centrifuged off and dried in fluidized bed dryers at 90.degree. The bulk density of the finished product can vary between 800 and 1200 g / l, depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating processes and substances used for coating are widely described in the patent literature. In principle, according to the invention, all commercially available Percar bonate types can be used, as are offered, for example, by Solvay lnterox, Degussa, Kemira or Akzo.

In the bleaching agents used, the foam content of these substances is from Depending on the application. While common universal detergents between 5 and 30 wt .-%, preferably between 7.5 and 25% by weight and in particular between 12.5 and 22.5% by weight Containing bleach, the levels are in bleach or bleach boosters preparation forms between 15 and 50% by weight, preferably between 22.5 and 45% by weight us in particular between 30 and 40% by weight.

In addition to the bleaching agents used, the foams according to the invention can Contain bleach activator (s), which is preferred in the context of the present invention. Bleach activators are incorporated into detergents and cleaning agents in order to to achieve an improved bleaching effect at temperatures of 60 ° C and below chen. As bleach activators can be compounds that are under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 up to 4 carbon atoms, and / or optionally substituted perbenzoic acid be set. Suitable substances are the O- and / or N-acyl groups of the above C number of carbon atoms and / or optionally substituted benzoyl groups. Prefers are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n- Nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides de, especially 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, too so-called bleaching catalysts can be incorporated into the moldings. With these Fabrics are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or  -carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing ones Tripod ligands as well as Co, Fe, Cu and Ru amine complexes are used as bleaching catalysts usable.

If the foams according to the invention contain bleach activators, they each contain Weil based on the total foam, between 0.5 and 30 wt .-%, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight of one or several bleach activators or bleach catalysts. Depending on the purpose of the produced foams, these amounts can vary. So are in typical universal detergent bleach activator contents between 0.5 and 10 wt .-%, preferably betw between 2 and 8 wt .-% and in particular between 4 and 6 wt .-% usual, while Bleaching preparations may have higher contents, for example between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular between 10 and Can have 20 wt .-%. The expert is free in his formulation not restricted and can make the bleaching more or less bleaching Manufacture detergents, cleaning agents or bleach preparations by using the Bleach activator and bleach content varied.

A particularly preferred bleach activator is the N, N, N ', N'- Tetraacetyl ethylenediamine, which is widely used in detergents and cleaning agents. Accordingly, preferred foams are characterized in that as bleach tivator tetraacetylethylenediamine is used in the amounts mentioned above.

The foams can be optical brighteners of the diaminostilbene di derivative type contain sulfonic acid or its alkali metal salts. Are suitable for. B. salts of 4,4'- Bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or the like Compounds which are built up and which replace the morpholino group with a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino wear group. Brighteners of the substituted diphenylstyryl type can also be used to be essential, e.g. B. 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) diphenyl. Mixtures too the aforementioned brighteners can be used. The optical brighteners are in the foams according to the invention as ingredient c) in concentrations between 0.01 and 1% by weight, preferably between 0.05 and 0.5% by weight and in particular between 0.1 and 0.25% by weight, based in each case on the total foam, used.  

Enzymes in particular come from the hydrolase classes such as the Pro teases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned in question. All these Hydrolases contribute to the removal of stains such as protein-, fat- or starchy stains and graying. Cellulases and other glyco sylhydrolases can also remove pilling and microfibrils contribute to color retention and increase the softness of the textile. To bleach or to inhibit color transfer, oxidoreductases can also be used the. From bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as the enzymatic action obtained from their genetically modified variants fabrics. Proteases of the subtilisin type and in particular proteases are preferably which are obtained from Bacillus lentus. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or we lipolytically enzymes or protease and cellulase or from cellulase and lipase or lipoly enzymes or protease, amylase and lipase or lipolytic we enzymes or protease, lipase or lipolytically active enzymes and cellules se, but especially protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such li Cutinases are known enzymes. Also peroxidases or oxi in some cases, these have proven to be suitable. To the suitable amylases count in particular alpha-amylases, iso-amylases, pullulanases and pectinases. As Cellulases are preferably cellobiohydrolases, endoglucanases and Glucosidases, which are also called cellobiases, or mixtures of these set. Since different types of cellulase are characterized by their CMCase and avicelase Activities can be differentiated by targeted mixtures of the cellulases desired activities.

