DE19816741A1 - Self-crosslinking aqueous preparation useful as binder for coatings etc., as an adhesive or in treating leather - Google Patents

Abstract

A self-crosslinking aqueous preparation contains an aqueous dispersion of an anhydride group (AH)-containing copolymer (P); and a crosslinker (A) with a primary and/or secondary amine group (AM). A self-crosslinking aqueous preparation contains (i) an aqueous dispersion of an anhydride group (AH)-containing copolymer (P) obtained by radical aqueous emulsion copolymerisation of ethylenically-unsaturated monomers (M) comprising at least a monomer (M1) which is an anhydride of an unsaturated 3-8C carboxylic acid and a comonomer (M2); and (ii) a crosslinker (A) with a primary and/or secondary amine group (AM), this being (A1) a compound with at least 2 AMs; (A2) a compound with at least 1 AM and a siloxane group; (A3) an aminoalcohol; or (A4) a polymer with AMs. An Independent claim is also included for preparation of the composition by mixing an aqueous dispersion of copolymer (P) with (A), optionally in dissolved or dispersed form.

Description

The present invention relates to self-crosslinking, aqueous preparations which

• (i) at least one copolymer P in having anhydride groups AH Form of an aqueous dispersion, and
• (ii) contains at least one crosslinking substance A.

For the application properties of aqueous polymers It is often an advantage if the polymers have a high molecular weight. So a high Mo improves molecular weight usually the mechanical strength of the poly mere. At the same time, their sensitivity to solutions Influences reduced, which is particularly the case with coatings is an advantage. In the case of adhesives, a high molecule improves lar weight is important for the stability of the bond sion.

As a rule, a high molecular weight is achieved by adding of crosslinking monomers in the polymerization reaction tion. In a number of applications aqueous polymer dis persions, however, it can be an advantage if the network tion does not already take place during the polymerization, but instead only afterwards. The reason for this is on the one hand hen that through a crosslinking during the polymerization craze tion the film-forming properties of the polymer dispersions be reduced. On the other hand, a subsequent Networking is basically the interparticular networking of the poly merisate particles in the film, leading to an improvement in chemical and mechanical resistance of polymer films based such dispersions.

For example, US Pat. No. 4,048,130 describes aqueous polymers satdispersionen known, which N-methylolamides ethylenisch un saturated carboxylic acids, e.g. B. N-methylol methacrylamide, einpolyme included. Subsequent networking takes place in derar term polymers, however, only at elevated temperature (at for example 150 to 200 ° C) instead. In addition, the networking free of harmful formaldehyde.  

Self-crosslinking binders are in the form of EP-A-372 295 aqueous preparations are known which ent ent at least one polymer hold which contain by reacting an anhydride groups receives the polymer with a low molecular weight compound is at least one blocked amino group and little at least one functionality that is reactive towards the anhydride group having. Such preparations are preferably used for one stove enamels used. The subsequent networking takes place only at an elevated temperature. In addition, the anhydride polymers containing groups by radical polymerization made in an organic solvent, then with the blocked amines in a separate reaction in an orga African solvent and only then in another Process step converted into an aqueous preparation. This The procedure is too complex for many applications.

EP-A-620 234 describes aqueous polymer dispersions knows that the methacrylic anhydride as a crosslinking monomer lymerized included. The presence of the cross-linking meth acrylic anhydride causes an increase in the minimum film formation temperature. The aqueous polymer disper described there ions are used as binders for pigment-containing paints puts.

The present invention has for its object preparation ready on the basis of aqueous polymer dispersions make a subsequent, adhere to the polymerization craze enable subsequent self-networking. The self ver Networking should be carried out even at low temperatures (e.g. room temperature temperature) take place and do not lead to a release health lead dangerous substances. Furthermore, the aqueous Polymer dispersion available in the simplest possible way be.

This task could be solved by an aqueous preparation tion containing at least one anhydride groups AH Copolymer P in the form of an aqueous polymer dispersion and we at least one crosslinking compound A, which is selected is among compounds with at least two primary and / or se secondary amino groups, polymers containing amino groups, ami alcohols and aminosiloxanes.

