DE19735958A1 - Thermally curable aqueous binding agent containing activated carbon - Google Patents

Abstract

A thermally curable, aqueous composition (I) comprises (A) a polymer, prepared by radical polymerisation and containing 10-100 wt.% of polymerised alpha , beta -ethylenically unsaturated mono- or dicarboxylic acid and/or anhydride; (B) an alcoholamine containing at least 2 hydroxy groups; (C) 0.1-30 wt.% (w.r.t. (A) + (B)) of activated carbon and/or carbon molecular sieve. A binding agent (II) contains the composition (I). An Independent claim is included for a moulded article, (III) , low in odour, that is prepared by impregnation of a substrate with (I) and/or (II) followed by curing of the impregnated substrate.

Description

The present invention relates to thermally curable, aqueous Compositions containing at least one carboxylate or carboxylate group-containing polymer, at least one alkanolamine and Ak tivkohle contain, as well as the use of such preparations as a binder for low-odor molded articles.

The consolidation of sheet-like fiber structures, for example wise nonwovens, moldings such as fiberboard or chipboard ten, etc. is often done chemically using egg polymeric binder. To increase strength, esp special the wet and heat resistance, are often bandage used medium which ent crosslinker which releases formaldehyde hold. However, there is a risk of formaldehyde emissions.

To avoid formaldehyde emissions, numbers have already been paid rich alternatives to the previously known binders are featured beat. For example, binders are known from US Pat. No. 4,076,917 which carboxylic acid or carboxylic anhydride-containing polymers and contain β-hydroxyalkylamides as crosslinkers. The molar ver Ratio of carboxyl groups to hydroxyl groups is preferred 1: 1. The disadvantage is the relatively complex production of the β-hydroxyalkylamides.

EP-A-445 578 discloses plates made of finely divided materials, such as known glass fibers, in which mixtures of high molecular weight polycarboxylic acids and polyhydric alcohols, Alkanolamines or polyvalent amines act as binders. As high molecular weight polycarboxylic acids, polyacrylic acid, Co polymers of methyl methacrylate / n-butyl acrylate / methacrylic acid and described from methyl methacrylate / methacrylic acid. As multivalued Alcohols or alkanolamines are 2-hydroxymethylbutane-1,4-diol, Trimethylolpropane, glycerin, poly (methyl methacrylate-co-hydroxy propyl acrylate), diethanolamine and triethanolamine.

EP-A-583 086 discloses formaldehyde-free, aqueous binders for the production of nonwoven fabrics, in particular glass fiber nonwovens, known. The binders contain a polycarboxylic acid with min at least two carboxylic acid groups and optionally also anhydride groups. Polyacrylic acid is used in particular. The bin detergent also contains a polyol, for example glycerol, Bis- [N, N-Di (β-hydroxyethyl) adipamide, pentaerythritol, diethylene glycol  kol, ethylene glycol, gluconic acid, β-D-lactose, sucrose, polyvinyl alcohol, diisopropanolamine, 2- (2-aminoethylamino) ethanol, tri ethanolamine, tris (hydroxymethylamino) methane and diethanolamine. These binders require a phosphorus-containing reaction accelerator to ensure sufficient strength of the glass fiber fleece to reach. It should be noted that the presence of such a reaction accelerator can only be dispensed with can, if a highly reactive polyol is used. As high reactive polyols are called the β-hydroxyalkylamides.

EP-A-651 088 describes corresponding binders for sub strate made of cellulose fiber. These binders contain mandatory a reaction accelerator containing phosphorus.

EP-A-672 920 describes formaldehyde-free binders, impregnants or Coating agent, which is a polymer, which to 2 to 100 wt .-% of an ethylenically unsaturated acid or Acid anhydride is built up as a comonomer and at least one Contain polyol. The polyols are substi tuated triazine, triazinetrione, benzene or cyclohexyl derivatives, the polyol residues are always in the 1,3,5-position of those mentioned Rings. Despite a high drying temperature with these binders on glass fiber fleece only little wet tear strength achieved. In the context of comparative tests also amine-containing crosslinking agents and predominantly linear built polyols tested. It should be noted that amine crosslinking agents containing flocculant and that the over linear polyols lead to weaker crosslinking ren than the cyclic polyols.

DE-A-22 14 450 describes a copolymer which consists of 80 to 99% by weight of ethylene and 1 to 20% by weight of maleic anhydride is building. The copolymer is, together with a crosslinking medium, in powder form or in dispersion in an aqueous Medium used for surface coating. As a networking medium, an amino group-containing polyalcohol is used. Around To cause crosslinking, however, must be heated up to 300 ° C become.

EP-A-257 567 describes a polymer composition which he is preserved by emulsion polymerization of ethylenically un saturated monomers, such as olefins, vinyl aromatic compounds, α, β-ethylenically unsaturated carboxylic acids and their esters, ethyl niche unsaturated dicarboxylic acid anhydrides and vinyl halides. A solution is dissolved in water or alkali during the polymerization Lich or dispersible resin with a number average mole Specular weight from about 500 to about 20,000 added to the flow  to influence properties of the polymer composition. The Resin is made from olefins, vinyl aromatic compounds, α, β-ethyls nically unsaturated carboxylic acids and the esters thereof or ethy Lenically unsaturated dicarboxylic acid anhydrides. As alkaline medium in which the resin mentioned is soluble or dispersed ammonium hydroxide is specified. The together is for the production of formaldehyde-free coatings of wooden substrates.

EP-A-576 128 describes repulpable adhesive compositions tongues that have an acidic polymer component and a low acidity Contain polymer component. The low acid polymer component is based on a monomeric mixture of 40 to 95% of an alkyl acrylate or methacrylate and 5 to 60% of an ethylenically un saturated acid, such as acrylic acid or methacrylic acid. The acid poor polymer component is based on a monomer mixture of 90 up to 100% of an alkyl acrylate or alkyl methacrylate and 0 to 10% an ethylenically unsaturated acid. The production of the Setting takes place by aqueous emulsion polymerization, wherein the acid-rich polymer component in the presence of the low-acid Polymer component or vice versa is polymerized. The pH of the Composition is made by adding ammonium hydroxide or Sodium hydroxide set to the desired value. The Together Setting is as a pressure sensitive adhesive, lamination adhesive fabric, adhesive for textile fabrics, tiles and packaging and usable as wood glue.

A binder is disclosed in US-A-4,420,583 and EP-A-098091 composition of an acid-rich polymer dispersion and egg Nem solution polymer described. The latex is based on one Monomer composition of vinyl aromatics and alkyl (meth) acrylates and up to 20% of an ethylenically unsaturated acid. The Lö Solution polymer contains at least 10% of a (halogen hydroxy propyl) containing monomer. The composition is stable in storage and hardens after adding base (NaOH or similar) Room temperature. For formaldehyde-free binders, Glue and coatings use.

US-A-5,314,943 describes a mixture consisting of a Polymer dispersion and a water-soluble copolymer and their Use as a binder for nonwovens. The polymer ent in addition to vinyl aromatics and alkyl (meth) acrylates, preferably holds bi functional monomers such as butadiene and vinyl acrylates. The Lö Solution polymer is contained in up to 5% of the mixture consists of 25-60% of an ethylenically unsaturated monocarbon acid and 40-75% of an ethylenically unsaturated dicarbon acid. The composition is characterized by a low Vis  viscosity and high strength in the hardened state. The high temperatures that are necessary for curing are disadvantageous are agile.

US-A-4,868,016 describes a composition based on at least one thermoplastic, in aqueous alkaline Medium insoluble latex polymer and at least one alkali-soluble polymer that is not compatible with the latex polymer. The latex polymer is a water-dispersed polymer that consists of Acrylic or methacrylic acid esters, vinyl aromatic compound and vinyl esters can be constructed and additionally 0.5 to 3% by weight of an ethylenically unsaturated carboxylic acid contains. The alkali-soluble polymer is also from the ge called monomers, but contains 10 to 60 wt .-% an ethylenically unsaturated carboxylic acid. To adjust the pH value to <7, the composition ammonia, triethyl contain amine, ethylamine or dimethylhydroxyethylamine. she is useful for coating substrates.

The aforementioned moldings often still contain volatile Be constituents, the z. T. perceived as an unpleasant smell the. Volatile components are, for example, residual monomers, non-polymerizable impurities of the monomers and cursed degradation products of the polymers. Volatile, odor-causing be Components are in particular also low molecular weight amines, which often as a crosslinker or crosslinking aid or for the purpose neutralization are contained in binders. A noticeable one Release of odor-forming components is particularly then to be recorded when the moldings are subjected to thermal stress, for example if the products are in the loft or in the automobile expansion can be used. Temperatures are often high here enough to lead to an unacceptable odor nuisance to lead. From DE-A 30 23 023 it is known in principle that aqueous polymer dispersions by adding activated carbon can be designed with low odor. The use of activated carbon for low-odor design of thermally curable preparations gene containing amino alcohols is not suggested.

The present invention is based, formally to provide anhydrous binders for moldings which allow rapid curing at low temperature and the sub strat good mechanical properties and a high climate resistance lend. In addition, the shaped bodies obtainable in this way are said to be no annoying odors even at elevated temperatures to lead. Furthermore, such shaped articles, provided they are in the car mobilbau are used, a positive fogging behavior point. Fogging or window fogging means that inwen  fogging of windows in motor vehicles on the Emission of volatile components from vehicle interiors materials. (A detailed discussion of the Window foggings can be found e.g. B. in D. Eisele, Melliand Textbe richte 1987, pp. 206-215 and P. Hardt et al., Textilpraxis In ternational, 49 (1994), pp. 163-167.)

