DE102004057588A1 - Producing modified open-cell foams, e.g. useful as cleaning materials, comprises treatment with an aqueous formulation of an aminal or hemiaminal or a copolymer of a hydroxy-, beta-dicarbonyl- or epoxy-functional monomer - Google Patents

Abstract

Producing modified open-cell foams comprises contacting a starting open-cell foam with an aqueous formulation of an aminal or hemiaminal or a copolymer of a hydroxy-, beta -dicarbonyl- or epoxy-functional monomer. The starting foam has a density of 5-500 kg/m 3> and an average pore diameter of 1 mu m to 1 mm. Independent claims are also included for: (1) modified open-cell foams produced as above; (2) cleaning materials, filters, air humidifiers, cosmetic articles, water distributors, packaging products, soundproofing products and buildings insulation made from or comprising the modified open-cell foams; (3) composite materials comprising the modified open-cell foams on curved or flat, rigid or flexible substrates.

Description

• (a) offenzellige Schaumstoffe mit einer Dichte im Bereich von 5 bis 500 kg/m³ und einem mittleren Porendurchmesser im Bereich von 1 μm bis 1 mm
• (b) mit wässriger Formulierung von mindestens einer Verbindung 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.

The present invention relates to a process for the preparation of modified open-cell foams, characterized in that

• (A) open-cell 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
• (b) with aqueous formulation of at least one compound having at least one semiaminal or aminal group per molecule or at least one copolymer which contains at least one OH-group-containing or β-dicarbonyl-containing or epoxide group-containing comonomer in copolymerized form.

Farther The present invention relates to the use of modified according to the invention open-cell foams for the production of cleaning materials, Filters, humidifiers, water distributors, packaging elements, Sound insulation elements such as anti-vibration elements or building insulation.

foams, especially so-called open-cell foams, find applications in numerous applications. In particular open-celled foams made of synthetic materials have proven to be versatile. Examples include seat cushions, filter materials, air conditioners and automotive parts, cleaning materials continue.

at Cleaning materials made from foams, it is observed that after a relatively short period of use, for example after about 10 minutes, as far as destroyed, that no cleaning effect more can be achieved. Appropriate cleaning materials will be Furthermore fast unsightly. Manufacturer of cleaning materials such as cleaning sponges Therefore recommend cleaning materials according to appropriate and in Generally quite short period of use, for example 10 minutes, to dispose of what the consumer is detrimental. In addition, be sensitive surfaces in many cases damaged by scratches, abrasion or blindness.

In US 6,608,118 It is proposed to compress foams of melamine under the action of heat, for example for 4 minutes at 270 ° C to compress. This gives foams with better mechanical properties, which can be easily cut, for example.

In EP 0 633 283 and DE 100 11 388 It is recommended to reinforce melamine resin foams by, for example, impregnating them with a silicone emulsion. However, silicone-impregnated foams are not useful as cleaning materials, leaving streaks in use. In DE 100 11 388 it is further recommended to spray melamine resin foams with monomeric fluoroalkyl esters to make them oil repellent.

In DE 102 20 896 It is proposed to provide thermoset foam blanks with chemically inert binders containing an adhesive component. Out DE 102 09 601 It is known that by adding acid to thermosetting foam blanks such as melamine resin or phenolic resin or urea or bases can cause hydrolysis, in particular an acid-catalyzed hydrolysis of the resin.

The technical characteristics known from the prior art foams or foams can be related to cleaning effect, stability and water or oil absorption but still improving. Furthermore, the from the state of the Technik known foams as in many cases too little flexible.

It Therefore, the object was to provide foams, which the disadvantages of the materials known from the prior art avoid. It was still the task of a process for the preparation to provide new foams. It was also the task Uses for To provide foams, and the task was to process to provide for the use of foams.

Accordingly, became Found the initially defined method.

• (a) offenzellige Schaumstoffe mit einer Dichte im Bereich von 5 bis 500 kg/m³ und einem mittleren Porendurchmesser im Bereich von 1 μm bis 1 mm
• (b) mit wässriger Formulierung von mindestens einer Verbindung von mindestens einer Verbindung mit mindestens einer Halbaminal- oder Aminalgruppe pro Molekül kontaktiert.

The method defined at the outset is characterized by processes for the production of modified open-cell foams, characterized in that

• (A) open-cell 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
• (b) contacting with aqueous formulation of at least one compound of at least one compound having at least one semiaminal or aminal group per molecule.

in the In the context of the present invention, aqueous formulation for solutions, Emulsions or dispersions are available.

there at least one compound in step (b) is preferably to a compound that is not in the production of unmodified Foam (a) was used.

In an embodiment The present invention is open-celled according to the invention modified foams to those based on synthetic organic foam, for example based on organic unmodified foams such as foams based on of polyurethane foams or aminoplast foams, for example from urea-formaldehyde resins, furthermore foams based on phenol-formaldehyde resins and in particular Foams based on polyurethanes or aminoplast-formaldehyde resins, in particular melamine-formaldehyde resins, with foams on Basis of polyurethanes in the context of the present invention also as Polyurethane foams and foams based on melamine-formaldehyde resins also be referred to as melamine foams.

among them is to be understood that according to the invention foams made of open-cell Foams that produces synthetic organic materials include, preferably polyurethane foams or aminoplast foams and in particular melamine foams.