Accordingly, the present invention relates to self-crosslinking, aqueous preparations comprising:

• i) at least one copolymer P in having anhydride groups AH Form of an aqueous dispersion, available from radicals aqueous emulsion polymerization ethylenically unsaturated ter monomers M, wherein the monomers M at least one monomer M1, selected from the anhydrides monoethylenically unsaturated saturated carboxylic acids with 3 to 8 carbon atoms, and at least one copolymerizable with the monomers M1, different from it Include monomer M2, and
• ii) at least one crosslinking substance A with at least one primary and / or secondary amino group AM, selected from
  Compounds A1 which have at least two primary and / or secondary amino groups AM per molecule,
  Compounds A2 which have at least one primary or secondary amino group AM and one siloxane group,
  Amino alcohols (compounds A3) and
  Polymer AP with several primary and / or secondary amino groups AM.

Preferred monomers M1 are methacrylic anhydride, acrylic acid hydride and itaconic anhydride. Particularly preferred monomer M1 is methacrylic anhydride. The proportion of the monomers M1 in the Ge total amount of the monomers M to be polymerized is generally in the range from 0.1 to 30% by weight, preferably in the range from 0.1 to 20% by weight, particularly preferably in the range from 0.2 to 10 % By weight and especially in the range from 0.5 to 5% by weight.

Suitable monomers M2 are all those monoethylenically unsaturated monomers which are copolymerizable with the monomers M1. In general, they are hydrophobic monomers with a limited water solubility (ie <60 g / l at 25 ° C), as are usually used for radical, aqueous emulsion polymerization. Typical M2 monomers are selected from vinyl aromatic monomers such as styrene, α-methylstyrene, ortho-chlorostyrene or vinyltoluenes, vinyl esters of C ₁ -C ₁₈ -, preferably C ₁ -C ₁₂ -monocarboxylic acids, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate , Vinyl hexanoate, vinyl 2-ethylhe xanoate, vinyl decanoate, vinyl laurate, vinyl stearate and vinyl ester of Versatic® acids (Versatic® acids are branched, aliphatic carboxylic acids with 5 to 11 carbon atoms). Furthermore, esters of β, β-ethylenically unsaturated C ₃ -C ₈ mono- or dicarboxylic acids with preferably C ₁ -C ₁₂ and in particular C ₁ -C ₈ alkanols or C ₅ -C ₈ cycloalkanols are suitable. Suitable C ₁ -C ₁₂ -alkanols are, for example, methanol, ethanol, n-propanol, i-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, n-hexanol and 2-ethylhexanol. Suitable cycloalkanols are, for example, cyclopentanol or cyclohexanol. Particularly suitable are esters of acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid or fumaric acid. Specifically, these are esters of acrylic acid and methacrylic acid, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid isopropyl ester, (meth) acrylic acid n-butyl ester, (meth) acrylic acid isobutyl ester, (meth) acrylic acid-1 -hexyl ester, (meth) acrylic acid tert-butyl ester, (meth) acrylic acid 2-ethylhexyl ester, maleic acid dimethyl ester or maleic acid di-n-butyl ester. In addition, C ₄ -C ₈ conjugated dienes such as 1,3-butadiene, isoprene or chloroprene, C ₂ -C ₆ olefins such as ethylene, propene, 1-butene and isobutene, or vinyl chloride can be used as monomers M2 will. The said monomers M2 preferably make up 80 to 99.9% by weight, in particular 90 to 99.8% by weight and especially 95 to 99.5% by weight, based on the total weight of the monomers used. In a preferred embodiment of the present invention, the monomers M2 comprise at least two mutually different monomers M2a and M2b. These are preferably selected from the aforementioned vinyl aromatic monomers, the esters of acrylic acid and methacrylic acid with C ₁ -C ₁₂ -alkanols, the vinyl esters of aliphatic C ₁ -C ₁₂ -carboxylic acids and ethylene and vinyl chloride. The latter monomers are preferably used in combination with vinyl acetate or vinyl propionate.

