MXPA00001475A - Aqueous compositions - Google Patents

Abstract

The invention relates to the use of thermally hardenable, aqueous compositions as binders for shaped bodies. Said compositions contain a low-acid and a high-acid polymerizate component as well as a hydroxyalkylated amine.

Description

"USING THERMALLY CURRENT AQUEOUS COMPOSITIONS AS AGGLUTINANTS FOR CONFORMED ITEMS" The present invention relates to the use of thermally curable aqueous compositions comprising a polymer component of low acid content and rich in acid and also a hydroxyalkylated amine as binders for shaped articles. Leaf-like fibrous structures, for example, continuous fiber tapes, shaped articles such as cardboard of old papers, etc., are often chemically consolidated using a polymeric binder. To improve the concentration, especially the concentrations of wet and heat resistance, binders comprising formaldehyde scavenging crosslinking agents are frequently used. This means, however, that there is a danger of formaldehyde emissions. Various alternatives to the binders of the prior art have been proposed to avoid formaldehyde emissions. For example, U.S. Patent Number A-4,076,917 discloses binders comprising polymers containing carboxylic acid. or carboxylic anhydride, with beta-hydroxyalkylamides as crosslinking agents. The molar ratio of carboxyl to hydroxyls is preferably 1: 1. A disadvantage is the relatively expensive production of beta-hydroxyalkylamides. Patent Number EP-A-445 578 discloses composite sheets of finely divided materials, for example glass fibers, wherein the mixtures of polycarboxylic acids of high molecular weight and polyhydric alcohols, alkanolamines or polyvalent amines act as binders. The polycarboxylic acids of high molecular mass described are polyacrylic acid, copolymers of methyl methacrylate / n-butylacrylate / methacrylic acid, and methyl methacrylate / methacrylic acid. The polyhydric alcohols and the alkanolamines employed are 2-hydroxymethyl-1,4-butanediol, trimethylolpropane, glycerol, poly (methyl methacrylate-co-hydroxypropyl acrylate), diethanolamine and triethanolamine. However, the sheets obtained are not sufficiently resistant to water. Patent Number EP-A-583 086 discloses aqueous binders free from formaldehyde to produce continuous fiber tapes, especially continuous glass fiber tapes. The binders comprise a polycarboxylic acid containing at least two carboxyls with or without anhydride groups. The polyacrylic acid in particular is used. The binder further comprises a polyol, for example, glycerol, bis UN, -di (beta-hydroxyethyl)] adipamide, pentaerythritol, diethylene glycol, ethylene glycol, gluconic acid, beta-D-lactose, sucrose, polyvinyl alcohol, diisopropanolamine, 2- (2-aminoethylamino) ethanol, triethanolamine, tris (hydroxymethylamino) methane and diethanolamine. These binders require a phosphorus-containing reaction accelerant to obtain continuous glass fiber tapes having suitable concentrations. It will be seen that the presence of this reaction accelerant can only be exhibited if a highly reactive polyol is used. The beta-hydroxyalkylamides are mentioned as highly reactive polyols. Patent Number EP-A-651 0B8 describes the corresponding binders for substrates composed of cellulose fiber. For these binders the inclusion of a phosphorus-containing reaction accelerant is mandatory. Patent Number EP-A-672 920 discloses formaldehyde-free bonding, impregnation or coating compositions comprising a polymer, constituted by 2 percent to 100 weight percent of an ethylenically unsaturated acid or acid anhydride as the comonomer , and at least one polyol. The polyols are substituted triazine, triazinetrione, benzene or cyclohexyl derivatives, the polyol radicals being always placed in the 1,3,5 positions of - The aforementioned rings. Despite high drying temperature, the binders provide only low tensile strength strengths in continuous fiberglass webs. Amine-containing crosslinking agents and predominantly linear polyols are also tested as part of the comparison experiments. It will be noted that crosslinking agents containing amine have a flocculating effect and that predominantly linear polyols lead to weaker crosslinking than cyclic polyols. Patent No. DE-A-22 14 450 discloses a copolymer comprised of 80 percent to 99 percent ethylene and 1 percent to 20 percent by weight maleic anhydride. The copolymer, in powder form or in dispersion in an aqueous medium, is used for surface coating together with a crosslinking agent. The crosslinking agent used is a polyalcohol containing amino. The cross-linking of the system, however, requires heating up to 300 ° C. Patent Number EP-A-257 567 discloses a polymer composition which is obtainable by emulsion polymerization of ethylenically unsaturated monomers, such as olefins, vinylaromatic compounds, alpha, beta-ethylenically unsaturated carboxylic acids and their esters, dicarboxylic anhydrides ethylenically unsaturated and vinyl halides. In the course of the polymerization, a water or alkali or dispersible water-soluble resin having a wet-average molecular weight of from about 500 to about 20,000 is added in order to influence the flow properties of the polymer composition. The resin is composed of olefins, vinylaromatic compounds, alpha, beta-ethylenically unsaturated carboxylic acids and the esters thereof or the ethylenically unsaturated dicarboxylic anhydrides. Ammonium hydroxide is indicated as an alkaline medium in which the resin must be soluble or dispersible. The composition can be used to produce coatings free of formaldehyde on wood substrates. Patent Number EP-A-576 128 discloses whippable adhesive compositions comprising an acid-rich polymer component and a low-acid polymer component. The acid-rich component is based on a monomer mixture of about 40 percent to 95 percent of an alkyl acrylate or alkyl methacrylate and 5 percent to 60 percent of an ethylenically unsaturated acid such as acrylic acid or methacrylic the low acid component is based on a monomer mixture of 90 percent to 100 percent of an alkyl acrylate or alkyl methacrylate and from 0 percent to 10 percent of an ethylenically unsaturated acid. The composition is prepared by aqueous emulsion polymerization, the acid-rich polymer component being polymerized in the presence of the low acid content polymer component or vice versa. The pH of the composition is adjusted to the desired level by adding ammonium hydroxide or sodium hydroxide. The composition can be used as a pressure sensitive adhesive, laminating adhesive, textile adhesive, tile adhesive and packaging adhesive, and a wood gum. U.S. Patent Number A-4,420, 583 and Patent Number EP-A -098 091 both describe a binder composition comprising an acid-rich polymer dispersion and a polymer in solution. The base of the latex is a monomer composition of vinylaromatic compounds and alkyl (meth) acrylates and up to 20 percent of an ethylenically unsaturated acid. The polymer in solution contains at least 10 percent of a monomer comprising (halohydroxypropyl) ammonium groups. The composition is stable during storage and is cured at room temperature after being added to the base (NaOH or the like). It is used for binders free of formaldehyde adhesives and coatings.

- US Patent Number A-5,314,943 discloses a mixture and consisting of a polymer dispersion and a water soluble copolymer, and its use as a binder for continuous fiber tapes. The polymer includes not only vinylaromatic compounds and alkyl (meth) acrylates but also preferably bifunctional monomers such as butadiene and vinyl acrylates. The content of the polymer mixture in solution is up to 5 percent, and the polymer itself consists of 25 percent to 60 percent of an ethylenically unsaturated monocarboxylic acid and from 40 percent to 75 percent of an ethylenically dicarboxylic acid unsaturated The disadvantages are the high temperatures required for healing. U.S. Patent No. 4,868,016 discloses a composition based on at least one thermoplastic latex polymer, insoluble in an aqueous alkaline medium, and at least one alkali soluble polymer, which is incompatible with the latex polymer. The latex polymer is an aqueous dispersed polymer which can be composed of acrylic or methacrylic esters, vinylaromatic compounds and vinyl esters and which further comprises from 0.5 percent to 3 percent by weight of an ethylenically unsaturated carboxylic acid, - in copolymerized form. The alkali-soluble polymer is composed of the same monomers but contains from 10 percent to 60 percent by weight of an ethylenically unsaturated carboxylic acid. To set a pH of > 7, the composition may contain ammonia, triethylamine, ethylamine or dimethylhydroxyethylamine. One of its possible uses is to provide substrates with a coating. It is an object of the present invention to provide formaldehyde-free binders for shaped articles which allow rapid curing at a low temperature and which impart good mechanical properties and high climatic resistance to the substrate. We have found that this object is achieved by using a composition comprising a polymer having few carboxyl groups, a polymer rich in carboxyl groups, and an amine having at least two hydroxyalkyl groups. The present invention therefore provides means for the use of thermally curable compositions comprising A) at least one polymer, obtainable by free radical polymerization, comprising < 5 percent by weight of an alpha, beta-ethylenically unsaturated mono- or dicarboxylic acid, in copolymerized form, B) "at least one polymer, obtainable by means of - free radical polymerization, comprising > 15 weight percent of an alpha, beta-ethylenically unsaturated mono- or dicarboxylic acid, in copolymerized form, and C) at least one alkanolamine having at least two OH groups. For the purposes of the present invention, the alkyl is preferably straight or branched chain alkyl of 1 to 18 carbon atoms, especially 1 to 12 carbon atoms and, preferably specific alkyl of 1 to 6 carbon atoms, such such as methyl, ethyl, n-propyl, i-propyl, n-butyl, secondary butyl, tertiary butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-dodecyl or n-stearyl. The hydroxyalkyl is preferably alkyl of hydroxy-1 to 6 carbon atoms and, in particular, 2-hydroxyethyl and 2- or 3-hydroxypropyl. The cycloalkyl is preferably cyclohexyl of 5 to 7 carbon atoms especially cyclopentyl and cyclohexyl. The aryl is preferably phenyl or naphthyl.

