DE19949591A1 - Thermally curable, aqueous composition, useful as a binding agent for fibrous or particulate materials comprises carboxyl group containing copolymer, a higher functional beta-hydroxyalkylamine and optionally a surfactant - Google Patents

Abstract

A thermally curable, aqueous composition comprises at least a carboxyl group containing copolymer, a higher functional beta -hydroxyalkylamine and optionally a surfactant. A thermally curable, aqueous composition (I) comprises: (A) at least a carboxyl group containing copolymer prepared from 50-99.5 wt.% of an ethylenically unsaturated mono- and/or dicarboxylic acid, 0.5-50 wt.% of an ethylenically unsaturated compound, preferably an ethylenically unsaturated monocarboxylic acid ester or half esters or diesters of ethylenically unsaturated dicarboxylic acids with at least a hydroxyl group containing amine and up to 20 wt.% of other monomers; (B) at least a higher functional beta -hydroxyalkylamine; and (C) optionally a surfactant. Independent claims are included for the following: (i) the carboxyl group containing copolymer; (ii) a process for the production of the composition (I) by reaction of an ethylenically unsaturated mono- and/or dicarboxylic acid or corresponding derivative with a hydroxyl group containing amine and reaction of the resulting ester product with an ethylenically unsaturated mono- and/or dicarboxylic acid and/or their anhydrides and optionally other monomers to form a carboxyl group containing copolymer with reaction of the copolymer with a higher function beta -hydroxylalkylamine and optionally a surfactant and other additives; and (iii) a bonded substrate prepared by treatment with the composition (I) followed by curing.

Description

The present invention relates to thermally curable, aqueous Compositions, their preparation and their use as bin detergent for moldings.

Thermally curable binders are widely used widespread and represent sales products with sales they mainly include those based on phenol and formaldehyde Glue and impregnation resins. However, these have the disadvantage that considerable quantities of phenol, For maldehyde and low molecular weight condensation products thereof ver fleeting. The reluctance of these environmentally harmful substances is connected with great effort. It can also release it of formaldehyde from the phenol-formaldehyde resins containing Products come what especially when used in ge closed rooms is disadvantageous.

Alternative developments are in the area of polycarboxylic acid ren, the thermally with higher functional, hydroxyl group be crosslinked by esterification reactions.

From US 4 076 917 binders are known which carbon polymers containing acid or anhydride and β-hydroxyalkylamides included as crosslinker. The molar ratio of carboxyl group Pen to hydroxyl groups is preferably 1: 1. The disadvantage is that relatively complex preparation of the β-hydroxyalkylamides. A ent speaking binder is known from US-A 5 340 868.

EP-A-445 578 discloses plates made of finely divided materials known in which mixtures of high molecular weight polycarboxylic acids and polyhydric alcohols, alkanolamines or polyhydric ami act as binders.

From EP-A-583 086 formaldehyde-free, aqueous binders are used Production of nonwoven fabrics, in particular glass fiber nonwovens, be knows. These binders require a phosphorus-containing one  Reaction accelerator to ensure sufficient strength of the glass fa to reach servliese. The binders contain a polycar bonic acid with at least two carboxylic acid groups and given if also anhydride groups. The binder also contains a Polyol, e.g. B. glycerin, bis- [N, N-di (β-hydroxyethyl) adipamide, pen taerythritol, diethylene glycol, ethylene glycol, gluconic acid, β-D-Lac tose, sucrose, polyvinyl alcohol, diisopropanolamine, 2- (2-amino ethylamino) ethanol, triethanolamine, tris (hydroxymethylamino) me than or diethanolamine. It should be noted that the 1 Presence of a phosphorus-containing reaction accelerator only can be dispensed with if a highly reactive polyol is used becomes. The β-hydroxyalkylamides are highly reactive polyols called.

In EP-A 651 088 corresponding binders for sub Strate from cellulose fibers described. Contain these binders mandatory a reaction accelerator containing phosphorus.

DE-A-44 08 688 discloses formaldehyde-free binders for fa seriform fabrics known. A Mi combination of a polycarboxylic acid and aromatic or cycloali phatic polyols used. Despite a very high dry temperature (230 ° C) with this binder on glass Servliesen achieved only low wet tensile strengths.

DE-A-196 06 394 discloses formaldehyde-free, aqueous binders tel known. These contain a radical polymer tion obtained polymer, which consists of 5 to 100 wt .-% of egg an ethylenically unsaturated acid anhydride or an ethyl nically unsaturated dicarboxylic acid, the carboxylic acid groups of which Can form anhydride group exists. Contain these binders an alkanolamine with at least two hydroxyl groups and less than 1.5% by weight, based on the sum of polymer and alkanolamine, a phosphorus-containing reaction accelerator gers.

DE-A-196 21 573 describes thermally curable, aqueous compositions described solutions that use a polymer based on ethy lenically unsaturated mono- or dicarboxylic acids and various Highly functional β-hydroxyalkylamines as crosslinking components contain.

DE-A-196 06 393 and DE-A-196 06 392 disclose the Ver use of formaldehyde - free aqueous binders as described in DE-A-196 06 394 are disclosed as binders for fibers,  Chips or chips for the production of moldings or as loading layering agent for moldings.