The enzymes can be adsorbed on carriers or embedded in coating substances. to protect them against premature decomposition. The proportion of enzymes, enzyme mixture Genes or enzyme granules can for example about 0.1 to 5 wt .-%, preferably 0.5 up to about 4.5% by weight.

In addition, the foams can also contain components as ingredient c), which positively affect the oil and fat washability from textiles (so-called soil right pellents). This effect becomes particularly clear when a textile is soiled previously several times with a detergent according to the invention, the oil and contains fat-dissolving component, was washed. Among the preferred oil and fat sol Send components include, for example, nonionic cellulose ethers such as methylcel cellulose and methyl hydroxypropyl cellulose with a methoxyl group content of 15 up to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic cellulose ether, as well as those known from the prior art Polymers of phthalic acid and / or terephthalic acid or their derivatives, ins special polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Especially be of these, the sulfonated derivatives of phthalic and terephthalic acids are preferred re-polymers.

Further preferred foams characterized in that they contain silver as ingredient c) protective agents from the group of triazoles, benzotriazoles, bisbenzotriazoles, Aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes, particularly preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.01 to 5% by weight, preferably from 0.05 to 4% by weight and in particular from 0.5 to 3% by weight, each based on the weight of the foam.

The corrosion inhibitors mentioned can protect the items to be washed or the Ma be included, with silver protection in the area of automatic dishwashing medium have a special meaning. The known substances of State of the art. In general, silver protection agents can be selected from the Group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the Al kylaminotriazole and the transition metal salts or complexes are used. Be benzotriazole and / or alkylaminotriazole are particularly preferred. One finds In cleaner formulations, active chlorine-containing agents, which corrode can significantly reduce the silver surface. In chlorine-free cleaners, be especially oxygen and nitrogen-containing organic redox-active compounds, such as two and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallus acid, phloroglucin, pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts, the are selected from the group of manganese and / or cobalt salts and / or complexes,  particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the Cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfates. Zinc compounds can also be used to prevent corrosion on the wash ware be used.

Another object of the present invention is a manufacturing method for the foams according to the invention. This process for the production of foams by applying a solution, melt, emulsion or suspension containing at least one active substance with a gaseous medium and foaming is characterized in that the solution, melt, suspension or emulsion is based on its weight

• a) 40 to 90% by weight of one or more water-soluble polymers,
• b) 10 to 59.99% by weight of one or more substances from the group of builders, Acidifying agents, chelating agents, deposit-inhibiting polymers or nonionic surfactants,
• c) 0 to 50% by weight of one or more auxiliaries and / or fillers
• d) 0.01 to 30% by weight of a foaming gas (blowing agent)

contains.

The ingredients a) to c) have been described in detail above. As ingredient d) any gases or gas mixtures can be used for foaming. At Games for gases used in technology are nitrogen, oxygen, noble gases and noble gas mixtures such as helium, neon, argon and their mixtures, Kohlendi oxide etc. For cost reasons, according to the invention, air is preferably used as a foam gas used. If the components to be foamed are stable to oxidation, can the gaseous medium also consist entirely or partially of ozone, which makes it oxidative destructible impurities or discolourations in the media to be foamed side or a germ infestation of these components can be prevented.

Volatile compounds can also be used as foaming gases. Here For example, lower ethers such as dimethyl ether and diethyl ether are suitable. The blowing agents known from spray cans such as propane or butane are also within the scope of the present invention as a foaming gas. The decisive factor is the suitability as ingredient d) only that the substance hollow under the processing conditions Create spaces and thus create foam structures from the mixture of ingredients that can.

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

Of course, fabrics can also be used, which are under the working area Release conditions of the manufacturing process. This is where natri comes in Hydrogen carbonate, para-toluenesulfonyl hydrazide, 4,4'-oxybis (benzenesulfonyl hydrazide) or mixtures of acids and hydrogen carbonates. Here are inventive Processes preferred in which solid substances as blowing agents at room temperature Release gases at the extrusion temperature, in amounts of 0.5-10% by weight, preferably as 1-7.5 wt .-% each based on the mass of the polymer or the Polymerge mixes can be used.