Component (A): - - The component (A) used can be any polymer that is capable of being obtained by free radical polymerization and containing < 5 weight percent of an alpha, beta-ethylenically unsaturated mono- or di-carboxylic acid in copolymerized form. In general, this polymer will be obtained by emulsion polymerization. It is also possible, however, to use polymers obtainable by another kind of polymerization, suspension polymerization being an example. The polymer is preferably used in the form of a dispersion having in particular a polymer content within the range of 40 percent to 80 percent by weight, especially 50 percent to 75 percent by weight. This dispersion can be a primary dispersion, in other words a dispersion as obtained from the emulsion polymerization, of a secondary dispersion, in other words a dispersion obtained by taking an already isolated polymer and subsequently dispersing it in the dispersion medium. The dispersion medium involved is usually water. It is also possible, however, that organic solvents miscible in water are present, such as alcohols and ketones, examples being methanol, ethanol, n-propanol, isopropanol, n-butanol, acetone and methylethyl ketone.

The alpha, beta-ethylenically unsaturated mono- and di-carboxylic acids involved are, in particular, those having from 3 to 6 carbon atoms. Examples are acrylic, methacrylic, crotonic, fumaric, maleic, 2-methylmaleic or itaconic acids and also the monoesters of the ethylenically unsaturated dicarboxylic acids such as the monoalkyl esters of maleic acid of the alkanols of 1 to 8 carbon atoms. The polymer (A) can also comprise, in copolymerized form, any ethylenically unsaturated monomer (monomers b) which can be copolymerized with the mono- or di-carboxylic acid. These monomers are: vinylaromatic compounds, such as styrene, alpha-methylstyrene and vinyltoluenes (bi monomers). Linear 1-olefins, branched chain 1-olefins or cyclic olefins (b) monomers, such as ethene, propene, butene, isobutene, pentene, cyclopentene, hexene, cyclohexene, octene, 2,4,4-trimethyl- 1-pentene alone or mixed with 2,4,4-trimethyl-2-pentene, olefin of 8 to 10 carbon atoms, 1-dodecene, olefin of 12 to 14 carbon atoms, octadecene, 1-eicosene (C20) 1 olefin of 20 to 24 carbon atoms; Oligoolefins prepared with metallocene catalysis and having a - - terminal double bond, such as oligopropene, oligohexene and oligooctadecene; olefins prepared by cationic polymerization and having a high content of alpha-olefin, such as polyisobutene. Preferably, however, no ethene or linear 1-olefin is copolymerized in the polymer.

Butadiene.

The vinyl and allyl alkyl ethers having from 1 to 40 carbon atoms in the alkyl, it is also possible for the alkyl to carry other substituents such as hydroxyl, amino or dialkylamino or one or more alkoxylate groups (monomers 03), the examples methyl, ethyl, propyl, isobutyl, 2-ethylhexyl, cyclohexyl, 4-hydroxybutyl, decyl, dodecyl, octadecyl, 2- (diethylamino) ethyl, 2- (di-n-butylamino) ethyl and methyl diglycol vinyl ether, and the corresponding allyl ethers and / or mixtures thereof Alkyl-substituted acrylamides and acrylamides (monomers 04), such as acrylamide, methacrylamide, N-tert-butylacrylamide and N-methyl (meth) acrylamide. (monomers 05), such as styrenesulfonate, allylsulfonic acid, methallylsulfonic, vinylsulphonic, allyloxybenzenesulfonic, and 2-acrylamido-2-methylpropanesulfonic acid, and their corresponding alkali metal salts or ammonium salts, and / or mixtures thereof. alkyl esters of 1 to 8 carbon atoms or esters of 1 to 4 hydroxyalkyl atoms of mono- or di-carboxylic acids of 3 to 6 carbon atoms (see above), especially of acrylic, methacrylic or maleic acid, or the esters of these acids with alcohols of 1 to 18 carbon atoms which are alkoxylated with from 2 to 50 moles of ethylene, propylene or butylene oxide or mixtures of these oxides (monomers bg), examples being (meth) acrylate of methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylhexyl, hydroxyethyl or hydroxypropyl, 1,4-butanediol monoacrylate, dibutyl maleate, ethyldiglycol acrylate, methyl polyglycol acrylate (11 EO), (meth) acrylic esters of oxo-alcohol of 13/15 carbon atoms which has been reacted with 3, 5, 7, 10 or 30 moles of ethylene oxide, and / or mixtures thereof. Alkylaminoalkyl (meth) acrylates or alkylaminoalkyl (meth) acrylamides, or their quaternization products (b? Monomers), examples being 2- (N, N-dimethylamino) ethyl (meth) acrylate, (meth) acrylate 3- (N, N-dimethylamino) ropyl, 2- (N, N, N-trimethylammonium) ethyl (meth) acrylate chloride, 2-dimethylaminoethyl (meth) acrylamide, 3-dimethylaminopropyl (meth) acrylamide and chloride of 3-trimethylammoniopropyl (meth) acrylamide. Vinyl and allyl esters of monocarboxylic acids of 1 to 30 carbon atoms (bg monomers), such as vinyl formate, acetate, propionate, butylate, valerate, 2-ethylhexanoate, nonanoate, decanoate, pivalate, palmitate, stearate and laurate. As additional monomers, bg, there may be mentioned: N-vinylformamide, N-vinyl-N-methyl ormamide, styrene, alpha-methylstyrene, 3-methylstyrene, butadiene, N-vinylpyrrolidone, N-vinylimidazole, l-vinyl-2-methylimidazole. , l-vinyl-2-methylimidazoline, N-vinylcaprolactam, acrylonitrile, methacrylonitrile, allyl alcohol, 2-vinylpyridine, 4-vinylpyridine, diallyldimethylammonium chloride, vinylidene chloride, vinyl chloride, acrolein, methacrolein and vinylcarbazole and / or mixtures thereof. The preferred monomers are also the aforementioned esters of acrylic and methacrylic acid, the vinylaromatic compounds, butadiene, esters of vinyl (meth) acrylonitrile and the aforementioned (meth) acrylamides. Particularly preferred monomers are methyl acrylate, ethyl acrylates, butyl acrylates, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylates, hydroxyethyl acrylates, hydroxypropyl acrylate, hydroxybutyl acrylates, hydroxyethyl methacrylate, styrene, butadiene. , vinyl acetate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide and / or N-butylacrylamide. The polymers can be prepared by customary polymerization techniques, for example by bulk polymerization of free radical, emulsion, suspension, dispersion, precipitation and solution. These polymerization techniques are preferably operated in the absence of oxygen, preferably in a stream of nitrogen. All polymerization methods use the usual apparatus, examples being stirred containers, cascades of stirred vessels, autoclaves, tube reactors and kneading apparatus. It is preferred to operate by the emulsion, precipitation or suspension polymerization method. Specific preference is given to the emulsion polymerization method in an aqueous medium.