The to exercise the method according to the invention used unmodified open-celled foams (a) in the context of the present invention quite generally as unmodified foams (a). The exercise the method according to the invention used unmodified open-celled foams (a) in the following described.

to exercise the production process according to the invention one starts from open-celled foams (a), in particular from Foams in which at least 50% of all lamellae are open, preferably 60 to 100% and more preferably 65 to 99.9% according to DIN ISO 4590.

When Starting material used foams (a) are preferably hard foams, that is within the meaning of the present invention Foams which, with a compression of 40%, have a compression hardness of 1 kPa or more, determined according to DIN 53577.

Foams used as starting material (a) 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 .

When Starting material used open-celled foams (a) may have a average 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, open-cell foams (a) used as starting material may have a maximum of 20, preferably a maximum of 15 and more 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, open-cell foams (a) used as starting material 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 according to DIN 66131.

In an embodiment of the present invention have used as starting material foams (a) a sound absorption coefficient of more than 50%, measured according to 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 used as starting material open-celled foams (a) a sound absorption coefficient of more than 0.5 measured to DIN 52212 at a frequency of 2000 Hz and a layer thickness of the relevant foam (a) of 40 mm.

When Starting material used open-celled foams (a) can be any have geometric shapes, such as plates, balls, cylinders, Powder, cube, Flakes, cuboids, calipers, Rods or round, rectangular or square columns. The size dimensions used as starting material foams (a) are not critical, if they can be mechanically compressed mechanically. Prefers become plates, cylinders, cubes, Cuboid or rectangular columns, in usual Devices can be mechanically compressed.

In an embodiment The present invention is open-celled foams (A) of synthetic organic material, preferably of polyurethane foams or of melamine foams.

• i) einem oder mehreren Polyisocyanaten, d.h. Verbindungen mit zwei oder mehr Isocyanatgruppen,
• ii) mit einer oder mehreren Verbindungen mit mindestens zwei Gruppen, die gegenüber Isocyanat reaktiv sind, in Gegenwart von
• iii) einem oder mehreren Treibmitteln,
• iv) einem oder mehreren Startern
• v) und einem oder mehreren Katalysatoren sowie
• vi) sogenannten Zellöffnern.

Polyurethane foams which are particularly suitable as starting material for carrying out the process according to the invention are known as such. Their preparation succeeds, for example, by implementing

• i) one or more polyisocyanates, ie compounds having two or more isocyanate groups,
• ii) with one or more compounds having at least two isocyanate-reactive groups in the presence of
• iii) one or more propellants,
• iv) one or more starters
• v) and one or more catalysts as well
• vi) so-called cell openers.

there can Starter iv) and propellant iii) be identical.

Examples for suitable Polyisocyanates i) are known per se aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyvalent compounds with two or more isocyanate groups.

Specific examples are:
C ₄ -C ₁₂ -alkylene diisocyanates, preferably hexamethylene-1,6-diisocyanate;
Cycloaliphatic diisocyanates, such as cyclohexane-1,3- and cyclohexane-1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI),
preferably aromatic di- and polyisocyanates, such as 2,4- and 2,6-toluene diisocyanate and corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and corresponding isomer mixtures, mixtures of 4 , 4'- and 2,4'-diphenylmethane diisocyanates, polyphenyl polymethylene polyisocyanates, mixtures of 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates (Roh -MDI) and mixtures of crude MDI with toluene diisocyanates. Polyisocyanates can be used individually or in the form of mixtures.

When examples for ii) compounds having at least two groups opposite to isocyanate are reactive, are di- and polyols, especially polyether polyols (Polyalkylene glycols) prepared by methods known per se be, for example by alkali metal hydroxide-catalyzed polymerization of one or more alkylene oxides such as ethylene oxide, Propylene oxide or butylene oxide are available.

All particularly preferred compounds ii) are ethylene glycol, propylene glycol, Butylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, Dipropylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, Pentaethylene glycol, hexaethylene glycol.

When Propellants iii) are suitable: water, inert gases, in particular Carbon dioxide, and so-called physical blowing agents. In physical Propellants are compared to the insert components inert compounds, which are usually liquid at room temperature and evaporate under the conditions of the urethane reaction. Preferably the boiling point of these compounds is below 110 ° C, especially below 80 ° C. To The physical blowing agents also include inert gases, the be introduced into or dissolved in the insert components i) and ii), for example, carbon dioxide, nitrogen or noble gases.

Suitable compounds which are liquid at room temperature are for the most part selected from the group containing alkanes and / or cycloalkanes having 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 create open cells is out EP-A 0 351 614 known.

When Starters iv) are suitable, for example: water, organic dicarboxylic acids, aliphatic and aromatic, optionally N-mono-, N, N- and N, N'-dialkyl-substituted diamines having 1 to 4 carbon atoms in the alkyl radical, e.g. if necessary, N-mono- and N, N-dialkyl substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexamethylenediamine, aniline, phenylenediamines, 2,3-, 2,4-, 3,4- and 2,6-toluenediamine and 4,4'-, 2,4'- and 2,2'-diamino-diphenylmethane.

When Catalysts v) are the catalysts known in polyurethane chemistry suitable, for example tertiary Amines, e.g. Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2,2,2) octane and the like and in particular organic metal compounds such as titanic acid esters, Iron compounds such as e.g. Iron (III) acetylacetonate, tin compounds, e.g. Tin diacetate, tin dioctoate, tin dilaurate or the dialkyl derivatives of tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin diacetate and dibutyltin dilaurate.