EP-A-118 333 describes the preparation of graft polymers by polymerizing acrylic acid in the presence of polyal kylenoxiden, the proportion of acrylic acid in the range of 3 to 15%, based on the polyalkylene oxide.

WO-A-92/07883 describes the polymerization of ethylenically unsaturated monocarboxylic acids in the presence of aromatic sul fonic acids and possibly those containing hydroxyl groups Compound (e.g. polyalkylene oxides). With the hydroxyl groups containing compound are substances that Ver find application in the textile sector. The polymers according to the invention sate are used in textile manufacturing / processing and Textile cleaning, such as B. as a complexing agent, surfactant, defoaming antistatic agents etc.

EP-A-98 803 describes the production of water-soluble or water-dispersible graft polymers from ethylenic containing unsaturated carboxylic acids and polyglycol ether chains Surfactants. The graft polymers are prepared by Polymerization of the unsaturated monomers in the presence of the ten side. The use of the graft polymers obtained in this way extends to antifoam, antistatic, builder, emulga gates, padding aids, wetting agents, paper deaerators, Sludge dewatering aids, textile aids, graying inhibitors, detergents.

The production of heat-resistant flow is known from US Pat. No. 5,143,582 materials using a thermosetting, heat resistant binder known to be free of formaldehyde. The binder is obtained by mixing a carboxylic acid groups, carboxylic acid anhydride groups or carboxylic acid salt groups having polymer and a β-hydroxyalkylamide crosslinker. Self-curing polymers are obtained by copolymerization of the β-hydroxyalkylamides with monomers containing carboxy groups.

The binders listed above are partly in shape aldehyde and phenol free, but have disadvantages in that they do not optimally wet or re-wet the substrates to be set their hardening are not sufficiently flexible. Therefore dispose using the formaldehyde-free binders of Stan of the molded parts manufactured in technology often do not have mecha properties that would be desirable.  

The object of the invention is therefore, thermally curable bandage Provide agents that both formaldehyde and phenol are free, but compared to the known binders have further advantages in the application. In particular sol len binders with improved wetting properties to be provided substrates.

This object is surprisingly achieved by the thermally curable, aqueous composition containing

• - At least one copolymer containing carboxyl groups, which is composed of
  • 50 to 99.5% by weight of at least one ethylenically unsaturated mono- and / or dicarboxylic acid,
  • 0.5 to 50% by weight of at least one ethylenically unsaturated compound which is selected from the esters of ethylenically unsaturated monocarboxylic acids and the half esters and diesters of ethylenically unsaturated dicarboxylic acids with an amine having at least one hydroxyl group,
  • - up to 20% by weight of at least one further monomer;
• - At least one more functional β-hydroxyalkylamine, and
• - optionally at least one surfactant.

The copolymers containing car boxyl groups used in the compositions according to the invention thus contain 50 to 99.5% by weight, preferably 70 to 99% by weight, of structural units which are derived from ethylenically unsaturated monocarboxylic acids, ethylenically unsaturated dicarboxylic acids and / or their Derive half esters with C ₁ to C ₂₂ alkanols. Some or all of these acids can also be present in the copolymer in the form of a salt. The acid form is preferred.

In the preparation of the copolymer containing carboxyl groups In addition to the aforementioned monomers, the anhydrides can also be saturated of ethylenically unsaturated monocarboxylic acids and anhydrides use of ethylenically unsaturated dicarboxylic acids.

Particularly preferred monomers for the production of the carboxyl Copolymers containing groups are maleic acid, maleic acid reanhydride, acrylic acid, methacrylic acid, acrylic anhydride, Methacrylic anhydride, itaconic acid, 1,2,3-tetrahydrophthalic acid  and their anhydrides, as well as the alkali and ammonium salts or Mi made of it.

The copolymer particularly preferably contains structural elements built in, which differs from acrylic acid or a mixture of acrylic acid and maleic acid in the ratio of 95: 5 to 40:60, in particular derive in the ratio of 90: 10 to 50: 50.

The copo used in the compositions according to the invention Lymerisat also contains 0.5 to 50 wt .-%, preferably 1 to 30% by weight, at least one ethylenically unsaturated compound, which is selected from the esters of ethylenically unsaturated Mo nocarboxylic acids and the half-esters and diesters ethylenically un saturated dicarboxylic acids with at least one hydroxyl group term amine, in copolymerized form.

Monocarboxylic acids suitable as components of the esters are the aforementioned C ₃ to C ₁₀ monocarboxylic acids, in particular acrylic acid, methacrylic acid, crotonic acid, and mixtures thereof.

Suitable dicarboxylic acids as components of the half esters and diesters are the aforementioned C ₄ - to C ₈ dicarboxylic acids, in particular fumaric acid, maleic acid, 2-methyl maleic acid, itaconic acid, and mixtures thereof.

The amine with at least one hydroxyl group is preferably selected from secondary and tertiary amines which have at least one C ₆ -C ₂₂ -alkyl, C ₆ -C ₂₂ -alkenyl, aryl-C ₆ -C ₂₂ -alkyl or Aryl-C ₆ - to C ₂₂ -alkenyl radical, where the alkenyl group 1, 2 or 3 may not have adjacent double bonds.