The use of aqueous emulsion polymerization provides polymers having a weight average molecular weight of from 1,000 to 2,000,000, preferably from 5,000 to 500,000. The K values usually fall within the range of 15 to 150 (1 weight percent concentration in "dimethylformamide.) The average weight particle size (which is determined by means of an ultracentrifuge) preferably falls within the scale from 50 to 1000 nm The dispersion can have a mono or polymodal particle size distribution The emulsion polymerization can be carried out in such a way that the volume solids content is within the 20 percent scale at 70 percent, preferably 30 percent to 60 percent Emulsion polymerization with the aforementioned carboxyl-containing monomers is conventionally carried out, as described, for example, in Patent Number DE-A-31 34 222 or in US Patent Number A-5,100,582 The polymerization is preferably carried out in the presence of compounds that form free radicals (initiators). Preferably, 0.05 percent to 15 percent by weight, with specific preference of 0.2 percent to 8 percent by weight, of these compounds, based on the monomers used in the polymerization, is required. Examples of suitable polymerization initiators are peroxides, hydroperoxides, peroxodisulfates, percarbonates, peroxo esters, hydrogen peroxide and azo compounds. Examples of initiators that may be "either soluble or insoluble in water, or hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxodicarbonate, dilauroyl peroxide, methylethyl ketone peroxide, di-tert-butyl peroxide, acetylacetone peroxide , tertiary butyl hydroperoxide, eumenal hydroperoxide, tertiary butyl perneodecanoate, tertiary-butyl tertiary-pervivalate, tertiary butyl perpivalate, tertiary butyl perneohexanoate, tertiary butyl per-2-ethylhexanoate, tertiary butyl perbenzoate, lithium peroxodisulfates , sodium, potassium and ammonium, azodiisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2- (carba oylazo) isobutyronitrile and 4,4-azobis (4-cyanovaleric acid) can also be used as polymerization initiators The redox initiator systems The initiators can be used alone or mixed with one another, examples being mixtures of hydrogen peroxide and peroxodisulfat or sodium For polymerization in an aqueous medium, it is preferred to employ water-soluble initiators. To prepare polymers of low average molecular weight, it is often convenient to carry out the copolymerization in the presence of regulators. This can be done using conventional regulators, examples being SH-organic containing compounds such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, tertiary butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and tertiary dodecyl mercaptan, aldehydes from 1 to 4 carbon atoms, such as formaldehyde, acetaldehyde, propionaldehyde, hydroxylammonium salts, such as hydroxylammonium sulfate, formic acid, sodium bisulfite or isopropanol. Polymerization regulators are usually employed in amounts of 0.1 percent to 10 percent by weight, based on the monomers. To prepare the relatively high molecular weight copolymers it is often convenient to carry out the polymerization in the presence of crosslinking agents. These crosslinking agents are compounds having two or more ethylenically unsaturated groups, such as diacrylates or dimethacrylates of at least saturated dihydric alcohols, examples being ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, dimethacrylate 1,2-propylene glycol, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, hexanediol diacrylate, hexanedioldimetacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methylpentanediol diacrylate and 3-methylpentanediol dimethacrylate. The acrylic and methacrylic esters of alcohols having more than two OH groups can also be used as crosslinking agents, the examples being trimethylolpropane triacrylate and trimethylolpropane trimethylacrylate. An additional class of crosslinking agents is that of the diacrylates or dimethacrylates of polyethylene glycols or polypropylene glycols having molecular weights in each case from 200 to 9000. In addition to the homopolymers of ethylene oxide and / or propylene oxide it is also possible to employ copolymers of block of ethylene oxide and propylene oxide or the copolymers of ethylene oxide and propylene oxide wherein the units of ethylene oxide and propylene oxide are randomly distributed. Oligomers of ethylene oxide and / or propylene oxide are also suitable for preparing the crosslinking agents, examples being diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate and / or tetraethylene glycol dimethacrylate. . Additional suitable crosslinking agents are vinyl acrylate, vinyl methacrylate, vinyl itaconate, divinyl adipate, divinyl butanediol ether, trivinyl ether of trimethylolpropane, allyl acrylate, allyl methacrylate, triallyl ether of pentaerythritol, triallyl - sucrose, pentaalylsucrose, methylenebis (meth) acrylamide, divinylethylene urea, divinylpropylene urea, divinylbenzene, divinyl dioxane, triallyl cyanurate, tetraallylsilane, tetravinylsilane and bis- or poly-acrylsiloxanes (eg, Tergomers® from Th. Goldschmidt AG). The crosslinking agents are preferably used in amounts of 10 parts per million to 5 weight percent, based on the monomers to be polymerized. When operating in accordance with the emulsion polymerization, precipitation, suspension or dispersion method it can be advantageous to stabilize the droplets or particles of the polymer by means of surfactant auxiliaries. These auxiliaries are typically emulsifiers or protective colloids. Anionic, nonionic, cationic and amphoteric emulsifiers are suitable. Preference is given to anionic emulsifiers of which the examples are alkylbenzenesulfonic acids, sulfonated fatty acids. sulfosuccinates, fatty alcohol sulphates, alkylphenol sulfates and fatty alcohol ether sulfates. As non-ionic emulsifiers it is possible, for example, to use alkylphenol ethoxylates, primary alcohol ethoxylates, fatty acid ethoxylates, alkanolamide ethoxylates, fatty amine ethoxylates, EO / PO block copolymers and alkyl polyglucosides. The cationic and amphoteric emulsifiers which can be used are quaternized amino alkoxylates, alkylbetaines, alkylamidobetaines and / or sulfobetaines, for example. Examples of typical protective colloids are cellulose derivatives, polyethylene glycol, polypropylene glycol, ethylene glycol and propylene glycol copolymers, polyvinyl acetate, polyvinyl alcohol, polyvinyl ethers, starch and starch derivatives, dextran, polyvinyl pyrrolidone, polyvinyl pyridine, polyethylene imine , polyvinylimidazole, polyvinylsuccinimide, polyvinyl-2-methylsuccinimide, polyvinyl-1,3-oxazolid-2-one, polyvinyl-2-methylimidazoline and copolymers containing maleic acid or maleic anhydride, as described, for example, in the patent DE 2 501 123. Emulsifiers or protective colloids are usually used in concentrations of 0.05 percent to 20 percent by weight, based on the monomers.

- If the polymerization is carried out in an aqueous emulsion or dilution, then the monomers can be completely or partially neutralized by customary inorganic or organic bases before or during the polymerization. Examples of suitable bases are alkali metal or alkaline earth metal compounds such as sodium, potassium or calcium hydroxide, sodium carbonate, ammonia and primary, secondary or tertiary amines, such as di- or tri-ethanolane. Preferably, before or during the polymerization, the ethylenically unsaturated carboxylic acids are not neutralized. Preferably, no neutralizing agent is added, in addition to the component (C) after the polymerization of any of them. The polymerization can be carried out in a customary manner in accordance with a large number of variants, continuously or discontinuously. If the addition polymer is prepared by the method of solution polymerization, precipitation or suspension in a solvent or mixture of volatile solvents in steam, then the solvent can be separated by introducing steam, in order to arrive at an aqueous solution or aqueous dispersion. The polymer can also be separated by a drying process of the organic diluent.

Component (B): From 15 percent to 100 percent by weight of component (B), preferably from 20 percent to 100 percent by weight, and preferably from 40 percent to 100 percent by weight is composed of at least one ethylenically unsaturated mono- or di-carboxylic acid. The polymer may also be entirely or partially in the form of a salt, even when the acidic form is preferred. The polymer, both in the acidic form and in the salt form, preferably soluble in water. It is essentially free of carboxylic anhydride structures. The weight average molecular weight of component (B) is greater than 500 and usually less than 5 million. The ~ K values of polymers (according to H. Fikentscher, Cellulose-Chemie 13 (1932), pages 58 to 64, 71 and 74), which are a measure of molecular weight, are generally within the range of 10 to 150 (measured in solution of concentration in weight of 1 percent). The polymer generally has at least 4 carboxyl groups, or salt groups deriving therefrom, per polymer chain. The ethylenically unsaturated carboxylic acids that can be used have already been specified above in relation to the component (A). The polymers can also be obtained by starting from mono- or di-carboxylic anhydrides ethylenically unsaturated, alone or mixed with the carboxylic acids mentioned above. The functions of the anhydride are converted into carboxyl groups under the polymerization conditions, for example polymerization by solution or emulsion in the aqueous medium, or by reaction with an acid or a base after the polymerization. The ethylenically unsaturated carboxylic anhydrides which are used are in particular maleic, itaconic, acrylic and methacrylic anhydride. The monomers "particularly preferred for preparing component B are acrylic and methacrylic acid, methacrylic anhydride, maleic anhydride, maleic acid, methyl methacrylate, tertiary butyl methacrylate, ethyl acrylate, n-butyl acrylate, 2-acrylate, hydroxyethyl, styrene and acrylamido-2-methylpropanesulfonic acid In addition, of the mono- or dicarboxylic acids, the polymer (B) can also comprise from 0 to 85 weight percent, preferably from 0 to 80 percent. percent by weight and, in particular, from 0 percent to 60 percent by weight of at least one additional monomer in copolymerized form The monomers that can be used have already been specified above in relation to the component (A) which is identified therein as monomers b). The implementation of polymerization, and the auxiliaries, have already been described above in relation to component (A). In addition, from the polymerization technique specified above in relation to the component (A), the polymers (B) can also be prepared by solution polymerization. The use of aqueous free radical solution polymerization provides water soluble polymers and copolymers starting preferably from 50 percent to 100 percent by weight of the carboxylic acids mentioned above, carboxylic anhydrides, monoesters or a mixture of two or more of these compounds Its weight-average molecular weight usually falls within the range of 5D0 to 1,000,000, preferably 2000 to 200,000. The K values of the polymers generally fall within the range of 10 to 150, preferably 15 to 100 (which are measured in a solution in water of concentration of 1 weight percent). The solids content is generally within the range of 10 percent to 80 percent by weight, preferably 20 percent to 65 percent by weight. The polymerization can be carried out at a temperature of 20 ° C to 300 ° C, preferably of 60 ° C to - - 200 ° C. Solution polymerization is conventionally carried out as described, for example, in Patent Number EP-A-75 820 or DE-A-36 20 149. Polymer (B) can also be obtained by grafting maleic acid and / or the maleic anhydride and / or a mixture of monomers comprising maleic acid or maleic anhydride in a graft base. Examples of suitable grafting bases are monosaccharides, oligosaccharides, modified polysaccharides and alkyl polyglycol ethers. These graft polymers are described, for example, in Patent Number DE-A-4 003 172 and EP-A-116 930.