When cell opener vi) are exemplary polar polyether polyols (polyalkylene glycols) to name, these are those with a high content of ethylene oxide in the chain, preferably at least 50% by weight. These work by segregation and influence on the surface tension during the foaming a cell-opening.

i) to vi) are in the usual proportions in polyurethane chemistry used.

• vii) einem Melamin-Formaldehyd-Vorkondensat, das neben Formaldehyd weitere Carbonylverbindungen wie beispielsweise Aldehyde einkondensiert enthalten können,
• viii) ein oder mehrere Treibmittel,
• ix) einen oder mehrere Emulgatoren,
• x) einen oder mehrere Härter.

Melamine foams which are particularly suitable as starting material for carrying out the preparation process according to the invention are known as such. Their preparation succeeds, for example, by foaming of

• vii) a melamine-formaldehyde precondensate which, in addition to formaldehyde, may contain further carbonyl compounds such as, for example, aldehydes,
• viii) one or more propellants,
• ix) one or more emulsifiers,
• x) one or more hardeners.

Melamine-formaldehyde precondensates vii) 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, Ac rolein, furfurol, Glyoxal, phthalaldehyde and Terephthaldialdehyd condensed contain.

When Propellant viii) you can use the same compounds as under iii).

As emulsifiers ix) 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 poly-ethoxylated 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.

Suitable hardeners x) are, in particular, acidic compounds, for example inorganic compounds Brønsted acids, for example sulfuric acid or phosphoric acid, organic Brønsted acids such as acetic acid or formic acid, Lewis acids and so-called latent acids.

Examples for suitable Melamine foams can be found in EP-A 0 017 672.

Of course, as starting material used foams (a) may contain additives and additives that are common in foam chemistry, such as antioxidants, flame retardants, fillers, colorants such as pigments or dyes and biocides, for example

Farther you go to exercise of the present invention of at least one compound having at least a half-amine or aminal group per molecule or from at least one Copolymer containing at least one OH-containing or β-dicarbonyl-containing or epoxy group-containing comonomer or n-butyl acrylate in copolymerized form.

in the The following are compounds used with at least one hemiacetal or aminal group per molecule and copolymers containing at least one OH group-containing or β-dicarbonyl group-containing or Epoxy group-containing comonomer or n-butyl acrylate copolymerized also briefly referred to as compound (b) or as (b). Compound (b) is obtainable, for example, by condensation of at least one nitrogen-containing compound (B1) and at least a carbonyl compound (B2) and optionally further compounds (B3) and optionally further reactions after the condensation.

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-phthaldialdehyde, 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 In the present invention, compound (b) 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-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,
(-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) 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-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,
(-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 the same 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, isobutyl, 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), in particular of the general formula Ia and Ib, are known per se. Compounds (b), 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) 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-do decyl; 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.

einpolymerisiert 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

in copolymerized form, 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 use such copolymers as (b), which is a compound of the general Contain formula III in copolymerized form with X = OH, such are Copolymers which does not copolymerize ethylene as a comonomer are preferred contain.

• – 0 bis 15 Gew.-%, bevorzugt 0,5 bis 10 Gew.-% mindestens ein Comonomer der allgemeinen Formel II oder III,
• – 0 bis 80 Gew.-% n-Butylacrylat,
• – 0 bis 80 Gew.-% mindestens einen weiteren (Meth)acrylsäure-C₁-C₁₀-Alkylester,
• – 0 bis 20 Gew.-%, bevorzugt 0,1 bis 15 Gew.-% ein oder mehrere weitere Comonomere wie beispielsweise (Meth)acrylsäure, vinylaromatischen Verbindungen wie beispielsweise Styrol, (Meth)acrylnitril und (Meth)acrylamid.

In one embodiment of the present invention, those copolymers are chosen as (b) which contain in copolymerized form:

• - 0 to 15 wt .-%, preferably 0.5 to 10 wt .-% of at least one comonomer of the general formula II or III,
• From 0 to 80% by weight of n-butyl acrylate,
• From 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 contain used in step (b) aqueous Formulation in the range of 1 to 60 wt .-%, preferably 10 to 40 % By weight of compound (b).

Around contacting unmodified foams (a) with compound (b), Different techniques are conceivable.

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

In another embodiment The present invention is for the practice of the method according to the invention so before that one is watery Formulation of compound (b) on unmodified foam (a) scrape. After soaking or squeezing or calendering or spraying may result in even distribution the formulation and setting the desired concentration between squeezed at least two, for example, rotating rollers become.

In an embodiment The present invention may be followed by contacting unmodified foam (a) and aqueous formulation of compound (b) 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 the production process according to the invention one contacts unmodified foam (a) and aqueous formulation of compound (b) 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 the production process according to the invention one contacts unmodified foam (a) and aqueous formulation of compound (b) first at temperatures in the range of 0 ° C up to 50 ° C and changes then the temperature, for example, one heats up to temperatures in the Range of 60 ° C up to 250 ° C, preferably from 65 ° C up to 180 ° C.