The amine is preferably hydroxyalkylated and / or alkoxylated. Alkoxylated amines preferably have one or two alkylene oxide residues with terminal hydroxyl groups. Preferably point the alkylene oxide radicals are each 1 to 100, preferably 1 to 50, the same or different alkylene oxide units, randomly distributed or in the form of blocks. Preferred alkylene oxides are ethylene oxide, propylene oxide and / or butylene oxide. Is particularly preferred Ethylene oxide.

The polymer preferably contains an unsaturated compound based on an amine component, which is at least one amine of the general formula

R ^c NR ^a R ^b

built-in, where
R ^c is C ₆ - to C ₂₂ -alkyl, C ₆ - to C ₂₂ alkenyl, aryl-C ₆ -C ₂₂ alkyl or aryl-C ₆ -C ₂₂ alkenyl, wherein the alkenyl group 1, 2 or 3 may not have adjacent double bonds,
R ^a for hydroxy-C ₁ -C ₆ alkyl or a radical of the formula II

- (CH ₂ CH ₂ O) _x (CH ₂ CH (CH ₃ ) O) _y -H (II)

stands, where
in the formula II the order of the alkylene oxide units is arbitrary and x and y independently of one another represent an integer from 0 to 100, preferably 0 to 50, the sum of x and y being <1,
R ^{b is} hydrogen, C ₁ - to C ₂₂ -alkyl, hydroxy-C ₁ -C ₆ -alkyl, C ₆ - to C ₂₂ -alkenyl, aryl-C ₆ -C ₂₂ -alkyl, aryl-C ₆ -C ₂₂ -alkenyl or C ₅ - to C ₈ -cycloalkyl, where the alkenyl radical 1, 2 or 3 may not have adjacent double bonds, or R ^{b represents} a radical of the formula III

- (CH ₂ CH ₂ O) _v (CH ₂ CH (CH ₃ ) O) _w -H (III)

stands, where
in the formula III the order of the alkylene oxide units is arbitrary and v and w independently of one another represent an integer from 0 to 100, preferably 0 to 50.

R ^c is preferably C ₈ -C ₂₀ -alkyl or C ₈ -C ₂₀ -alkenyl, where the alkenyl radical may have 1, 2 or 3 non-adjacent double bonds. R ^c is preferably the hydrocarbon radical of a saturated or mono- or polyunsaturated fatty acid. Preferred radicals R ^c are e.g. B. n-octyl, ethylhexyl, un decyl, lauryl, tridecyl, myristyl, pentadecyl, palmityl, margari nyl, stearyl, palmitoleinyl, oleyl and linolyl.

The amine component is preferably an alkoxylated fatty amine or an alkoxylated fatty amine mixture. The ethoxylates are particularly preferred. In particular, alkoxy late amines based on naturally occurring fatty acids are used, such as. B. tallow fatty amines which contain predominantly saturated and unsaturated C ₁₄ -, C ₁₆ - and C ₁₈ -alkylamines or coconut amines which contain saturated, mono- and di-unsaturated C ₆ -C ₂₂ -, preferably C ₁₂ -C ₁₄ -alkylamines. Suitable for alkoxylation amine mixtures z. B. various Armenen® brands from Akzo or Noram® brands from Ceca.

Suitable, commercially available alkoxylated amines are e.g. B. the Noramox® brands from Ceca, preferably ethoxylated oleyl amines, such as Noramox® 05 (5 EO units), and those under Lutensol®FA brand products from BASF AG.

The copolymerization of the aforementioned esters, half esters and die ster generally causes a reduction in the interfaces tension of the compositions according to the invention.

The esterification for the preparation of the esters, half-esters and diesters described above is carried out by customary methods known to the skilled worker. To prepare esters of unsaturated monocarboxylic acids, the free acids or suitable derivatives, such as anhydrides, halides, for. As chlorides, and (C ₁ - to C ₄ ) alkyl esters can be used. Half-esters of unsaturated dicarboxylic acids are preferably prepared starting from the corresponding dicarboxylic acid anhydrides. The reaction is preferably carried out in the presence of a catalyst, such as. B. a dialkyl titanate or an acid such as sulfuric acid, toluenesulfonic acid or methanesulfonic acid. The reaction is generally carried out at reaction temperatures of 60 to 200 ° C. According to a suitable embodiment, the reaction takes place in the presence of an inert gas, such as nitrogen. Water formed in the reaction can be removed from the reaction mixture by suitable measures, such as distillation. If desired, the reaction can be carried out in the presence of customary polymerization inhibitors. The esterification reaction can be carried out essentially completely or only up to a partial conversion. If desired, one of the ester components, preferably the hydroxyl-containing amine, can be used in excess. The proportion of ester formation can be determined using infrared spectroscopy.

According to a preferred embodiment, the production takes place the unsaturated esters or half esters and their further implementation to the copolymers used according to the invention without Intermediate isolation of the esters and preferably in succession in the same reaction vessel.

