DE102005023801A1 - Mixture, useful as surface cleaning agents and shower gels, comprises pieces of open-cell aminoplastic foam material with a defined average diameter, water, surfactants and optionally an oil phase or a fat phase - Google Patents

Abstract

Mixture (A) comprises pieces of open-cell aminoplastic foam material with an average diameter of 50 mu m to 5 mm (average weight), water, at least one surfactant and optionally an oil phase or a fat phase. Independent claims are included for: (1) a method for cleaning surfaces comprising using (A) as the cleaning agent and (2) the preparation of (A).

Description

• (a) offenzelligen Aminoplastschaumstoffen mit einer Dichte im Bereich von 5 bis 500 kg/m³ und einem mittleren Porendurchmesser im Bereich von 1 μm bis 1 mm oder
• (b) offenzelligen Aminoplastschaumstoffen mit einer Dichte im Bereich von 5 bis 500 kg/m³ und einem mittleren Porendurchmesser im Bereich von 1 μm bis 1 mm, die man behandelt hat (b1) mit wässriger Formulierung von mindestens einer Verbindung (b-1) mit mindestens einer Halbaminal- oder Aminalgruppe pro Molekül oder mindestens einem Copolymer, das mindestens ein OH-gruppenhaltiges oder β-Dicarbonylgruppenhaltiges oder Epoxidgruppenhaltiges Comonomer einpolymerisiert enthält, oder (b2) mit mindestens einem bei Zimmertemperatur festem Carboxylgruppen-haltigen und/oder Carbonsäureestergruppen-haltigen Polymerisat (b-2) mit einem Molekulargewicht M_n im Bereich von 1.000 bis 1.000.000 g/mol,

wobei die verwendeten Aminoplastschaumstoffstücke einen mittleren Durchmesser im Bereich von 0,1 mm bis 50 mm aufweisen.The present invention relates to a process for cleaning surfaces using aminoplast foam pieces made from

• (A) open-cell aminoplast foams having a density in the range of 5 to 500 kg / m ³ and an average pore diameter in the range of 1 .mu.m to 1 mm or
• (b) open cell aminoplast foams having a density in the range of 5 to 500 kg / m ³ and an average pore diameter in the range of 1 μm to 1 mm, which has been treated (b1) with aqueous formulation of at least one compound (b-1) with at least one semiaminal or aminal group per molecule or at least one copolymer which contains in copolymerized form at least one comonomer containing OH groups or β-dicarbonyl groups or containing epoxide groups, or (b2) with at least one polymer containing carboxyl groups at room temperature and / or carboxylic ester groups (b-2) having a molecular weight M _n in the range of 1,000 to 1,000,000 g / mol,

wherein the aminoplast foam pieces used have an average diameter in the range of 0.1 mm to 50 mm.

• (a) offenzelligen Aminoplastschaumstoffen mit einer Dichte im Bereich von 5 bis 500 kg/m³ und einem mittleren Porendurchmesser im Bereich von 1 μm bis 1 mm oder
• (b) offenzelligen Aminoplastschaumstoffen mit einer Dichte im Bereich von 5 bis 500 kg/m³ und einem mittleren Porendurchmesser im Bereich von 1 μm bis 1 mm, die man behandelt hat (b1) mit wässriger Formulierung von mindestens einer Verbindung (b-1) mit mindestens einer Halbaminal- oder Aminalgruppe pro Molekül oder mindestens einem Copolymer, das mindestens ein OH-gruppenhaltiges oder β-Dicarbonylgruppenhaltiges oder Epoxidgruppenhaltiges Comonomer einpolymerisiert enthält, oder (b2) mit mindestens einem bei Zimmertemperatur festem Carboxylgruppen-haltigen und/oder Carbonsäureestergruppen-haltigen Polymerisat (b-2) mit einem Molekulargewicht M_n im Bereich von 1.000 bis 1.000.000 g/mol,

wobei die verwendeten Aminoplastschaumstoffstücke einen mittleren Durchmesser im Bereich von 0,1 mm bis 5 mm aufweisen.Furthermore, the present invention relates Aminoplastschaumstoffstücke, made from

• (A) open-cell aminoplast foams having a density in the range of 5 to 500 kg / m ³ and an average pore diameter in the range of 1 .mu.m to 1 mm or
• (b) open cell aminoplast foams having a density in the range of 5 to 500 kg / m ³ and an average pore diameter in the range of 1 μm to 1 mm, which has been treated (b1) with aqueous formulation of at least one compound (b-1) with at least one semiaminal or aminal group per molecule or at least one copolymer which contains in copolymerized form at least one comonomer containing OH groups or β-dicarbonyl groups or containing epoxide groups, or (b2) with at least one polymer containing carboxyl groups at room temperature and / or carboxylic ester groups (b-2) having a molecular weight M _n in the range of 1,000 to 1,000,000 g / mol,

wherein the aminoplast foam pieces used have an average diameter in the range of 0.1 mm to 5 mm.

Farther The present invention relates to the use of aminoplast foam pieces according to the invention.

Heavy accessible Surfaces, for example, interior surfaces of devices, are difficult to clean mechanically without damaging them. In many cases must be the device in question take apart and then clean, which always with effort and especially in the case of commercially used equipment with Dead times is connected. equipment in solution or dip detergents can attack seals and with appropriate size of cleaning device be impractical. Also, not all contaminants can be in solvent remove well. In many cases one observes that either large amounts of solvent are required or that a fine film of the relevant impurity on the surface to be cleaned remains. Inaccessible Can place even larger quantities remain on contamination on the surface to be cleaned. The application strong abrasives such as steel wool or emery can cause mechanical damage on the surface to be cleaned and thus cause, for example, on the device to be cleaned.

It So the task was to provide a method by which Help yourself to cleaning hard-to-reach surfaces leave no mechanical damage to the surface.

It continued to provide the task, tools to provide, with their help to clean hard-to-reach surfaces to let.

Accordingly the method defined at the beginning was found.

The The initially defined method is a method for the purification of Surfaces. surfaces in the sense of the present invention may be flat or curved. surfaces For the purposes of the present invention, smooth, that is unstructured, or be structured. Structured surfaces in the sense of the present Invention can in regular or irregular intervals surveys and / or depressions, each having the same or preferably may have different shape. The mentioned elevations and / or depressions can have any shape, preferred are angular or round elevations, grooves, ridges, grooves, Pores, teeth, Spikes and cutting.

In an embodiment of the present invention the said elevations or depressions a mean distance in the range of 100 nm to 1 cm, preferably 1 .mu.m to 1 mm and have a mean Height or Depth in the range of 100 nm to 5 mm, preferably 1 micron to 5 mm.

The Distance and the height or depth of said surveys or depressions can be after to determine known methods, for example by microscopy, Laser reflectometry and in particular needle scanning. The distance the aforementioned surveys or depressions are determined, for example by determining the mean distance of the mean height.

Height or depth and distance of said elevations or depressions are preferably defined in the context of the present invention as follows: A local maximum (maximum 1) is selected on the structured surface to be cleaned. Starting from maximum 1 as the center, one moves in concentric circles of maximum 1 and detects further local maxima, for example maximum 2. The idea is to cut the structured surface to be cleaned by planes a, which contain maximum 1 and maximum 2 and approximately perpendicular to a compensation surface with respect to the structured surface to be cleaned. The latter is defined by the fact that the respective plane a to other levels b, which include relatively far to the distance between maximum 1 and maximum 2 maxima (about 100x the distance between the respective maxima) of the structured surface to be cleaned, are approximately perpendicular. By intersecting the cleansing structured surface with the planes a, one obtains curves that run from maximum 1 to maximum 2. Now it is important to look for the intermediate minimum (1, 2) and the height and distance of the maxima 1 and 2. Place a straight line g (1, 2) through Maximum 1 and Maximum 2 and obtain directly the distance d (1, 2) over the classical distance definition of Euclidean geometry. Now one looks for that parallel p (1, 2) to g (1, 2) within plane a, which touches the structured surface to be cleaned and has maximum distance to g (1, 2). The point of contact is the minimum (1, 2) and the mean height h (1, 2) of the maxima 1 and 2 is the distance between p (1, 2) and g (1, 2) determined by the classical methods of Euclidean geometry , In the context of this document, maximum 1 is then a true maximum if there is at least one further maximum 2, such that h (1, 2)> 0.2 × d (1, 2), preferably h (1, 2)> 0 , 33 × d (1, 2), more preferably h (1, 2)> 0.5 × d (1, 2). Furthermore, h (1, 2)> 5 nm must apply in order to exclude atomic structures safely. If no such maximum 2 is found, then maximum 1 is rather to be regarded as "ripple." For all maxima 1 and in turn all the associated maxima 2 for which the above condition holds, it is now possible to derive from the associated h (1, 2) and d ( 1, 2) the average height and the mean distance are calculated via a length-weighted averaging as follows: h (medium) = sum over all maxima 1 and 2 of (h (1, 2)) ² / sum over all maxima 1 and 2 of h (1, 2) and d (middle) = sum over all maxima 1 and 2 of (d (1, 2)) ² / sum over all maxima 1 and 2 of d (1, 2).

If the structured surfaces to be cleaned have elevations, so can the surveys, for example, consist of the same material like the rest Surface. In another embodiment the elevations consist of a different material than the rest of the surface, for example Called emery paper and sandpaper.

In an embodiment According to the present invention surfaces to be cleaned are at least partially preferably more than 50% of metals or alloys, such as Iron, nickel, chromium, aluminum, steel such as. B. carbon steel, but also Cr-V steel, Cr-V-Mo steel or Co-steel, copper, brass, tungsten carbide, Cobalt, tungsten, titanium, zirconium.

In another embodiment of the present invention surfaces to be cleaned consist of oxide or ceramic materials such as silica, silica, silicon carbide, silicon nitride, boron carbide, boron nitride, alumina, magnesia, titania, zirconia, mixed silicates, spinels, diamond, each crystallized Form, in amorphous form or as glass can exist. Special designs of oxidic materials, for example, structured stones, concrete, Ke ramik, clay, porcelain, grinding, cutting and grinding discs and whetstones.

In another embodiment The present invention consists of surfaces to be cleaned organic polymers, for example thermosets or thermoplasts. exemplary be polystyrene, polypropylene, polyester, polyamide, polyoxymethylene ("POM"), polyethylene, polyacrylonitrile, Polymethacrylate and copolymers such. For example, acrylonitrile-butadiene-styrene called.

In an embodiment The present invention relates to structured surfaces such surfaces, which one by sand or shot blasting, embossing, lithographic structuring provided with a structuring.

In a preferred embodiment The present invention relates to surfaces to be cleaned hard to reach Surfaces, These are, for example, such surfaces as you can by hand can not reach. Preferred examples are interior surfaces of Devices, containers or tools, in particular inner surfaces of reaction vessels, kneading tools, Gears, motors, agitators and ball bearings. Other preferred examples are interior surfaces of Pipelines, such as pipelines or in pumps.

In another embodiment The present invention cleans surfaces such as wallpaper, Ceramics such as tiles or sinks or bathtubs, Floors, for example made of laminate or linoleum or parquet, furniture such as table tops or kitchen fronts. Also surfaces of household appliances such as electrical appliances, e.g. Refrigerators, let yourself good by the method according to the invention clean.

In carrying out the process according to the invention, structured or non-structured surfaces of impurities containing at least one substance selected are purified
Fats, oils, waxes, for example polyethylene waxes, paraffin waxes, paraffin oils, ester oils, native oils and fats, greases, bearing fats, sturgeon fats, montan waxes,
Metal salts of anionic surfactants such as lime soap,
Biofilms, for example mold or pseudomonate biofilms,
Polymers, for example paint splashes, polyurethane foam, silicones (polysiloxanes), metal oxides, for example copper, lead or nickel oxide or rust formed by, for example, corrosion, or rust particles or flash rust, in particular iron oxides,
Metal hydroxides and metal carbonates, which may be neutral, acidic or basic, in particular iron, copper, nickel hydroxide, aluminum hydroxide, magnesium hydroxide, MgCO ₃ , basic MgCO ₃ , CaCO ₃ , basic copper carbonate, wherein metal oxides, metal carbonates and metal hydroxides by corrosion of the parent metal the structured surface of a tool or workpiece, for example, or may have been deposited secondarily,
Residues of lubricants, such as partially coked or partially or completely gummy lubricants, and broken emulsions. By way of example may be mentioned: resinated native ester oils to z. Chain saws or coked oils on polyester filament fiber spinning hotplates,
Deposits and caking z. Cement or plaster,
household-like soils such as house dust, also mixed with fats, grease from the kitchen area, also in resinous form, for example, cooking fat or cooking oil.