Surprisingly, it has now been found that this problem has been solved when using a composition that has at least one Polymer with carboxyl or carboxylate groups, at least one Ent with at least two hydroxyalkyl groups and activated carbon hold.

The present invention relates to low-odor, thermally curable compositions containing

• A) at least one available through radical polymerization Polymer that ≧ 10 wt .-% of an α, β-ethylenically unsaturated took mono- or dicarboxylic acid and / or their anhydrides contains polymerized,
• B) at least one alkanolamine with at least two hydroxyalkyl groups and
• C) 0.1 to 30 wt .-%, based on the total amount of the components ten A and B, activated carbon and / or carbon molecular sieves.

In the context of the present invention, alkyl preferably represents straight-chain or branched C ₁ -C ₁₈ -alkyl radicals, in particular C ₁ -C ₁₂ - and particularly preferably C ₁ -C ₆ -alkyl radicals, such as methyl, ethyl, n-propyl, i-propyl , n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-dodecyl or n-stearyl. Hydroxyalkyl preferably represents hydroxy-C ₁ -C ₆ -alkyl and in particular 2-hydroxyethyl and 2- or 3-hydroxypropyl. Cycloalkyl is preferably C ₅ -C ₇ cyclohexyl, especially cyclopentyl and cyclohexyl. Aryl is preferably phenyl or naphthyl.

The compositions according to the invention contain as a component A a polymer P1, which is 10 to 100 wt .-%, preferably 20 to 100 wt .-%, in particular 40 to 100 wt .-% and very special preferably 50 to 100 wt .-% of at least one ethylenically unsaturated mono- or dicarboxylic acid (monomer a) is built up. The polymer can also be partially or completely in the form of egg nes salt are present, the acidic form is preferred. You are in essentially free of carboxylic acid anhydride structures.  

The weight average molecular weight of the polymer is P1 greater than 500 and generally less than 5 million. The K values of the polymers, which are a measure of the molecular weight represent, are generally in the range of 5 to 150 (ge measure in 1 wt .-% solution). The K value is a relative Vis coefficient of viscosity, which is determined in analogy to DIN 53726 (see see H. Fikentscher, Cellulosechemie, Vol. 13, 1932, pp. 58-64 and Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 23, p. 967-968).

The polymer must have an average of at least 4 carboxylic acid groups and / or salt groups derived therefrom per polymer chain ten.

Useful ethylenically unsaturated carboxylic acids are in particular C ₃ -C ₆ carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methylmalic acid and itaconic acid, and half esters of ethylenically unsaturated dicarboxylic acids, such as, for. B. Maleic acid monoalkyl esters of C ₁ -C ₈ alcohols.

The polymers can also start from ethylenically unsaturated saturated mono- or dicarboxylic acid anhydrides, optionally in Mixture with the carboxylic acids mentioned can be obtained. The Anhydride functions are under the polymerization conditions, e.g. B. in solution or emulsion polymerization in aqueous Medium, or following the polymerization by reaction converted into carboxylic acid groups with an acid or base. Useful ethylenically unsaturated carboxylic anhydrides are especially maleic anhydride, itaconic anhydride, acrylic acid anhydride and methacrylic anhydride.

In addition to the previously mentioned monomers (monomers a), the polymer P1 can also contain from 0 to 90% by weight, preferably from 0 to 80% by weight, in particular from 0 to 60% by weight and particularly preferably from 0 to 50% by weight , polymerized ent hold at least one other monomer. Useful comonomers are:
Vinylaromatic compounds such as styrene, α-methylstyrene and vinyltoluenes (monomers b ₁ );
Linear 1-olefins, branched-chain 1-olefins or cyclic olefins (monomers b ₂ ), such as, for. B. ethene, propene, butene, isobutene, pentene, cyclopentene, hexene, cyclohexene, octene, 2,4,4-tri methyl-1-pentene optionally in a mixture with 2,4,4-tri methyl-2-pentene, C ₈ -C ₁₀ olefin, 1-dodecene, C ₁₂ -C ₁₄ olefin, octa decene, 1-eicosen (C ₂₀ ), C ₂₀ -C ₂₄ olefin; Metallocene-catalyzed oligoolefins with a terminal double bond, such as. B. oligopropene, oligohexene and oligooctadecene; olefins produced by cationic polymerization with a high α-olefin content, such as. B. polyisobutene. However, preferably no marriage or linear 1-olefin is polymerized into the polymer;
Butadiene;
Vinyl and allyl alkyl ethers having 1 to 40 carbon atoms in the alkyl radical, where the alkyl radical can also carry further substituents such as a hydroxyl group, an amino or dialkylamino group or one or more alkoxylate groups (monomers b ₃ ), such as, for. B. methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, iso butyl vinyl ether, 2-ethylhexyl vinyl ether, vinyl cyclohexyl ether, vinyl 4-hydroxybutyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2- (diethylamino) ethyl vinyl ether, 2- (di-n-butylamino) ethyl vinyl ether, and methyl diglycol the corresponding allyl ethers or mixtures thereof;
Acrylamides and alkyl-substituted acrylamides (monomers b ₄ ), such as. B. acrylamide, methacrylamide, N-tert-butylacrylamide, N-methyl- (meth) acrylamide;
Monomers containing sulfo groups (monomers b ₅ ), such as, for. B. allylsulfonic acid, methallylsulfonic acid, styrene sulfonate, vinyl sulfonic acid, allyloxybenzenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, their corresponding alkali metal or ammonium salts or mixtures thereof;
C ₁ to C ₈ alkyl esters or C ₁ to C ₄ hydroxyalkyl esters of acrylic acid, methacrylic acid or maleic acid or esters of C ₁ to C ₁₈ alcohols alkoxylated with from 2 to 50 mol of ethylene oxide, propylene oxide, butylene oxide or mixtures thereof Acrylic acid, meth acrylic acid or maleic acid (monomers b ₆ ), such as. B.
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, Hydroxy propyl (meth) acrylate, butanediol-1,4-monocacrylate, maleic acid dibutyl ester, ethyl diglycol acrylate, methyl polyglycol acrylate (11 EO), (meth) acrylic acid ester of C ₁₃ / C ₁₅ - reacted with 3,5,7,10 or 30 mol ethylene oxide. Oxo alcohol or mixtures thereof;
Alkylaminoalkyl (meth) acrylates or alkylaminoalkyl (meth) acryl amides or their quaternization products (monomers b ₇ ) such as. B. 2- (N, N-Dimethylamino) ethyl (meth) acrylate, 3- (N, N-Dimethylamino) propyl (meth) acrylate, 2- (N, N, N-trimethylammonium) ethyl (meth) acrylate -chloride, 2-dimethylaminoethyl (meth) acrylamide, 3-dimethylaminopropyl (meth) acrylamide, 3-trimethylammonium propyl (meth) acrylamide chloride;
Vinyl and allyl esters of C ₁ - to C ₃₀ -nocarboxylic acids (Mono mers b ₈ ), such as. B. vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl 2-ethylhexanoate, vinyl nonoate, vinyl decanoate, vinyl pivalate, vinyl palmitate, vinyl stearate, vinyl laurate.

The following may also be mentioned as further monomers b ₉ :
N-vinylformamide, N-vinyl-N-methylformamide, styrene, α-methyl styrene, 3-methylstyrene, butadiene, N-vinylpyrrolidone, N-vinylimi dazol, 1-vinyl-2-methylimidazole, 1-vinyl-2-methyl imidazoline, N-vinylcaprolactam, acrylonitrile, methacylnitrile, allyl alcohol, 2-vinylpyridine, 4-vinylpyridine, diallyldimethylammonium chloride, vinylidene chloride, vinyl chloride, acrolein, methacrolein and vinyl carbazole or mixtures thereof.

Preferred further monomers are the esters of acrylic mentioned acid and methacrylic acid, the vinyl aromatic compounds, Butadiene, vinyl ester, (meth) acrylonitrile and those mentioned (Meth) acrylamides.

Particularly preferred comonomers b are methyl acrylate and ethyl acrylate lat, butyl acrylates, 2-ethylhexyl acrylate, methyl methacrylate, Bu tyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, Hy hydroxybutyl acrylates, hydroxyethyl methacrylate, styrene, butadiene, Vinyl acetate, acrylonitrile, methacrylonitrile, acrylamide, methacrylic amide and / or N-butyl acrylamide.

The polymers can be prepared using customary polymerization processes are produced, e.g. B. by radical substance, Emulsion, suspension, dispersion, precipitation and solution polymerization. In the polymerization process mentioned preferably worked in the absence of oxygen, preferably in a stream of nitrogen. For all polymerization methods the usual equipment used, e.g. B. stirred kettle, stirred kettle cascades, autoclaves, tube reactors and kneaders. Is preferred according to the method of solution, emulsion, precipitation or suspension sion polymerization worked. Those are particularly preferred Methods of solution and emulsion polymerization in aqueous Medium.

The application of aqueous radical solution polymerization is preferred for water-soluble polymers and copolymers P1 which preferably from 50 to 100% by weight of the carboxylic acid mentioned  ren, carboxylic anhydrides, half esters or a mixture of two or more of these connections are established. Your weight average molecular weight is generally in the range of 500 to 1,000,000, preferably 2,000 to 200,000. The K values of the Polymers are generally in the range from 5 to 150 preferably 15 to 100 (measured in 1 wt .-% solution in water). The solids content is generally in the range from 10 to 80 % By weight, preferably 20 to 65% by weight. The polymerization can at temperatures from 20 to 300, preferably from 60 to 200 ° C. be performed. Implementation of solution polymerization takes place in the usual way, e.g. B. as in EP-A-75 820 or DE-A-36 20 149.