Component (C): Suitable as component (C) are the alkanolamines of the formula Rb I R N Rc wherein Ra is H, alkyl of 1 to 10 carbon atoms or hydroxyalkyl of 1 to 10 carbon atoms and R ^ and Rc are hydroxyalkyl of 1 to 10 carbon atoms.

Preferably, R and Rc are independently hydroxyalkyl of 2 to 5 carbon atoms and Ra is H, alkyl of 1 to 5 carbon atoms and hydroxyalkyl of 2 to 5 carbon atoms. Examples of the compounds of this formula are diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, methyldiethanolamine, butyldiethanolamine and methyldiisopropanolamine. Specific preference is given to triethanolamine. Also suitable are alkanolamines which are selected from water-soluble, linear or branched aliphatic compounds comprising per molecule at least two amino functional groups of type (a) or type (b) R R R Rt N N (a) (b) wherein R is hydroxyalkyl and R 'is alkyl. The related alkanolamines preferably comprise at least one compound of the formula I: R R? / NAN (I) R "R3 wherein A is alkylene of 2 to 18 carbon atoms which is unsubstituted or substituted by one or more groups which are independently selected from alkyl, hydroxyalkyl, cycloalkyl, OH and NR6R7, wherein R ^ and R7 are independently H, hydroxyalkyl or alkyl, and which has not been interrupted or interrupted by one or more oxygen and / or NR ~ groups; wherein R ^ is H, hydroxyalkyl, (CH2) nNR6R7, wherein n is 2 to 5 and R6 and R7 are as defined above, or alkyl, which in turn is interrupted by one or more N groups. .5 wherein R ^ is as defined above, and / or is substituted by one or more of the groups of NR6R7, wherein R6 and R7 are as defined above; or A is a radical of the formula: where o, q and s are independently 0 or an integer from 1 to 6, p and r are independently 1 or 2 and t is 0, 1 or 2, it is also possible that the cycloaliphatic radicals - - they are substituted by 1, 2 or 3 alkyls, and R1, R ^ and R3 and R4 independently are H, hydroxyalkyl, alkyl or cycloalkyl, the compounds having at least two, and preferably at least three, hydroxyalkyls per molecule. Compound (C) is particularly preferred: (1) The compounds of the formula RJ R¿ N A? _ N (the) R2 R ~ wherein A] _ is alkylene of 2 to 12 carbon atoms which is unsubstituted or substituted by at least one alkyl and / or at least one group of NR6R7, wherein R6 and R7 are independently alkyl or hydroxyalkyl, and R1, R3, R3 and R4 independently are hydroxyalkyl or H, or one of R3 and R2 and / or one of R3 and R4 is alkyl or cycloalkyl. Particularly useful compounds of this type are the compounds of the following formulas: where x is 2 to 12, especially 2, 3, 6, 8, 10 or 12, Other compounds of the formula la are the aminals of the formula O X = 1-12 (2) The compounds of the formula Ib RJ R 'N A2 _ N Ib) R¿ R- wherein 2 is alkylene of 2 to 8 carbon atoms which is interrupted by at least one group of NR ^ wherein R ^ (or each R ^ independently) is hydroxyalkyl or alkyl, and R ^, R ^, R3 and R4 independently are hydroxyalkyl or H. The radical 2 is preferably interrupted by one or two groups of NR5. Particularly useful compounds of this type are the compounds of the following formulas: OH OH N '• N' CHi OH OH (3) The compounds of the formula le: R R N A3 N (Ic) R2 R wherein 3 is alkylene of 2 to 8 carbon atoms which is interrupted by at least one group of NR wherein R ^ is H, hydroxyalkyl or CH2CH2NR6R7, R ^, R2, R3 and R are independently alkyl which is not interrupted or which is interrupted by at least one group of NR5 and / or is not substituted or substituted by at least one group of NR ^ R7, R5 is H, hydroxyalkyl or -R8NR6R7 and R and R7 are independently H, hydroxyalkyl or R8NRßR7 , R8 is an ethylene or propylene radical, wherein (on average) at least 3Q percent, in particular the > 60 percent and preferably > 80 percent of the nitrogens (capable of hydroxyalkylating) carry a hydroxyalkyl. The alkylene group having 2 to 8 carbon atoms is preferably interrupted by at least two groups of NR ^. Particularly useful compounds of this type are the reaction products of ethylene oxide with polyethyleneimines of various molecular weights having two or more structural elements NR ^ R7 and NR ^. Useful polyethyleneimines are those whose weight average molecular weight falls within the range of 400 to 2,000,000. The diagrammatic formula presented below is intended to illustrate this type of compounds: wherein R5 is H, hydroxyethyl or -R8NRßR7 and R6 and R7 are H, hydroxyethyl or -R8NR ^ R7 and R8 is (CH2), wherein on average > 40 percent, especially > 60 percent and, with specific preference, > 80 percent of the NH capable of being ethoxylated from polyethylenimine have been reacted with ethylene oxide. (4) The compounds of the formula RJ R4 \ / N A5 _ N (ie; / \ R2 R ° where A5 is alkylene of 6 to 18 carbon atoms which is interrupted by at least one group of NR ^ wherein R ^ is (CH2) nNR6R7 or alkyl which is uninterrupted or interrupted by at least one "group of NR ^ wherein R ^ is (CH2) nR6R7 or alkyl and / or is unsubstituted or substituted by at least one group of NR ^ R7, n is 2 or 3 and R1, R2, R, R4, R6 and R7 are id pending hydroxyalkyl or H. Particularly useful compounds of this type are polyamines of the formulas: - (5) The compounds of the formula If RJ R¿ N __ A6 N (If) R2 R wherein Ag is alkylene of 2 to 12 carbon atoms which are interrupted by at least one oxygen, and R ^, R2, R and R4 are independently hydroxyalkyl or H.

The alkylene chain is preferably interrupted by 1, 2 or 3 oxygens. Particularly useful compounds of this type are the compounds of the following formulas: 6) The compounds of the formula Ig, where o, q and s independently are 0 or an integer within the scale of 1 to 6; pyr are independently 1 or 2, and t is 0, 1 or 2, and wherein the cycloaliphatic rings can also be substituted by 1, 2 or 3 alkyls, and R1, R2, R3 and R4 are independently hydroxyalkyl or H. The compounds particularly useful of this type are: ' [1) Polyalkanolamines obtainable by condensation of di- or tri-alkanolamines with themselves or with one another, in the presence or absence of mono- or polyhydric alcohols or mono- or polyfunctional amines.

- - An example of these oligomeric or polymeric compounds is the condensation product, prepared from triethanol, which is represented in an idealized form by the following diagrammatic formula: R R \ / N CH2 _ CH2 0 CH2 _ CH2 N / \ R R R = CH2 CH2 OH R O CH2 CH2 0 CH2 CH2 N R Compounds of the formulas Ia, Ib (except for the aminals), Le, Id, Le, If and Ig can be prepared by reacting the corresponding polyamines with alkylene oxides. The reaction of amines with alkylene oxide, especially ethylene oxide and propylene in the corresponding alkanolamines is known in principle. It is carried out by reacting the amines with the alkylene oxides in the presence of a proton donor generally water - preferably at a temperature of 30 ° C to 120 ° C under atmospheric pressure or superatmospheric preferably of 1 to 5 bar, using approximately one equivalent of the alkylene oxide per N-H function to be alkoxylated. For the almost complete alkoxylation, a small excess of alkylene oxide can be used even when it is preferred to employ the stoichiometric amount, or even a slightly smaller amount thereof, of an alkylene oxide in relation to the N-H functions. The alkoxylation can be carried out with an alkylene oxide or with a mixture of two or more alkylene oxides. Alternatively, the alkoxylation can be carried out successively with two or more alkylene oxides. Suitable catalysts other than water are alcohols or acids, even when water is preferred (with respect to the alkoxylation of amines, see N. Schdnfeld, Grenzfláchenaktive Ethylenoxid-Addukte, pages 29 to 33, issenchaftliche Verlagsgesellschaft mbH, Stuttgart 1976 or SP McManus et al., Synth, Comm. 3 (1973) 177). The amount of water used as the catalyst and / or the solvent can be varied depending on what is required. In the case of liquid amines of low viscosity, the amounts of water of 1 percent to 5 percent are sufficient to catalyze the reaction. The highly viscous or polymeric solid amines are advantageously reacted as solutions or dispersions in water; in this case, the amount of water can be 10 percent to 90 percent.