Further examples for Impurities to be removed are labels, for example with ballpoint pen or felt-tip pen.

impurities can on surfaces to be cleaned evenly or be distributed unevenly, for example in the form of spots, edges, splashes, or as Movie.

to execution of the method according to the invention, in connection with the present invention also inventive cleaning method For example, it is possible to proceed in such a way that several pieces of aminoplast foam are used, which has a mean diameter in the range of 0.1 mm to 50 mm (Weight average), preferably 0.5 mm to 1 cm and especially preferably 1 mm to 5 mm. The size of the invention used aminoplast and their size distribution can be determined by methods known per se, such as z. B. measuring a sample of Reinigungskörperchen, but also sieving or air views.

Aminoplast foam pieces used according to the invention can have a broad or a narrow Have diameter distribution. If the quotient of diameter (mass average) to diameter (number average) is formed, the quotient can be, for example, in the range from 1.1 to 10, preferably 1.2 to 3.

Used according to the invention aminoplast can regular or irregular Have shape. examples for regular Shapes are cubes, Cuboid, spheres, ellipsoids. Examples of irregular forms are granules, shreds and schnitzel.

Used according to the invention not only an aminoplast foam piece, but several, are preferred at least 10, more preferably at least 100 and most especially preferably at least 500. The number of Aminoplastschaumstoffstücke used fits one to the size and the Shape of the surface to be cleaned.

During the execution the cleaning process according to the invention can be mixed, for example by shaking, stirring with, for example, one or more stirring, pneumatic stirring or by operating the tool concerned without substrates. So it is preferable stirred vessels, agitators, Gear or kneading tools with multiple aminoplast foam pieces too feed and then turn on.

When Duration for the cleaning process in question can be, for example, lasting in the range of one minute to 48 hours, preferably 5 minutes to choose 24 hours and more preferably one to 10 hours.

to execution the cleaning process according to the invention you can have several pieces Aminoplast foam in dry or in with, for example, water use moistened form.

in the Connection to the cleaning according to the invention can residues of aminoplast foam pieces, for example, with compressed air or with the help of an organic solvent or water, if necessary and desired is.

• (a) offenzelligen Aminoplastschaumstoffen mit einer Dichte im Bereich von 5 bis 500 kg/m³ und einem mittleren Porendurchmesser im Bereich von 1 μm bis 1 mm,
• (b) offenzelligen Aminoplastschaumstoffen mit einer Dichte im Bereich von 5 bis 500 kg/m³ und einem mittleren Porendurchmesser im Bereich von 1 μm bis 1 mm, die man behandelt hat (b1) mit wässriger Formulierung von mindestens einer Verbindung (b-1) mit mindestens einer Halbaminal- oder Aminalgruppe pro Molekül oder mindestens einem Copolymer, das mindestens ein OH-gruppenhaltiges oder β-Dicarbonylgruppenhaltiges oder Epoxidgruppenhaltiges Comonomer einpolymerisiert enthält, oder (b2) mit mindestens einem bei Zimmertemperatur festem Carboxylgruppen-haltigen und/oder Carbonsäureestergruppen-haltigen Polymerisat (b-2) mit einem Molekulargewicht M_n im Bereich von 1.000 bis 1.000.000 g/mol.

Aminoplast foam pieces are used to carry out the cleaning process according to the invention. Aminoplast foam pieces can be made

• (a) open-celled aminoplast foams having a density in the range from 5 to 500 kg / m ³ and an average pore diameter in the range from 1 μm to 1 mm,
• (b) open cell aminoplast foams having a density in the range of 5 to 500 kg / m ³ and an average pore diameter in the range of 1 μm to 1 mm, which has been treated (b1) with aqueous formulation of at least one compound (b-1) with at least one semiaminal or aminal group per molecule or at least one copolymer which contains in copolymerized form at least one comonomer containing OH groups or β-dicarbonyl groups or containing epoxide groups, or (b2) with at least one polymer containing carboxyl groups at room temperature and / or carboxylic ester groups (b-2) having a molecular weight M _n in the range of 1,000 to 1,000,000 g / mol.

there at least one compound (b-1) is preferable to a compound that is not in the production of aminoplast foam (b) was used.

In an embodiment the present invention is used according to the invention open-cell aminoplast foams to those based on synthetic organic foam, for example from urea-formaldehyde resins, in particular Aminoplast foams based on aminoplast-formaldehyde resins, in particular melamine-formaldehyde resins, wherein Aminoplastschaumstoffe based on melamine-formaldehyde resins also as melamine foams be designated.

The to exercise the method according to the invention used unmodified open-cell aminoplast foams (a) are in the context of the present invention quite generally as unmodified Aminoplastschaumstoffe (a). The to exercise the cleaning process according to the invention used unmodified open-cell aminoplast foams (a) will be described in more detail below described.

For carrying out the process according to the invention, it is possible to start from open-celled aminoplast foams (a), in particular from aminoplastic foams, in which at least 50% of all lamellae of are preferably 60 to 100% and more preferably 65 to 99.9%, determined according to DIN ISO 4590.

Used according to the invention Aminoplast foams (a) are in one embodiment of the present invention Invention hard aminoplast foams, which are within the meaning of the present invention Invention Aminoplast foams, which at a compression of 40% a compression hardness of 1 kPa or more, determined according to DIN 53577.

Aminoplast foams (a) used according to the invention have a density in the range of 5 to 500 kg / m ³ , preferably 6 to 300 kg / m ³ and particularly preferably in the range of 7 to 300 kg / m ³ .

Used according to the invention Aminoplast foams (a) can a mean pore diameter (number average) in the range of 1 micron to 1 mm preferably 50 to 500 μm, determined by evaluation of microscopic images on sections.

In one embodiment of the present invention, aminoplast foams (a) used according to the invention may have a maximum of 20, preferably a maximum of 15, and particularly preferably a maximum of 10 pores per m ² , which have a diameter in the range of up to 20 mm. The remaining pores usually have a smaller diameter.

In one embodiment of the present invention, aminoplast foams (a) used according to the invention have a BET surface area in the range from 0.1 to 50 m ² / g, preferably 0.5 to 20 m ² / g, determined to DIN 66131.

In an embodiment of the present invention have aminoplast foams used in the invention (a) a sound absorption level of over 50%, measured after DIN 52215 at a frequency of 2000 Hz and one layer thickness of the relevant foam (a) of 50 mm.

In a special embodiment of the present invention have open-cell aminoplast foams used in the invention (a) a sound absorption coefficient of more than 0.5, measured after DIN 52212 at a frequency of 2000 Hz and one layer thickness of the relevant foam (a) of 40 mm.

When Starting material used open-cell Aminoplastschaumstoffe (a) can have any geometric shapes, such as plates, Balls, cylinders, powder, cubes, Flakes, cuboids, calipers, Rods or round, rectangular or square columns and preferably slices, cone-shaped or pin-shaped Embodiments. The size dimensions of aminoplast foams used as starting material (a) are not critical if they are mechanically compressed mechanically can. Prefers become plates, cylinders, cubes, Cuboid or rectangular columns, in usual Devices can be mechanically compressed, and particularly preferred Slices, cone-shaped or pin-shaped Embodiments.

• i) einem Melamin-Formaldehyd-Vorkondensat, das neben Formaldehyd weitere Carbonylverbindungen wie beispielsweise Aldehyde einkondensiert enthalten kann, in Gegenwart von
• ii) einem oder mehreren Treibmitteln,
• iii) gegebenenfalls einem oder mehreren Emulgatoren,
• iv) einem oder mehreren Härtern.

As starting material for carrying out the method according to the invention particularly suitable melamine foams (a) are known as such. Their preparation succeeds, for example, by foaming of

• i) a melamine-formaldehyde precondensate which, in addition to formaldehyde, may comprise further carbonyl compounds, such as, for example, aldehydes, condensed in the presence of
• ii) one or more propellants,
• iii) optionally one or more emulsifiers,
• iv) one or more hardeners.

Melamine-formaldehyde precondensates i) can be unmodified, you can but also be modified, for example, up to 20 mol% of the melamine be replaced by other known Durolastbildner, for example alkyl-substituted melamine, urea, urethane, carboxylic acid amides, Dicyandiamide, guanidine, sulphurylamide, sulphonic acid amides, aliphatic amines, Phenol and phenol derivatives. As further Carbonylverbindungen beside Formaldehyde can modified melamine-formaldehyde precondensates, for example acetaldehyde, Trimethylolacetaldehy, acrolein, furfurol, glyoxal, phthalaldehyde and Terephthaldialdehyd condensed.

Suitable blowing agents ii) are: water, inert gases, in particular carbon dioxide, and so-called physical blowing agents. Physical blowing agents are compounds which are inert with respect to the starting components and which are preferably liquid at room temperature and under the conditions of Evaporate aminoplast formation. The boiling point of these compounds is preferably below 110 ° C., in particular below 80 ° C. The physical blowing agents also include inert gases which are introduced into or dissolved in the starting components i) and ii), for example carbon dioxide, nitrogen or noble gases.

suitable liquid at room temperature Connections are selected from the group containing alkanes and / or cycloalkanes with at least 4 carbon atoms, dialkyl ethers, esters, ketones, acetals, fluoroalkanes having 1 to 8 carbon atoms, and tetraalkylsilanes having 1 to 3 Carbon atoms in the alkyl chain, in particular tetramethylsilane.

When Examples are: propane, n-butane, iso- and cyclobutane, n-, iso- and cyclopentane, cyclohexane, dimethyl ether, methyl ethyl ether, Methyl tert-butyl ether, formic acid methyl ester, acetone and fluorinated alkanes which can be degraded in the troposphere and therefore for the ozone layer is harmless, such as trifluoromethane, difluoromethane, 1,1,1,3,3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane, 1,1,1-trifluoro-2,2,2-trichloroethane, 1,1,2-trifluoro-1,2,2-trichloroethane, Difluoroethane and heptafluoropropane. The named physical Blowing agents can used alone or in any combination with each other become.

Of the Use of perfluoroalkanes to produce fine cells is out EP-A 0 351 614 known.

As emulsifiers iii) it is possible to use customary nonionic, anionic, cationic or betainic surfactants, in particular C ₁₂ -C ₃₀ -alkyl sulfonates, preferably C ₁₂ -C ₁₈ -alkyl sulfonates and polyoxyethylenated C ₁₀ -C ₂₀ -alkyl alcohols, in particular of the formula R ^{6 is} -O (CH ₂ -CH ₂ -O) _x -H, wherein R ^{6 is} selected from C ₁₀ -C ₂₀ alkyl and x may, for example, be an integer in the range of 5 to 100.

When Harder iv) are especially acidic compounds in question, such as inorganic Brønsted acids, e.g. sulfuric acid or phosphoric acid, Organic Brønsted acids such as for example, acetic acid or formic acid, Lewis acids and also so-called latent acids.

Examples for suitable Melamine foams and processes for their preparation are found in EP-A 0 017 672.

Of course, aminoplast foams used in the present invention may contain (a) additives and adjuvants conventional in foam chemistry, for example, antioxidants, flame retardants, fillers, colorants such as pigments or dyes, and biocides, for example

to execution the cleaning process according to the invention one can either use unmodified aminoplast foams (a), which are described above, or preferably so-called modified Aminoplast foams (b), whose preparation is described below becomes.

• (b1) mindestens einer Verbindung mit mindestens einer Halbaminal- oder Aminalgruppe pro Molekül aus oder von mindestens einem Copolymer, das mindestens ein OH-gruppenhaltiges oder β-Dicarbonylgruppen-haltiges oder Epoxidgruppenhaltiges Comonomer oder n-Butylacrylat einpolymerisiert enthält, oder
• (b2) mit mindestens einem bei Zimmertemperatur festem Carboxylgruppen-haltigen und/oder Carbonsäureestergruppen-haltigen Polymerisat (b-2) mit einem Molekulargewicht M_n im Bereich von 1.000 bis 1.000.000 g/mol.