In another embodiment the production process according to the invention one contacts unmodified foam (a) and aqueous formulation of compound (b) first at temperatures in the range of 0 ° C up to 120 ° C and changes Thereafter, the temperature, for example, is heated to temperatures in the 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) 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 is carried out to carry out the inventive method while contacting unmodified foam (a) with aqueous Formulation of compound (b) at atmospheric pressure. In another embodiment The present invention is carried out to carry out the inventive method under increased Pressure, for example, when pressing in the range of 1.1 bar to 10 bar. In another embodiment The present invention is carried out to carry out the inventive method under reduced pressure, for example at pressures in the range of 0.1 mbar up to 900 mbar, preferably up to 100 mbar.

In an embodiment In the present invention, unmodified foam is contacted (a) with aqueous Formulation of compound (b) such that compound (b) as possible even in all Dimensions over unmodified foam (a) is distributed. Suitable methods are methods with a high order efficiency. exemplary be 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 In the present invention, unmodified foam is contacted (a) with aqueous Formulation of compound (b) such that an uneven distribution of aqueous Formulation of compound (b) on unmodified foam (a) causes. So you can in one embodiment of the present Invention, for example, unmodified foam (a) with aqueous Spray formulation of compound (b) non-uniformly and then act to let. In another embodiment The present invention can be unmodified foam (a) incomplete with watery Soak the formulation of compound (b). In another embodiment The present invention can be a part of unmodified Foam (a) once and another part of unmodified Foam (a) at least twice with aqueous formulation of compound (b) contact. In another embodiment, one soaks unmodified foam (a) with aqueous formulation of compound (b) completely and rinses clean the top layer with, for example, water again. Then you leave act. This coats unmodified foam (a) at the core; the outer surface remains uncoated.

If unmodified foam (a) with aqueous formulation of compound (b) contacted so as to give an uneven distribution of aqueous Formulation of compound (b) on unmodified foam (a) has been achieved, for example, by reaching each other let it act on a period of 2 minutes or more that is not just the outermost layer unmodified foam (a) with aqueous formulation of compound (b) is contacted.

If unmodified foam (a) with aqueous formulation of compound (b) contacted so as to have an uneven distribution of aqueous Formulation of compound (b) on unmodified foam (a) has been modified, it can according to the invention modified foam on his Cross section have uneven mechanical properties. For example, it is possible that according to the invention to the Bodies in which he shares with larger proportions at watery Formulation of compound (b) has been contacted, softer is considered to be in the places where he is using less watery Formulation of compound (b) has been contacted.

In an embodiment The present invention can be in some cases not wanted uneven distribution the aqueous Formulation of compound (b) by calendering on perforated Balance rollers or perforated plates. The formation of an uneven distribution of watery Formulation of compound (b) can thereby be 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 The present invention is carried out after contacting Squeezing between two opposite directions rotating rollers on a defined fleet intake, for example in the range of 20 to 800 wt .-%, based on the weight of the unmodified Foam (a). The concentration of compound (b) 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 for exposure in the context of the present invention.

In an embodiment The present invention can be accomplished by thermal drying by heating to temperatures in the range of 20 ° C to 150 ° C, for example via a Period from 10 seconds to 20 hours.

In addition to the aqueous formulation of compound (b), according to the invention unmodified foam (a) can be contacted with at least one catalyst (c). 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) suitable ammonium salts are ammonium salts from Group ammonium chloride, ammonium nitrate, ammonium sulphate, ammonium oxalate, Diammonium phosphate or mixtures of the ammonium salts described above.

When Catalyst (c) 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 Insert catalyst (c).

Very particularly preferred as catalyst (c) 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 their hydrates, and most preferably MgCl ₂ , especially in the form of its hexahydrate.

Based compound (b) is preferably set one-third to one-twentieth the weight of catalyst (c), determined respectively without optional available water of hydration.

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

In an embodiment In the present invention, unmodified foam is contacted (a) with aqueous solution of compound (b) and optionally catalyst (c) in a pH in the range of 3.0 to 7.5, wherein the desired pH optionally by adding acid, Lye or a buffer can be adjusted. The usage a buffer is preferred.

In one embodiment of the present invention, at least one unmodified foam (a) can be contacted not only with aqueous formulation of compound (b) and optionally catalyst (c), but also with at least one additive (d) 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), further 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.

This can be done, for example, by using at least one unmodified foam (a) in different operations or preferably simultaneously with an aqueous formulation of Ver Bond (b) and with at least one additive (d) contacted.

In an embodiment The present invention can be applied to aqueous formulation of compound (b) add one or more additives (d), for example in proportions of from 0 to a total of 50% by weight, based on (b) 0.001 to 30 wt .-%, particularly preferably 0.01 to 25 wt .-%, completely particularly preferably 0.1 to 20 wt .-%.

to execution the method according to the invention one can continue after exposure to aqueous Formulation of compound (b) and optionally catalyst (c) and optionally at least one additive (d) on unmodified Foam (a) one or more times mechanically compress. The Mechanical compression can be carried out batchwise or preferably perform continuously, discontinuously, for example by pressing or plates, continuously for example by rollers or calenders. When to calender hopes so you can perform one or more calendering passes, such as 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) and optionally catalyst (c) and optionally at least one additive (d) 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) and optionally catalyst (c) and optionally at least one additive (d) dries first, refrained from moistening and then mechanically compressed, for example calendered.