Under the conditions described for the alkoxylation in the presence of water, essentially only the -NH groups are reacted. The alkoxylation with the resulting OH groups is generally not carried out essentially without monoalkoxylation of the NH groups (in other words, no more than 1 mole of alkylene oxide is added per mole of NH). The average degree of alkoxylation of the active NH groups is preferably > 75 percent in the case of compounds that have less than 5 nitrogens per molecule. Examples of starting polyamines that can be used are alpha, omega-oligomethylenediamines, such as 1,2-ethylenediamine, 1,3-propanediamine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1,12-dodecamethylenediamine, 2, 2-dimethyl-1,3-propanediamine, 1,2-propanediamine, 2- (ethylamino) ethylamine, 2- (methylamino) -propylamine, N- (2-aminoethyl) -1,2-ethanediamine, N- (2- aminoethyl) -1,3-propanediamine, N- (2-aminoethyl) -N-methylpropanediamine, N, N-bis- (3-aminopropyl) -ethylenediamine, 4-aminoethyl-l, 8-octanodia ina, 2-butyl- 2-ethyl-l, 5-pentanediamine, 2,2,4-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, 1,3-diaminpentane, 3-isopropylaminopropylamine, triethylenetetramine or tetraethylenepentamine.

The oligo- and poly-N- (beta-hydroxyethyl) amino compounds (aminals) can also be prepared by condensing the aliphatic dialdehydes with diethanolamine. The poly-N- (beta-hydroxyethyl) amino compounds (8) are obtained, as described for example in the US Patent Number A-4, 505, 839 and Patent Number DE-A-3 206 459, by condensation of triethanolamine in poly (triethanolamine) or by thermal condensation of alkanol amines in hydroxyl-containing polyethers. The alkanolamines can also be condensed, as described in Patent Number DE-A-1 243 874, in the presence of mono- and / or polyfunctional primary or secondary amines or mono- and / or polyhydric alcohols. Depending on the condensation conditions, the molecular weight of these products and therefore their viscosity can be varied within a large scale. The weight average molecular weights - of these polycondensates are usually from 200 to 100,000. The compounds of the formulas can be prepared by alkoxylation of the dendrimer polyamides, which synthesis by the addition of Michael of aliphatic diamines in acrylonitrile and subsequent catalytic hydrogenation is described in Patent Number WO 93/14147. An example of this is the hydrogenated adduct of - - 4 moles of acrylonitrile and ethylenediamine. This hexamine with 4 primary amino groups can also be reacted in a similar manner to form the N-14 amine with 8 primary amino groups. Instead of ethylenediamine it is also possible to use other aliphatic di- and poly-amines. Similarly, amino-containing polymers, such as polyethylene imine, can be reacted with ethylene oxide in an aqueous solution to form useful poly-N- (beta-hydroxyethyl) amino compounds, the degree of which is generally the conversion of the present NH functions of the > 40 percent, in particular from > 60 percent and preferably of > 80 percent. The preparation of polyethyleneimine is common knowledge. The polyethyleneimines within the molecular weight scale Mw = 800 to 2,000,000, for example, are capable of being obtained from BASF under the name Lupasol®. Polyethylene imines usually consist of branched polymer chains and therefore contain primary, secondary or tertiary amino groups. Their relationship is usually about 1: 2: 1. However, at very low molecular weights, higher proportions of the primary amino groups are also possible. The essentially linear polyethyleneimines, which are - capable of being obtained by specific synthesis, they are also suitable for this application. Polymeric alkylenes with primary and / or secondary amino groups that can be used in novel compositions after alkoxylation are described in Encyclopedia of Polymer Science and Engineering, H. Mark (Editor) Revised Edition, Volume 1, pages 680 a 739, John Wiley &; Sons Inc., New York, 1985. Another possibility is to prepare the polyalkyleneimines substituted with hydroxyalkyl by polymerizing the N-hydroxyalkylaziridines. In addition, alkoxylated allylamine polymers and copolymers can also be used in novel compositions. The compounds of the formula If can be prepared from oxamines, such as 4,7-dioxadecane-1, 10-diamine, 4,9-dioxadecane-1, 12-diamine, 4,11-dioxatetradecane-1, 4- diamine, 4,9-dioxadodecane-1, 12-diamine and 4,7,1-trioxatridecane-1, 13-diamine. Suitable starting amines also include polyoxyalkyleneamines, which are sold by Huntsman under the name Jeffamine®. Examples are diaphragms Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, Jeffamine ED-600, Jéffamine ED-900, Jeffamine ED-2001, Jeffamine EDR-148 and Jeffamine T-triamines. 403, Jeffamine T-3000 and Jeffamine T-5000. The reaction products of aromatic polyamines with alkylene oxide are in principle also suitable for use in novel compositions. Component (A) and component (B) are preferably used in a weight ratio (A: B) within the range of 50: 1 to 1:50, preferably 20: 1 to 1:20, in particular from 1:15 to 15: 1 and, with specific preference, from 5: 1 to 1: 5 (based on the active ingredients). The weight ratio of component (B) to component (C) preferably falls within the scale of 100: 1 to 1: 1, preferably 50: 1 to 15: 1 and, with specific preference of 30: 1 to 2: 1 (based on each case in the active ingredients). The compositions are prepared by mixing the components at room temperature or even at elevated temperature. It has been found particularly appropriate to employ component (A) as an aqueous dispersion and component (B) as an aqueous solution. Preferably, the component (B) is introduced as an aqueous solution, and the component (A) or an aqueous dispersion is added to this solution with stirring. Component (C) can be used undiluted or as a solution 4 aqueous with a concentration of preference of > 25 percent. The viscosity of novel aqueous compositions, with an active ingredient content of 40 weight percent (the sum of components A and B), generally falls within the range of 10 to 100,000 mPa.s, which is measured in a rotary viscometer in accordance with DIN 53019 at 23 ° C at a shear rate of 250 s-1. Preference is given to viscosities of 20 to 20,000 mPa.s, with specific preference of 50 to 5000 mPa.s. If the component (A) and / or (B) is an emulsion polymer, it can be used, with a comparable molecular weight or K-value, to prepare the compositions which have a lower viscosity than with the acid-containing polymers. The novel compositions may contain a reaction accelerant, but are preferably free of this accelerator Suitable reaction accelerators include, for example, alkali metal hypophosphites, phosphites, polyphosphates, dihydrogen phosphates, polyphosphoric acid, hypophosphoric acid , phosphoric acid, alkylphosphinic acid or the oligomers or polymers of these salts and acids Additional suitable catalysts include strong acids such as "sulfuric acid" and "sulfuric acid". p-toluenesulfonic. Similarly, polymeric sulfonic acids, for example poly (acrylamido-2-methylpropanesulfonic acid), poly (vinylsulfonic acid), poly (p-styrenesulfonic acid), poly (sulfopropyl methacrylate) acids and polymeric phosphonic acids, such as poly (vinylphosphonic acid), and the copolymers derived therefrom with the comonomers described above, are suitable. It is also possible to incorporate the accelerating sulfonic acid or the phosphonic acid into the polymer (B) containing the acid using the corresponding monomers such as, for example, acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, p-styrenesulfonic acid, acid sulfopropylmethacrylate or vinylphosphonic acid as a ~ comonomer in the preparation of polymeric carboxylic acids. Also suitable as catalysts are organotitanates and organozirconates, examples being triethanol titanate, titanium chelate. ETAM and tetrabutyl zirconate, sold for example by Hüls. In addition, novel compositions may include customary additives depending on the intended application. For example, they may include bactericides or fungicides. In addition, they can include a nitrofobicization agent to improve the water resistance of the treated substrates. Suitable hydrophobicizing agents are customary aqueous paraffin dispersions or silicones. The compositions may further include wetting agents, thickeners, plasticizers, retention agents, pigments and fillers or fillers. Finally, novel compositions may include customary flame retardant agents such as aluminum silicates, aluminum hydroxides, borates and / or phosphates. The compositions frequently also include coupling reagents, such as alkoxysilanes, for example 3-aminopropyltriethoxysilane, soluble or emulsifiable oils as lubricants and fine dustproofing agents, and also wetting aids. The novel compositions can also be used in a mixture with other binders, for example urea-formaldehyde resins, elamina-formaldehyde resins or phenol-formaldehyde resin and also with epoxy resins. The novel compositions are free of formaldehyde. This means that the novel compositions do not comprise any significant amounts of formaldehyde and therefore do not release any significant amounts of formaldehyde during drying and / or curing. In general, the compositions comprise <; 100 parts per million formaldehyde. They make it possible to produce shaped articles with a short cure time and confer excellent mechanical properties on the shaped articles. The thermally curable formaldehyde-free compositions of this invention are essentially not crosslinked and therefore are thermoplastic during use. If necessary, however, they can pre-crosslink to a small degree. - ~~ During heating, the water present in the compositions evaporates, and the composition undergoes healing. These processes can be carried out in succession or simultaneously. The cure in the present context will be understood as meaning the chemical alteration of the composition, for example cross-linking through the formation of covalent bonds between the different constituents of the compositions, the formation of ionic interactions and groupings, and the formation of hydrogen bonds. In addition, the cure may be accompanied by physical changes in the binder, the examples being the processes of demixing (separation), phase transitions or phase inversion.