The use of aqueous emulsion polymerization is recommended for polymers P1, which consist of 10 to 50 wt .-% of those mentioned Carboxylic acids, carboxylic anhydrides, half esters or mixtures there of are built up. They preferably have a weight average Molecular weight of 1,000 to 2,000,000, preferably 5,000 to 500,000. The K values are generally in the range of 10 up to 150 (1% by weight in dimethylformamide). The weight average Particle size (determined using an ultracentrifuge) is preferred example in the range from 50 to 1000 nm. The dispersion can be monomo have dale or polymodal particle size distribution. The Emulsion polymerization can be carried out so that the Solid volume content in the range of 20 to 70%, preferably 30 to 60%.

Carrying out the emulsion polymerization with the mentioned Monomers containing carboxylic acid groups are usually carried out Way, e.g. B. as in DE-A-31 34 222 or US-A-5,100,582 be wrote.

The polymerization is preferably carried out in the presence of radicals forming compounds (initiators) carried out. You need of these compounds, preferably 0.05 to 15, especially preferably 0.2 to 8 wt .-%, based on that of the Polymerisa tion used monomers.

Suitable polymerization initiators are, for example, Per oxides, hydroperoxides, peroxodisulfates, percarbonates, peroxoesters, Hydrogen peroxide and azo compounds. Examples of initiato ren, which can be water-soluble or water-insoluble, are hydrogen peroxide, dibenzoyl peroxide, dicyclohexylperoxi dicarbonate, dilauroyl peroxide, methyl ethyl ketone peroxide, di-tert.- Butyl peroxide, acetylacetone peroxide, tert-butyl hydroperoxide, Cumene hydroperoxide, tert-butyl perneodecanoate, tert-amyl perpiva lat, tert-butyl perpivalate, tert-butyl perneohexanoate, tert-Bu  tylper-2-ethylhexanoate, tert-butyl perbenzoate, lithium, Sodium, potassium and ammonium peroxydisulfate, azodiisobutyro nitrile, 2,2'-azohis (2-amidinopropane) dihydrochloride, 2- (carbamoyl azo) isobutyronitrile and 4,4-azobis (4-cyanovaleric acid). Also the known redox initiator systems can be used as polymerizations initiators can be used.

The initiators can be used alone or as a mixture with one another be applied, e.g. B. mixtures of hydrogen peroxide and Sodium peroxydisulfate. For polymerization in an aqueous medium water-soluble initiators are preferably used.

In order to produce polymers with a low average molecular weight, it is often expedient to carry out the copolymerization in the presence of regulators. Conventional regulators can be used for this, such as, for example, organic SH groups containing compounds such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, tert-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan, C ₁ - bis C ₄ aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, hydroxylammonium salts such as hydroxylammonium sulfate, formic acid, sodium bisulfite or isopropanol. The polymerization regulators are generally used in amounts of 0.1 to 10% by weight, based on the monomers.

It is often useful to produce higher molecular weight copolymers moderate to ar in the polymerization in the presence of crosslinkers work. Such crosslinkers are compounds with two or more ethylenically unsaturated groups, such as diacrylates or dimethacrylates of at least divalent saturated alcohol fetch like B. ethylene glycol diacrylate, ethylene glycol dimeth acrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimeth acrylate, butanediol-1,4-diacrylate, butanediol-1,4-dimethacrylate, Hexanediol diacrylate, hexanediol dimethacrylate, neopentyl glycol di acrylate, neopentyl glycol dimethacrylate, 3-methylpentanediol di acrylate and 3-methylpentanediol dimethacrylate. Also the acrylic acid and Methacrylic acid ester of alcohols with more than 2 OH groups can be used as crosslinkers, e.g. B. Trimethylolpropane triacrylate or trimethylolpropane trimethacrylate. Another Class of crosslinkers are diacrylates or dimethacrylates from Polyethylene glycols or polypropylene glycols with molecular weight weight from 200 to 9,000 each. Divinylbenzene is also ge is suitable.  

The crosslinkers are preferably used in amounts of 10 ppm to 5 wt .-%, based on the monomers to be polymerized puts.

Is by the method of emulsion, precipitation, suspension or Dispersion polymerization worked, so it can be beneficial be, the polymer droplets or polymer particles by border stabilize surface-active auxiliaries. Typically emulsifiers or protective colloids are used for this. Coming anionic, nonionic, cationic and amphoteric emulsifiers into consideration. Anionic emulsifiers are preferred, for example as alkylbenzenesulfonic acids, sulfonated fatty acids, sulfo succinates, fatty alcohol sulfates, alkylphenol sulfates and fatty alcohol ether sulfates. As nonionic emulsifiers, for example wise alkylphenol ethoxylates, primary alcohol ethoxylates, fatty acid ethoxylates, alkanolamide ethoxylates, fatty amine ethoxylates, EO / PO block copolymers and alkyl polyglucosides can be used.

Amino alkoxylates, alkyl betaines, Alkylamidobetaines and / or sulfobetaines can be used.

Typical protective colloids are, for example, cellulose derivatives, Polyethylene glycol, polypropylene glycol, copolymers from Ethylene glycol and propylene glycol, polyvinyl acetate, polyvinyl alcohol, polyvinyl ether, starch and starch derivatives, dextran, Polyvinylpyrrolidone, polyvinylpyridine, polyethyleneimine, poly vinylimidazole, polyvinylsuccinimide, polyvinyl-2-methylsuccinimide, Polyvinyl-1,3-oxazolidone-2, polyvinyl-2-methylimidazoline and Copolymers containing maleic acid or maleic anhydride, as they e.g. B. are described in DE 25 01 123.

The emulsifiers or protective colloids are usually in Concentrations of 0.05 to 20% by weight, based on the monomers, used.

If polymerization is carried out in aqueous emulsion, solution or dilution, can the monomers completely before or during the polymerization or in part by conventional, inorganic or organic bases be neutralized.

The ethylenically unsaturated carbon are particularly preferred acids not neutralized before and during the polymerization. No neutralization is preferred even after the polymerization detergent, apart from the alkanolamine (B), added.  

If the polymer is by the method of a solution, precipitation or Suspension polymerization in a steam-volatile Solvent or solvent mixture prepared, so it can Solvents are separated by introducing steam, so as to arrive at an aqueous solution or dispersion. The Polymer can also from the organic diluent a drying process can be separated.

The polymer P1 can also be obtained by grafting maleic acid or Maleic anhydride or a maleic acid or maleic acid monomer mixture containing anhydride on a graft base be preserved. Suitable graft bases are, for example Monosaccharides, oligosaccharides, modified polysaccharides and Alkyl polyglycol ether. Such graft polymers are examples as described in DE-A-40 03 172 and EP-A-116 930.

Alkanolamines of the formula are suitable as component (B):

in which R ^{a represents} an H atom, a C ₁ -C ₁₀ alkyl group or a C ₁ -C ₁₀ hydroxyalkyl group and R ^b and R ^{c represent} a C ₁ -C ₁₀ hydroxyalkyl group.

R ^b and R ^c are particularly preferably, independently of one another, a C ₂ -C ₅ -hydroxyalkyl group and R ^a for an H atom, a C ₁ -C ₅ -alkyl group or a C ₂ -C ₅ -hydroxyalkyl group.

As compounds of formula I z. B. Diethanolamine, Tri ethanolamine, diisopropanolamine, triisopropanolamine, methyldi ethanolamine, butyldiethanolamine and methyldiisopropanolamine called. Triethanolamine is particularly preferred.

Also suitable are alkanolamines which are selected from water-soluble, linear or branched aliphatic compounds which contain at least two functional amino groups of type (a) or of type (b) per molecule.

where R is hydroxyalkyl and R 'is alkyl. This is preferably at least one compound of the formula I:

wherein
A represents C ₂ -C ₁₈ alkylene which is optionally substituted by one or more groups which are selected independently of one another from alkyl, hydroxyalkyl, cycloalkyl, OH and NR ⁶ R ⁷ , where R ⁶ and R ⁷ independently of one another are H. , Hydroxy alkyl or alkyl,
and which is optionally interrupted by one or more oxygen atoms and / or NR ⁵ groups, where R ^{5 is} H, hydroxyalkyl, (CH ₂ ) _n NR ⁶ R ⁷ , where n is 2 to 5 and R ⁶ and R ⁷ have the meanings given above, or alkyl, which in turn is interrupted by one or more NR ⁵ groups, where R ^{5 has} the meanings given above and / or by one or more NR ⁶ R ⁷ groups, where R ⁶ and R ^{7 has} the meanings given above;
or A represents a radical of the formula:

wherein
o, q and s independently of one another represent 0 or an integer from 1 to 6,
p and r independently of one another represent 1 or 2 and t represents 0.1 or 2,
the cycloaliphatic radicals can also be substituted by 1, 2 or 3 alkyl radicals and
R ¹ , R ² and R ³ and R ⁴ independently of one another represent H, hydroxyalkyl, alkyl or cycloalkyl, the compounds having at least two, preferably at least three, hydroxyalkyl groups per molecule.

The following are particularly preferred as component (B):
(1) Compounds of Formula Ia

wherein
A _{1 represents} C ₂ -C ₁₂ alkylene which is optionally substituted by at least one alkyl group and / or at least one NR ⁶ R ⁷ group, where R ⁶ and R ⁷ independently of one another represent alkyl or hydroxyalkyl and
R ¹ , R ² , R ³ and R ⁴ independently of one another represent hydroxyalkyl or H or one of the radicals R ¹ and R ² and / or one of the radicals R ³ and R ^{4 represents} alkyl or cycloalkyl.