To produce modified aminoplast foams (b), one starts, for example, from one or more unmodified aminoplast foams (a) which can be prepared as described above. Aminoplast foam (a) can be treated with prior to carrying out the cleaning process according to the invention

• (b1) at least one compound having at least one semiaminal or aminal group per molecule or from at least one copolymer which contains at least one OH group-containing or β-dicarbonyl-containing or epoxy group-containing comonomer or n-butyl acrylate in copolymerized form, or
• (b2) having at least one solid at room temperature carboxyl-containing and / or carboxylic acid ester group-containing polymer (b-2) having a molecular weight M _n in the range of 1,000 to 1,000,000 g / mol.

In the following, compounds having at least one semiaminal or aminal group per molecule and copolymers which contain at least one OH group-containing or β-dicarbonyl-containing or epoxide group-containing comonomer or n-butyl acrylate in copolymerized form, also briefly as compound (b-1 ) or (b-1). Compound (b-1) is obtainable, for example, by condensing at least one nitrogen-containing compound (B1) and at least one carbonyl compound (B2) and given if further compounds (B3) and optionally further reactions after the condensation.

Preferably treated with (b-1) or (b-2) in the form of aqueous formulations. in the In the context of the present invention, aqueous formulation for aqueous solutions, Emulsions or dispersions are available.

Examples for nitrogen-containing Compounds (B1) are urea, N, N'-dimethylurea, triazone, tetrahydropyrimidinones, Imidazolinones, tetrahydro-4H-1,3,5-oxadiazin-4-ones, alkyl carbamates, methoxyethyl carbamates and (meth) acrylic acid methylolamide.

Examples of carbonyl compounds (B2) are
Ketones, in particular di (C ₁ -C ₁₀ alkyl) ketones, preferably mono-, di- and polyaldehydes, in particular C ₁ -C ₁₀ -Alkylmonoaldehyde such as acetaldehyde or propionaldehyde and very particularly preferably formaldehyde, furthermore dialdehydes such as glyoxal or Phthalaldehyde such as 1,2-phthalaldehyde, butanedial, glutaric dialdehyde and hexane-1,6-dial.

Examples of particularly preferred further compounds (B3) are monohydric or polyhydric alcohols, for example C ₁ -C ₁₀ -alkanols, in particular methanol, ethanol, n-propanol and n-butanol, furthermore ethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol , 1,6-hexanediol, 1,12-dodecanediol, glycerol, diethylene glycol, dipropylene glycol, polyethylene glycols having an average of up to 200, preferably from 3 to 20 ethylene oxide units per molecule (number average), polypropylene glycols having an average of up to 200, preferably from 3 up to 20 propylene oxide units per molecule (number average), polytetrahydrofuran having an average of up to 200, preferably from 3 to 20 1,4-butanediol units per molecule (number average) as well as mono-C ₁ -C ₁₀ alkyl-capped mono- , Di- or polyethylene or -propylene glycols having on average up to 200, preferably from 3 to 20 alkylene oxide units per molecule (number average).

Examples for further Reactions after condensation are esterifications, etherifications and radical (co) polymerizations.

In an embodiment According to the present invention, compound (b-1) can be prepared from at least a nitrogen-containing compound (B1), at least two carbonyl compounds (B2) and, for example, up to 3 different further compounds (B3).

wobei die Variablen wie folgt definiert sind:
R¹, R² verschieden oder vorzugsweise gleich und gewählt aus Wasserstoff, C₁-C₁₂-Alkyl, verzweigt oder unverzweigt, ausgewählt aus Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, iso-Heptyl, n-Octyl, n-Nonyl, n-Decyl und n-Dodecyl; bevorzugt C₁-C₆-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethyl-propyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Bu-tyl,
(-CH₂-CH2-O)m-R5, (-CHCH3-CH2-O)m-R5, (-CH2-CHCH3-O)m-R5, (-CH2-CH2-CH2-O)m-R5, (-CH2-CH2-CH2-CH2-O)m-R5,
x gleich oder verschieden und eine ganze Zahl gewählt aus null und eins, wobei in Formel Ia mindestens ein x gleich eins gewählt wird; in Formel Ib können beide x gleich null gewählt werden,
m ist eine ganze Zahl im Bereich von 1 bis 20,
R³, R⁴ verschieden oder vorzugsweise gleich und gewählt aus Wasserstoff, C₁-C₁₂-Alkyl, verzweigt oder unverzweigt, ausgewählt aus Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, iso-Heptyl, n-Octyl, n-Nonyl, n-Decyl und n-Dodecyl; bevorzugt C₁-C₆-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl, oder gemeinsam C₂-C₄-Alkylen wie beispielsweise -CH₂-CH₂-, -(CH₂)₃- oder -(CH₂)₄-,
R⁵ gleich oder verschieden und gewählt aus C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl
und insbesondere Wasserstoff.Particularly preferred examples of compounds (b-1) are those of the general formula Ia to Ib

where the variables are defined as follows:
R ¹ , R ^{2 are} different or preferably identical and selected from hydrogen, C ₁ -C ₁₂ -alkyl, branched or unbranched, selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec. Butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n- Heptyl, isoheptyl, n-octyl, n-nonyl, n-decyl and n-dodecyl; preferably C ₁ -C ₆ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. Pentyl, neo-pentyl, 1,2-dimethyl-propyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, more preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, iso Propyl, n-butyl, iso-butyl, sec-butyl and tert -butyl,
(-CH ₂ -CH ₂ -O) m -R 5, (-CHCH 3 -CH ₂ -O) m -R 5, (-CH ₂ -CHCH 3 -O) m -R 5, (-CH ₂ -CH ₂ -CH ₂ -O) m -R 5 , (-CH 2 -CH 2 -CH 2 -CH 2 -O) m -R 5,
x is the same or different and an integer selected from zero and one, wherein in formula Ia at least one x is selected equal to one; in formula Ib both x can be chosen to be zero,
m is an integer in the range of 1 to 20,
R ³ , R ^{4 are} different or preferably identical and selected from hydrogen, C ₁ -C ₁₂ -alkyl, branched or unbranched, selected from among methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec. Butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n- heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl and n-dodecyl; preferably C ₁ -C ₆ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, more preferably C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, iso-propyl , n-butyl, iso-butyl, sec-butyl and tert-butyl, or together are C ₂ -C ₄ -alkylene, such as -CH ₂ -CH ₂ -, - (CH ₂ ) ₃ - or - (CH _{2 4} -,
R ^{5 is} identical or different and selected from C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl
and especially hydrogen.

Compounds (b-1) in particular of the general formula Ia and Ib are known per se. Compounds (b-1), in particular of the general formula Ia and Ib, are generally not pure according to a defined formula; Usually intermolecular rearrangements of the radicals R ¹ to R ⁴ , that is, for example, Um-Aminalisierungsreaktionen, and also condensation reactions and cleavage reactions are observed to some extent. The formula Ia or Ib given above is to be understood in the sense that it defines the stoichiometric ratios of the substituents and also encompasses intermolecular rearrangement products and condensation products.

wobei die Variablen wie folgt definiert sind:
R⁶ gewählt aus Wasserstoff und C₁-C₁₂-Alkyl, bevorzugt lineares C₁-C₁₂-Alkyl, ausgewählt aus Methyl, Ethyl, n-Propyl, n-Butyl, n-Pentyl, n-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl und n-Dodecyl; bevorzugt lineares C₁-C₆-Alkyl wie Methyl, Ethyl, n-Propyl, n-Butyl, n-Pentyl, iso-Pentyl, n-Hexyl, besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl und n-Butyl, wobei Wasserstoff und Methyl ganz besonders bevorzugt sind,
R⁷ verschieden oder vorzugsweise gleich und gewählt aus C₁-C₁₂-Alkyl, bevorzugt lineares C₁-C₁₂-Alkyl, ausgewählt aus Methyl, Ethyl, n-Propyl, n-Butyl, n-Pentyl, n-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl und n-Dodecyl; bevorzugt lineares C₁-C₆-Alkyl wie Methyl, Ethyl, n-Propyl, n-Butyl, n-Pentyl, iso-Pentyl, n-Hexyl, besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl und n-Butyl,
und besonders bevorzugt Wasserstoff.Another group of compounds (b-1) which are preferably used are homo- and in particular copolymers of compounds of general formula II

where the variables are defined as follows:
R ^{6 is} selected from hydrogen and C ₁ -C ₁₂ -alkyl, preferably linear C ₁ -C ₁₂ -alkyl, selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and n-dodecyl; preferably linear C ₁ -C ₆ -alkyl, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, isopentyl, n-hexyl, particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n- Propyl and n-butyl, with hydrogen and methyl being particularly preferred,
R ^{7 is} different or preferably identical and selected from C ₁ -C ₁₂ -alkyl, preferably linear C ₁ -C ₁₂ -alkyl, selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n Heptyl, n-octyl, n-nonyl, n-decyl and n-dodecyl; preferably linear C ₁ -C ₆ -alkyl, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, isopentyl, n-hexyl, particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n- Propyl and n-butyl,
and particularly preferably hydrogen.

In formula II, very particular preference is given to both variables R ⁷ being hydrogen and R ^{6 being} selected from methyl or hydrogen.

Preferably used homopolymers and copolymers of compounds of general formula II may, for example, have molecular weights M _w in the range from 10,000 to 250,000 g / mol, preferably from 20,000 to 240,000 g / mol.

If it is desired to use copolymers of one or more compounds of the general formula II, copolymers of one or more compounds of the general formula II with one or preferably at least two comonomers are preferably selected
one or more (meth) acrylic acid C ₁ -C ₁₀ -alkyl esters, in particular with methyl acrylate, ethyl acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
(Meth) acrylic acid,
vinyl aromatic compounds such as styrene,
(Meth) acrylonitrile and
(Meth) acrylamide.

einpolymersiert enthalten, wobei die Variablen wie folgt definiert sind:
R⁸ gewählt aus C₁-C₁₂-Alkyl, bevorzugt lineares C₁-C₁₂-Alkyl, ausgewählt aus Methyl, Ethyl, n-Propyl, n-Butyl, n-Pentyl, n-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl und n-Dodecyl; bevorzugt lineares C₁-C₆-Alkyl wie Methyl, Ethyl, n-Propyl, n-Butyl, n-Pentyl, iso-Pentyl, n-Hexyl, besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl und n-Butyl,
und ganz besonders bevorzugt Wasserstoff,
X gewählt aus OH, Glycidyl, 2-Hydroxyethyl, 3-Hydroxypropyl,

wobei
R⁹ gewählt aus C₁-C₁₂-Alkyl, verzweigt oder unverzweigt, ausgewählt aus Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, iso-Heptyl, n-Octyl, n-Nonyl, n-Decyl und n-Dodecyl, bevorzugt C₁-C₆-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl, ganz besonders bevorzugt Methyl.If it is desired to use copolymers which contain at least one OH group-containing or β-dicarbonyl-containing or epoxy group-containing comonomer or n-butyl acrylate in copolymerized form, preference is given to using copolymers which contain at least one comonomer of the general formula III

polymerized, the variables being defined as follows:
R ^{8 is} selected from C ₁ -C ₁₂ -alkyl, preferably linear C ₁ -C ₁₂ -alkyl, selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n- Octyl, n-nonyl, n-decyl and n-dodecyl; preferably linear C ₁ -C ₆ -alkyl, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, isopentyl, n-hexyl, particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n- Propyl and n-butyl,
and most preferably hydrogen,
X is selected from OH, glycidyl, 2-hydroxyethyl, 3-hydroxypropyl,

in which
R ^{9 is} selected from C ₁ -C ₁₂ -alkyl, branched or unbranched, selected from among methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n- Pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl and n-dodecyl, preferably C ₁ -C ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl , n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, more preferably C ₁ -C ₄ -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, most preferably methyl.