In an embodiment of the present invention are relieved by mechanical compression contacting and allowing aqueous formulation of compound (b) and optionally catalyst (c) and optionally at least an aggregate (d) the hard unmodified foams per se (a) soft and flexible.

In an embodiment The present invention can be used after contacting and soaking of watery Formulation of compound (b) and optionally catalyst (c) and optionally at least one additive (d) on unmodified Thermally fix foam (a), before or after mechanical Compress or between two mechanical compression steps. For example, at temperatures of 120 ° C to 250 ° C over a period of 5 seconds thermally fix for up to 120 minutes. Suitable apparatuses are for example microwave ovens, Plate presses, 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.

In an embodiment The present invention can be used after contacting and soaking of watery Formulation of compound (b) and optionally catalyst (c) and optionally at least one additive (d) on unmodified Foam (a) thermally fix, after or preferably before mechanical compression or between two mechanical ones 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, the mechanical compression and the thermal fixing are combined, for example by passing foam one or more times over hot rolls or calenders after being soaked in and optionally drying, or pressing it one or more times between hot plates. Of course, you can calender several times and compress one or more times with cold rolls and one or more times with hot rolls. Under hot should in connection with the present Temperatures in the range of 100 to 250 ° C, preferably 120 to 200 ° C understood.

One Another object of the present invention are modified Foams, available according to the method of the invention, which are also referred to below as foams according to the invention.

Modified foams according to the invention have a density in the range of 5 to 1000 kg / m ³ , preferably 6 to 500 kg / m ³ and particularly preferably in the range of 7 to 300 kg / m ³ . The density of the foam according to the invention is influenced on the one hand by the degree of coating with compound (b) and optionally catalyst (c) and optionally at least one additive (d) 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.

Modified according to the invention Foams preferably contain in the range of 0.1 to 80 wt .-%, preferably 2 to 60% by weight, particularly preferably 5 to 50% by weight, based on the weight of the corresponding unmodified foam (a), to solid from (b).

Modified according to the invention Foams or produced by the process according to the invention Foams are characterized by overall advantageous properties from the disadvantages described above such as short service life, damage sensitive surfaces and avoid unsightly appearance. They show improved Cleaning performance or cleaning effect, good hydrolysis resistance, improved acid resistance, good sound absorption and are - for example when used to make cleaning materials - especially durable. They pollute very slowly. Possibly soiled foams according to the invention can be easily destroyed clean. Furthermore, inventively modified foams are characterized or modified foams according to the invention through high resistance against oxidizing agents, in particular gaseous oxidizing agents such as For example, ozone and oxygen. Furthermore, modified according to the invention Foams are very flexible and can be easily put in mechanically desired Bring forms. Furthermore have modified according to the invention Foams have a pleasant cloth-like feel and are special gentle on the cleaning of sensitive surfaces.

Farther are modified according to the invention Foams for Uses in the cosmetics sector suitable, for example as towels or Make-up removal pads or for Hygiene products.

Especially advantageous are the inventively modified foams in all applications where flexibility of the material is required is.

Another object of the present invention is the use of modified open-celled foams according to the invention or modified according to the invention open-celled foams for the production of cleaning materials such as plaster sponges, brushes, wipes, mops, cleaning wipes, cleaning granules or oil-absorbing materials, filters such as air filters, pond filters, aquarium filters , Water filters, or as a matrix for ceramic filters,
Humidifiers, water distributors,
Packaging elements, in particular for shock-sensitive or water-sensitive goods, vibration-inhibiting elements, sound insulation elements, building insulation, in particular roof insulation and wall insulation.

A further subject of the present invention is a process for the production of cleaning materials using modified foams according to the invention or foams modified according to the invention. Another object of the present invention is a process for the production of filters using modified foams according to the invention or modified foams according to the invention. A further subject of the present invention is a process for the production of humidifiers using modified foams according to the invention or foams modified according to the invention. Another object of the present invention is a process for the preparation of cosmetic articles using modified foams according to the invention or modified foams according to the invention. A further subject of the present invention is a process for the production of water distributors using modified foams according to the invention or foams modified according to the invention. Another object of the present invention is a process for the preparation of packaging elements using modified foams of erfindungsge invention or modified foams. A further subject of the present invention is a process for the production of soundproofing elements using modified foams according to the invention or foams modified according to the invention. Another object of the present invention is a process for the production of building insulation using modified foams of the invention or modified according to the invention foams.

Do you wish modified according to the invention To use foams for the production of filters, so are bag filters and matrices of ceramic filters are preferred. Do you wish modified according to the invention To use foams for the production of automotive parts are in particular ventilation units prefers.

One Another object of the present invention are cleaning materials, Filters, humidifiers, cosmetic articles, water distributors, packaging elements, Sound insulation elements and building insulation, prepared using or containing modified according to the invention Foams or inventively modified Foams.

you can be modified according to the invention For example, mechanically combining foams with other materials, for example, with stems, primitives for example broom, with Textiles, leather, polymers such as polyurethane or Wood.

you can be modified according to the invention Print well foams, for example by the ink-jet process or with pigmented pastes.

The Invention will be explained by working examples.

working examples

I.1 Preparation of unmodified Foam (a)

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. Unmodified foam (a.1) was obtained.