As a consequence of curing, the solubility of the composition decreases and, for example, the water-soluble compositions are converted into materials that are partially or extensively insoluble in water. The degree of cure can be characterized by extraction experiments in compositions cured in suitable solvents such as water or acetone. The greater the degree of cure, the greater amount of cured material remains insoluble and therefore the greater the gelling fraction. The curing temperatures are from 75 ° C to 250 ° C, preferably from 90 ° C to 200 ° C. The duration and temperature of the heating influence the degree of healing. An advantage of the novel compositions is that they can be cured at comparatively low temperatures. For example, the marked crosslinking is carried out even at a temperature of 100 ° C to 130 ° C. Healing can also be carried out in two or more stages. For example, a first step with a curing temperature and time can be carried out in such a way that only a low degree of cure is achieved, while the essentially complete cure is carried out in a second step. This second step can be carried out spatially and chronologically separated from the first step. It makes it possible, for example, to use the novel compositions to produce semi-finished articles impregnated with binder which are shaped and cured until they are completed elsewhere. The compositions are used in particular as binders to produce shaped articles such as fibers or chips. The chips or fibers can be composed of renewable raw materials or synthetic or natural fibers, for example, of garment waste. Suitable renewable raw materials include, in particular, henequen, jute, flax, coconut fibers, banana fibers, hemp and cork. Specific preference is given to wood fibers or wood chips. Preferably shaped articles have a density of 0.2 to 1.0 gram per cubic centimeter at 23 ° C. The proposed configured items include, in particular, sheets. Its thickness is usually at least 1 millimeter, preferably at least 2 millimeters. Interior automotive parts are also suitable, the examples being inner door liners, dashboard members and package racks. The weight of the binder used is generally 0.5 percent to 40 percent by weight, preferably 1 percent to 30 percent by weight (solids / binder, calculated as the sum of A + B), based on the substrate (fibers or chips). The fibers or chips may be coated directly with the binder or mixed with the aqueous binder. The viscosity of the aqueous binder preferably (and especially for the production of shaped articles of wood fibers or wood chips) adjusted to within the range of 10 to 10,000, with specific preference of 50 to 5,000, and, preferably very specific , from 100 to 2,500 mPa.s (DIN 53019, rotary viscometer at 250 s - ^). The mixture of fibers, swarf and binder can be pre-dried, for example at a temperature of 10 ° C to 150 ° C and then pressed, for example at temperatures of 50 ° C to 250 ° C, preferably 100 ° C. ° C to 240 ° C and, with specific preference of 120 ° C to 225 ° C and pressures of generally from 2 to 1,000 bar, preferably from 10 to 750 bar and, with specific preference from 50 to 500 bar to provide shaped articles. ~ Binders are particularly suitable for producing wood-based materials such as old paperboard and fiberboard (for example, Ullmanns Encyclopaedia der technischen Chemie, Fourth Edition 1976, Volume 12, pages 709 to 727), which can be produced by ligating the crushed wood, for example wood chips and wood fibers The water resistance of the wood-based materials can be increased by adding a commercially available aqueous paraffin dispersion or other hydrophobicizing agent. to the binder or before or subsequently, to fibers or shavings. The manufacture of the old paperboard is common knowledge and is described, for example, in H.J. Deppe, K. ERnst Taschenbuch der Spanplattentechnik, Second Edition, Velag Leinfelden 1982. Preference is given to the use of shavings whose size is on average within the range of 0.1 to 4 millimeters, in particular 0.2 to 2 millimeters, and which have a water content of less than 6 weight percent. However, it is also possible to use distinctly thicker shavings and shavings having a higher moisture content. The binder is applied as evenly as possible to the wood chips using a weight ratio of the binder to wood chips, based on the active ingredients (which is calculated as A) + B) preferably from 0.02: 1 to 0.3 :1. A uniform distribution can be obtained, for example, by spraying a finely divided form of the binder towards the chips. The resin-treated wood chips are then sprayed to form a layer with a very uniform surface, the thickness of the layer of the desired thickness depending on the finished old paperboard. The sprayed layer is pressed at temperature for example from 100 ° C to 250 ° C, preferably from 120 ° C to 225 ° C and using pressures that are usually from 10 to 750 bar, to form a board. The required pressure times can vary within a wide range and usually ranges from 15 seconds to 30 minutes. The wood fibers of appropriate quality required for the manufacture of fiber board of medium density old papers (MDF) of the binders can be produced by crushing the bark-free wood chips in mills or special refineries at a temperature of approximately 180 ° C. . To apply the binder thereto, the wood fibers are usually suspended in a stream of air and the binder is blown into the resulting fiber stream (blowing line process). The ratio of the wood fiber to the binder based on the dry content and the solids content, respectively, is usually from 40: 1 to 2: 1, preferably from 20: 1 to 4: 1. The resin fibers are dried in the fiber stream at a temperature of 130 ° C to 180 ° C, for example, sprayed to form a continuous ribbon of fiber, and compressed at pressures of 20 to 40 bar to form boards or shaped articles . Resin-treated wood fibers also, as described for example in Patent Number DE-OS 2 417 243, can be processed to form a transportable fiber mat. This semi-finished product can then be further processed in a separate second step, spatially and chronologically to form boards or molded parts such as interior door linings of motor vehicles. Other natural fiber materials likewise, for example henequen, jute, hemp, flax, coconut fibers, banana fibers and other natural fibers, can be processed into boards and molded parts using the binders. Natural fiber materials can also be used in blends with synthetic fibers for example polypropylene, polyethylene, polyesters, polyamides or polyacrylonitrile. These synthetic fibers in this case can also function as co-binders together with the novel binder. The proportion of synthetic fibers in this case is preferably less than 50 percent by weight, in particular less than 30 percent by weight and, very specifically, less than 10 percent by weight, based on all chips or fibers . The fibers can be processed by the method used for old wooden paper cartons. Alternatively, the preformed natural fiber mats can be impregnated with the novel binders, with or without the addition of wetting aids. The impregnated mats are then pressed in a wet state with binder or predrying, for example at a temperature of from 100 ° C to 250 ° C at pressures of 10 to 100 bar, to form boards or molded parts. The shaped articles obtained according to the invention have low water absorption, under thick swelling after storage in water, high strength and exemption of formaldehyde. In addition, the novel compositions can be used as binders for impregnating coating materials for organic and / or inorganic fiber composite boards, non-fibrous mineral fillers or fillers and also starch and / or aqueous polymer dispersions. The materials of coating and impregnation confer in the boards of high modulus of flexion and great resistance to the humidity. The production of these boards is already known. The boards of this class generally use acoustic insulation boards. The thickness of the boards within the scale of approximately 5 to 30 millimeters, preferably within the range of 10 to 25 millimeters. The length of the edge of the square or rectangular boards usually falls within the range of 200 to 2,000 millimeters. In addition, the novelty compositions may comprise auxiliaries customary in coating and impregnation technology. Examples of these finely divided inert fillers or fillers such as aluminum silicates, quartz, precipitated or pyrogenic silica, light or heavy spar, talc, dolomite or calcium carbonate; Coloration pigments, such as titanium white, zinc white, iron oxide black, etc. foam inhibitors, such as modified dimethylpolysiloxanes and adhesion promoters and also preservatives. Components (A), (B) and (C) are usually present in the coating material in an amount of 1 percent to 65 percent by weight. The proportion of inert filler materials is generally from 0 percent to 85 percent by weight, while that of water is at least 10 percent by weight. The compositions are used in a conventional manner by application to a substrate, for example by spraying, rolling, molding or impregnation. The amounts applied based on the sum - of the components (A) and (B) in the composition, usually are from 2 to 100 grams per square meter. The quantities of additives to be used are known to an expert worker and depend in each specific case on the desired properties and the use to which they are intended. The compositions of the invention are also suitable for use as binders for insulating materials composed of inorganic fibers such as mineral fibers or glass fibers. These insulation agents are produced industrially by spun fusions of corresponding mineral raw materials; see US Patent Number A-2,550,465, US Patent Number A-2,830,648, Patent Number EP-A-354 913, and Patent Number EP-A-567 480. The composition is then dispersed to the freshly prepared inorganic fibers while still remaining. hot The water then evaporates considerably leaving the composition adhering to the fibers as a viscous material in an essentially uncured state. A fiber mat including the continuous binder produced in this way is transported on appropriate conveyor belts through a curing furnace. Here, the mat is cured at a temperature of 100 ° C to 200 ° C to form a rigid matrix. After curing, the insulating mats are processed to form a signal in an appropriate manner. The predominant proportion of the mineral or glass fibers used in the insulation materials is of a diameter within the range of 0.5 to micrometers and a length within the scale of 0.5 to centimeters The novel compositions are also suitable for use as binders for continuous fiber tapes. Suitable fiber continuous fibers include, for example, fiber tapes composed of cellulose, cellulose acetate, cellulose esters and ethers, cotton, hemp, animal fibers, such as wool or hair, and especially continuous tapes of synthetic or inorganic fibers. , examples being aramid, carbon, polyacrylonitrile, polyester, minerals, PVC or glass fibers. If they are used as binders for continuous fiber tapes, the novel compositions may include, for example, the following additives: silicates, silicones, boron-containing compounds, lubricants, wetting agents. Preference is given to continuous fiberglass ribbons. The unbound continuous fiber ribbons, the - continuous fiberglass ribbons in particular, are bonded, ie, consolidated, by the novel binder For this purpose, the binder of the invention is applied to the unbonded fiber web, for example by coating, impregnation or saturation preferably in a fiber / polymer weight ratio (A) and (B) (solids) from 10: 1 to 1: 1, preferably particularly from 6: 1 to 3: 1. In this case, the binder is preferably used in the form of a dilute aqueous formulation with a water content of 95 percent to 40 percent by weight. After application of the binder to the non-bonded fiber web, the web is generally dried at temperatures from 100 ° C to 400 ° C, in particular from 130 ° C to 280 ° C, and preferably very specific. from 130 ° C to 230 ° C, during a period of preference from 10 seconds to 10 minutes, in particular from 10 seconds to 3 minutes. The resulting bonded fiber web has a high concentration in the wet and dry state. The novel binders allow, in particular, short drying times and also low drying temperatures.