Do you wish to use such copolymers as (b-1), which is a compound of contained in copolymerized form of general formula III with X = OH, see above those copolymers are preferred which do not use ethylene as a comonomer incorporated in copolymerized form.

In one embodiment of the present invention, those copolymers are selected as (b-1) which contain in copolymerized form:
to 15% by weight, preferably 0.5 to 10% by weight, of at least one comonomer of the general formula II or III,
From 0 to 80% by weight of n-butyl acrylate,
0 to 80% by weight of at least one further (meth) acrylic acid C ₁ -C ₁₀ -alkyl ester,
0 to 20 wt .-%, preferably 0.1 to 15 wt .-% of one or more other comonomers such as (meth) acrylic acid, vinyl aromatic compounds such as styrene, (meth) acrylonitrile and (meth) acrylamide.

Do you wish use copolymers of the general formula II or III, Thus, it is preferable to use random copolymers, which after known methods can be produced, for example by Emulsion polymerization.

In an embodiment of the present invention for modifying aminoplast foam (b) used aqueous Formulation in the range of 1 to 60% by weight, preferably 10 to 40% by weight Compound (b-1).

Around Contact aminoplast foams (b) with compound (b-1), Different techniques are conceivable.

The Contact can be accomplished, for example, by immersion of aminoplast foam (b) in aqueous formulation of compound (b-1), by impregnation of aminoplast foam (b) with aqueous formulation of compound (b-1), by watering unmodified foam (b) with aqueous formulation of compound (b-1), by incomplete or preferably complete spray of aminoplast foam (b) with aqueous formulation of compound (b-1), or by calendering aqueous formulation of compound (b-1) on aminoplast foam (b).

In another embodiment of the present invention, the procedure is to aqueous Formulation of compound (b-1) on aminoplast foam (b) by doctoring. After soaking or knife-coating or calendering or spraying, for uniform distribution of the formulation and adjustment of the desired concentration between at least two, for example, rotating rolls can be squeezed off.

In an embodiment According to the present invention, aminoplast foam may be used after contacting (b) and aqueous Formulation of compound (b-1) interact, for example via a Period in the range of 0.1 seconds to 24 hours, preferably 0.5 Seconds to 10 hours and more preferably 1 second to 6 Hours.

In an embodiment one contacts Aminoplastschaumstoff (b) and aqueous formulation of compound (b-1) at temperatures in the range of 0 ° C to 250 ° C, preferably 5 ° C to 190 ° C and more preferably 10 to 180 ° C.

In an embodiment contacting aminoplast foam (b) and aqueous formulation of compound (b-1) first at temperatures in the range of 0 ° C up to 50 ° C and changes then the temperature, for example, it is heated to temperatures in Range of 60 ° C up to 250 ° C, preferably from 65 ° C up to 180 ° C.

In another embodiment one contacts Aminoplastschaumstoff (b) and aqueous formulation of compound (b-1) first at temperatures in the range of 0 ° C up to 120 ° C and changes then the temperature, for example, it is heated to temperatures in Range of 30 ° C up to 250 ° C, preferably from 125 ° C up to 200 ° C.

In a preferred embodiment of the present invention the amounts of starting materials unmodified foam (a) and aqueous Formulation of compound (b-1) such that the product according to the invention a much higher one Density has as the relevant unmodified foam (a).

In an embodiment The present invention operates during the contacting of aminoplast foam (b) with aqueous Formulation of compound (b-1) at atmospheric pressure. In another embodiment you work under elevated Pressure, for example, when pressing in the range of 1.1 bar to 10 bar. In another embodiment the present invention is carried out under reduced pressure, for example, when pressing in the range from 0.1 mbar to 900 mbar, preferably up to 100 mbar.

In an embodiment Contact aminoplast foam (b) with aqueous formulation of compound (b-1) so that compound (b-1) is as uniform as possible in all Dimensions over Aminoplastschaumstoff (b) is distributed. Suitable methods are Methods with a high degree of application efficiency. Exemplary called: complete Soak, Diving, flooding, drumming, spraying, such as Air Spray, Airless spraying, further high-speed atomization, coating, knife coating, Calendering, brushing, rolling, wiping, rolling, spinning, Centrifuge.

In another embodiment Contact aminoplast foam (b) with aqueous formulation of compound (b-1) so that one has an uneven distribution of aqueous Formulation of Compound (b-1) on Aminoplast Foam (b) causes. So you can, for example Aminoplastschaumstoff (b) with aqueous Spray formulation of compound (b-1) unevenly and allow to act. In another embodiment can Aminoplastschaumstoff (b) incomplete with aqueous formulation of compound (b-1) soak. In another embodiment can one part of Aminoplastschaumstoff (b) once and a other part of aminoplast foam (b) at least twice with aqueous Contact formulation of compound (b-1). In another Execution form steeped Aminoplast foam (b) with aqueous formulation of compound (b-1) completely and rinses clean the top layer with, for example, water again. Then you leave act. As a result, aminoplast foam (b) is coated in the Core; the outer surface remains uncoated.

If Aminoplast foam (b) with aqueous formulation of compound (b-1) contacted so that you have an uneven distribution aqueous Formulation of Compound (b-1) on Aminoplast Foam (b) has effected, it is achieved, for example, by interacting with each other let over a period of 2 minutes or more that is not just the outermost layer of aminoplast foam (b) with aqueous formulation of compound (b-1) is contacted.

When contacting aminoplast foam (b) with aqueous formulation of compound (b-1) such that uneven distribution of aqueous formulation of compound (b-1) onto aminoplast foamed material (b), modified foam may have non-uniform mechanical properties across its cross-section. Thus, for example, it is possible that at the sites where it has been contacted with relatively large amounts of aqueous formulation of compound (b-1), it is softer than at the sites where it reacts with less aqueous formulation of compound (b-1). 1) has been contacted.

In an embodiment you can get one in some cases not desirable in itself uneven distribution the aqueous Formulation of compound (b-1) by calendering on perforated Balance rollers or perforated plates. The formation of an uneven distribution of watery Formulation of compound (b-1) can be thereby reduced at least two perforated rollers, that one has a vacuum suction on at least one perforated roller or at least one perforated plate performs.

In a special embodiment one sets after contacting by squeezing between two opposite rotating rollers on a defined fleet intake, for example in the range of 20 to 800% by weight, based on the weight of the aminoplast foam (B). The concentration of compound (b-1) in the formulation is between 1 and 99% by weight.

In an embodiment The present invention may be followed by flushing, for example with one or more solvents and preferably with water.

In an embodiment The present invention may be followed by contacting and optionally rinsing dry, for example mechanically by z. B. wringing or Calendering, in particular by squeezing by two rollers, or thermally, for example in microwave ovens, hot air blowers or in drying cabinets, in particular Vacuum drying cabinets, where you have drying cabinets for example, operate at temperatures in the range of 30 to 150 ° C. can. Under vacuum one can in connection with vacuum drying cupboards a Understand pressure, for example in the range of 0.1 to 850 mbar.

The Time for one if desired conducted Dry steps expended, belong not by definition to the contact time.

In an embodiment one can accomplish thermal drying by heating up Temperatures in the range of 20 ° C up to 150 ° C, for example about a period of 10 seconds to 20 hours.

In addition to the aqueous formulation of compound (b-1), according to the invention, it is possible to contact aminoplast foam (b) with at least one catalyst (c-1). Suitable examples are metal and ammonium salts and inorganic or organic acids. Suitable metal salts are, for example, metal halides, metal sulfates, metal nitrates, metal tetrafluoroborates, metal phosphates or mixtures thereof. Examples are magnesium chloride, magnesium sulfate, zinc chloride, lithium chloride, lithium bromide, boron trifluoride, aluminum chloride, aluminum sulfate, alums such as KAl (SO ₄ ) ₂ .12H ₂ O, zinc nitrate, sodium tetrafluoroborate, and mixtures of the metal salts described above.

When Catalyst (c-1) suitable ammonium salts are ammonium salts the group ammonium chloride, ammonium nitrate, ammonium sulphate, ammonium oxalate, Diammonium phosphate or mixtures of the ammonium salts described above.

When Catalyst (c-1) are suitable inorganic and organic acids maleic acid, formic acid, Citric acid, Tartaric acid, oxalic acid, p-toluenesulfonic acid, Hydrochloric acid, Sulfuric acid, boric acid and their mixtures.

Of course you can also mixtures of, for example, at least one metal salt and at least one ammonium salt or at least one metal salt or ammonium salt and at least one organic or inorganic Acid as Use catalyst (c-1).

Very particularly preferred as catalyst (c-1) are Brønsted acid catalysts, for example ZnCl ₂ , Zn (NO ₃ ) ₂ , in each case also in the form of their hydrates, NH ₄ Cl, MgSO ₄ , Al ₂ (SO ₄ ) ₃ , in each case also in the form of their hydrates, and most preferably MgCl ₂ , especially in the form of its hexahydrate.

Based on compound (b-1) is preferably used a third to one One-twentieth of the weight of catalyst (c-1), determined respectively without any available water of hydration.

Prefers are magnesium chloride, zinc chloride, magnesium sulfate, aluminum sulfate used. Particularly preferred is magnesium chloride.

In an embodiment Aminoplast foam (b) is contacted with aqueous solution of compound (b-1) and optionally catalyst (c-1) at a pH in the range of 3.0 to 7.5, with the desired pH optionally by addition of acid, alkali or a buffer can be adjusted. The use of a buffer is preferred.

In one embodiment, at least one aminoplast foam (b) may be contacted not only with aqueous formulation of compound (b-1) and optionally catalyst (c-1) but also with at least one additive (d-1) selected from
Biocides, such as silver particles or monomeric or polymeric organic biocides such as phenoxyethanol, phenoxypropanol, glyoxal, thiadiazines, 2,4-dichlorobenzyl alcohols and preferably isothiazolone derivatives such as MIT (2-methyl-3 (2H) -isothiazolone), CMIT (5 -Chloro-2-methyl-3 (2H) -isothiazolone), CIT (5-chloro-3 (2H) -isothiazolone), BIT (1,2-benzisothiazol-3 (2H) -one), furthermore copolymers of N, N-di-C ₁ -C ₁₀ -alkyl-ω-amino-C ₂ -C ₄ -alkyl (meth) acrylate, in particular copolymers of ethylene with N, N-di-methyl-2-aminoethyl (meth) acrylate,
one or more surfactants, which may be anionic, cationic or non-ionic, activated carbon,
Colorants such as dyes or pigments,
Fragrances such as perfume,
Hydrophobizing or oleophobicizing agents, for example fluorocarbon resins or fluorocarbon waxes,
Odor scavengers, for example cyclodextrins, and
Microcapsules filled with at least one active ingredient such as care oil, one or more biocides, perfume, odor trap, microcapsules for the purposes of the present invention may be, for example spherical inside hollow particles having an average outer diameter in the range of 1 to 100 microns, for example melamine Formaldehyde resin or may be constructed of polymethyl methacrylate.

To For example, you can proceed so that you at least one Aminoplastschaumstoff (b) in different operations or preferably simultaneously with aqueous formulation of compound (b-1) and contacted with at least one additive (d-1).

In an embodiment one can be watery Formulation of compound (b-1) one or more additives (d-1), for example in proportions of 0 to a total of 50 Wt .-%, based on (b-1), preferably 0.001 to 30 wt .-%, especially preferably 0.01 to 25 wt .-%, most preferably 0.1 to 20 Wt .-%.

you may continue to act after aqueous formulation of compound (b-1) and optionally catalyst (c-1) and optionally at least an additive (d-1) on Aminoplastschaumstoff (b) on or compress mechanically several times. The mechanical compression can it is carried out discontinuously or preferably continuously, discontinuously for example, by pressing or plates, continuously, for example through rollers or calenders. If you want calendering, so one can perform one or more calendering passes, for example one up to twenty calender passages, preferred are five up to ten calendar passes.

In an embodiment The present invention is mechanically compressed to one Degree of compaction in the range of 1: 1.2 to 1:20, preferably 1 : 2.5 to 1:10.

In an embodiment The present invention is calendered before drying.