A conversion is preferred for the preparation of the copolymers tion product from a dicarboxylic acid anhydride, preferably Ma linseic anhydride, and one of the previously described hydroxyl group-containing amines used.

The preparation of the polymers can advantageously also by po Implementation analogously. For this purpose, a polymer that 80 to 100 wt .-% of at least one ethylenically unsaturated  Contains mono- and / or dicarboxylic acid incorporated, with at least a hydroxyl-containing amine are implemented.

Suitable ethylenically unsaturated mono- and dicarboxylic acids are those mentioned above. Suitable amines which have at least one hydroxyl group are also those mentioned above. If desired, the acids in the polymer used for the polymer-analogous reaction can be partially or completely in the form of a derivative, preferably a C ₁ -C ₆ -alkyl ester.

According to a suitable embodiment, the copolymers used according to the invention contain at least one compound incorporated as a further monomer, which is selected from olefins, preferably ethene, propene, n-butene, isobutene and / or diisobutene, vinyl aromatics, preferably styrene, esters α, β -ethylenically unsaturated mono- and / or dicarboxylic acids with C ₁ -C ₂₂ -alkanols, preferably (meth) acrylic acid esters, and mixtures thereof.

Preferred further monomers are

• - Linear and branched chain 1-olefins or cyclic olefins such as. B. ethene, propene, butene, isobutene, diisobutene, pentene, cyclopentene, hexene, cyclohexene, octene, 2,4,4-trimethyl-1-pen ten optionally mixed with 2,4,4-trimethyl-2-pentene, C ₈ to C ₁₀ olefin, 1-dodecene, C ₁₂ to C ₁₄ olefin, octadecene, 1-eicosen (C ₂₀ ), C ₂₀ to C ₂₄ olefin; Metallocene-catalyzed oligo-olefins 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;
• Esters of preferably 3 to 6 carbon atoms containing α, β-monoethylenically unsaturated mono- or dicarboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid with C ₁ -C ₁₂ , preferably C ₁ -C ₈ alkanols . Such esters are in particular methyl, ethyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl and 2-ethylhexyl acrylate and / or methacrylate;
• - Vinylaromatic compounds, preferably styrene, a-methyl styrene, o-chlorostyrene, vinyl toluenes and mixtures thereof.

Particularly preferred further monomers are ethene, propene and isobu ten, diibutene, styrene, methyl (meth) acrylate, ethyl (meth) acrylate, N-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and mixtures  from that. The copolymers are preferably prepared by radical polymerization in bulk or in solution.

The solution polymerisation is usually carried out in Water as a solvent. However, it can also be mixed with water bare organic solvents such as alcohols and ketones for example methanol, ethanol, n-propanol, iso-propanol, n-buta nol, acetone or methyl ethyl ketone, up to a proportion of about 30 vol .-% be included.

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 10, especially preferably 0.2 to 5 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 initiators which can be water-soluble or water-insoluble are hydrogen peroxide, dibenzoyl peroxide, dicyclohexylperoxy dicarbonate, dilauroyl peroxide, methyl ethyl ketone peroxide, di-tert.-butyl peroxide, acetylacetone peroxide, tert.-butyl hydroperoxide, amyl-butyl hydroperyl peroxide, tert-butyl hydroperyl peroxide lat, tert-butyl perpivalate, tert-butyl perneohexanoate, tert-butyl per-2-ethylhexanoate, tert-butyl perbenzoate, lithium, sodium, potassium and ammonium peroxydisulfate, azodiisobutyro nitrile, 2,2'-azobis (2nd -amininopropane) dihydrochloride, 2- (carbamoyl azo) isobutyronitrile and 4,4-azobis (4-cyanovaleric acid). The known redox initiator systems such. B. H ₂ O ₂ / ascorbic acid or t-butyl hydroperoxide / sodium hydroxymethanesulfinate can be used as polymerization initiators.

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.

The invention also relates to the carbo described above copolymers containing xyl groups.

The thermally curable, aqueous composition according to the invention tongues contain in addition to the carboxyl groups described above containing copolymers at least one more functional β-hydroxylalkylamine. The weight ratio is preferably  between copolymer and β-hydroxyalkylamine 1: 1 to 1: 0.01 before increases 1: 1 to 1: 0.1.

As higher functional β-hydroxyalkylamines, preference is given to compounds of the formula

into question, where R ^{1 is} an H atom, a C ₁ to C ₁₀ alkyl group, a C ₁ to C ₁₀ hydroxyalkyl group or a radical of the formula IV

- (CH ₂ CH ₂ O) _x (CH ₂ CH (CH ₃ ) O) _y -H (IV)

stands, where
in formula IV the order of the alkylene oxide units is arbitrary and x and y independently of one another represent an integer from 0 to 100, the sum of x and y <1 and R ² and R ³ independently of one another for a C ₁ - to C ₁₀ hydroxyalkyl group.

R ² and R ³ are particularly preferably independently of one another a C ₂ to C ₅ hydroxyalkyl group and R ^{1 is} an H atom, a C ₁ to C ₅ alkyl group or a C ₂ to C ₅ hydroxyalkyl group.