The following properties were determined on the unmodified foam (a.1) from Example I.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 Modified Inventive foams

indem man je einen Schaumstoffquader vollständig in die wässrige Dispersion tauchte und 2 Minuten mit wässriger Dispersion bedeckt ließ. Anschließend entnahm man die Schaumstoffquader aus der betreffenden wässrigen Dispersion und quetschte überschüssige wässrige Dispersion ab, indem man durch zwei sich gegenläufig drehende Walzen führte, die einen Durchmesser von 150 mm und einen Abstand von 8 mm aufwiesen und sich mit einer Geschwindigkeit von 32 Umdrehungen/min drehten. Dadurch wurde eine Flottenaufnahme von 520 Gew.-% erreicht.Unmodified foam (a.1) from Example I.1 was cut into foam blocks with the dimensions 9 cm × 4 cm × 4 cm. The foam cubes weighed in the range of 1.00 to 1.33 g. Subsequently, several unmodified foam pieces were contacted with a weight according to Table 1 with an aq dispersion containing 81 g / l N, N'-dimethyl-4,5-dihydroxyimidazolinone (I b.1) and 18 g / l MgCl ₂ .6H ₂ O,

by completely immersing a foam cuboid in the aqueous dispersion and allowing it to be covered with aqueous dispersion for 2 minutes. The foam cubes were then removed from the aqueous dispersion concerned and the excess aqueous dispersion was squeezed off by passing through two counter-rotating rollers having a diameter of 150 mm and a spacing of 8 mm and moving at a speed of 32 revolutions / min turned. As a result, a liquor pickup of 520 wt .-% was achieved.

After that you dried over a period of 4 hours at 80 ° C in a drying oven. Subsequently was thermally fixed in a drying oven at 150 ° C for 10 minutes. One received modified according to the invention Foam S1.1.

II. Production of others modified according to the invention foams

II.1 Production of Inventive Modified Foam S1.2

The experiment according to I.2 was repeated, but contact was made with an aqueous dispersion of
120 g / l (I b.1) and
57.8 g / l MgCl ₂ .6H ₂ O.

The foam cuboid was removed 5 seconds after immersion, squeezed like
described above and reached a liquor pick-up of 540 wt .-%. It was then fixed thermally without prior drying for 15 minutes at 150 ° C in a drying oven.

you received modified according to the invention Foam S1.2.

II.2 Preparation of Inventive Modified Foam S2.1

It was sprayed cuboid (dimensions: 9 cm x 4 cm x 4 cm) of unmodified foam (a.1) with an aqueous dispersion containing
112.5 g / l (I b.2) and
61.4 g / l MgCl ₂ .6H ₂ O.

you let 2 Minutes, then squeeze as described under I.2 and fixed thermally for 20 minutes at 140 ° C in a drying oven. One reached a liquor pickup of 425 wt .-%.

you received modified according to the invention Foam S2.1.

II.3 Preparation of Modified Inventive foams

Several unmodified foam pieces from Example I.1 were contacted with a weight according to Table 1 with an aqueous dispersion containing
112.5 g / l (I b.2) and
61.4 g / l MgCl ₂ .6H ₂ O,
by completely immersing a foam cuboid in the aqueous dispersion and allowing it to be covered with aqueous dispersion for 2 minutes. The foam cubes were then removed from the aqueous dispersion concerned and the excess aqueous dispersion was squeezed off by passing through two counter-rotating rollers having a diameter of 150 mm and a spacing of 5 mm and moving at a speed of 32 revolutions / min turned. As a result, a liquor uptake of 110 wt .-% was achieved.

After that you dried over a period of one hour at 80 ° C in a drying oven. Subsequently was thermally fixed in a drying oven at 160 ° C for 10 minutes. One received modified according to the invention Foam S2.2.

II.4 Preparation of modified according to the invention Foam S2.3

Several unmodified foam pieces from Example I.1 were contacted with a weight according to Table 1 with an aqueous dispersion containing
60 g / l (I b.2) and
25 g / l MgCl ₂ .6H ₂ O,
by completely immersing a foam cuboid in the aqueous dispersion and allowing it to be covered with aqueous dispersion for 2 minutes. The foam cubes were then removed from the aqueous dispersion concerned and the excess aqueous dispersion was squeezed off by passing through two counter-rotating rollers having a diameter of 150 mm and a spacing of 8 mm and moving at a speed of 32 revolutions / min turned. As a result, a liquor uptake of 725 wt .-% was achieved.

After that was fixed thermally in a drying oven for 10 minutes at 150 ° C (without previous Dry). There was obtained modified foam according to the invention S2.3.

II.5 Preparation of Inventive Modified Foam S2.4

you proceeded as described in Example II.4, but dried before fixing for 2 hours at 80 ° C in a drying oven and fixed thermally for 5 minutes at 180 ° C. One received modified according to the invention Foam S2.4.

The Stock pickup was determined before drying to give one Value of 450% by weight.

Table 1: Inventive modified foams (stated in% by weight based on the weight of the unmodified foam)

III. Use of modified according to the invention Foams and non-modified foams as cleaning cloths

Modified according to the invention Foams and unmodified foam were each used as plaster sponges.

you Moistened modified invention Foams and unmodified foam each with water at.