In an embodiment The present invention proceeds in such a way that after contacting and exposing to aqueous Formulation of compound (b-1) and optionally catalyst (c-1) and optionally at least one additive (d-1) dries first, then moistened with water and then mechanically compressed, for example calendered.

In another embodiment The present invention proceeds in such a way that after contacting and exposing to aqueous Formulation of compound (b-1) and optionally catalyst (c-1) and optionally at least one additive (d-1) is first dried, refrained from moistening and then mechanically compressed, for example calendered.

In one embodiment of the present invention, mechanical compression is achieved after contacting and reacting with aqueous formulation of compound (b-1) and optionally catalyst (c-1) and optionally at least one additive (d-1), the hard unmodified aminoplast foams (a) which are hard and flexible.

In an embodiment The present invention can be used after contacting and soaking of watery Formulation of compound (b-1) and optionally catalyst (c-1) and optionally at least one additive (d-1) Aminoplast foam (b) thermally fix, before or after mechanical compression or between two mechanical ones Compression steps. You can, for example, at temperatures from 120 ° C up to 250 ° C over a Thermally fix period of 5 seconds to 120 minutes. suitable Apparatuses are, for example, microwave ovens, plate pressing plants, with Hot air blowers, electric or gas ovens heated drying cabinets, heated rolling mills or continuously operated drying facilities.

you may dry before thermal fixation as described above.

you can after contacting and exposing to aqueous Formulation of compound (b-1) and optionally catalyst (c-1) and optionally at least one additive (d-1) Thermoplastically fix aminoplast foam (b) to or preferably before mechanical compression or between two mechanical compression steps. You can, for example at temperatures of 150 ° C up to 200 ° C over a Thermally fix a period of 30 seconds to 120 minutes. suitable Apparatuses are, for example, drying ovens.

In a special embodiment combining mechanical compression and thermal fixation, For example, by foam after exposure and optionally drying one or more times over hot rolls or calender leads or one or more times between hot plates pressed. Naturally You can also calander multiple times and with one or more times cold rollers and compressed one or more times with hot rollers. Under to be hot in the context of the present invention temperatures in the range from 100 to 250 ° C, preferably 120 to 200 ° C be understood.

Aminoplast foams modified as described above have a density in the range of 5 to 1000 kg / m ³ , preferably 6 to 500 kg / m ³ and more preferably in the range of 7 to 300 kg / m ³ . The density of the foam of the invention is on the one hand by the degree of occupancy with compound (b-1) and optionally catalyst (c-1) and optionally at least one additive (d-1) influenced and on the other hand by the degree of compaction of the starting material. By suitable choice of occupancy and degree of compaction, density and hardness or flexibility can be set as desired.

In another embodiment of the present invention, open-cell aminoplast foams (b) are used which have been treated with at least one carboxyl group-containing and / or room temperature solid carboxyl-containing and / or carboxylic acid ester group-containing polymer (b-2) having a room temperature Molecular weight M _n in the range of 1,000 to 1,000,000 g / mol.

Under solid at room temperature carboxyl-containing and / or carboxylic ester groups-containing Polymers (b-2) are in one embodiment of the present invention Invention to understand such polymers, which has a melting point from above 25 ° C, preferably over 50 ° C, determined through DSC.

at Room temperature solid carboxyl-containing and / or carboxylic acid ester group-containing and / or Carbonsäureestergruppen-containing Polymers (b-2) can Homopolymers or copolymers of ethylenically unsaturated Mono- or dicarboxylic acids be.

In an embodiment The present invention is used in accordance with the invention solid at room temperature carboxyl-containing and / or carboxylic ester groups-containing Polymers (b-2) to organic polymers derived from the material made of the open-cell foam (a) is different are.

At room temperature solid carboxyl-containing and / or carboxylic acid ester group-containing polymers (b-2) polymers with a glass transition temperature T _g in the range of -50 to 150 ° C, preferably -25 to 120 ° C and particularly preferably -20 to 100 ° C be.

In a preferred embodiment of the present invention is at least one room temperature-solid carboxyl-containing and / or carboxylic acid ester group-containing polymer (b-2) a copolymer of at least one ethylenically unsaturated carboxylic acid selected from ethylenically unsaturated mono- and dicarboxylic acids, and in particular a copolymer of (meth) acrylic acid.

• (C) Ethylen,
• (D) mindestens einer ethylenisch ungesättigten Carbonsäure,
• (E) gegebenenfalls weiteren Comonomeren.

In a preferred embodiment of the present invention, at least one carboxyl group-containing and / or carboxylic acid ester group-containing polymer (b-2) which is solid at room temperature is a copolymer obtainable by copolymerization of

• (C) ethylene,
• (D) at least one ethylenically unsaturated carboxylic acid,
• (E) optionally further comonomers.

Especially preferred at room temperature solid carboxyl group-containing and / or Carbonsäureestergruppen-containing Polymers (b-2) are described in more detail below.

• (C) 60 bis 95 Gew.-%, bevorzugt 65 bis 85 Gew.-% Ethylen und
• (D) 5 bis 40 Gew.-%, bevorzugt 15 bis 35 Gew.-% mindestens einer ethylenisch ungesättigten Carbonsäure

wobei Angaben in Gew.-% auf gesamtes bei Zimmertemperatur festes Carboxylgruppen-haltiges und/oder Carbonsäureestergruppen-haltiges Polymerisat (b-2) bezogen sind.Particular preference is given at room temperature to carboxyl-containing and / or carboxylic ester-containing polymer (b-2) at room temperature to ethylene copolymers which contain in copolymerized form as comonomers:

• (C) 60 to 95 wt .-%, preferably 65 to 85 wt .-% of ethylene and
• (D) 5 to 40 wt .-%, preferably 15 to 35 wt .-% of at least one ethylenically unsaturated carboxylic acid

where in wt .-% to total at room temperature solid carboxyl-containing and / or carboxylic acid ester group-containing polymer (b-2) are based.

At least one ethylenically unsaturated carboxylic acid is preferably a carboxylic acid of the general formula III

In formula III, the radicals are defined as follows:
R ^{10 is} selected from hydrogen and C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso -Pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl ; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
R ¹¹ selected from hydrogen, C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso -Pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl ; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
COOH, COOCH ₃ , COOC ₂ H ₅ ,
most preferably R ^{11 is} hydrogen and R ^{10 is} hydrogen or methyl.

R¹² gewählt aus C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl.
R¹³ gewählt aus Wasserstoff, C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
R¹⁴ gewählt aus Wasserstoff, C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
COOCH₃, COOC₂H₅,
weiterhin
vinylaromatische Verbindungen wie beispielsweise α-Methylstyrol und insbesondere Styrol,
Isobuten und
α-Olefinen wie beispielsweise CH₂=CH-n-C₁₆H₃₃, CH₂=CH-n-C₁₈H₃₇, CH₂=CH-n-C₂₀H₄₁ und CH₂=CH-n-C₂₂H₄₅.By way of example, ethylene copolymer which is solid at room temperature and contains carboxyl group-containing and / or carboxylic acid ester group-containing polymer (b-2) may be up to 40% by weight, preferably up to 35% by weight, based in each case on the sum of ethylene (C). and copolymerized or copolymerized ethylenically unsaturated ethylenically unsaturated carboxylic acid (s) (D), one or more further comonomers (E) in copolymerized form, for example
Vinyl, allyl and methallyl esters of C ₁ -C ₁₀ -alkylcarboxylic acids or of formic acid, for example vinyl formate, vinyl propionate and in particular vinyl acetate,
one or more ethylenically unsaturated carboxylic acid esters, preferably of the formula IV

R ¹² selected from C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl sec.-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl and tert-butyl.
R ^{13 is} selected from hydrogen, C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso -Pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl ; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
R ^{14 is} selected from hydrogen, C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso -Pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl ; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
COOCH ₃ , COOC ₂ H ₅ ,
Farther
vinylaromatic compounds such as α-methylstyrene and especially styrene,
Isobutene and
α-olefins such as CH ₂ = CH-nC ₁₆ H ₃₃ , CH ₂ = CH-nC ₁₈ H ₃₇ , CH ₂ = CH-nC ₂₀ H ₄₁ and CH ₂ = CH-nC ₂₂ H ₄₅ .

Most preferably, in formula IV, R ^{14 is} hydrogen and R ^{13 is} hydrogen or methyl.

In formula IV, R ¹⁴ is very particularly preferably hydrogen and R ^{13 is} hydrogen or methyl and R ^{12 is} selected from methyl, ethyl, n-butyl and 2-ethylhexyl.

above ethylene copolymers described can be advantageous by known free-radically initiated copolymerization under high pressure conditions manufacture, for example in stirred high-pressure autoclave or in high pressure tube reactors. Production in stirred high pressure autoclave is preferred. stirred High pressure autoclave are known per se, a description will find one in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, keywords: Waxes, Bd. A 28, p. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996. They are predominantly related to the length / diameter ratio at intervals of 5: 1 to 30: 1, preferably 10: 1 to 20: 1. The same applicable high-pressure tube reactors can also be found in Ullmann's Encyclopedia of Industrial Chemistry 5th edition, keywords: Waxes, Vol. A 28, p. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996th

suitable Printing conditions for the copolymerization under high pressure conditions are 500 to 4000 bar, preferably 1500 to 2500 bar. The reaction temperatures are in the range of 170 to 300 ° C, preferably in the range of 200 to 280 ° C.

modified Aminoplast foams preferably contain in the range of 0.1 to 80 wt .-%, preferably 2 to 60 wt .-%, particularly preferably 5 to 50 wt .-%, based on the weight of the corresponding aminoplast foam (b) to solid from (b-1) or (b-2).

In a special embodiment of the present invention one the cleaning process according to the invention in the presence of at least one additive selected from organic solvents, aqueous solutions of at least one surfactant Fabric, salt solutions, aqueous Acids or Alkalis.

Examples of particularly preferred acids are phosphoric acid, sulfuric acid, hydrochloric acid, methanesulfonic acid, toluenesulfonic acid, acetic acid, formic acid, citric acid, propionic acid, oxalic acid, tartaric acid and nitric acid. Also acidic phosphoric esters of. C ₁ -C ₁₀ -alkanols are suitable acids.

Examples for special preferred alkalis are alkali solutions such as potassium hydroxide and caustic soda.

Examples for special preferred organic solvents are turpentine, paraffinic, isoparaffinic and naphthenic Hydrocarbons (eg "mineral oil"), acetone, tetrahydrofuran, Dimethylformamide, ethyl acetate and ethanol, also denatured Ethanol.

Examples of surfactants are cationic surfactants and preferably anionic and nonionic surfactants. In this case, those surfactants whose organic ion is positively charged, referred to as cationic surfactants, and those surfactants whose organic ion is negatively charged, as anionic surfactants. Examples of particularly preferred anionic surfactants are alkali metal and ammonium salts of C ₈ -C ₁₂ alkyl sulfates, alkali metal and ammonium salts of sulfuric acid C ₁₂ -C ₁₈ alkyl halides of ethoxylated alkanols (degree of ethoxylation: 4 to 30) and alkali metal and ammonium salts of ethoxylated C ₄ -C ₁₂ alkyl phenols (degree of ethoxylation: 3 to 50), of C ₁₂ -C ₁₈ -alkylsulfonic acids and of C ₉ -C ₁₈ -alkylarylsulfonic acids (aryl radical: phenyl, tolyl, naphthyl).

Examples of particularly preferred surface-active substances are C ₄ -C ₂₀ -alkanol ethoxylates, in particular of the formula C ₄ -C ₂₀ -alkyl- (EO) _y -OH, where the HLB value of these alkanolethoxilates is WC Griffin, ie 20 times that of Mass fraction of ethylene oxide (EO) in the molecule, between 2 and 19, preferably between 6 and 15, more preferably between 8 and 14.

Further preferred surfactants are polyalkylene oxides and alkanol alkoxylates, e.g. B. EO-PO Blockcopoylmere and surfactants of the composition C ₄ -C ₂₀ alkyl (EO, PO, BuO, PeO) _y -OH, where PO is propylene oxide, BuO for butylene oxide and PeO for pentylene oxide and block and random structures possible are. If the HLB value is calculated to be 20 times the mass fraction of ethylene oxide plus 10 times the mass fraction of further alkylene oxide, for example propylene oxide, it is between 2 and 19, preferably between 6 and 15, particularly preferably between 8 and 14.