In preferred embodiments, the gaseous is used to produce the foams Medium is blown into liquids, or the foaming is achieved by violent Beating, shaking, splashing or stirring liquid in the gas concerned atmosphere. Because of the lighter and more controllable and feasible foaming mung is within the scope of the present invention, the generation of foam by one blow the gaseous medium ("fumigation") compared to the other variants Lich preferred. Fumigation takes place continuously depending on the desired process variant nuously or discontinuously via perforated plates, sintered discs, sieve inserts, Venturidü sen, inline mixers, homogenizers or other common systems. As part of the before lying invention are also self-foaming systems in which the foaming gas formed by chemical reaction of the components with each other is preferred. Even before the foam collapses, the liquid, semi-liquid solidify or highly viscous cell webs to solids, whereby the foam stabilizes and a "fe ster foam "is formed.  

Solutions, dispersions, emulsions or are available as the liquid to be foamed Melting, the latter being preferred in the context of the present invention.

Alternatively, more viscous systems can be foamed up to Foaming from plastic masses can go. In the latter case, it is advisable plasticizing the mixture of ingredients a) to c) in an extruder and the extru the exit to be supplied with propellant. This process delivers sta bile foams and ecfocdert not that the raw material mixture melted, dissolved or must be dispersed.

The foams according to the invention can depend on the production of its composition as a finished washing or cleaning agent packed and sold, but it is also possible to combine them with other ingredients a compound detergent or cleaning agent. Erfin Foams according to the invention with an open cell structure can also be used as carrier material serve for further ingredients. So is the absorption of nonionic surfactants, fragrances, paraf fin or silicone oils or other liquid substances in the invention Foams easily possible. Here, the amount of substance absorbed is for example 20 to 1000 wt .-% additive, based on the unadditized foam.

Examples

The mixtures given below were made in a Brabender twin-screw kneader (DSK) 42/7 processed. The DSK works with counter-rotating screws, which means that an ex extremely good mixing is guaranteed. The temperatures for processing the Mixtures in the three zones along the screw were 140 ° C and 147 ° C in the outlet nozzle.

The blends were extruded through a extrusion die at 50 rpm. The diameter the nozzle was 4 mm, the correspondingly foamed strands had a diameter water 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 sulfate 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 bicarbonate 6.8%

Foam 3

The processing temperatures must be higher depending on the selected blowing agent in the case of foam 3 there are temperatures of 180-190 ° C at the outlet nozzle of the extruder required. The foamed polymer must rise at these temperatures then be cooled quickly, otherwise the foam will collapse. This can e.g. B. by cooling with liquid nitrogen or other coolants in which the Polyvinyl alcohol is not soluble or only sparingly soluble, such as. B. with solid carbon dioxide chilled 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 (equimolar mixture of citric acid + sodium hydrogen carbonate) 9.0%

Claims (14)

1. Solid foam, 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 builders, acidifying agents, chelate complexing agents, scale-inhibiting polymers or nonionic surfactants,
• c) 0 to 50% by weight of one or more auxiliaries and / or fillers.

2. Foam according to claim 1, characterized in that the or the water-soluble polymer (s) is / are selected from:

• a) and their salts
• b) polymethacrylic acids and their salts
• c) polyvinylpyrrolidone,
• d) vinyl pyrrolidone / vinyl ester copolymers,
• e) cellulose ethers
• f) polyvinyl acetates, polyvinyl alcohols and their copolymers
• g) graft copolymers of polyethylene glycols and vinyl acetate
• h) alkyl acrylamide / acrylic acid copolymers and their salts
• i) alkyl acrylamide / methacrylic acid copolymers and their salts
• j) alkyl acrylamide / methyl methacrylic acid copolymers and their salts
• k) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• l) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• m) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• n) alkyl acrylamide / alkyl methacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and their salts
• o) copolymers
  • 1. xiii-i) unsaturated carboxylic acids and their salts
  • 2. xiii-ii) cationically derivatized unsaturated carboxylic acids and their salts
• p) Acrylamidoalkyltrialkylammoniumchlorid / acrylic acid copolymers and their alkali and ammonium salts
• q) Acrylamidoalkyltrialkylammoniumchlorid / methacrylic acid copolymers and their alkali and ammonium salts
• r) Methacroylethylbetaine / methacrylate copolymers
• s) vinyl acetate / crotonic acid copolymers
• t) Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
• u) 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
• v) grafted copolymers from the copolymerization of
  • 1. xx-i) at least one monomer of the non-ionic type,
  • 2. xx-ii) at least one monomer of the ionic type,
• w) by copolymerization of at least one monomer of each of the three copolymers obtained following the groups:
  • 1. xxi-i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
  • 2. xxi-i) unsaturated carboxylic acids,
  • 3. xxi-iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol.