Furthermore, the copolymer P can also contain monomers M3 different from the monomers M1 and M2 in copolymerized form, which have an increased solubility in water, ie <60 g / l at 25 ° C. and 1 bar. These monomers can be copolymerized in amounts of up to 10% by weight, preferably up to 5% by weight, based on the total amount of monomers. Such monomers increase the stability of the polymer dispersions used as binders. The monomers M3 include monomers M3a which contain acidic groups such as β, β-monoethylenic unsaturated mono- and dicarboxylic acids with 3 to 10 carbon atoms as well as ethylenically unsaturated sulphonic acids, phosphonic acids or ethylenically unsaturated dihydrogen phosphates and their water-soluble salts. Preferred monomers M3a are ethylenically unsaturated C ₃ -C ₈ carboxylic acids or C ₄ -C ₈ dicarboxylic acids, e.g. B. itaconic acid, crotonic acid, vinyl acetic acid, acrylamidoglycolic acid and especially acrylic acid and methacrylic acid, further sulfonic acids, such as vinyl and allylsulfonic acid, (meth) acrylamidoethanesulfonic acid, 2- (meth) acrylamido-2-methopropanesulfonic acid, phosphonic acids such as vinylphosphonic acid, allylphosphonic acid and 2-acrylamido-2-methylpropane-1-phosphonic acid, and their alkali metal salts, especially their sodium salts. The monomers M3 also include neutral or nonionic, modifying monomers M3b, e.g. B. the amides or the N-alkylol amides of the copolymerizable carboxylic acids mentioned, for example acrylamide, methacrylamide, N-methylolacrylamide and N-methylol methacrylamide or the hydroxyalkyl esters of the copoly merizable carboxylic acids mentioned, for. B. hydroxyethyl acrylate, hydroxy propyl acrylate and hydroxybutyl acrylate and corresponding meth acrylates. Nitriles α, β-monoethylenically unsaturated ter C ₃ -C ₈ carboxylic acids, such as acrylonitrile or methacrylonitrile, are also suitable.

Furthermore, the copolymer P can contain crosslinking monomers M4 in a polymerized form. If desired, these are used in a subordinate amount, ie in amounts of 0.01 to 2% by weight, based on the total amount of monomers. These are preferably monomers which have two non-conjugated, ethylenically unsaturated bonds, for. B. the diesters of dihydric alcohols with β, β-monoethylenic unsaturated C ₃ -C ₈ -carbonsäu ren, for. B. glycol bisacrylate or esters of α, β-unsaturated car acids with alkenols, for. B. bicyclodecenyl (meth) acrylate, fer ner divinylbenzene, N, N'-divinylurea, N, N'Divinylimidazolon non, diallyl phthalate etc. In a preferred embodiment, the polymer P contains no monomers M4 copolymerized.

The glass transition temperature of the copolymers P depends in the first place on the desired application. It is usually in the range from -80 ° C to + 100 ° C and preferably in the range from -60 ° C to + 70 ° C. In a special embodiment, which is suitable, for example, for pressure sensitive adhesives or for flexible coating compositions and for sealing compositions, the glass transition temperature of the copolymer P is below 0 ° C. In another embodiment of the invention, which is suitable, for example, as a binder in pigment-containing preparations, such as dispersion paints, or block-resistant paints, the copolymer P has a glass transition temperature between 0 and + 50 ° C. Here it proves to be helpful to estimate the glass transition temperature T _{g of} the dispersed polymer. According to Fox (TG Fox, Bull. Am. Phys. Soc. (Ser. II) 1, 123 [1956] and Ullmann's Encyclopedia of Industrial Chemistry, Weinheim (1980), pp. 17, 18) the following applies to the glass transition temperature of copolymers large molar masses in good nutrition

where X ¹ , X ^2,. . ., X ⁿ the mass fractions 1, 2 ,. . ., n and T _g ¹ , T _g ² _,. . ., T _g ^{n are} the glass transition temperatures of only one of the monomers 1, 2 ,. . ., n mean polymers in degrees Kelvin. The latter are e.g. B. from Ullmann's Encyclopedia of Industrial Chemical Chemistry, VCH, Weinheim, Vol. A 21 (1992) p. 169 or from J. Brandrup, EH Immergut, Polymer Handbook 3rd ed, J. Wiley, New York 1989.