Do you wish the cleaning process according to the invention in the presence of at least one additive, so For example, you can aminoplast foam with liquid additive then clean as described above. The Contacting can be done, for example, by soaking, spraying or impregnating happen.

in the Cleaning process according to the invention Aminoplastschaumstoffstücke used can be made from aminoplast foam for example, by making ready. Suitable confectioning are casting, for example, Punching, cutting, chopping, plucking, sawing, grinding, mulling, shearing.

at exercise the method according to the invention Abrasion is produced from aminoplast foam, which in turn cleans, but on surfaces to be cleaned not abrasive. Impurities are to be purified from the surface removed and taken up in or aminoplast foam pieces. The to be cleaned surface So it is good for a very good cleaning effect.

• (a) offenzelligen Aminoplastschaumstoffen mit einer Dichte im Bereich von 5 bis 500 kg/m³ und einem mittleren Porendurchmesser im Bereich von 1 μm bis 1 mm, oder
• (b) offenzelligen Aminoplastschaumstoffen mit einer Dichte im Bereich von 5 bis 500 kg/m³ und einem mittleren Porendurchmesser im Bereich von 1 μm bis 1 mm, die man behandelt hat (b1) mit wässriger Fonrmlierung von mindestens einer Verbindung (b-1) mit mindestens einer Halbaminal- oder Aminalgruppe pro Molekül oder mindestens einem Copolymer, das mindestens ein OH-gruppenhaltiges oder β-Dicarbonylgruppenhaltiges oder Epoxidgruppenhaltiges Comonomer einpolymerisiert enthält, oder (b2) mit mindestens einem bei Zimmertemperatur festem Carboxylgruppen-haltigen und/oder Carbonsäureestergruppen-haltigen Polymerisat (b-2) mit einem Molekulargewicht M_n im Bereich von 1.000 bis 1.000.000 g/mol,

wobei die erfindungsgemäßen Aminoplastschaumstoffstücke einen mittleren Durchmesser im Bereich von 0,1 bis 5 mm (Gewichtsmittel), bevorzugt 1 mm bis 3 mm aufweisen.Another object of the present invention are Aminoplastschaumstoffstücke, made from

• (A) open-cell aminoplast foams having a density in the range of 5 to 500 kg / m ³ and an average pore diameter in the range of 1 .mu.m to 1 mm, or
• (b) open-celled aminoplast foams having a density in the range from 5 to 500 kg / m ³ and an average pore diameter in the range from 1 μm to 1 mm, which has been treated (b1) with aqueous formulation of at least one compound (b-1) with at least one semiaminal or aminal group per molecule or at least one copolymer which contains in copolymerized form at least one comonomer containing OH groups or β-dicarbonyl groups or containing epoxide groups, or (b2) with at least one polymer containing carboxyl groups at room temperature and / or carboxylic ester groups (b-2) having a molecular weight M _n in the range of 1,000 to 1,000,000 g / mol,

wherein the aminoplast foam pieces according to the invention have an average diameter in the range of 0.1 to 5 mm (weight average), preferably 1 mm to 3 mm.

One Another object of the present invention is the use of aminoplast foam pieces according to the invention Cleaning of surfaces, especially of hard to reach Surfaces.

One Another object of the present invention is a method for cleaning surfaces under Use of Aminoplastschaumstoffstücken invention, modified or unmodified, characterized in that the surfaces with treated composite, comprising a flexible pad and thereon fixed Aminoplastschaumstoffstücke. The treatment can be carried out by rubbing once or twice, wiping, Scrub or polish the surface to be cleaned with done a composite mentioned above. In this case, the above mentioned composite used in humidified or dry form become.

Another object of the present invention are composites comprising a flexible Unterla ge and fixed thereon Aminoplastschaumstoffstücke invention. Composites according to the invention comprise aminoplast foam pieces according to the invention, which are fixed on a preferably flexible backing. Under flexible documents are understood to mean such materials that can be bent manually without breaking or irreversible change, for example by cracking or stress whitening.

In a preferred embodiment According to the present invention, composites according to the invention are characterized that you choose a fibrous substrate as a flexible pad.

Suitable fibrous substrates are, for example:
Paper, cardboard, leather, imitation leather, foams and in particular textile materials such as woven, knitted or crocheted fabrics, filaments, fibers, microfibers, nonwovens made of natural, synthetic or mixtures of natural or synthetic fibers and optionally one or more binders , Natural fibers may be, for example, cotton, wool, flax, hemp, ramie. Synthetic fibers may be, for example, polyamide, polyester, modified polyester, polyester blend fabrics, polyamide blend fabrics, polyacrylonitrile, triacetate, acetate, polycarbonate, polypropylene, polyvinyl chloride, polyester microfibers, and glass fiber fabrics.

Specific examples for fibrous substrates are sponge cloths, for example, made using synthetic fibers Nonwovens.

The preferably flexible pad and in particular fibrous substrate can have any shape and size.

In an embodiment According to the present invention, composites according to the invention are characterized that aminoplast foam pieces according to the invention, in particular those having a mean diameter in the range of 0.1 to 5 mm, in a 0.1 to 10 mm thick layer on the flexible base are fixed.

In a special embodiment of the present invention are Aminoplastschaumstoffstücke invention, in particular those having a mean diameter in the range of 0.1 to 5 mm, in a 0.1 to 10 mm thick layer on individual threads as fixed flexible pad. Such composites can be, for example How to use dental floss to clean hard-to-reach surfaces.

In a special embodiment of the present invention are Aminoplastschaumstoffstücke invention, in particular those having a mean diameter in the range of 0.1 to 5 mm, in a 0.1 to 10 mm thick layer on individual fibers or Fixed microfibers as a flexible pad. Made of such coated Fibers or microfibers can be produced, for example, nonwovens.

One Another object of the present invention is a method for the production of composites according to the invention, also inventive production process called, characterized in that the flexible pad with a preferably aqueous Aminoplast, containing aminoplast foam pieces according to the invention, treated and then dry.

you For example, the treatment may be by coating such as Scrape, apply, paddle. Furthermore, you can through spray to treat. By the treatment according to the invention can be a complete Film of preferably aqueous Formulation containing Aminoplastschaumstoffstücke invention Substrate or even an incomplete film, for example Pattern has. For this one can use methods known per se, for example, using templates, preferably by aqueous Written, sprayed or with the help of robots z. B. movable robot arms distributed.

In a special embodiment the present invention is used to coat the back side of a composite according to the invention, ie the side on which no aminoplast foam pieces according to the invention are fixed are, with a nourishing substance. Among caring substances become natural, for example or synthetic waxes, natural or synthetic oils and polishes understood. Such special composites according to the invention also have a nourishing or cleansing surface sealing effect.

Suitable aqueous aminoplast foam unit formulations which are suitable for carrying out the preparation process according to the invention can be used in addition to aminoplast foam pieces according to the invention and solvents, for example organic solvent such as, for example, ethanol, or preferably water, furthermore contain one or more resins (α) or polymers (β).

The aminoplast foam piece formulation used according to the invention is preferably a paste, emulsion, dispersion, solution or suspension which, in addition to organic solvent or preferably water, contains aminoplast foam pieces and
one or more resins (α) or polymers (β)
contains.

In an embodiment The present invention has used aminoplast foam piece formulation according to the invention a dynamic viscosity from above 50 to 200 dPa.s, determined at 23 ° C, preferably in the range of 60 to 180 dPa · s. Leave dynamic viscosities For example, determine with a Brookfield viscometer.

resins (α) or Polymers (β) can any organic resins or polymers will be and close respectively Copolymers with. Examples of preferred polymers (β) may be mentioned: Ester group-containing polymers, Amidgruppenhaitige polymers, Ethergruppenhaltige Polymers containing urethane-containing polymers, ester groups, ether groups, Amide groups or urethane groups be part of the main chain can or Can form side chains. Preferred organic polymers (β) are polyurethanes and polyacrylates, especially anionic polyurethanes.

In a preferred embodiment of the present invention, aminoplast foam formulation used according to the invention comprises at least one resin (α) selected from compounds of formula Ia and Ib, or at least one polymer (β) selected from preferably anionic polyurethanes, (co) polymers of (Meth) acrylic acid C ₁ -C ₁₀ -alkyl esters and copolymers of (meth) acrylic acid C ₁ -C ₁₀ -alkyl esters with at least one ethylenically unsaturated compound.

In one embodiment of the present invention, the aminoplast foam formulation used according to the invention contains two or more different polymers (β), for example two different polyurethanes or two different (co) polymers of (co) polymers of (meth) acrylic C ₁ -C ₁₀ -alkyl or a polyurethane and a (co) polymer of (meth) acrylic acid C ₁ -C ₁₀ -alkyl ester.

In an embodiment In the present invention, polymer (β) has a dynamic viscosity in the range from 1 to 300 mPa.s, preferably 5 to 100 mPa · s, measured at 25 ° C.

anionic Polyurethanes in the context of the present invention are, for example available by reaction of one or more aromatic or preferably aliphatic or cycloaliphatic diisocyanates with one or several polyester diols.

suitable Aromatic diisocyanates are, for example, 2,4-tolylene diisocyanate and 2,4'-diphenylmethane diisocyanate (2,4'-MDI). suitable Aliphatic diisocyanates are, for example, hexamethylene diisocyanate and dodecamethylene diisocyanate.

suitable cycloaliphatic diisocyanates are, for example, 2,4'-methylenebis (cyclohexyl) diisocyanate, 4-methylcyclohexane-1,3-diisocyanate (H-TDI), isophorone diisocyanate (IPDI) and bis-4,4'-cyclohexylmethylene diisocyanate.

suitable Polyester diols are available by polycondensation of one or more, preferably aliphatic or cycloaliphatic diols and one or more aromatic or preferably aliphatic dicarboxylic acids.

When Aliphatic diols are for example: ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,12-dodecanediol, Propylene glycol (1,2-propanediol), butylene glycol (1,2-butanediol), Neopentylglycol.

When Cycloaliphatic diols are, for example: cis-1,4-cyclohexanedimethanol, trans-1,4-cyclohexanedimethanol, cis-1,3-cyclohexanedimethanol, trans-1,3-cyclohexanedimethanol.

When aromatic dicarboxylic acids For example, terephthalic acid, phthalic acid and especially isophthalic acid into consideration.

When aliphatic dicarboxylic acids For example, succinic acid, glutaric and especially adipic acid into consideration.

All particularly suitable polyester diols are obtainable for example by Polycondensate of at least two different aliphatic or cycloaliphatic diols having at least one aromatic or preferably aliphatic dicarboxylic acid, for example from isophthalic acid, adipic acid and 1,4-cyclohexanedimethanol or adipic acid, Neopentyl glycol and 1,6-hexanediol.

In an embodiment of the present invention have particularly suitable polyester diols a acid number in the range of 0.1 to 200 mg KOH / g polyester diol, determined according to DIN 53402.

In another embodiment of the present invention have particularly suitable polyester diols a hydroxyl number in the range of 10 to 200 mg KOH / g polyester diol, determined according to DIN 53240.

(Co) polymers of (meth) acrylic acid C ₁ -C ₁₀ -alkyl esters and copolymers of (meth) acrylic acid C ₁ -C ₁₀ -alkyl esters with at least one ethylenically unsaturated compound are, for example, block copolymers and preferably random copolymers copolymerized as comonomers contain:
From 40 to 95% by weight, preferably from 50 to 90% by weight, of one or more (meth) acrylic acid C ₁ -C ₁₀ -alkyl esters, preferably (meth) acrylic acid C ₄ -C ₈ -alkyl esters, for example (meth) methyl acrylate, (meth) acrylic acid ethyl ester, (meth) acrylic acid n-propyl ester, (meth) acrylic acid iso-propyl ester, (meth) acrylic acid n-decyl ester, preferably (meth) acrylic acid n-butyl ester, (meth) acrylic acid iso butyl ester, (meth) acrylic acid n-hexyl ester, (meth) acrylic acid n-octyl ester, (meth) acrylic acid 2-ethylhexyl ester, more preferably (meth) acrylic acid n-butyl ester and (meth) acrylic acid 2-ethylhexyl ester,
0.1 to 10% by weight, preferably 1 to 5% by weight, of one or more ethylenically unsaturated carboxylic acids, for example methacrylic acid or, in particular, acrylic acid,
0 to 50 wt .-%, preferably 1 to 40 wt .-% of at least one further ethylenically unsaturated compound selected from
vinyl aromatic compounds such as α-methylstyrene, para-methylstyrene, para-n-butylstyrene and especially styrene,
(Meth) acrylonitrile,
N-methylol (meth) acrylamide,
Vinyl esters of aliphatic carboxylic acids, for example vinyl propionate and in particular vinyl acetate.