Continuous fiber tapes especially bonded to glass fiber webs are suitable for use as or in roofing membranes, as backing materials for wall papers or linings or as covering material for floor coverings, eg, coverings of floor composed of PVC. When used as roofing membranes, bonded fiber webs are usually coated with asphalt. The aqueous compositions according to the invention can also be used to produce foamed boards or shaped articles. For this purpose, the water present in the composition is first "removed at temperatures of <; 100 ° C decreasing to a level of < 20 percent by weight. The resulting viscous composition is then formed into a foam at temperatures of > 100 ° C, preferably 120 ° C to 300 ° C. Residual water "still present in the mixture and / or the gaseous products formed in the curing reaction can serve as blowing agents The resultant cross-linked polymer foams can be used, for example, for thermal and acoustic insulation. The novel compositions can be used to impregnate paper, which is subsequently dried under mild conditions, to produce laminates, for example 2 for decorative applications, in accordance with known techniques. In a second step, heat and pressure are used to apply these laminates to the substrates to be coated under conditions that are selected so that the binder will cure. The compositions of the invention are also suitable as formaldehyde-free core sand binders for producing casting molds and cores for melting metal in accordance with conventional processes. They are also suitable as binders for producing sandpaper and abrasive paper by processes such as those commonly carried out with phenolic resins. The examples that will be given below illustrate the invention. In the examples, SC represents the solids content as determined from the weight loss of a defined sample during drying at 120 ° C for 2 hours. The viscosity was determined at 250 seconds - '- in accordance with DIN 53019 at 23 ° C (using a Physica Reoestera). The K value of component (B) was determined using an aqueous solution of concentration of 1 weight percent of the polymer by a method similar to DIN 53726. The determination of the particle diameter of the polymer of average weight for component (B) was by almost elastic light scattering in a diluted sample of B dispersions using a light scattering photometer (Malvern Autosizer), the dispersions having been adjusted to a solids content of 0.01 weight percent using an aqueous sodium lauryl sulfate solution of concentration of 2 percent by weight.

I. Preparation component (A) Al Polymer Solution A glass container with a capacity of 4 liters with another agitator was charged with 590 grams of water, 4.7 grams of an aqueous sodium lauryl sulfate solution of 15 percent concentration, 35 grams of styrene, 35 grams of acrylate of ethyl and 2.1 grams of acrylic acid and this initial charge was heated to 85 ° C. At 85 ° C, the addition of the feed stream 1 and the feed stream 2 was started simultaneously. The feed stream 1 consisted of a stirred emulsion of 550 grams of water, 88.6 grams of a solution of sodium lauryl sulfate of 15 percent concentration, 665 grams of styrene, 665 grams of ethyl acrylate and 40 grams of acrylic acid The feed stream 1 was supplied in a regulated manner through the course of 3 hours.The feed stream 2 was a solution of 8.4 grams of sodium peroxodisulfate in 200 - grams of water and was supplied in a regulated manner through a 3.5-hour course. The mixture was subsequently cooled to 70 ° C. Then, 14 grams of an aqueous solution of 10 percent concentration of tertiary butyl hydroperoxide and 6.3 grams of an aqueous saline solution of 20 percent concentration of sodium hydroxymethanesulfinate were added through the course of 1 hour.

SC: 39 percent; pH: 3.2; viscosity: 65 mPas; Average particle diameter in weight: 196 nm.

A2 polymer dispersion A 2-liter glass polymerization vessel with anchor stirrer was charged with 448 grams of water and heated to 80 ° C. The apparatus was flushed with nitrogen, 10 weight percent of the total amount of feed stream 1 and 20 weight percent of the total amount of feed stream 2 were added at once to the polymerization vessel and the The mixture was stirred at 80 ° C for 15 minutes. Then 80 ° C, the remainder of the feed stream 1 was fed continuously through the course of 3 hours and the remainder of the feed stream 2, at a separate point of supply continuously through the course of 3.5 hours. The result was a polymer dispersion having a solids content of 45.2 percent, a viscosity of 30 mPas and a pH of 2.5. The average particle diameter of the polymer was 163 nm.

Current 1 of 426 grams of feedwater: 2.9 grams of aqueous phosphoric acid of 75 percent by weight concentration 36 grams of an aqueous solution of 40 percent by weight concentration of ethoxylated oleylmonoamine having an average degree of ethoxylation of 12 361 grams of styrene 217 grams of methyl methacrylate 144 grams of n-butyl acrylate Current 2 of 56 grams of feed water: 1.8 grams of Azostarter V 50 (Wako Chemicals GmbH) II. Preparation component (B) Solution Bl of polymer: - - The preparation examples of the Patent Number EP-A-075 820 were attracted to prepare a copolymer consisting of 55 weight percent acrylic acid and 45 weight percent maleic acid. "The free radical initiator employed was hydrogen peroxide and the polymerization temperature was 130 ° C. The solids content of the resulting aqueous polymer solution was 50 weight percent, its pH was 0.8 and its viscosity was 110. mPas The K value of the polymer was 12.4.

Solubion B2 of polymer: An acrylic acid homopolymer was prepared in analogy with the preparation of the solution Bl of the polymer. The solids content of the resulting aqueous polymer solution was 35 weight percent, its pH of 1.0 and its viscosity of 160 mPas. The K value of the polymer was 24.

III. Binder formulations Example 1 (composition according to the invention) 70 grams of triethanolamine (component C) was added with stirring to 470 grams of the aqueous polymer solution Bl. 200 grams of solution Al de - - Aqueous polymer was added to the resulting mixture through the course of 15 minutes with stirring (100 revolutions per minute). The solids content of the composition was 53 percent and its pH was 3.1. The viscosity was 190 mPas.

Example 2 (composition according to the invention) 85 grams of triethanolamine (component C) were added with stirring to 400 grams of the aqueous polymer solution B2. 200 grams of the aqueous polymer solution A2 was added to the resulting mixture over the course of 15 minutes with stirring (100 revolutions per minute) The solids content of the composition was 46 percent and its pH was 3.6 The viscosity was 110 mPas.

Comparison Example 1 Al dispersion without additives was used as the binder.

Comparison Example 2 The polymer solution Bl without additives was used as the binder.

- Comparison Example 3 130 grams of triethanolamine were added (component C) with stirring at 870 grams of solution Bl of the aqueous polymer. The solids content of the composition was 56 percent and its pH was 3.4. The viscosity found was 580 mPas.

Comparison Example 4 130 grams of triethanolamine were added (component C) with agitation at 870 grams of dispersion A2 of aqueous polymer. The solids content of the composition was 47 percent and its pH was 5.1. The viscosity found was 165 mPas.

IV. Test as binders for natural fiber mats The binders of the examples and comparison examples mentioned above were diluted with water to a solids content of 25 percent. Jute / henequen mats of approximately 1 centimeter thickness (manufactured by Braunschweiger Jute- und Flachs-Industriebetriebe GmbH) were impregnated with the binder liquid of 25 percent concentration using a roller so that 25 percent by weight of Non-volatile binder components were applied, based on the weight of the dry fiber. The impregnated fiber mats (35 x 30 centimeters) were dried in a convection oven at 80 ° C until a residual moisture content of 10 percent, based on dry fiber, were pressed using a hydraulic press at a temperature of 200 ° C under pressure of 1.5 N / square millimeter. The pressing time was 2 minutes. The bending concentration (FS) was measured by means of the three-point bend test in accordance with DIN 52352 at different temperatures (23 ° C, 60 ° C and 100 ° C). Thickness swelling (TS) was determined as the relative increase in thickness of 2 x 2 cm sections of fiber mats pressed after storage for 2 hours and 24 hours, respectively, in water at 23 ° C. The climatic stability was calculated on the basis of the 3 x 10 cm sections of the pressed fiber mats that had been stored in a conditioning cabinet at 80 ° C and 90% relative atmospheric humidity for 1 day and 7 days, respectively. The concentration of the test specimens was then evaluated on the basis of a scale of classifications from 1 to 5, 1 representing a very high concentration and 5 representing a very low concentration. The results of the experiments are summarized in Table 1. Table 1 Ex. 1 Ex. 2 CEj. CEj. CEj. CEj 1 * 2 * 3 * 4 * Thickness of the blade [mm] 1.60 1.49 1.65 1.59 1.55 1.47 Density [grams / cm- ^ J 0.72 0.78 0.69 0.72 0.76 0.80 FS 23 ° C [N / mm2] 32.9 34.1 29.4 35.5 22.5 FS 60 ° C [N / mm2] 26.0 26.7 6.1 12.6 28.8 3.2 FS 100 ° C [N / mm2] 20.7 19.0 2.0 2.9 22.6 n.d.