Particularly useful compounds of this type are the compounds of the following formulas:

where x is 2 to 12, in particular 2, 3, 6, 8, 10 or 12,

Compounds of the formula Ia are also the aminals of the formula

(2) Compounds of Formula Ib

wherein
A _{2 represents} C ₂ -C ₈ alkylene which is interrupted by at least one NR ⁵ group, where R ⁵ (or the radicals R ⁵ independently of one another) stands for hydroxyalkyl or alkyl and
R ¹ , R ² , R ³ and R ^{4 are} independently hydroxyalkyl or H.

The radical A ₂ is preferably interrupted by one or two groups NR ⁵ . Particularly useful compounds of this type are the compounds of the following formulas:

(3) Compounds of Formula Ic

wherein
A _{3 represents} C ₂ -C ₈ alkylene which is interrupted by at least one NR ⁵ group, where R ^{5 represents} H, hydroxyalkyl or CH ₂ CH ₂ NR ⁶ R ⁷ ,
R ¹ , R ² , R ³ and R ⁴ independently of one another represent alkyl which is optionally interrupted by at least one NR ⁵ group and / or is substituted by at least one NR ⁶ R ⁷ group,
R ^{5 represents} H, hydroxyalkyl or -R ⁸ NR ⁶ R ⁷ and
R ⁶ and R ⁷ independently of one another are H, hydroxyalkyl or -R ⁸ NR ⁶ R ⁷ ,
R ^{8 represents} an ethylene or propylene radical,
where (on average) at least 30%, in particular <60% and preferably <80% of the (hydroxyalkylatable) N atoms carry a hydroxyalkyl group.

The C ₂ -C ₈ alkylene group is preferably interrupted by at least two groups NR ⁵ . Particularly useful compounds of this type are reaction products of ethylene oxide with polyethyleneimines of different molecular weights with a plurality of structural elements NR ⁶ R ⁷ and NR ⁵ . Useful polyethyleneimines are those whose weight average molecular weight is in the range from 400 to 2,000,000. The following schematic formula is intended to illustrate the compound of this type:

wherein
R ^{5 stands} for H, hydroxyethyl or -R ⁸ NR ⁶ R ⁷ and R ⁶ and R ^{7 stands} for H, hydroxyethyl or -R ⁸ NR ⁶ R ⁷ and R ^{8 stands} for (CH ₂ ) ₂ , with on average <40% , in particular <60% and particularly preferably <80% of the ethoxylatable NH functions of the polyethyleneimine are reacted with ethylene oxide.
(4) Compounds of Formula Ie

wherein
A _{5 is} C ₆ -C ₁₈ alkylene which is interrupted by at least one NR ⁵ group, where R ^{5 is} (CH ₂ ) _n NR ⁶ R ⁷ or alkyl which is optionally by at least one NR ⁵ group, where R ^{5 is} (CH ₂ ) _n R ⁶ R ⁷ or alkyl, is interrupted and / or is substituted by at least one NR ⁶ R ⁷ group,
n stands for 2 or 3 and
R ¹ , R ² , R ³ , R ⁴ , R ⁶ and R ^{7 are} independently hydroxy alkyl or H.

Particularly useful compounds of this type are polyamines of the formula:

(5) compounds of the formula If

wherein
A _{6 represents} C ₂ -C ₁₂ alkylene which is interrupted by at least one oxygen atom and
R ¹ , R ² , R ³ and R ^{4 are} independently hydroxyalkyl or H.

The alkylene chain is preferably interrupted by 1, 2 or 3 oxygen atoms. Particularly useful compounds of this type are the compounds of the following formulas:

(6) Compounds of the formula Ig

wherein
o, q and s independently represent 0 or an integer in the range from 1 to 6;
p and r independently of one another represent 1 or 2 and represent 0.1 or 2,
wherein the cycloaliphatic rings can also be substituted by 1, 2 or 3 alkyl radicals, and
R ¹ , R ² , R ³ and R ^{4 are} independently hydroxyalkyl or H.

Particularly useful compounds of this type are

(7) Polyalkanolamines obtainable by condensing Di- or trialkanolamines with themselves or with one another, optionally in the presence of mono- or polyhydric alcohols get or mono- or polyvalent amines.

An example of such oligomeric or polymeric compounds is the condensation product made from triethanol, which is ideally represented by the following schematic formula:

The compounds of the formulas Ia, Ib (except those mentioned Aminale), Ic, Id, Ie, If and Ig can be implemented by implementing the ent speaking polyamines are prepared with alkylene oxides.  

The reaction of amines with alkylene oxides, especially ethylene oxide and propylene oxide, to the corresponding alkanolamines is in Principle known. For this purpose, the amines in the presence of a Proton donor - generally water - with the alkylene oxides, preferably at temperatures between 30 and 120 ° C, below normal pressure or under increased pressure, preferably at 1 to 5 bar, implemented by approximately one per N-H function to be alkoxylated Equivalent of the alkylene oxide is used. To be as full as possible Permanent oxyalkylation can be a slight excess of alkylene oxide are used, but preferably the stoichio is used metric amount or even a slight deficit of the alkylene oxides towards the N-H functions. The oxyalkylation can with an alkylene oxide or with a mixture of two or more ren alkylene oxides take place. The alkoxylation can optionally be carried out with two or more alkylene oxides also take place in succession.

In addition to water, alcohols or acids also come as catalysts Question, but water is preferred (for the oxyalkylation of amines see. N. Schönfeld, Interface-Active Ethylene Oxide Adducts, Pp. 29-33, Wissenschaftliche Verlagsgesellschaft mbH, Stuttgart 1976 or S.P. McManus et al., Synth. Comm. 3, 177 (1973)).

The amount of water used as catalyst and / or solvent can fluctuate depending on requirements and needs. With liquid, low-viscosity amines range from 1 to 5% water to catalyze the reaction. Solid, highly viscous or polymeric amines are advantageously dissolved in water or dis pervades around; the amount of water can then be between 10 and 90% carry.

Under the conditions described for the oxyalkylation in In the presence of water essentially only the -NH groups implemented. An oxalkylation of the resulting OH groups takes place usually not take place, so essentially a monoalkoxy of the NH groups (i.e. a maximum of 1 per mole of NH mol of alkylene oxide added).

The average degree of alkoxylation of the active NH groups is at Compounds with less than 5 nitrogen atoms per molecule preferably <75%.

For example, one can use as starting polyamines α, ω-oligomethylenediamines such as 1,2-ethylenediamine, 1,3-propanedi amine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1,12-dode camethylene diamine, 2,2-dimethyl-1,3-propane diamine, 1,2-propane diamine amine, 2- (ethylamino) ethylamine, 2- (methylamino) propylamine, N- (2-aminoethyl) -1,2-ethanediamine, N- (2-aminoethyl) -1,3-propane  diamine, N- (2-aminoethyl) -N-methylpropane diamine, N, N-bis- (3-amino propyl) ethylenediamine, 4-aminoethyl-1,8-octanediamine, 2-Bu tyl-2-ethyl-1,5-pentanediamine, 2,2,4-trimethylhexamethylene diamine, 2-methylpentamethylene diamine, 1,3-diaminopentane, 3-isopropylamino propylamine, triethylenetetramine or tetraethylene pentamine.

Oligo and poly-N- (β-hydroxyethyl) amino compounds (aminals) can also by condensation of aliphatic dialdehydes and Diethanolamine can be produced.

Poly-N- (β-hydroxyethyl) amino compounds (8) are obtained as for example in US-A-4,505,839 and DE-A-32 06 459 described by thermal condensation of triethanolamine Poly (triethanolamine) or by thermal condensation of Alka nolamines to hydroxyl-containing polyethers. The condensation the alkanolamines can, as described in DE-A-12 43 874, in Presence of mono- or polyvalent primary or secondary amines or monohydric or polyhydric alcohols. Depending on the condensation conditions, the molecular weight of these products and so that their viscosity can be varied within a wide range.

The weight average molecular weights of these polycondensates are usually between 200 and 100,000.

The compounds of the formulas Ie can be prepared by alkoxylation so-called dendrimer polyamines are produced, the Synthesis by Michael addition of aliphatic diamines Acrylonitrile and subsequent catalytic hydrogenation in the 93/14147 is described. An example of this is that hydrogenated adduct of 4 mol acrylonitrile and ethylenediamine. This Hexamine with 4 primary amino groups can continue in an analogous manner are converted to the N-14-amine with 8 primary amino groups. Instead of ethylenediamine, other aliphatic di- and Polyamines are used.

Polymers containing amino groups, such as polyethyleneimine, can also be converted into useful compounds of the formula Ic with ethylene oxide in aqueous solution to give useful poly-N- (β-hydroxyethyl) amino compounds, the degree of conversion of the NH functions present generally being <40%. , in particular <60% and preferably <80%. The production of polyethyleneimine is generally known. Polyethyleneimines in the molecular weight range M _w = 800 to 2,000,000 are available, for example, from BASF under the name Lupasol®. Polyethyleneimines usually consist of branched polymer chains and therefore contain primary, secondary and tertiary amino groups. Their ratio is usually about 1: 2: 1. However, with very low molecular weights, higher proportions of primary amino groups are also possible. Largely linear polyethyleneimines, which are accessible via special manufacturing processes, are also suitable for this application.