In a preferred embodiment of the present invention, organic polymer (β) is composed of
From 40 to 95% by weight, preferably from 50 to 90% by weight, of at least one (meth) acrylic acid C ₁ -C ₁₀ -alkyl ester, preferably ethyl acrylate, n-butyl acrylate and / or 2-ethylhexyl acrylate,
0.1 to 10 wt .-%, preferably 1 to 5 wt .-% of methacrylic acid or acrylic acid in particular, and
0 to 50 wt .-%, preferably 1 to 40 wt .-% of at least one ethylenically unsaturated compound, in particular styrene, vinyl acetate or (meth) acrylonitrile.

In one embodiment of the present invention, a polymer (β) is a self-crosslinking (co) polymer, for example prepared from one or more (meth) acrylic acid C ₁ -C ₁₀ -alkyl esters with acrylic acid and N-methylol (meth) acrylamide.

In a specific embodiment of the present invention, the aminoplast foam formulation used according to the invention comprises a mixture of at least two organic polymers (β) containing 40 to 99.9% by weight of a thermally crosslinkable copolymer of (meth) acrylic acid C ₁ -C ₁₀ - Alkyl esters with (meth) acrylic acid and optionally further ethylenically unsaturated compounds, and 0.1 to 60 wt .-% of anionic polyurethane, wherein in wt .-% in each case based on the solids content of the relevant mixture.

According to the invention for use upcoming aminoplast foam piece formulation may also contain excipients, for example biocides, surfactants, Activated carbon, colorants, fragrances, odor traps, defoamers or Thickener.

Suitable defoamers are, for example, silicone-containing defoamers, for example those of the formula HO- (CH ₂ ) ₃ - (CH ₃ ) Si [OSi (CH ₃ ) ₃ ] ₂ or HO- (CH ₂ ) ₃ - (CH ₃ ) Si [OSi ( CH ₃ ) ₃ ] [OSi (CH ₃ ) ₂ OSi (CH ₃ ) ₃ ], not alkoxylated or each alkoxylated with up to 20 equivalents of alkylene oxide and in particular ethylene oxide. Silicone-free antifoams are also suitable, for example polyalkoxylated alcohols, for example fatty alcohol alcohol xylates, preferably 2 to 50-fold ethoxylated preferably unbranched C ₁₀ -C ₂₀ -alkanols, unbranched C ₁₀ -C ₂₀ -alkanols and 2-ethylhexan-1-ol. Further suitable defoamers are fatty acid C ₈ -C ₂₀ -alkyl esters, preferably C ₁₀ -C ₂₀ -alkyl stearates, in which C ₈ -C ₂₀ -alkyl, preferably C ₁₀ -C ₂₀ -alkyl, may be unbranched or branched.

suitable Thickeners are, for example, natural or synthetic thickeners. Preference is given to the use of synthetic thickeners, for example of generally liquid solutions of synthetic polymers in, for example, white oil or as aqueous Solutions. Polymers suitable as thickeners contain acid groups which are completely or be neutralized to a certain percentage with ammonia. During the fixing process, ammonia is released, causing the pH is lowered and the actual fixation begins. That for the fixation necessary lowering of the pH value can alternatively by addition of nonvolatile acids such as. Citric acid, Succinic acid, glutaric or malic acid.

mit Molekulargewichten M_w im Bereich von 100.000 bis 200.000 g/mol, wobei R¹² gleich oder verschieden sein kann und für Wasserstoff oder Methyl steht.Preferred examples of synthetic thickeners are copolymers having from 85 to 95% by weight of acrylic acid, from 4 to 14% by weight of acrylamide and up to 1% by weight, preferably up to 0.1% by weight of the (meth) acrylamide derivative of Formula IV

having molecular weights M _w in the range of 100,000 to 200,000 g / mol, where R ^{12 may be the} same or different and is hydrogen or methyl.

Further used in accordance with the invention upcoming aminoplast foam piece formulation contained adjuvants are, for example, fastness improvers, plasticizers, handle improvers, Wetting agents, leveling agents, water softeners such as complexing agents, Urea, agents such as biocides or flame retardants, and dispersants.

Examples for special suitable plasticizers are ester compounds selected from the groups of aliphatic fully esterified with alkanols or aromatic di- or polycarboxylic acids and at least simply with alkanol esterified phosphoric acid.

Preferred examples of aromatic di- or polycarboxylic acids completely esterified with C ₁ -C ₁₀ -alkanol are phthalic acid, isophthalic acid and mellitic acid completely esterified with alkanol; exemplified by its: di-n-octyl phthalate, di-n-nonyl phthalate, di-n-decyl phthalate, di-n-octyl isophthalate, di-n-nonyl isophthalate, di-n-decyl isophthalate.

Preferred examples of aliphatic di- or polycarboxylic acids completely esterified with C ₁ -C ₁₀ -alkanol are, for example, dimethyl adipate, diethyl adipate, diisobutyl adipate, glutaric acid dimethyl ester, glutaric acid diethyl ester, di-n-butyl glutarate, diisobutyl glutarate, dimethyl succinate, diethyl succinate, succinic acid. n-butyl ester diisobutyl succinate and mixtures of the abovementioned compounds.

Preferred examples of phosphoric acid which is at least monoesterified with C ₁ -C ₁₀ -alkanol are C ₁ -C ₁₀ -alkyl-di-C ₆ -C ₁₄ -aryl phosphates, such as isodecyldiphenyl phosphate.

Further suitable examples of plasticizers are at least monohydric or aromatic di- or polyols, at least monosubstituted with C ₁ -C ₁₀ -alkylcarboxylic acid.

Preferred examples of aliphatic or aromatic di- or polyols at least monoesterified with C ₁ -C ₁₀ -alkylcarboxylic acid is 2,2,4-trimethylpentane-1,3-diol monoisobutyrate.

Further suitable plasticizers are polyesters obtainable by polycondensation of aliphatic dicarboxylic acid and aliphatic diol, for example adipic acid or succinic acid and 1,2-propanediol, preferably with an M _w of 200 g / mol, and polypropylene glycol alkylphenyl ethers, preferably with an M _w of 450 g / mol.

Other suitable plasticizers are etherified with two different alcohols polypropylene glycol koles having a molecular weight M _w in the range of 400 to 800 g / mol, preferably one of the alcohols may be an alkanol, in particular a C ₁ -C ₁₀ alkanol and the other alcohol is preferably an aromatic alcohol, for example o-cresol, m Cresol, p-cresol and in particular phenol can be.

In one embodiment of the present invention contains aminoplast foam piece formulation used according to the invention
in the range from 1 to 99% by weight, preferably from 10 to 80% by weight, particularly preferably from 30 to 70% by weight, of aminoplast foam pieces according to the invention,
in the range from 99 to 1% by weight, preferably 90 to 20% by weight, particularly preferably 70 to 30% by weight, of resin (α) or polymer (β),
optionally in the range from 0.1 to 20% by weight, preferably 0.5 to 10% by weight, particularly preferably 1 to 5% by weight of auxiliaries,
the rest is solvent and especially water.

If it is desired to use such aminoplast foam unit formulations which contain resin (α), it is possible to add one or more catalysts, selected from metal and ammonium salts and inorganic or organic acids, to the aminoplast foam unit formulation used according to the invention. Suitable metal salts are, for example, metal halides, metal sulfates, metal nitrates, metal tetrafluoroborates, metal phosphates or mixtures thereof. Examples are magnesium chloride, magnesium sulfate, zinc chloride, lithium chloride, lithium bromide, boron trifluoride, aluminum chloride, aluminum sulfate, alums such as KAl (SO ₄ ) ₂ .12H ₂ O, zinc nitrate, sodium tetrafluoroborate and mixtures of the metal salts mentioned above. Suitable ammonium salts are, for example, ammonium chloride and ammonium sulfate. Suitable acids are, for example, dilute aqueous inorganic acids such as hydrochloric acid or sulfuric acid and organic acids such as formic acid, acetic acid, p-toluenesulfonic acid, methanesulfonic acid, amidopropanesulfonic acid.

In an embodiment The present invention is dried following the treatment of flexible pad with aminoplast foam piece formulation; for example at temperatures in the range of 20 to 190 ° C, preferably from 50 to 170 ° C.

One Another object of the present invention are aminoplast foam unit formulations, preferably aqueous aminoplast, containing at least aminoplast foam pieces according to the invention and at least one resin (α) or polymer (β). Aminoplast foam piece formulations according to the invention are to carry out the production process according to the invention particularly suitable.

In an embodiment of the present invention has aminoplast foam piece formulation according to the invention a dynamic viscosity from above 50 to 200 dPa.s, determined at 23 ° C, preferably in the range of 60 to 180 dPa · s.

In one embodiment of the present invention, the aminoplast foam formulation of the invention comprises
in the range from 1 to 99% by weight, preferably from 10 to 80% by weight, particularly preferably from 30 to 70% by weight, of aminoplast foam pieces according to the invention,
in the range from 99 to 1% by weight, preferably 90 to 20% by weight, particularly preferably 70 to 30% by weight, of resin (α) or polymer (β),
optionally in the range from 0.1 to 20% by weight, preferably 0.5 to 10% by weight, particularly preferably 1 to 5% by weight of auxiliaries,
the rest is solvent and especially water.

One Another object of the present invention is a method for the preparation of aminoplast foam piece formulations according to the invention. Aminoplast foam piece formulations according to the invention For example, it is possible to prepare by mixing Aminoplastschaumstoffstücken invention, resin (α) or Polymer (β) and at least one solvent, preferably water, and optionally one or more excipients.

The Invention will be explained by working examples. Indicate% Weight percentages unless expressly stated otherwise.

Working examples "

I.1 Production of Aminoplast Foam (A.1)

In became an open vessel a spray-dried Melamine / formaldehyde precondensate (molar ratio 1: 3, molecular weight about 500 g / mol) to an aqueous solution containing 3% by weight of formic acid and 1.5 % of the sodium salt of a mixture of alkyl sulfonates with 12 bis 18 carbon atoms in the alkyl radical (emulsifier K 30 from Bayer AG), where the percentages based on the melamine / formaldehyde precondensate are given. The concentration of melamine / formaldehyde precondensate, based on the total mixture of melamine / formaldehyde precondensate and water was 74% by weight. The mixture thus obtained was stirred vigorously, then 20% by weight of n-pentane were added. It was so long (about 3 min long), until a homogeneous-looking dispersion was formed. This was on aufgerakelt a Teflonized glass fabric as a carrier material and in a drying cabinet in which an air temperature of 150 ° C prevailed, foamed and hardened. As a melt temperature in the foam, the boiling point of n-pentane which under these conditions is 37.0 ° C. After 7 to 8 minutes, the maximum height of rise of the foam was reached. The foam was still another 10 min at 150 ° C in a drying oven left; subsequently He was at 180 ° C for 30 min annealed. This gave (unmodified) Aminoplastschaumstoff (a.1).

The following properties were determined on unmodified foam (a.1):
99.6% open-cell according to DIN ISO 4590,
Compression hardness (40%) 1.3 kPa determined according to DIN 53577,
Density 7.6 kg / m ³ determined according to EN ISO 845,
mean pore diameter 210 μm, determined by analysis of microscopic images on sections,
BET surface area of 6.4 m ² / g, determined according to DIN 66131,
Sound absorption of 93%, determined according to DIN 52215,
Sound absorption of more than 0.9, determined according to DIN 52212.