Diethanolamine, triethanolamine and diisopro are particularly preferred panolamine, triisopropanolamine, methyldiethanolamine, butyldietha nolamine and methyldiisopropanolamine, especially triethanolamine.

Further preferred β-hydroxyalkylamines are the amines disclosed as component A in DE 196 21 573, which are hereby made to the disclosure content of the present invention by reference. These preferably include linear or branched aliphatic compounds which have at least two functional amino groups of type (a) or (b) per molecule

wherein R is hydroxyalkyl and R 'is alkyl, preferably a compound of 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. , Hydro xyalkyl 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 can be interrupted by one or more NR ⁵ groups, where R ^{5 has} the meanings given above and / or substituted by one or more NR ⁶ R ⁷ groups, where R ⁶ and R ^{7 have} 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 are} independently H, hydroxyalkyl, alkyl or cycloalkyl.

Preferred higher-functional β-hydroxyalkylamines are in particular at least double ethoxylated amines with a molecular weight of below 1000 g / mol, e.g. B. diethanolamine, triethanolamine and ethoxylated diethylenetriamine, preferably an ethoxylated Diethylenetriamine, in which on average all bound to nitrogen Hydrogen atoms are simply ethoxylated.  

According to a suitable embodiment, the fiction contains moderate, thermally curable, aqueous composition at least one Surfactant with the hydroxyl group described above Amine can be identical, but does not have to.

If the compositions according to the invention are at least one additional surfactant contain at least one amine that the previous hydroxyl used to prepare the esters and half-esters corresponds to group-containing amines, this can be desired if added to the compositions separately or in the manufacture position of the esters mentioned already a corresponding transfer shot can be used.

The compositions according to the invention preferably contain 0 to 50% by weight, preferably 0.1 to 40% by weight, based on the copolymer of at least one surface-active, alkoxylated, preferably ethoxylated or propoxylated, alkylamine as additional surfactants. Preferred alkyl amines are the alkyl amines of the formula R ^c NR ^a R ^b , as previously defined, which are also contained in the copolymer 1, alkyl alkyl of the formula

in which R is an alkyl, alkenyl or alkylvinyl radical with at least Represents 6 carbon atoms and m and n independently ≧ 1, are particularly preferred. Preferred radicals R have 8 up to 22 carbon atoms.

Other suitable long-chain amines are, for example, those distributed by AKZO under the name "Ethomeen" ethoxylated amines, such as. B. Ethomeen C / 15, a polyoxyethy len- (5) cocoamine or Ethomeen S / 12, an oleyl bis (2-hydroxy ethyl) amine or Ethomeen T / 25, a polyoxyethylene (15) tallowa min.

Preferred additional surfactants are long chain ethoxylated ones Mono- and diamines. For the production of the Zu however, other long chain primary, secondary or tertiary aliphatic amines can be used. At games for this are the products sold by AKZO Armies DMOD (oleyldimethylamine), armies M2C (dicocomethylamine), Armies NCMD (N-cocomorpholine), armies 2C (dicocoamine) or armies 12D (n-dodecylamine).  

If desired, the composition according to the invention can additionally contain at least one further crosslinker. Be preferred amine or amide crosslinkers containing at least two hydroxyl groups. Preferred crosslinkers are the alkanolamines described in DE-A-197 29 161, to which reference is hereby made in full. Suitable crosslinkers are furthermore in particular the β-hydroxyalkylamides of the formula described in US Pat. No. 5,143,582

Particularly preferred β-hydroxyalkylamides are those in which R ^{1 is} H, a lower alkyl or HO (R ³ ) ₂ C (R ² ) ₂ C-, n and n 'are each 1, -A- - (CH ² ) _m - is, m is 0 to 8, preferably 2 to 8, R ^{2 are} both H and one of the R ³ groups is each H, and the other is H or a C ₁ - to C ₅ -alkyl.

To achieve better curing with low curing temperatures or to achieve faster curing the composition of the invention a reaction accelerator are added, preferably a phosphorus-containing reaction accelerator, particularly preferably hypophosphorous acid or its Salts, for example their alkali or alkaline earth salts. The Re Action accelerator is preferred in an amount of up to 3 wt .-% admixed.

The compositions according to the invention can furthermore contain customary additives sentences 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 wetting agents, thickeners, pla agents, retention aids, pigments and fillers contain.

Finally, the compositions according to the invention may che fire retardants such. B. aluminum silicates, aluminum hy 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 tel 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, phenol-formaldehyde resins or epoxy resins can be used.

The composition according to the invention is produced preferably by solution polymerization to produce a carbo copolymer containing xyl groups and subsequent addition of other components of the composition. This is preferably done Solution polymerization in water. However, it can also be done with water miscible organic solvents such as alcohols and ketones for example methanol, ethanol, acetone, and their mixtures with Water can be used.

The invention also relates to a method for producing a composition as described above, wherein

• a) at least one ethylenically unsaturated monocarboxylic acid or a derivative thereof and / or at least one ethylenically unsung saturated dicarboxylic acid or a derivative thereof with at least a hydroxyl group-containing amine in an esterification reaction implementation,
• b) the reaction product (s) from step i) with at least an ethylenically unsaturated mono- and / or dicarboxylic acid and / or their anhydrides and optionally at least one further monomer to a carboxyl-containing copo implements lymerisat, and
• c) the copolymer from step ii) with at least one higher functional β-hydroxyalkylamine, optionally at least a surfactant and possibly other additives.