3. Foam according to one of claims 1 or 2, characterized in that the or the water soluble polymer (s) is selected from homopolymers of vinylal alcohol, copolymers of vinyl alcohol with copolymerizable monomers or Hy hydrolysis products of vinyl ester homopolymers or vinyl ester copolymers with co polymerizable monomers. 4. Foam according to claim 3, 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.   5. Foam according to claim 3 or 4, characterized in that the water-soluble polymer is a polyvinyl alcohol, the molecular weight of which is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , particularly preferably from 12,000 up to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 . 6. Foam according to one of claims 1 or 2, characterized in that the or the water-soluble polymer (s) is / are selected from polyurethanes from diisocyanates (I) and diols (II)
O = C = NR ¹ -N = C = O (VII),
HOR ² -OH (VIII),
the diols being selected at least in part from polyethylene glycols (II a) and / or polypropylene glycols (II b)
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 each represent numbers from 5 to 2000. 7. Foam according to claim 6, characterized in that the water-soluble polymer is a polyurethane made from diisocyanates (VII) and diols (VIII)
O = C = NR ¹ -N = C = O (VII),
HOR ² -OH (VIII),
where R ¹ for a methylene-ethylene-propylene, butylene, pentylene group or for - (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 or isophorone (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 - with n = 4 to 1999. 8. Foam according to one of claims 6 or 7, characterized in that the ser-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 stands} for - (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 from 5 to 199 and k is a number from 1 to 2000. 9. Foam according to one of claims 1 to 8, characterized in that it the / water-soluble polymer (s) in amounts of 45 to 87.5% by weight, preferably of 50 to 85% by weight, particularly preferably from 55 to 82.5% by weight and in particular from 60 to 80% by weight. 10. Foam according to one of claims 1 to 9, characterized in that it as In Content b) 12.5 to 55 wt .-%, preferably 15 to 50 wt .-%, especially before adds 17.5 to 45% by weight and in particular 20 to 40% by weight of one or more contains nonionic surfactants. 11. Foam according to one of claims 1 to 10, characterized in that it as Ingredient c) one or more substances from the groups of colors and fragrances, Contains adjusting agents, binders, humectants and / or salts. 12. Process for producing foams by applying a solution, melt. Emulsion or suspension containing at least one active substance, with a gaseous medium and foaming, characterized in that the solution, melt, suspension or emulsion based on their weight

• a) 40 to 90% by weight of one or more water-soluble polymers,
• b) 10 to 59.99% by weight of one or more substances from the group of builders, acidifying agents, chelating agents, deposit-inhibiting polymers or non-ionic surfactants,
• c) 0 to 50% by weight of one or more auxiliaries and / or fillers
• d) contains 0.01 to 30% by weight of a foaming gas (blowing agent).

13. The method according to claim 12, characterized in that as a blowing agent Room temperature gaseous substances from the group carbon dioxide, nitrogen, Distick oxide, propane, butane, dimethyl ether and mixtures thereof, in amounts of 0.01 up to 20% by weight, preferably from 0.05 to 15% by weight, particularly preferably from 0.1 up to 10 wt .-% and in particular from 0.25 to 5 wt .-%, each based on the Mass of the solution, melt, emulsion or suspension can be used. 14. The method according to claim 12, characterized in that as a blowing agent Substances which are solid at room temperature and which release gases at the extrusion temperature, in Amounts of 0.5-10 wt .-%, preferably 1-7.5 wt .-% each based on the Mass of the polymer or the polymer mixture are used.