TS 2 h [%] 20 65 31 55 TS 24 h [%] 12 15 21 135 57 89 Classification before climate storage 1 Classification after 1 day of climate storage Table 1 (continued) Classification after 7 days of climate storage * Comparison Example n. d. = not determinable The results show the - superior properties of the compositions of the invention (Examples 1 and 2) compared to the components (A) and (B) alone (Comparison Examples 1 and 2) and in relation to the compositions which are not according to the invention (Comparison Examples 3 and 4).

Claims (19)

- CLAIMS

1. The use of a thermally curable aqueous composition comprising A) at least one polymer, obtainable by free radical polymerization, comprising < 5 percent by weight of an alpha-, beta-ethylenically unsaturated, alpha or beta-ethylenically unsaturated acid, in copolymerized form, B) at least one polymer, obtainable by free-radical polymerization, comprising > 15 weight percent of an alpha, beta-ethylenically unsaturated mono- or dicarboxylic acid, in copolymerized form, and C) at least one alkanolamine having at least two hydroxyalkyl groups. as a binder for a shaped article.

2. The use according to claim 1, wherein component (A) contains sno- or di-carboxylic acid of 3 to 6 carbon atoms, alpha, beta-ethylenically unsaturated, especially acrylic or methacrylic acid, in copolymerized form.

3. The use according to claim 1 or 2, wherein the component (A) contains as the main monomer an ester of acrylic or methacrylic acid with an alkanol of 1 to 12 carbon atoms, a vinylaromatic compound, an ester of vinyl, of a monocarboxylic acid of 2 to 12 carbon atoms, or an alkyl vinyl ether of 1 to 12 carbon atoms, in copolymerized form.

4. The use according to any of the preceding claims, wherein component (B) contains > 20 weight percent, in particular; > 40 weight percent of the mono- or di-carboxylic acid in copolymerized form.

5. The use according to any of the preceding claims, wherein the component (B) contains, as the mono- or di-carboxylic acid, in copolymerized form, at least one compound selected from acrylic, methacrylic acid, crotonic, fumaric, maleic, 2-methylmaleic and itaconic.

6. The use according to any of the preceding claims, wherein the component (B) comprises other ethylenically unsaturated monomers in copolymerized form, which are selected from esters of (meth) acrylic acid with monoalcohols of 1 to 12 carbon atoms. carbon, or dialcohols, vinylaromatic compounds, butadiene, aliphatic vinyl esters of monocarboxylic acids of 2 to 12 carbon atoms, (meth) acrylonitrile, (meth) acrylamide, N-alkyl (meth) acrylamides of 1 to 6 atoms of carbon and (meth) acrylamides of N, N-di-alkyl of 1 to 6 carbon atoms

7. The use according to any of the preceding claims, wherein component (C) is selected from diethanolamine, triethanolamine and water-soluble linear or branched aliphatic compounds comprising per molecule at least two amino functional groups of type (a) or type (b) R R R R N [a) (b) wherein R is hydroxyalkyl and R 'is alkyl.

8. The use according to any of the preceding claims, wherein the component (C) employed comprises at least one compound of the formula I RJ R4 \ NAN (I) / \ R2 R- wherein A is alkylene of 2 to 18 carbon atoms which is unsubstituted or substituted by one or more groups which are independently selected from alkyl, hydroxyalkyl, cycloalkyl, OH and NR R7, wherein R6 and R7 independently are H, hydroxyalkyl or alkyl, and which is not interrupted or interrupted by one or more oxygen and / or NR5 groups wherein R5 is H, hydroxyalkyl, (CH2) nNR6R7, wherein n is 2 to 5 and R5 and R7 are as defined above, or alkyl, which in turn may be interrupted by one or more groups of R ^ where R ~ > is as defined above, and / or may be substituted by one or more groups of NR ^ R7, where R ^ and R7 are as defined above; s a radical of the formula: where o, qys independently are 0 or an integer from 1 to 6, pyr independently are 1 or 2 and t is 0, 1 or 2, it also being possible for the cycloaliphatic radicals to be substituted by 1, 2 or 3 alkyls, and R1, R2 and R3 and R4 independently are H, hydroxyalkyl, alkyl or cycloalkyl.

9. The use according to claim 8, wherein the component (C) is selected from at least one compound of the formula la: R1 R4 \ / N A? _ N da) / \ R2 - R3 wherein A ^ is alkylene of 2 to 12 carbon atoms which is unsubstituted or substituted by at least one alkyl and / or at least one group of NR ^ R7, wherein R ^ and R7 are independently alkyla or hydroxyalkyl , and R1, R2, R3 and R4 are independently hydroxyalkyl or H, or one of R ^ and R2 and / or one of R3 and R4 is alkyl or cycloalkyl.

10. The use according to claim 8, wherein the component (C) is selected from at least one compound of the formula Ib: RJ R4 \ / N A2 _ N (Ib) / R2 R- where A2 is alkylene of 2 to 8 carbon atoms which is interrupted by at least one group of NR5 wherein R ^ (or each R ^ independently) is hydroxyalkyl or alkyl, and R1, R2, R3 and R4 are independently hydroxyalkyl or H.

11. The use according to claim, wherein the component (C) is selected from at least n compound of the formula le: RJ R ^ \ / N A3 _ N: ic) / R2 R ~ wherein A3 is alkylene of 2 to 8 carbon atoms which is interrupted by at least one group of NR wherein R ^ is H, hydroxyalkyl or CH2CH2NR6R7, R !, R2, R and R4 They are independently alkyl which is not interrupted or is interrupted by at least one group of NR ^ and / or is substituted or unsubstituted by at least one group of NR ^ R7, R5 is H, hydroxyalkyl or -R8NR6R7 and R6 and R7 independently are H, hydroxyalkyl or R8NRßR7, and R8 is an ethylene or propylene radical, wherein (on average) at least 30 percent of the nitrogens carry a hydroxyalkyl.

12. The use according to claim 11, wherein the component (C) is a reaction product of a polyethylenimine with ethylene oxide.

13. The use according to claim 8, wherein the component (C) is selected from at least one compound of the formula le: RJ R4 / N A5 N (le) / R2 R3 where A5 is alkylene from 6 to 18 carbon atoms which is interrupted by at least one group of NR5 wherein R ^ is (CH2) nNRgR7 or alkyl that is not interrupted or interrupted by at least one group of NR ^ wherein R ^ is (C ^ JnR ^ R7 or alkyl and / or is unsubstituted or substituted by at least one group of NR ^ R7, n is 2 or 3 and R1, R2, R, R4, R6 and R7 are independently - - hydroxyalkyl or H.

14. The use according to claim 8, wherein the component (C) is selected from at least one compound of the formula If: R 1 R a / N _ A 6 N (If) R 2 - wherein Ag is alkylene of 2 to 12 carbon atoms which is interrupted by at least one oxygen, and R1, R2, R3 and R4 independently are hydroxyalkyl or H.

15. The use according to claim 8, wherein component (C) comprises polyalkanolamines which are capable of being obtained by condensation of dialkanolamines and / or trialkanolamines with themselves, in the presence or absence of mono- or polyhydric alcohols or mono- or polyfunctional amines.

16. The use according to any of claims 7 to 15, wherein the hydroxyalkyl of component (C) in the above-mentioned definitions is a hydroxypropyl or hydroxyethyl. - -

17. The use according to any of the preceding claims, wherein the composition comprises the components (A) and (B) in a weight ratio (based on solids) of 50: 1 to 1:50 and comprises the components (B ) and (C) in a weight ratio of 100: 1 to 1: 1.

18. The use according to any of the preceding claims, wherein the molar ratio of carboxyl of component (A) and (B) to hydroxyls of component (C) is within the range of 20: 1 to 1: 5. . 19. The use according to any of the preceding claims, wherein the composition further comprises a reaction accelerant. 20. The use according to any of the preceding claims, wherein the composition is used as a binder for a shaped article comprising finely divided materials, especially fibers or chips. 21. A thermally curable aqueous composition according to any one of claims 1 to

19. 22. A composition according to claim 21, wherein component (C) is selected from a linear water soluble aliphatic compound or - branched which is defined as in any of claims 1 and 8 to 16. 23. A binder comprising a composition according to claim 21 or 22. 24. A shaped article obtainable by impregnating a substrate with a composition in accordance with -la. claim 21 or 22, or with a binder in accordance with that claimed in claim 23 and curing the impregnated substrate. 25. A shaped article according to claim 24, which is a sheet made of finely divided materials, especially a cardboard board of old papers and fibreboard, an insulation element or a continuous fiber tape.