The thermally curable compositions according to the invention possible the production of moldings with a short curing time and give the moldings excellent mechanical properties create. In general, they advantageously ensure excellent elasticity. Advantageously, he show compositions according to the invention have excellent wetting the substrate particle. The improved network properties are on the reduction in the interfacial tension of the composition recycled, which is achieved in that the copolymer  based on at least one ester of a hydroxyl group Has amine structurally formally surfactant side chains.

The binder compositions according to the invention have a Surface tension of at most 55 mN / m, preferably at most 50 mN / m, on.

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 they contain 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.

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. phase changes or phase inversions.

The curing temperatures are between 75 and 250 ° C, preferred between 90 and 220 ° C, particularly preferably between 100 and 200 ° 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 should be chosen so that 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 fa serous or granular substrates, such as for the manufacture of mold bodies made of fibers, chips or chips. It can it is from renewable raw materials or synthetics cal or natural fibers, e.g. B. act out of clothing waste. Sisal, jute, Flax, coconut fibers, kenaf, banana fibers, hemp and cork. Wood fibers or wood chips are particularly preferred.

Another object of the invention is a bound sub strat, obtainable by treating a substrate with an aq composition as described above and subsequent Hardening. The substrate is preferably in the form of a shaped body in front.

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

In particular, plates and contoured molded parts come into consideration as moldings. Their thickness is generally at least 1 mm, preferably at least 2 mm, and their surface is typically 200 to 200,000 cm ² . In particular, wood fiber and chipboard, cork boards, blocks and molds, insulation boards and rolls, z. B. from mineral and glass fibers, automotive interior parts, for. B. interior door panels, Armaturenträ ger, hat racks, etc.

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 5000 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. predried at temperatures of 10 to 150 ° C. are and then to the moldings, for. B. at Temperatu ren from 50 to 250 ° C, preferably 100 to 240 ° C and particularly preferably 120 to 225 ° C and pressures generally 2 to  1000 bar, preferably 10 to 750 bar, particularly preferably 20 up to 500 bar to be pressed to 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 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 chips, the weight Ratio of solid binder: 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 required pressing times 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 the binders 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 masses give the panels a high flexural modulus. The manufacturer development 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% by weight, 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-567 480. 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 form a firm but flexible matrix. After hardening the insulation mats are 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 fleece 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 mi grooves, 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, ver foams. As a blowing agent z. B. still ent in the mixture retained residual water and / or that arises during the hardening reaction serve gaseous reaction products. However, it can commercial blowing agents can also be added. That arise the cross-linked polymer foams can be used, for example, for thermal insulation insulation and 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 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 (advantageously 10 g / m ² ). In the wet base binder, the desired amount of abrasive grain, z. B. silicon carbide, corundum, etc. interspersed. After intermediate drying, a cover binder layer 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 compositions according to the invention are also suitable as formaldehyde-free sand binder for the production of castings men and cast cores for metal casting according to the usual thermi curing process (E. Flemming, W. Tilch, Formstoffe und  Molding process, German Verlag für Grundstoffindustrie, Stuttgart, 1993).

They are also suitable as binders for permanent mold insulation ten.

The formaldehyde-free, aqueous binders according to the invention are furthermore advantageously suitable as coating compositions or Im Impregnating agent for the stiffening coating of surfaces structures made of fibrous materials (e.g. soundproofing panels from mineral fibers, paper, cardboard). The coating has gone out hardening the function of increasing the rigidity of the molded body. To do this, the composition is impregnated onto the molded body , spraying, watering or in any other way wear. Especially when processing molded articles made of paper or cardboard, the binder stands out due to its low Surface tension in that it is well in the top Layers of the molded body penetrates. This generally enables higher binder application and / or faster processing work as this with a bandage known from the prior art means is possible. After application of the binder, the Shaped bodies either pre-dried to a semi-finished product and then cured in a stable shape or directly in one Form hardened to keep its shape.

The following non-limiting examples illustrate the Invention.

The surface tension was measured using a ring tensiometer from Lauda determines.

The viscosity of the compositions was determined in a viscometer from Brookfield (device DV 2) at 23 ° C. and 60 rpm with a Size 2 or 3 spindle determined.

The pH value was measured with a combination electrode.

example 1 Polymer from 3 parts of carboxylic acid monomers and 1 part of ethoxylated oleylamine

In a pressure reactor (anchor stirrer, 2 feed points) 15.2 Parts by weight of fully demineralized water, 6.73 parts by weight of malein acid anhydride, and 22.16 parts by weight of Lutensol®FA (ethoxylated  tes oleylamine from BASF AG). If necessary, 0.3% (based on monomers) phosphorous acid as a corrosion inhibitor added.