I.2 Preparation of aminoplast foam pieces according to the invention

I.2.1 Production of Aminoplastschaumstoffstücken invention by To cut

A cuboid made of aminoplast foam (a.1) was ground manually with a weighing knife until irregular aminoplast foam pieces according to the invention of 2 to 5 mm diameter had been produced. 10 pieces of aminoplast foam according to the invention (random sample) had the following dimensions (in mm) according to manual measurement:

I.2.2 Production of Aminoplastschaumstoffstücken invention by Grind

One Amino resin foam cuboid (a.1) was produced with the aid of a beater-knife-operated Laboratory analytical mill Ground (type A10) and then over a vibrating screen the mesh size 250 microns sieved. This gave aminoplast foam pieces according to the invention a mean diameter of up to 250 μm. The sieve residue was discarded.

II. Purification according to the invention of surfaces

100 ml of aminoplast foam pieces (loose fill) from Example I.2 were moistened with water and filled into a 300 ml stirred vessel with propeller stirrer (each made of stainless steel) with caking (CaCO ₃ ). The propeller stirrer was then switched on and operated at 1000 rpm for 6 hours. The mixing vessel was then emptied. Neither the surface of the propeller stirrer nor the inner surface of the vessel were scratched or polished. The caking was without residue even from welds and narrow angles and cracks removed.

III. Production of composites according to the invention

III.1 Preparation of Aminoplast foam piece formulations according to the invention

III.1.1 Production of Aminoplast foam piece formulation according to the invention AF 1.1

In a 150 ml polyethylene cup were mixed together:
0.6 g of aminoplast foam pieces from Example I.2.2 according to the invention
5 g of an aqueous dispersion (pH 3 to 4, not neutralized, solids content 50%) of a copolymer (β.1) of 75 wt .-% acrylic acid and 25 wt .-% maleic acid, crosslinked with 30 mol% triethanolamine. It was mixed until a spreadable, lump-free paste was present, and efrhielt Aminoplastschaumstoffstückformulierung invention AF-1.1.

III.1.2 Production of Aminoplast foam piece formulation according to the invention AF-1.2

In a 150 ml polyethylene cup were mixed together:
1 g of aminoplast foam pieces according to the invention from Example I.2.2
5 g of an aqueous dispersion (pH 3 to 4, not neutralized, solids content 50%) of a copolymer (β.1) of 75 wt .-% acrylic acid and 25 wt .-% maleic acid, crosslinked with 30 mol% triethanolamine. The mixture was mixed until a spreadable, lump-free paste was present, and obtained aminoplast foam piece formulation AF-1.2 according to the invention.

III.1.3 Production of Aminoplast foam piece formulation according to the invention AF 1.3

In a 150 ml polyethylene cup were mixed together:
1 g of aminoplast foam pieces according to the invention from Example I.2.2 and 1 g of water. A dry powder was obtained. Then you gave more
0.5 g of water and 5 g of an aqueous dispersion (pH 3 to 4, not neutralized, solids content 50%) of a copolymer (β.1) of 75 wt .-% of acrylic acid and 25 wt .-% maleic acid, crosslinked with 30 mol% triethanolamine. The mixture was mixed until a spreadable, lump-free paste was present, and the aminoplast foam piece formulation AF-1.3 according to the invention was obtained.

III.1.4 Production of Aminoplast foam piece formulation according to the invention AF 1.4

In a 150 ml polyethylene cup were mixed together:
1 g of aminoplast foam pieces according to the invention from Example I.2.2
5 g of an aqueous dispersion (pH 3 to 4, not neutralized, solids content 50%) of a copolymer (β.1) of 75 wt .-% acrylic acid and 25 wt .-% maleic acid, crosslinked with 30 mol% triethanolamine and neutralized with 25 wt .-% aqueous ammonia solution to a pH of 7. The mixture was mixed until a spreadable, lump-free paste was present, and obtained aminoplast foam piece formulation AF-1.4 according to the invention.

III.1.5 Production of Aminoplast foam piece formulation according to the invention AF-1.5

Polymer (β.2): polyurethane, made from
53.7 wt .-% polyester diol having a hydroxyl number of 55 mg KOH / g polyester diol and an acid number of 1.0 mg KOH / G polyester diol, which is prepared from adipic acid, 2,2-dimethylpropane-1,3-diol and 1,6-hexanediol (molar ratio 2: 0.4: 0.7), and
17.5 wt .-% isophorone diisocyanate and
14.8% by weight of 1,1'-methylenebis- (4-isocyanatocyclohexane)

In a 150 ml polyethylene cup were mixed together:
1 g of aminoplast foam pieces according to the invention from Example I.2.2
5 g of an aqueous dispersion (solids content 50%) of copolymer (β.2). The mixture was mixed until a spreadable, lump-free paste was present, and obtained according to the invention aminoplast foam piece formulation AF-1.5.

III.1.6 Production of Aminoplast foam piece formulation according to the invention AF-1.6

polymer (β.3): mixture of two hydrophilic polyurethanes prepared according to EP-A 1 426 391, Example 3.

In a 150 ml polyethylene cup were mixed together:
1 g of aminoplast foam pieces according to the invention from Example I.2.2
6.25 g of an aqueous dispersion (solids content 40%) of copolymer (β.3). The mixture was mixed until a spreadable, lump-free paste was present, and obtained aminoplast foam piece formulation AF-1.6 according to the invention.

III.1.7 Production of Aminoplast foam piece formulation according to the invention AF 1.7

Polymer (β.4): poly-n-butyl acrylate with a molecular weight M _w of 1,500,000 g / mol.

In a 150 ml polyethylene cup were mixed together:
1 g of aminoplast foam pieces according to the invention from Example I.2.2
6.25 g of an aqueous dispersion (solids content 40%) of copolymer (β.4). The mixture was mixed until a spreadable, lump-free paste was present, and obtained according to the invention aminoplast foam piece formulation AF-1.7.

III.2 Treatment According to the Invention of textile substrate

The flexible base used was a mixed fabric polyester / cotton 35/65, ultramarine blue, color RAL: No. 5002, basis weight: 240 m ² .

General rule:

With a spatula was an approximately 1 mm thick wet layer of Aminoplastschaumstoffstückformulierung invention according to the table 2 applied to the textile backing described above. It was dried two hours in a convection oven at the in Table 2 specified temperature. Compounds according to the invention were obtained according to the table Second

III.3 Cleaning surfaces with Compounds according to the invention

On a white one Desk top (plastic-coated wood) were strokes with a Parker ballpoint pen (blue) and a felt-tip pen (Staedler permanent Lumocolor, black, waterproof, M) painted.

n.b.:

nicht bestimmt

Optionally, composite according to the invention according to Table 1 was moistened with water and the desk top (surface) was cleaned by repeated gentle wiping with the respective dry or moistened composite according to the invention. The results are shown in Table 2. Table 1: Compounds according to the invention, production and cleaning properties

nb:

not determined

Claims (18)

A process for cleaning surfaces using aminoplast foam pieces made from (a) open cell aminoplast foams having a density in the range of 5 to 500 kg / m ³ and an average pore diameter in the range of 1 μm to 1 mm or (b) open celled aminoplast foams having a Density in the range of 5 to 500 kg / m ³ and an average pore diameter in the range of 1 micron to 1 mm, which has been treated (b1) with aqueous formulation of at least one compound (b-1) having at least one semiaminal or aminal group per molecule or at least one copolymer which contains at least one comonomer containing OH groups or containing β-dicarbonyl groups or containing epoxide groups, or (b2) having at least one solid at room temperature containing carboxyl groups and / or carboxylic acid ester groups containing polymer (b-2) with a Molecular weight M _w in the range of 1,000 to 1,000,000 g / mol, wherein the Ami used noplastschaumstoffstücke have a mean diameter (number average) in the range of 0.1 mm to 50 mm. Method according to claim 1, characterized in that that at least one compound (b-1) is not in production of open-cell foam (b) has been used. Method according to claim 1 or 2, characterized that one receives compound (b-1) by condensation of at least one nitrogen-containing compound (B1) and at least one carbonyl compound (B2) and optionally further compounds (B3) and optionally further reactions after the condensation. Method according to one of claims 1 to 3, characterized that surfaces to be cleaned are surfaces, the hard to reach are. Method according to one of claims 1 to 4, characterized that to be cleaned surfaces are selected from interior surfaces of gears, reaction vessels, kneading tools, agitators and ball bearings. Method according to one of claims 1 to 5, characterized by removing impurities by cleaning, containing at least one substance selected from fats, oils, waxes, Lime soap, biofilms, polymers, metal oxides, metal hydroxides, Remains of lubricants and broken emulsions. Method according to one of claims 1 to 6, characterized that it is carried out in the presence of an additive selected from organic solvents, aqueous solutions of at least one surfactant Substance, salt solutions and aqueous Acid or Lye. Method according to one of claims 1 to 7, characterized in that in (b) at least one compound (b-1) is selected from compounds of the general formula Ia to Ib

the variables are defined as follows: R ¹ , R ^{2 are} identical or different and selected from hydrogen, C ₁ -C ₁₂ -alkyl, branched or unbranched, (-CH ₂ -CH ₂ -O) _m -R ⁵ , (-CHCH ₃ -CH ₂ -O) _m -R ⁵ , (-CH ₂ -CHCH ₃ -O) _m -R ⁵ , (-CH ₂ -CH ₂ -CH ₂ -O) _m -R ⁵ , (- CH ₂ -CH ₂ -CH ₂ -CH ₂ -O) _m -R ⁵ , x is the same or different and an integer selected from zero and one, where in formula Ia at least one x is equal to 1, m is an integer in the range from 1 to 20, R ³ , R ^{4 are} identical or different and selected from hydrogen, C ₁ -C ₁₂ -alkyl, branched or unbranched, or together C ₂ -C ₄ -alkylene R ^{5 is} identical or different and selected from C C ₁ -C ₄ alkyl and hydrogen. Method according to one of claims 1 to 8, characterized at least one carboxylate group-containing and / or solid at room temperature Carboxylic ester group-containing polymer (b-2) is a copolymer obtainable by copolymerization from (C) ethylene, (d-1) at least one ethylenically unsaturated carboxylic acid or at least one ethylenically unsaturated carboxylic acid ester, (E) optionally further comonomers. Aminoplast foam pieces made from (a) open-celled aminoplast foams having a density in the range of 5 to 500 kg / m ³ and an average pore diameter in the range of 1 μm to 1 mm, or (b) open-celled aminoplast foams having a density in the range of 5 to 500 kg / m ³ and an average pore diameter in the range from 1 μm to 1 mm, which has been treated (b1) with aqueous formulation of at least one compound (b-1) having at least one semiaminal or aminal group per molecule or at least one copolymer, containing at least one OH group-containing or β-dicarbonyl-containing or epoxy-containing comonomer in copolymerized form, or (b2) having at least one solid at room temperature carboxyl-containing and / or carboxylic acid ester group-containing polymer (b-2) having a molecular weight M _w in the range from 1,000 to 1,000,000 g / mol, with the aminoplast foam pieces having an average diameter in the range of 0.1 to 5 mm (weight average). Use of Aminoplastschaumstoffstücken after Claim 10 for cleaning surfaces. Process for cleaning surfaces under Use of Aminoplastschaumstoffstücken according to claim 10, characterized characterized in that the surfaces are provided with a composite comprising a flexible pad and aminoplast foam pieces fixed thereon treated. Composite comprising a flexible pad and thereon fixed Aminoplastschaumstoffstücke according to claim 10. Composite according to claim 13, characterized in that wherein the flexible pad is selected from fibrous substrates. Composite according to claim 13 or 14, characterized that aminoplast foam pieces in a 0.1 to 10 mm thick layer on the flexible backing are fixed. Process for the preparation of compounds according to a the claims 13 to 15, characterized in that the flexible base with an aminoplast foam piece formulation containing aminoplast, treated and then dried. Method according to claim 16, characterized in that that the aminoplast foam piece formulation additionally at least one resin (α) or at least one polymer (β) contains. Aminoplast foam piece formulation containing aminoplast according to claim 10 and at least one resin (α) or at least one polymer (Β).