Polymeric alkyleneimines with primary and / or secondary amino groups pen which after oxalkylation in the composition according to the invention tongues can be used are described in "Encyclopedia of Polymer Science and Engineering ", H. Mark (Editor), Revised Edition, Volume 1, pp. 680-739, John Wiley & Sons Inc., New York, 1985.

It is also possible to use hydroxyalkyl substituted polyalkyleneimines by polymerization of N-hydroxyalkylaziridines.

Furthermore, oxyalkylated allylamine polymers and co polymers used in the compositions of the invention become.

The compounds of the formula If can be derived from Oxami such as 4,7-dioxadecane-1,10-diamine, 4,9-dioxadecane-1,12-diamine, 4,11-dioxatetradecane-1,14-diamine, 4,9-dioxadodecane-1,12-diamine, Prepare 4,7,10-trioxatridecane-1,13-diamine. Suitable starting Amines are also polyoxyalkylene amines manufactured by Huntsman are sold under the name Jeffamine®. Examples for this are the diamines, Jeffamine D-230, Jeffamine-D-400, Jeffamine D-2000, Jeffamine D-4000, Jeffamine ED-600, Jeffamine ED-900, Jeffamine ED-2001, Jeffamine EDR-148 and the Triamine Jeffamine T-403, Jeffamine T-3000 and Jeffamine T-5000.

Reaction products of aromatic polyamines with alkylene oxide are in principle also for use in the invention Suitable compositions.

The activated carbon used as component C generally has a specific surface area in the range from 500 to 2,500 m ² / g, preferably in the range from 800 to 1,800 m ² / g and in particular in the range from 1,000 to 1,500 m ² / g g on (Langmuir surface in accordance with DIN 66131). Activated carbon with a high content of micropores (pore diameter <2 nm; see also Ullmann's Encyclopedia of Technical Chemistry, 5 ed, Vol. A5, p. 126) is preferred. The pore volume of the activated carbon used is preferably in the range from 0.2 to 1.4 ml / g, in particular 0.4 to 0.8 ml / g. The micropores generally take up 0.2 to 1.4 ml / g, preferably 0.2 to 0.5 ml / g and in particular 0.3 to 0.4 ml / g. Suitable activated carbons are commercially available.

Suitable activated carbons include both coarse granules Grain sizes <500 µm, for example in the range from 0.5 to 5 mm also finely divided activated carbon powder with particle size <500 µm. Be Activated carbon powders are preferred, especially those with part Chen size <200 microns and most preferably <120 microns.

Instead of or together with the activated carbon, coal can also be used molecular sieves can be used. Carbon molecular sieves are z. B. from Ullmann's Encyclopedia of Industrial hemistry, 5th ed. Vol. B3, pp. 9-10 known and commercially available.

Furthermore, the thermally curable preparation can additionally be one of P1 contain various, low carboxyl group polymer P2, in particular if the polymer P1 has at least 50% by weight of Car contains monomers (a) copolymerized in boxyl groups.

As polymer P2, each can be by radical polymerization available polymer are used, the ≦ 5 wt .-% of a α, β-ethylenically unsaturated mono- or dicarboxylic acid contains contains. Generally, it will be one by Emul Sion polymerization act polymer obtained. In the same However, it is also possible to use polymers which by another type of polymerization, for example by Sus pension polymerization are available. Preferably that is Polymer used in the form of a dispersion, which in particular a polymer content in the range from 40 to 80% by weight, in particular has in particular 50 to 75 wt .-%. It can be a Act primary dispersion, d. H. a dispersion, as in the emulsion polymerization, or a secondary disperser sion, d. H. a dispersion that is caused by subsequent disper yaw an already isolated polymer in the Dispersionsme dium has been obtained.

The dispersion medium is usually water. It however, water-miscible organic solvents, such as alcohols and ketones, for example methanol, ethanol, n-Pro panol, isopropanol, n-butanol, acetone or methyl ethyl ketone, ent to be hold.

The polymer P2 is generally composed of:
60 to 100 parts by weight, preferably 80 to 100 parts by weight, based on the total weight of the monomers for the polymer P2, at least one copolymerizable monomer (main monomer),
0 to 35 parts by weight, preferably 0 to 20 parts by weight, at least one functional monomer (comonomer) and
0 to 5 parts by weight, preferably 0 to 3 parts by weight, of an α, β-unsaturated mono- or dicarboxylic acid.

The main monomer is preferably selected from

• - Esters of preferably 3 to 6 carbon atoms containing α, β-mono-ethylenically unsaturated mono- or dicarboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, with generally C ₁ -C ₁₂ -, preferably C ₁ -C ₈ - and especially C ₁ -C ₄ alkanols. Such esters are in particular methyl, ethyl, n-butyl, isobutyl, tert-butyl and 2-ethylhexyl acrylate and methacrylate;
• vinyl aromatic compounds, such as styrene, α-methylstyrene, o-chlorostyrene or vinyl toluenes;
• - Vinyl esters of C ₁ -C ₁₈ mono- or dicarboxylic acids such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate;
• - butadiene.

Particularly preferred main monomers are methyl methacrylate, Methyl acrylate, n-butyl methacrylate, t-butyl methacrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, styrene and vinyl acetate.

Suitable comonomers are, in particular, the monomers b2, b3, b4, b5, b7, b9 and also mentioned for P1

• - acrylonitrile, methacrylonitrile;
• - C ₁ - to C ₄ -hydroxyalkyl esters of C ₃ - to C ₆ -mono- or dicarboxylic acids (see above), in particular acrylic acid, methacrylic acid or maleic acid, or those containing 2 to 50 moles of ethylene oxide, propylene oxide, butylene oxide or mixtures thereof alkoxylated derivatives, or esters of C ₁ - to C ₁₈ -alcohols alkoxylated with 2 to 50 mol ethylene oxide, propylene oxide, butylene oxide or mixtures thereof with the acids mentioned (monomers b ₆ ), such as, for. B. hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, butanediol-1,4-monoacrylate, ethyl diglycol acrylate, methyl polyglycol acrylate (11 EO), (meth) acrylic acid ester of 3,5,7,10 or 30 mol Ethylene oxide reacted C ₁₃ / C ₁₅ oxo alcohol or mixtures thereof;
• - Vinylphosphonic acid, Vinylphosphonsäuredimethylester u. a. phosphorus-containing monomers;
• - Allyl esters of C ₁ to C ₃₀ monocarboxylic acids;
• - diallyldimethylammonium chloride, vinylidene chloride, vinyl chloride rid, acrolein, methacrolein;
• - Monomers containing 1,3-diketo groups, such as, for. B. Acetoaceto xyethyl (meth) acrylate or diacetone acrylamide, urea group Pen-containing monomers, such as ureidoethyl (meth) acrylate, acrylami doglycolic acid, methacrylamidoglycolate methyl ether;
• - Monomers containing silyl groups such as. B. Trimethoxysilyl propyl methacrylate;
• - Glycidyl group-containing monomers such. B. Glycidylmeth acrylate.

Furthermore, the comonomers mentioned can also be crosslinked under P1 polymerizing monomers.

Particularly preferred comonomers are hydroxyethyl acrylate, hydro xypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate. Hydroxyethyl acrylate and hydroxy are very particularly preferred ethyl methacrylate, especially in amounts of 2 to 20 wt .-%, be moved to total monomers P2.

The α, β-ethylenically unsaturated mono- and dicarboxylic acids are in particular those with 3 to 6 carbon atoms. Examples include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methylmaleic acid or itaconic acid and half esters of ethylenically unsaturated dicarboxylic acids, such as maleic acid monoalkyl esters of C ₁ -C ₈ alkanols.

The polymers can be prepared using conventional polymerization processes in the manner described for P1 are preferably produced however, by radical aqueous emulsion polymerization. For all polymerization methods become the usual equipment used, e.g. B. stirred kettle, stirred kettle cascade, autoclave, tube reactors and kneaders.

In a preferred embodiment, the polymers are P2 by radical aqueous emulsion polymerization in the presence of a polymer P1, the at least 50 wt .-% carbo Polymerized xyl group-containing monomers. Here core-shell polymers are obtained which form a core from the  Polymer P2 and a hydrophilic shell from the polymer P1 ent hold. Similar core-shell polymers are obtained if you are on a submitted emulsion of the polymers P2 for the Preparation of the polymer P1 required monomer mixture on top lymerized. The polymer P1 can be in solution in the for Production of P2 required reaction medium as a finished Polymer presented, or prepared in situ by going to first polymerizes a monomer mixture 1, which becomes a polymer P1 leads and then a monomer mixture 2 aufpolymeri siert, which leads to a polymer P2.

The auxiliaries required for the polymerization of P2, such as Initiators and possibly regulators, and surface-active Substances such as emulsifiers and protective colloids correspond to that for aids named P1.

It may also be advantageous to use monomers which like acidic groups Have carboxyl or sulfo groups with a suitable base neutralize before or during the polymerization. Suitable Bases are e.g. B. the alkali or alkaline earth metal hydroxides, the Alkaline earth metal oxides, the alkali metal carbonates, preferably the corresponding calcium, sodium or potassium salts, and ammo niac, primary, secondary or tertiary amines such as ethanolamine, di- or Trimethanolamine, triethylamine or morpholine. Is preferred however, no odor-forming amines. Particularly preferred neutralization is completely dispensed with.