The mixture was heated to 120 to 125 ° C. under a nitrogen atmosphere. After this temperature had been reached, feed 1, consisting of 17.46 parts by weight of fully demineralized water and 18.60 part by weight of acrylic acid, and within 5 h of feed 2, comprising 3.44 parts by weight of fully demineralized water and 2.13 parts by weight of hydrogen peroxide (30 %), evenly dosed. After feed 1 had ended, a further 2.88 parts by weight of demineralized water were added. During the polymerization, the pressure was kept at 2 to 3 bar by carefully releasing the pressure. After the end of the reaction, the mixture was cooled to 30 to 35 ° C. and 11.40 parts by weight of triethanolamine were carefully stirred in with cooling. The finished polymer solution was filled into containers via a filter.
pH value: 3.5, surface tension: 43 mN / m, viscosity: 595 mPas

Example 2 Polymer made from 9 parts of carboxylic acid monomers and 1 part of ethoxy gelled oleylamine

In a pressure reactor (anchor stirrer, 2 feed points) 15.2 parts by weight of demineralized water, 8.75 parts by weight of Ma linseic anhydride and 9.59 parts by weight of Lutensol OFA (ethoxy gelled oleylamine from BASF AG). If necessary 0.3% (based on monomers) phosphorous acid as corrosion hibitor added.

The mixture was heated to 120 to 125 ° C. under a nitrogen atmosphere. After this temperature had been reached, feed 1, consisting of 19.72 parts by weight of fully demineralized water and 24.16 parts by weight of acrylic acid, and within 5 h of feed 2, consisting of 2.80 parts by weight of demineralized water and 2.55 parts by weight of hydrogen peroxide (30 %), evenly dosed. After the end of feed 1, a further 2.43 parts by weight of fully demineralized water were added. During the polymerization, the pressure was kept at 2 to 3 bar by careful relaxation. After the end of the reaction, the mixture was cooled to 30 to 35 ° C. and 14.80 parts by weight of triethanolamine were carefully stirred in with cooling. The finished polymer solution was filled into containers via filters.
pH value: 3.4, surface tension: 49 mN / m, viscosity: 945 mPas

Example V1 (Comparison without amine containing hydroxyl groups)

The preparation was carried out analogously to Example 1 using the components listed below. When feed 1 had ended, a further 8.24 parts by weight of fully demineralized water were added. After the end of the reaction, 12.49 parts by weight of triethanolamine were stirred in.
Surface tension: 68 mN / m, viscosity: 1 150 mPas, pH 3.5
Template:
16.45 parts by weight of fully demineralized water
10.47 parts by weight of maleic anhydride
Inlet 1:
16.23 parts by weight of fully demineralized water
28.63 parts by weight of acrylic acid
Inlet 2:
5.41 parts by weight of fully demineralized water
2.08 parts by weight of H ₂ O ₂ (30%)

A) Testing as a binder for finely divided mineral materials

300 g quartz sand H34 were mixed with the binder compositions mixed at room temperature (5 wt .-% dry binder, be moved on sand). The moist mixtures are ent speaking metal mold test specimen (Fischer-Riegel) with the dimensions solutions 17 × 2.3 × 2.3 cm shaped, compressed and after being removed cured for 2 hours at 150 ° C in a convection oven. For compacting a type PRA ram from Georg Fischer AG was used.

The flexural strength of the Fischer bars produced in this way is determined in dry state at 23 ° C and 100 ° C test specimen temperature in egg type PFG strength tester with the PBV test device (From Georg Fischer, Schaffhausen / CH). Will continue also the flexural strength of the Fischer bars after an hour in La storage in demineralized water at 23 ° C, wet certainly.

Sand test specimen, 5% by weight binder

B) Testing as a stiffening coating of corrugated cardboard

A test specimen (20 × 20 cm) made from commercially available non-hydrophobic corrugated cardboard (basis weight 600 g / m ² ) is sprayed on both sides with a 35% by weight binder solution. The application amount is 20 g solid binder / m ² per side. After a flashing time of 10 minutes, the coating is cured for 2 minutes in a circulating air drying cabinet heated to 200 ° C.

The wetting time (= time for the complete Penetration of the binder into the cardboard) and the waterproof after hardening based on the penetration time of a drop of water in the coated cardboard.

Claims (18)

1. Thermally curable, aqueous composition containing

• - At least one copolymer containing carboxyl groups, which is composed of
  • 50 to 99.5% by weight of at least one ethylenically unsaturated mono- and / or dicarboxylic acid,
  • 0.5 to 50% by weight of at least one ethylenically unsaturated compound which is selected from the esters of ethylenically unsaturated monocarboxylic acids and the half-esters and diesters of ethylenically unsaturated dicarboxylic acids with an amine having at least one hydroxyl group,
  • - up to 20% by weight of at least one further monomer;
• - At least one more functional β-hydroxyalkylamine, and
• - optionally at least one surfactant.