From what has been said it is clear that the glass temperature of the Copo lymeren P both by a suitable main monomer M2, the one Glass temperature in the desired range, as well as by Combination of at least one monomer M2a, its homopolymer has a high glass transition temperature and at least one Monomer M2b, whose homopolymer has a low glass transition temperature, can be adjusted.

In a preferred embodiment of the present invention, the monomers M2 constituting the copolymer P comprise at least one monomer M2a, the homopolymer of which has a glass transition temperature T _g <30 ° C. for the limit of a very high molecular weight, and at least one monomer M2b, the homopolymer of which Glass transition temperature T _g <0 ° C. Monomers M2a which are suitable for this purpose are, for example, styrene, α-methylstyrene, methyl methacrylate, ethyl methacrylate, n- and isopropyl methacrylate, n-, iso- and tert-butyl methacrylate, vinyl acetate and tert-butyl acrylate, furthermore acrylonitrile and methacrylonitrile, wherein the nitriles preferably make up no more than 30% by weight of the monomers M2. Suitable monomers M2b are e.g. B. the C ₁ -C ₁₂ alkyl acrylates, butadiene, vinyl propionate, vinyl esters of Versatic® acids, in particular ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate. Monomer combinations M2a / M2b which comprise styrene and / or methyl methacrylate and also n-butyl acrylate and optionally 2-ethylhexyl acrylate are particularly preferred.

In a particularly preferred embodiment of the present invention, the copolymer P is composed of:

• i) 0 to 39.8% by weight, in particular 5 to 29.3% by weight, of monomers M2a, in particular styrene and / or methyl methacrylate,
• ii) 60 to 99.8% by weight, in particular 70 to 99.3% by weight, of monomers ren M2b, especially n-butyl acrylate and / or 2-ethylhexyl crylate,
• iii) 0.1 to 30% by weight, preferably 0.2 to 10% by weight, at least of a monomer M1, in particular methacrylic anhydride and
• iv) 0.1 to 5% by weight, preferably 0.2 to 3% by weight, of monomers M3, in particular an ethylenically unsaturated carboxylic acid, and particularly preferably acrylic acid or methacrylic acid,
  the parts by weight of the monomers M1, M2a, M2b and M3 add up to 100% by weight.

It has also proven to be advantageous if the polymer a particle of the copolymer P is a medium polymer particle Have diameters in the range of 50 to 1000 nm (determined by means of an ultracentrifuge or by means of photon correlation spectros Copy; for particle size determination see W.Mächtle, Angew. Ma Kromolecular Chemistry 1984, Vol. 185, 1025-1039, W. Mächtle ibid., 1988, Bad 162, 35-42). For preparations with a high solids content hold, e.g. B. <50 wt .-%, based on the total weight of the zu preparation, it is advantageous for reasons of viscosity if the weight average particle diameter of the polymer particles in the dispersion is <250 nm. The average particle diameter will preferably not exceed 600 nm.

The preparation of the aq used according to the invention Other polymer dispersions are carried out as already mentioned by radical aqueous emulsion polymerization of the above mono mere in the presence of at least one radical polymer onsinitiators and possibly a surfactant sub punch.