Are the polymers P2 by radical aqueous emulsions polymerisation produced, they fall as finely divided, stable Dispersion. The particle size of the polymer particles P2 in the Dispersion such as that caused by quasi-elastic light or determined using the analytical ultracentrifuge can generally be in the range from 20 to 1,500 nm and preferably 40 to 500 nm. The size distribution of the Particles in these dispersions can be monomodal or polymodal be. The molecular weights of the polymers P2 are in the Re gel in the range of 1,000 to 2,000,000 daltons (weight average) and especially in the range of 5,000 to 500,000 daltons. As a measure for the molecular weight, the K value of the polymers (according to Finkentscher, s. o.) can be used. It lies preferably in the range from 10 to 150 (1% by weight in DMF).

To produce the thermally curable composition according to the invention Components A, B and C as well as given if the polymer P2 ge together using known methods mixes. The order in which the mixing takes place irrelevant. However, component A is preferred with the  Mix polymer and then components B and C one after the other or add in premixed form. Component A is before preferably used as an aqueous solution or dispersion, wherein aqueous solutions of component A are particularly preferred, ins especially if A together with a dispersion of the polymer P2 is used. If necessary, it can be advantageous to Component A and optionally the dispersion of P2 to be diluted nen. Depending on the viscosity, the alkanolamine can be in pure form or in form diluted with water can be used, the content such solutions preferably <25 wt .-% alkanolamine, based on the solution. The components can be mixed at room temperature as well as at elevated temperature, e.g. B. at temperatures up to 100 ° C or above. It is finer possible the polymers P1 (component A) and / or P2 in the presence of the alkanolamine.

The quantitative ratios of component A (and possibly P2) for component B is usually chosen so that the molver ratio hydroxyl groups in component B to the carboxyl groups in Component A and optionally P2 in the range from 1:20 to 5: 1, in particular 1: 8 to 2: 1 and particularly preferably 1: 4 to 1: 1 lies.

This is usually due to weight ratios of polymer P1 to component B in the range from 100: 1 to 1: 1 (depending on the OH-Ge Halt the alkanolamine and the carboxyl group content in Kompo nente A) reached. Polymer P1 and component B are preferred in a weight ratio of 50: 1 to 2: 1 and in particular 10: 1 to 3: 1 used (always based on the active ingredients, i.e. Al kanolamine and polymer).

The activated carbon is preferably used in amounts of 0.5 to 30% by weight. and in particular in amounts of 1 to 10 wt .-% based on the Total amount of non-volatile, active ingredients in the Components A, B and P2 are used. (Active components are the pure alkanolamines, or the pure polymers P1 and P2, without usual auxiliaries or solvent or dispersant tel.)

Contains the thermally curable composition according to the invention in addition to the polymer P1 from component A, a polymer P2, see above the weight ratio of P1: P2 is in the range of 1:20 to 20: 1, preferably 1: 5 to 5: 1 and in particular 3: 1 to 1: 3.  

The pH of the compositions according to the invention is in the range range from 0 to 9, preferably 0.5 to 6, particularly preferably 1 to 4. Low pH values favor the thermal curing of the Compositions.

With an active ingredient content of 40% by weight, the viscosity of the aqueous compositions according to the invention is generally in the range from 10 to 100,000 mPa.s, measured in a rotary viscometer in accordance with DIN 53019 at 23 ° C. and a shear rate of 250 sec ^{. 1st} Viscosities from 20 to 20,000 mPa.s are preferred, particularly preferably from 30 to 5000 mPa.s.

The compositions according to the invention have a content of non-volatile proportions in the range of 20 to 75% by weight before adds 40 to 70 wt .-%.

The compositions of the invention can react contain accelerators, but preferably they are without such a reaction accelerator. Appropriate response accelerators are e.g. B. alkali metal hypophosphites, phosphites, -polyphosphate, -dihydrogenphosphate, polyphosphoric acid, hypo phosphoric acid, phosphoric acid, alkylphosphinic acid or oligomers or polymers of these salts and acids.

Strong acids such as, for. B. Sulfuric acid, p-toluenesulfonic acid. Also polymeric sulfonic acids, such as B. Poly (acrylamido-2-methylpropanesulfonic acid), poly (vinyl sulfonic acid), poly (p-styrene sulfonic acid), poly (sulfopropyl meth acrylate) and polymeric phosphonic acids such. B. Poly (vinylphosphon acid) and copolymers derived therefrom with the above The other comonomers are suitable.

It is also possible to use the accelerating sulfonic acid ren or phosphonic acids in the acidic polymer (A2) build by using the appropriate monomers such. B. Acrylic amido-2-methylpropanesulfonic acid, vinylsulfonic acid, p-styrenesul fonic acid, sulfopropyl methacrylate or vinylphosphonic acid in the Production of the polymeric carboxylic acids used as comonomer.

Also suitable as catalysts are organotitanates and Organ zirconates such as B. triethanol titanate, titanium chelate ETAM and Tetrabutyl zirconate, e.g. B. are sold by the Hüls company.

The compositions according to the invention can furthermore be customary Additives included depending on the application. For example they contain bactericides or fungicides. In addition, you can  they hydrophobic agents to increase the water resistance of the treated substrates included. Suitable water repellents are common aqueous paraffin dispersions or silicones. Further The compositions can include wetting agents, thickeners, Plasticizers, retention aids, pigments and fillers contain.

Finally, the compositions according to the invention may che fire retardants such. B. aluminum silicates, aluminum contain hydroxides, borates and / or phosphates.

Often the compositions also contain coupling reagents such as alkoxysilanes, for example 3-aminopropyltriethoxysilane, soluble or emulsifiable oils as lubricants and dust binders medium and wetting aids.

The compositions according to the invention can also be mixed with other binders, such as urea formaldehyde hyd resins, melamine-formaldehyde resins or phenol-formaldehyde resins, as well as used with epoxy resins.

The compositions according to the invention are free of formaldehyde. Formaldehyde-free means that the composition according to the invention tongues do not contain significant amounts of formaldehyde and even with drying and / or curing no significant amounts of Formaldehyde are released. Generally contain the Compositions <100 ppm formaldehyde. They enable the Her position of molded articles with a short curing time and lend the moldings have excellent mechanical properties.

The thermally curable, formaldehyde-free Compositions are essentially unchanged in use wets and therefore thermoplastic. If necessary, however a low degree of pre-networking can be set, e.g. B. by using monomers with two or more polymerisable groups.

When heated, the contained in the composition evaporates Water and the composition hardens. This pro Processes can take place sequentially or simultaneously. Under hardship In this context, the chemical change of the Understood the composition, e.g. B. networking through knotting of covalent bonds between the various components of the compositions, formation of ionic interactions and Clustering, formation of hydrogen bonds. Furthermore, at physical changes in the binder from the hardening  run, such as B. segregation processes, phase transformations or Phase inversion.

The curing temperatures are between 75 and 250 ° C, preferred between 90 and 200 ° C, particularly preferably between 100 and 180 ° C. Affect the duration and temperature of the heating the degree of curing. An advantage of the combination according to the invention settlements is that their hardening at comparatively low Temperatures can take place.

The curing can also take place in two or more stages. So can e.g. B. in a first step the curing temperature and -time be chosen so that he only a low degree of hardening is enough and largely complete curing in one two step. This second step can be spatial and take place separately from the first step. This will help for example the use of the composition according to the invention gene for the production of semi-finished products impregnated with binder possible, which are deformed and hardened elsewhere can.

The compositions are used in particular as binders for the Manufacture of molded articles from fibers, chips or chips used. These can be from renewable raw materials fabrics or synthetic or natural fibers, e.g. B. from Trade clothing waste. As renewable raw materials in particular special sisal, jute, flax, coconut fibers, kenaf, banana fibers, Called hemp and cork. Wood fibers or are particularly preferred Wood shavings.

The moldings preferably have a density of 0.2 to 1.4 g / cm ³ at 23 ° C.

In particular, plates and molded parts with an irregular contour can be considered as shaped bodies. Their thickness is generally at least 1 mm, preferably at least 2 mm, and their surface area is typically 200 to 200,000 cm ² . In particular, automotive interior parts, for. B. interior door panels, Ar maturträger, parcel shelves.

The amount by weight of the binder used is generally mean 0.5 to 40% by weight, preferably 1 to 30% by weight (bindemite tel solid), based on the substrate (fibers, chips or Chips).  

The fibers, chips or chips can be coated directly with the binder or mixed with the aqueous binder. The viscosity of the aqueous binder is preferably (in particular in the production of moldings from wood fibers or wood chips) to 10 to 10,000, particularly preferably to 50 to 5,000 and very particularly preferably to 100 to 2500 mPa.s (DIN 53019, rotational viscometer at 250 sec ^-1 ) is set.

The mixture of fibers, chips and chips and the bindemite tel can e.g. B. pre-dried at temperatures from 10 to 150 ° C. the and then to the moldings, for. B. at temperatures from 50 to 250 ° C, preferably 100 to 240 ° C and especially before draws 120 to 225 ° C and pressures generally 2 to 1000 bar, preferably 10 to 750 bar, particularly preferably 20 to 500 bar be pressed into the shaped bodies.

The binders are particularly suitable for the production of Wood-based materials such as chipboard and fiberboard (cf. Ullmann's Encyclopedia of Technical Chemistry, 4th edition 1976, Volume 12, pp. 709-727), which are made by gluing split wood, such as B. wood chips and wood fibers can be produced. The water resistance of wooden materials can be increased by adding a commercially available aqueous paraffin to the binder adds dispersion or other hydrophobizing agents, or this Water repellant before or after the fibers, Chips or chips.

The production of chipboard is well known and is for example in H.J. Deppe, K. Ernst Paperback of the Spanplat tentechnik, 2nd edition, published by Leinfelden 1982.