2. Composition according to claim 1, wherein the copolymer contains as ethylenically unsaturated mono- and / or dicarboxylic acid at least one compound which is selected from C ₃ -C ₁₀ monocarboxylic acids and C ₄ -C ₈ dicarboxylic acids, preferably acrylic acid, methacrylic acid, Crotonic acid, fumaric acid, maleic acid, 2-methylmaleic acid and itaconic acid. 3. Composition according to claim 2, wherein the copolymer as ethylenically unsaturated mono- and / or dicarboxylic acid, acrylic acid or a mixture of acrylic acid and maleic acid or anhydride in a molar ratio of 95: 5 to 40:60 before moves 90: 10 to 50: 50, contains. 4. Composition according to one of the preceding claims, where the amine having at least one hydroxyl group is selected from amines of the general formula
R ^c NR ^a R ^b
in which
R ^{c stands} for C ₆ - to C ₂₂ -alkyl, C ₆ - to C ₂₂ -alkenyl, aryl-C ₆ -C ₂₂ -alkyl or aryl-C ₆ -C ₂₂ -alkenyl, the alkenyl radical being 1, 2 or 3 can have non-adjacent double bonds,
R ^a for hydroxy-C ₁ -C ₆ alkyl or a radical of the formula II
- (CH ₂ CH ₂ O) _x (CH ₂ CH (CH ₃ ) O) _y -H (II)
stands, where
in the formula II the order of the alkylene oxide units is arbitrary and x and y independently of one another represent an integer from 0 to 100, the sum of x and y being <1,
R ^{b is} hydrogen, C ₁ - to C ₂₂ -alkyl, hydroxy-C ₁ -C ₆ -alkyl, C ₆ - to C ₂₂ -alkenyl, aryl-C ₆ -C ₂₂ -alkyl, aryl-C ₆ -C ₂₂ -alkenyl or C ₅ -C ₈ -cycloalkyl, where the alkenyl radical may have 1, 2 or 3 non-adjacent double bonds,
or R ^b for a radical of the formula III
- (CH ₂ CH ₂ O) _v (CH ₂ CH (CH ₃ ) O) _w -H (III)
stands, where
in the formula III the order of the alkylene oxide units is arbitrary and v and w independently of one another represent an integer from 0 to 100, and mixtures thereof. 5. Composition according to one of the preceding claims, where the copolymer contains at least one compound incorporated as a further monomer which is selected from olefins, preferably ethene, propene, n-butene, isobutene and / or diisobutene, vinylaromatics, preferably styrene, Esters of α, β-ethylenically unsaturated mono- and / or dicarboxylic acids with C ₁ - to C ₂₂ -alkanols, preferably (meth) acrylic acid esters, and mixtures thereof. 6. Composition according to one of the preceding claims, where at least one amine of the formula in the surfactant
R ^c NR ^a R ^b ,
as defined in claim 4. 7. Composition according to one of the preceding claims, where in the weight ratio of copolymer to higher functionality lem β-hydroxyalkylamine 1: 1 to 1: 0.01, preferably 1: 1 to 1: 0.1. 8. Composition according to one of the preceding claims, where the higher functional β-hydroxyalkylamine is selected amines with at least two hydroxyl groups. 9. The composition according to claim 8, wherein the higher functional β-hydroxylamine is a water-soluble, linear or branched aliphatic compound which contains at least two functional amino groups of type (a) or of type (b) per molecule.
wherein R is hydroxyalkyl and R 'is alkyl, is preferably a compound of formula 1
wherein
A is 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,
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 are have meanings given above, or alkyl which in turn can be interrupted by one or more NR ⁵ groups, where R ^{5 has} the meanings given above and / or be substituted by one or more NR ⁶ R ⁷ groups, where R ⁶ and R ^{7 have} 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 are H, hydroxyalkyl, alkyl or cycloalkyl. 10. The composition according to any one of the preceding claims, the also at least one amine or amide crosslinker with mind contains at least two hydroxyl groups. 11. The composition according to any one of the preceding claims, the additionally contains at least one reaction accelerator. 12. The composition of claim 11, wherein the reaction accelerator is selected from compounds containing phosphorus gene, preferably hypophosphorous acid and its alkali and Alkaline earth salts. 13. The composition according to any one of the preceding claims, where the surface tension is at most 55 mN / m. 14. Carboxyl group-containing copolymer, as in one of the Claims 1 to 9 defined. 15. A method for producing a composition according to any one of claims 1 to 13, wherein

• a) reacting at least one ethylenically unsaturated monocarboxylic acid or a derivative thereof and / or at least one ethylenically unsaturated dicarboxylic acid or a derivative thereof with at least one hydroxyl-containing amine in an esterification reaction,
• b) the reaction product (s) from step i) with at least one ethylenically unsaturated mono- and / or dicarboxylic acid and / or their anhydrides and optionally at least one further monomer to give a copolymer containing carboxyl groups, and
• c) the copolymer from step ii) is mixed with at least one higher-functionality β-hydroxyalkylamine, optionally at least one surfactant and optionally further additives.

16. Bound substrate obtainable by treating a sub strats with a composition according to any one of claims 1 to 14 and subsequent hardening. 17. The substrate of claim 16 in the form of a shaped body. 18. Use of a composition according to one of claims 1 to 13 as binders for substrates, preferably moldings, particularly preferred for moldings made of fibrous or granular materials that are particularly selected from wood chips, wood fibers, textile fibers, glass fibers, mineral fa fibers, natural fibers, cork chips and sand.