Man cleaned over a period of 2 minutes manually each about 1 m ^{2 of} a painted plasterboard wall (rough), which was dirty with strips of rubber abrasion, shoe polish and waste oil, with one of the modified foams according to the invention from I.2 or II unmodified foam according to I.1. It obtained plastered walls according to Table 2, in which the quality of the plaster were assessed on visual impression. Furthermore, the dimensional stability of the plaster sponges was visually assessed.

Table 2: Unmodified foam (a.1) from I.1, modified foams according to the invention and their use as plaster sponges

IV. Production of further modified according to the invention foams

you cut unmodified foam (a.1) from Example I.1 into foam cubes with the dimensions 10 cm x 10 cm x 0.5 cm. The foam cubes weighed in the range of 0.35 to 0.48 g.

IV.1 Preparation of modified according to the invention Foam S1.3

It contacted a foam cuboid of IV. With a weight of 0.44 g with an aqueous dispersion of
81 g / l (b I.1) and
18 gg / l MgCl ₂ · 6 H ₂ O, by immersing it completely in the aqueous dispersion and two minutes by aqueous dispersion was covered. The foam cubes were then removed from the aqueous dispersion concerned and the excess aqueous dispersion was squeezed off by passing through two counter-rotating rollers having a diameter of 150 mm and a distance of 2 mm and moving at a speed of 32 revolutions / min turned. As a result, a fleet intake of 420% was achieved.

After that you dried over a period of 4 hours at 80 ° C in a drying oven. Subsequently was thermally fixed in a drying oven at 150 ° C for 10 minutes. It resulted an occupancy of 34 wt .-%, based on unmodified foam.

After that the treated foam was moistened with water and calendered, by passing it ten times through two counter-rotating rollers with 3.5-4 bar contact pressure led, wherein the treated foam is about one-third of its original Thick pressed (mechanically compressed) was. There were obtained modified according to the invention Foam S1.3, which had a pleasantly soft cloth-like handle and was flexible.

IV.2 Preparation of Inventively Modified Foam S1.4

It contacted a foam cuboid of IV. With a weight of 0.44 g with an aqueous dispersion of
81 g / l (b I.1) and
18 gg / l MgCl ₂ · 6 H ₂ O, by immersing it completely in the aqueous dispersion.

To For 5 seconds, the foam cuboid was removed from the respective cuboid aqueous Dispersion and squeezed excess aqueous dispersion by passing through two counter-rotating rollers, the a diameter of 150 mm and a distance of 2 mm and turned at a speed of 32 revolutions / min. As a result, a fleet intake of 420% was achieved.

After that calendered by passing the treated foam twelve times two in opposite directions rotating rollers with 3,5-4 bar contact pressure resulted, wherein the treated foam is about one-third of its original Thick pressed (mechanically compressed) was. Then fixed 15 minutes at 150 ° C in the drying cabinet. This resulted in an occupancy of 34 wt .-%, based on unmodified foam. There were obtained modified according to the invention Foam S1.4, which had a pleasantly soft cloth-like handle and was flexible.

IV.3 Preparation of Inventive Modified Foam S2.5

An IV foam foam having a weight of 0.48 g was sprayed with 3.9 times an aqueous dispersion containing
112.5 g / l (I b.2) and
61.4 g / l MgCl ₂ .6H ₂ O.

you let 2 Minutes, then squeezed excess aqueous dispersion by through two in opposite directions rotating rollers led, which had a diameter of 150 mm and a distance of 2 mm and turned at a speed of 32 revolutions / min. It reached a liquor pickup of 325 wt .-% and an occupancy of 37% by weight.

After that was fixed thermally in a drying oven for 15 minutes at 150 ° C (without previous Dry).

After that the treated foam was moistened with water and calendered, by giving it fifteen times through two in opposite directions rotating rollers with 3,5-4 bar contact pressure resulted, wherein the treated foam is about 40% of its original Thick pressed (mechanically compressed) was. There were obtained modified according to the invention Foam S2.5, which had a pleasantly soft cloth-like feel and was flexible.

IV.4 Preparation of Inventive Modified Foam S2.6

It was contacted a foam cuboid of IV. With a weight of 0.42 g completely in an aqueous dispersion containing
112.5 g / l (I b.2) and
61.4 g / l MgCl ₂ .6H ₂ O,
by dipping it completely in the aqueous dispersion. It was allowed to act for 2 minutes, then squeezed excess aqueous dispersion by passing through two counter-rotating rollers having a diameter of 150 mm and a distance of 2 mm and rotating at a speed of 32 revolutions / min. It reached a liquor pickup of 360 wt .-% and an occupancy of 41 wt .-%.

After that it was dried for one hour at 80 ° C. in a drying oven and fixed thermally in a drying oven 7.5 Minutes at 160 ° C.

After that The treated foam was moistened with water and compressed mechanically, by pressing it ten times with a platen press on a third of its original Thickness pressed. There was obtained modified foam according to the invention S2.6, which felt like soft leather and was very flexible.

IV.5 Preparation of Inventive Modified Foam S2.7

A foam matrix of IV. Having a weight of 0.46 g was contacted with an aqueous dispersion containing
60 g / l (I b.2) and
25 g / l MgCl ₂ .6H ₂ O,
by dipping it completely in the aqueous dispersion and allowing it to stand covered with aqueous dispersion for 2 minutes. Subsequently, the foam cuboid was removed from the relevant aqueous dispersion and Excess aqueous dispersion was squeezed by passing through two counter rotating rolls having a diameter of 150 mm and a distance of 2 mm and rotating at a speed of 32 revolutions / min. As a result, a liquor pickup of 725 wt .-% was achieved.