Chips with an average chip size are preferred is between 0.1 and 4 mm, in particular 0.2 and 2 mm, and the contain less than 6% by weight of water. However, it can also significantly coarser chips and those with higher moisture be used. The binder is as possible evenly applied to the wood shavings, the weight ratio Binder solid: wood chips preferably 0.02: 1 to 0.3: 1. A uniform distribution can be, for example achieve wisely by using the binder in finely divided form sprayed on the chips.

The glued wood chips then become a layer spread as uniform a surface as possible, whereby the Thickness of the layer according to the desired thickness of the finished chip plate aligns. The scattering layer is at a temperature of  e.g. B. 100 to 250 ° C, preferably from 120 to 225 ° C by application from pressures of usually 10 to 750 bar to a plate presses. The pressing times required can be in a wide range vary and are generally between 15 seconds to 30 minutes.

Made of medium density fibreboard (MDF) Wood fibers of suitable quality required for binding agents from bark-free wood chips by grinding in special mills or so-called refiners at temperatures of approx. 180 ° C be put.

For gluing, the wood fibers are generally covered with a Air flow whirled up and the binder in the so produced Fiber stream injected ("blow-line" process). The relationship Wood fibers to binders based on the dry content or Solids content is usually 40: 1 to 2: 1, preferably 20: 1 to 4: 1. The glued fibers are in the fiber stream at Temperatures of e.g. B. 130 to 180 ° C dried to a fiber spread non-woven and at pressures of 10 to 50 bar to plates or molded bodies.

The glued wood fibers can also, such as. B. in the DE-OS 24 17 243 described a portable fiber mat are processed. This semi-finished product can then be used in a second temporally and spatially separate step to plates or molded parts len, such as B. Next door panels of motor vehicles are processed.

Other natural fibers such as sisal, jute, hemp, flax, Coconut fibers, banana fibers and other natural fibers can be used with the Binders are processed into sheets and molded parts. The na Turf fibers can also be mixed with synthetic fibers, e.g. B. polypropylene, polyethylene, polyester, polyamides or poly acrylonitrile can be used. These plastic fibers can also as a cobinder in addition to the binder according to the invention act. The proportion of plastic fibers is preferred less than 50% by weight, in particular less than 30% by weight and very particularly preferably less than 10% by weight, based on all Chips, chips or fibers. The processing of the fibers can according to the process practiced with wood fiber boards gen. But it can also preformed natural fiber mats with the he binders according to the invention are impregnated, if appropriate with the addition of a wetting aid. The impregnated Mats are then pre-dried or wet with binder  Condition z. B. at temperatures between 100 and 250 ° C and pressures between 10 and 100 bar pressed into plates or molded parts.

Preferred have with the binders according to the invention in impregnated substrates with a residual moisture content of 3-20 wt .-%, based on the substrate to be bound.

The shaped bodies obtained according to the invention have a small one Water absorption, a low thickness swelling after water storage, good strength and are free of formaldehyde.

In addition, the compositions according to the invention can be used as Binder for coating and impregnating compounds for boards made of organic and / or inorganic fibers, not fibrous mineral fillers and starch and / or aqueous polymers use risk dispersions. The coating and impregnation materials give the panels a high flexural modulus and a high one Resistant to damp climates. The manufacture of such plates is known.

Such panels are usually used as soundproofing panels set. The thickness of the plates is usually in the range of about 5 to 30 mm, preferably in the range of 10 to 25 mm. The Edge length of the square or rectangular plates lies usually in the range of 200 to 2000 mm.

Furthermore, the compositions according to the invention can be used in the Coating and impregnation technology usual auxiliaries contain. Examples of these are finely divided inert fillers, such as aluminum silicates, quartz, precipitated or pyrogenic silica, Light and heavy spar, talc, dolomite or calcium carbonate; coloring pigments, such as titanium white, zinc white, iron oxide black etc., foam inhibitors, such as modified dimethylpolysiloxanes, and adhesion promoters and preservatives.

The components of the composition according to the invention are in the Coating composition generally in an amount of 1 to Contain 65 wt .-%. The proportion of inert fillers is generally from 0 to 85 wt .-%, the water content is at least at least 10% by weight.

The compositions are used in the customary manner by application to a substrate, for example by spraying, rolling, pouring or impregnation. The amounts applied, based on the dry content of the composition, are generally 2 to 100 g / m ² .

The amounts of additives to be used are known to the person skilled in the art knows and depends on the individual case in the individual case and the application.

The compositions according to the invention are also used as binders for insulating materials made of inorganic fibers, such as mineral fibers and Glass fibers are usable. Such insulation materials are technically Spinning melts of the corresponding mineral raw fabricated, see US-A-2,550,465, US-A-2,604,427, US-A-2,830,648, EP-A-354 913 and EP-A-5E7 480. The Together Settlement will then depend on the freshly made, still hot ones organic fibers sprayed on. The water then evaporates widely and the composition remains essentially uncured adhere to the fibers as a viscose mass. One this way provided endless, binder-containing fiber mat is approved by neten conveyor belts transported through a hardening furnace. There the mat hardens at temperatures in the range of approx. 100 to 200 ° C to a rigid matrix. After hardening, the Insulation mats assembled in a suitable manner.

The majority of the mine used in the insulation Ral or glass fibers have a diameter in the range from 0.5 to 20 µm and a length in the range of 0.5 to 10 cm.

The compositions according to the invention are also suitable as Binder for non-woven fabrics.

As nonwovens such. B. nonwovens made of cellulose, cellulose acetate, esters and ethers of cellulose, cotton, hemp, animal Fibers such as wool or hair and in particular nonwovens from synthe tables or inorganic fibers, e.g. B. aramid, carbon, Polyacrylonitrile, polyester, mineral, PVC or glass fibers called.

In the case of use as a binder for nonwovens can the compositions according to the invention z. B. the following addition substances contain: silicates, silicones, boron-containing compounds, Lubricants, wetting agents.

Glass fiber nonwovens are preferred. The unbound non-woven fabrics (Raw fiber fleeces), in particular made of glass fibers, are by the binders according to the invention bound, d. H. solidified.  

For this purpose, the binder according to the invention is preferably used in Weight ratio fiber / binder (solid) from 10: 1 to 1: 1, be particularly preferably from 6: 1 to 3: 1 on the raw fiber fleece z. B. applied by coating, impregnation, watering.

The binder is preferably in the form of a dilute aqueous preparation with 95 to 40 wt .-% water used.

After applying the binder to the raw fiber fleece he drying generally follows, preferably at 100 to 400, in particular 130 to 280 ° C, very particularly preferably 130 to 230 ° C over a period of preferably 10 seconds to 10 minutes, especially from 10 seconds to 3 minutes.

The bonded nonwoven fabric obtained has a high strength in dry and wet condition. The bindemite according to the invention tel especially allow short drying times and never Other drying temperatures.

The bonded nonwoven fabrics, in particular glass fiber nonwovens, are suitable for use as or in roofing membranes, as carrier materials for wallpaper or as an inliner or base material for floors coverings e.g. B. PVC.

When used as roofing membranes, the bonded fiber Nonwovens generally coated with bitumen.

The aqueous compositions according to the invention can be used continue to produce foamed sheets or moldings. To first the water contained in the composition Temperatures of <100 ° C up to a content of <20 wt .-% ent distant. The viscous composition thus obtained is then Temperatures <100 ° C, preferably at 120 to 300 ° C, foamed. As a blowing agent z. B. that still contained in the mixture Residual water and / or those arising during the hardening reaction serve gaseous reaction products. However, it can also han conventional blowing agents can be added. The resulting ver Networked polymer foams can be used, for example, for thermal insulation and be used for sound insulation.

The compositions according to the invention can be used Impregnation of paper and subsequent gentle drying so-called laminates, for. B. for decoration rative applications. These will be in a second Step on the substrate to be coated under the influence of  Laminated heat and pressure, the conditions chosen so be that the binder hardens.

The compositions according to the invention can furthermore be used for the manufacture of abrasive paper and abrasive articles in the manner conventionally carried out with phenolic resin as a binder. In the production of abrasive papers, a layer of the binders according to the invention is first applied as a base binder to a suitable backing paper (expediently 10 g / m ² ). The desired amount of abrasive grain is sprinkled into the moist base binder. After intermediate drying, a top coat is applied (e.g. 5 g / m ² ). The paper coated in this way is then tempered for 5 minutes at 170 ° C. for curing.

The hardness and Flexibility of the composition set to the desired level be put.

The compositions according to the invention are also suitable as a formaldehyde-free core sand binder for the production of cast iron Molds and cores for metal casting using the usual methods.

The herge using the preparations of the invention Molded bodies are low in odor compared to the below Use of known thermally curable preparations posed shaped bodies. They keep this quality with him high temperatures, for example above 50 ° C, at. Also at Temperatures above 70 ° C or even 80 ° C neither tend to invent preparations according to the invention, or those using such Formulations produced form a noticeable emis sion of odorous substances. It is also known aerosol formation during processing (so-called. "Qualming"), which occurs especially at elevated temperatures, both in the preparations according to the invention and in the Shaped bodies according to the invention reduced. Surprisingly ge hen these beneficial properties are not reduced tion of the mechanical properties of the mold according to the invention body hand in hand.

Furthermore, the activated carbon-containing fiber ver no or only one under the usual conditions low tendency to fogging, as z. B. determined in accordance with DIN 75201 can be. The fogging tendency of the activated carbon fiber ver Bundwerkstoffe is also under thermal stress. B. above 30 ° C lower than with activated carbon-free moldings.

Examples

The activated carbon Carboraffin®P from Lurgi was used (Langmuir surface: 1213 m ² / g according to DIN 66131, micropores volume: 0.357 ml / g).

Binder A

200 g of an aqueous solution of a copolymer consisting of 55 parts by weight of acrylic acid and 45 parts by weight of maleic acid (solids content 50%, pH 0.8, average molecular weight Mw = 3000) were mixed with 30 g of triethanolamine.
pH: 3.4
Viscosity: 580 mPas
Solids content: 56.5%.

Binder B

200 g of an aqueous solution of a copolymer consisting of 55 parts by weight of acrylic acid and 45 parts by weight of maleic acid (solids content 50%, pH 0.8, average molecular weight Mw = 3000) were mixed with 30 g of triethanolamine and 2.6 g of Carboraffin®P.
pH: 3.4
Viscosity: 630 mPas
Solids content: 57.0%.

Manufacture of chipboard

270 g of pine wood shavings (mean older size 1.2 mm; 95% of the chips between 0.3 and 2.5 mm) inner half of a minute 60 g of the by adding water to 45% Solids content adjusted binder solutions added.

After a mixing time of 2 minutes, the chips impregnated with binder were sprinkled into a 20 × 20 cm press mold and pre-compacted. Subsequently, at a press temperature of 200 ° C and a press pressure of 50 bar for three minutes to plates with a thickness of 0.6 cm and a density of 0.77 g / cm ^{3 was} pressed.

Checking the chipboard

The smell test was carried out based on the Volkswagen test regulation PV3900. For this purpose, chipboard samples (20 cm ³ volume) were stored in a sealed glass flask in a circulating air drying cabinet for 2 hours at 80 ° C. The test vessels were then cooled to 60 ° C, opened and immediately assessed by three testers for their smell. The samples were rated on the following rating scale:
Note 1: imperceptible smell
Grade 2: noticeable, not annoying smell
Grade 3: clearly noticeable but not yet annoying smell
Note 4: annoying smell
Grade 5 strong disturbing smell
Grade 6: unbearable smell.

The mean was formed from the three individual evaluations. The Results are shown in Table 1.

Furthermore, the fogging behavior of the test specimens according to the Volkswagen test specification PV 3015 (March edition) determined. For this the total carbon was determined using headspace gas chromatography emission of the test specimen determined. The results are in the table 1 specified.

Table 1

Claims (24)

1. Thermally curable, aqueous compositions containing

• A) at least one polymer P1 obtainable by free-radical polymerization, which contains 10 to 100% by weight of an α, β-ethylenically unsaturated mono- or dicarboxylic acid and / or its anhydride as copolymerized units, and
• B) at least one alkanolamine, with at least two hydroxyalkyl groups.
• C) 0.1 to 30 wt .-%, based on the total amount of components A and B, activated carbon and / or carbon molecular sieves.

2. Composition according to claim 1, wherein the polymer P1 20 to 100 wt .-%, in particular 40 to 100 wt .-% of the mono- or Polymerized dicarboxylic acid contains. 3. Composition according to one of the preceding claims, the polymer P1 as mono- or dicarboxylic acid min least contains a compound copolymerized, the out choose from acrylic acid, methacrylic acid, crotonic acid, Fumaric acid, maleic acid, 2-methyl maleic acid and itaconic acid. 4. Composition according to one of the preceding claims, wherein the polymer P1 contains other ethylenically unsaturated monomers copolymerized, which are selected from esters of (meth) acrylic acid with C ₁ -C ₁₂ monoalcohols or dialcohols, vinylaromatic compounds, butadiene, vinyl esters of aliphatic C ₂ -C ₁₂ monocarboxylic acids, C ₁ -C ₁₂ alkyl vinyl ethers, (meth) acrylonitrile, (meth) acrylamide, NC ₁ -C ₆ alkyl (meth) acrylamides and N, N-di-C ₁ -C ₆ - Alkyl (meth) acrylamides. 5. Composition according to one of the preceding claims, wherein the alkanolamine is selected from diethanolamine, triethanolamine and water-soluble, linear or branched aliphatic compounds which have at least two functional amino groups of type (a) or of type (b) per molecule
wherein R is hydroxyalkyl and R 'is alkyl, ent. 6. The composition according to claim 5, wherein at least one compound of the formula I is used as the alkanolamine
wherein
A represents C ₂ -C ₁₈ alkylene which is optionally substituted by one or more groups which are selected independently of one another from alkyl, hydroxyalkyl, cycloalkyl, OH and NR ⁶ R ⁷ , where R ⁶ and R ^{7 are} independent of one another represent H, hydroxyalkyl or alkyl, which is optionally interrupted by one or more oxygen atoms and / or NR ⁵ groups, where R ^{5 is} H, hydroxyalkyl, (CH ₂ ) _n NR ⁶ R ⁷ , where n is 2 to 5 is and R ⁶ and R ^{7 have} the meanings given above, or alkyl which in turn is interrupted by one or more NR ⁵ groups, where R ^{5 has} the meanings given above and / or by one or more NR ⁶ R ⁷ Groups can be substituted, where R ⁶ and R ^{7 have} the meanings given above, and R ¹ , R ² and R ³ and R ⁴ independently of one another are H, hydroxyalkyl, alkyl or cycloalkyl. 7. The composition according to claim 6, wherein the alkanolamine is selected from at least one compound of the formula Ia:
wherein
A _{1 represents} C ₂ -C ₁₂ alkylene which is optionally substituted by at least one alkyl group and / or at least one NR ⁶ R ⁷ group, where R ⁶ and R ⁷ independently of one another represent alkyl or hydroxyalkyl and
R ¹ , R ² , R ³ and R ⁴ independently of one another represent hydroxyalkyl or H or one of the radicals R ¹ and R ² and / or one of the radicals R ³ and R ^{7 represents} alkyl or cycloalkyl. 8. The composition according to claim 6, wherein the alkanolamine is selected from at least one compound of the formula Ib:
wherein
A _{2 represents} C ₂ -C ₈ alkylene which is interrupted by at least one NR ⁵ group, where R ⁵ (or the radicals R ⁵ independently of one another) stands for hydroxyalkyl or alkyl and
R ¹ , R ² , R ³ and R ⁴ independently of one another are hydroxyalkyl or. 9. The composition according to claim 6, wherein the alkanolamine is selected from at least one compound of the formula Ic:
wherein
A _{3 represents} C ₂ -C ₈ alkylene which is interrupted by at least one NR ⁵ group, where R ^{5 represents} H, hydroxyalkyl or CH ₂ CH ₂ NR ⁶ R ⁷ ,
R ¹ , R ² , R ³ and R ⁴ independently of one another represent alkyl which is optionally interrupted by at least one NR ⁵ group and / or is substituted by at least one NR ⁶ R ⁷ group,
R ^{5 represents} H, hydroxyalkyl or -R ⁸ NR ⁶ R ⁷ ,
R ⁶ and R ⁷ independently of one another are H, hydroxyalkyl or -R ⁸ NR ⁶ R ⁷ and
R ^{8 represents} an ethylene or propylene radical,
where (on average) at least 30% of the N atoms carry a hydroxyalkyl group. 10. The composition of claim 9, wherein it is the Alka nolamine with a reaction product of a polyethyleneimine Ethylene oxide.   11. Composition according to one of the preceding claims, where it is in the hydroxyalkyl group of the alkanolamine in the above definitions around a hydroxoxypropyl or hydroxy ethyl group. 12. Composition according to one of the preceding claims, the weight ratio of polymer P1 to alkanol min is in the range from 100: 1 to 1: 1. 13. The composition according to any one of the preceding claims, where with the activated carbon a mean particle size below 200 µm. 14. The composition according to any one of the preceding claims, where the activated carbon has a pore volume in the range of 0.2 to 1.4 ml / g. 15. The composition according to any one of the preceding claims, where the activated carbon has a specific surface (according to Lang muir) in the range from 500 to 2 500 m ² / g. 16. The composition according to any one of the preceding claims, where when the preparation additionally contains a polymer P2, by radical polymerization ethylenically unsaturated ter monomers is available, the monomers being less than 5 % By weight based on the total amount of monomers, monomers with Car include boxyl groups. 17. The composition of claim 16, wherein the weight ratio P1: P2 ranges from 1:20 to 20: 1. 18. The composition of claim 16 or 17, wherein the polymer P2 contains an α, β-ethylenically unsaturated C ₃ -C ₆ mono- or dicarboxylic acid, in particular acrylic acid or methacrylic acid, copolymerized. 19. The composition according to any one of claims 16 to 18, wherein the polymer P2 contains as the main monomer an ester of acrylic acid or methacrylic acid with a C ₁ -C ₁₂ alkanol, a vinyl aromatic compound or a vinyl ester of a C ₂ -C ₁₂ monocarboxylic acid in copolymerized form. 20. The composition according to any one of the preceding claims, the additionally contains a reaction accelerator.   21. A binder comprising a composition according to one of the Claims 1 to 20. 22. Low-odor molded article, obtainable by impregnating one Substrate with a composition according to one of the claims che 1 to 20 or a binder according to claim 21 and Aus harden the impregnated substrate. 23. Shaped body according to claim 22, wherein it is plates or Molded parts made of finely divided materials, especially chip panels and fiberboard, car interior trim, insulation materials or non-woven fabrics. 24. Use of a thermally curable, aqueous composition tongue according to one of claims 1 to 20 as a binder for low-odor shaped body made of fine-particle materials, esp especially from fibers, chips or chips.