After that was fixed thermally in a drying oven for 10 minutes at 150 ° C (without previous Dry).

After that the treated foam was moistened with water and calendered, by passing it ten times through two counter-rotating rollers with 3.5-4 bar contact pressure led, wherein the treated foam is about one-third of its original Thick pressed (mechanically compressed) was. There were obtained modified according to the invention Foam S2.7, which had a pleasantly soft cloth-like handle and was flexible.

IV.6 Preparation of Inventive Modified Foam S2.8

An IV foam having a weight of 0.35 g was contacted with an aqueous dispersion containing
60 g / l (I b.2) and
25 g / l MgCl ₂ .6H ₂ O,
by dipping it completely in the aqueous dispersion and allowing it to stand covered with aqueous dispersion for 2 minutes. The foam cubes were then removed from the aqueous dispersion concerned and the excess aqueous dispersion was squeezed off by passing through two counter-rotating rollers having a diameter of 150 mm and a distance of 2 mm and moving at a speed of 32 revolutions / min turned. As a result, a liquor pickup of 710 wt .-% was achieved.

After that you dried first 2 hours at 80 ° C in the drying cabinet. Thereafter, it was fixed thermally in a drying oven 5 minutes at 180 ° C.

After that The treated foam was moistened with water and compressed mechanically, by pressing it ten times with a platen press on a third of its original Thickness pressed. There was obtained modified foam according to the invention S2.8, which felt like soft chamois leather and was very flexible.

V. Use of Modified According to the Invention Foams of IV. And unmodified foams as cleaning cloths

Modified according to the invention Foams and unmodified foam were each used as cleaning cloths for Cleaning a sensitive surface of Plexiglas used.

Out unmodified foam (a.1) and modified from according to the invention IV foam were each about 0.5 cm thick circular discs (Diameter: 4.5 cm) cut out and on a weight (about 1600 g) glued. One received examinees. The candidates were moistened with water and with the help of a "Prüfbau-Quant-Scheuerprüfers" about 2000 times on Plexiglas rubbed. To assess whether the foams of the invention, the surface of the Plexiglas scratches less than the untreated foam, was the scratches on the friction surface in microscopic magnification (1 : 75) counted.

The untreated foam (a.1) averaged 31 scratches; with S1.4 9 scratches, with S2.5 2 scratches, with 52.7 7 scratches.

Claims (16)

Process for the preparation of modified open-cell foams, characterized in that: (a) open-cell 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) with aqueous formulation of at least one compound having at least one semiaminal or amino nalgruppe per molecule or at least one copolymer containing at least one OH group-containing or β-dicarbonyl-containing or epoxide-containing comonomer in copolymerized contacted. Method according to claim 1, characterized in that that at least one compound from step (b) is not used in the manufacture of open cell foam (a) has been used. Method according to claim 1 or 2, characterized that one receives compound (b) 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 one in addition With (c) contacting at least one catalyst. Method according to one of claims 1 to 4, characterized that one continues to be contacted with at least one aggregate (d), where additives (d) are chosen are derived from biocides, surfactants, activated carbon, colorants, fragrances, odor scavengers and microcapsules, filled with at least one active substance. Method according to one of claims 1 to 5, characterized that after contacting open cell foam (a), aqueous Formulation of compound (b), optionally catalyst (c) and optionally at least one additive (d) act lets and then mechanically compressed. Method according to one of claims 1 to 6, characterized that after contacting open cell foam (a), aqueous Formulation of compound (b), optionally catalyst (c) and optionally at least one additive (d) act lets and Thereafter thermally fixed. Method according to one of claims 1 to 6, characterized that after contacting open cell foam (a), aqueous Formulation of compound (b), optionally catalyst (c) and optionally at least one additive (d) act leaves, then mechanically compressed and then thermally fixed. Method according to one of claims 1 to 8, characterized that open-cell foams (a) are foams made of synthetic organic foam. Method according to one of claims 1 to 9, characterized that open-celled foams (a) are polyurethane foams or aminoplast foams. Method according to one of claims 1 to 10, characterized in that in step (b) with at least one compound 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, wherein in formula Ia at least one x is equal to 1, m is an integer in the range of 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 the} same or different and selected from C ₁ -C ₄ alkyl and hydrogen. Modified open-cell foams available after A method according to any one of claims 1 to 11. Use of modified open-cell foams, manufactured according to a method according to one of claims 1 to 11, as or for the production of cleaning materials, filters, Humidifiers, cosmetic articles, water distributors, packaging elements, Sound insulation elements or building insulation. Process for the production of cleaning materials, Filters, humidifiers, cosmetic articles, water distributors, Packaging elements, sound insulation elements or building insulation using modified open-cell foams, manufactured according to a method according to one of claims 1 to 11th Cleaning materials, filters, humidifiers, cosmetic Articles, water distributors, packaging elements, soundproofing elements and building insulation, manufactured using modified open-cell foams, manufactured according to a method according to one of claims 1 to 11th Cleaning materials, filters, humidifiers, cosmetic Articles, water distributors, packaging elements, soundproofing elements and building insulation, containing modified open-cell foams produced according to A method according to any one of claims 1 to 11.