Free radical polymerization initiators are all those which are capable of initiating a free radical aqueous emulsion polymerization. It can be both peroxides, e.g. B. alkali metal peroxodisulfates and azo compounds. Redox initiator systems are preferably used which consist of at least one organic reducing agent and at least one peroxide and / or hydroperoxide, e.g. B. tert-Bu tylhydroperoxid, hydrogen peroxide or peroxopivalate, are put together. As reducing agents come sulfur compounds, e.g. B. the sodium salt of hydroxymethanesulfinic acid, sodium sulfate, sodium disulfite, sodium thiosulfate or acetone bisulfite adduct, and also ascorbic acid, hydrazine or hydroxylamine. Redox initiator systems can also be used for this purpose, which contain a small amount of a metal compound soluble in the polymerization medium, the metallic component of which can occur in several valence levels, e.g. B. iron (II) sulfate, iron (II) EDTA complex in the form of the sodium salt, vanadium sulfate or CuCl ₂ . Peroxodisulfates such as sodium peroxodisulfate or ammonium peroxodisulfate are also preferred initiators. The amount of radical initiator systems used is preferably 0.1 to 2% by weight, based on the total amount of monomers to be polymerized.

Limit suitable for carrying out the emulsion polymerization Surfactants are the most common for these purposes protective colloids and emulsifiers used. The interfacial tive substances are usually used in amounts of up to 10% by weight, preferably 0.5 to 5% by weight and in particular 1 to 4% by weight, based on the monomers to be polymerized.

Suitable protective colloids are, for example, polyvinyl alcohols, Starch and cellulose derivatives or containing vinyl pyrrolidone Copolymers. A detailed description of other suitable The protective colloid can be found in Houben-Weyl, Methods of Orga African Chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme- Verlag, Stuttgart 1961, pp. 411-420. Mixtures of emulsifiers and / or protective colloids can be used.

Preferably only emulsifiers are used as surface-active substances, the relative molecular weights of which, in contrast to the protective colloids, are usually less than 2000. They can be both anionic, cationic and nonionic in nature. The anionic emulsifiers include alkali and ammonium salts of alkyl sulfates (alkyl radical: C ₈ -C ₁₂ ), of sulfuric acid semiesters of ethoxylated alkanols (EO degree: 2 to 50, alkyl radical: C ₁₂ to C ₁₈ ) and ethoxylated alkylphenols (EO degree : 3 to 50, alkyl radical: C ₄ -C ₉ ), of alkyl sulfonic acids (alkyl radical: C ₁₂ -C ₁₈ ) and of alkylarylsulfonic acids (alkyl radical: C ₉ to C ₁₂ ).

Anionic surfactants also count Mono- and dialkyl derivatives of sulfonylphenoxybenzenesulfonic acid Salts, especially their sodium, potassium or calcium salts. The alkyl groups in these compounds have in the Re gel 6 to 18 and in particular 6, 12 or 16 carbon atoms. Often technical mixtures are used, the proportion of 50 to Have 90 wt .-% of the monoalkylated product. This verb are well known, e.g. B. from US-A-4,269,749, and commercially available, for example as Dowfax® 2A1 (product no Chen of the Dow Chemical Company).

In addition to the anionic emulsifiers mentioned, nonionic emulsifiers can also be used. Suitable nonionic emulsifiers are araliphatic or aliphatic nonionic emulsifiers, for example ethoxylated mono-, di- and trialkyl phenols (EO grade: 3 to 50, alkyl radical: C ₄ -C ₉ ), ethoxylates of long-chain alcohols (EO grade: 3 to 50 , Alkyl radical: C ₈ -C ₃₆ ), and poly ethylene oxide / polypropylene oxide block copolymers. Preferred are ethoxylates of long-chain alkanols (alkyl radical: C ₁₀ -C ₂₂ , average degree of ethoxylation: 3 to 50) and among them particularly preferably those based on oxo alcohols and native alcohols with a linear or branched C ₁₂ -C ₁₈ alkyl radical and an ethoxylation degree of 8 to 50.

Anionic emulsifiers or combinations of are preferred at least one anionic and one nonionic emulsifier used. Other suitable emulsifiers can be found in Houben Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecule lare Stoffe, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 192-208).

The molecular weight of the polymers can be reduced by adding Amounts, usually up to 1 wt .-%, based on the polyme rising monomers, one or more, the molecular weight regulating substances, e.g. B. organic thio compounds, silanes, Allyl alcohols or aldehydes can be adjusted.

The emulsion polymerization can be both continuous and according to the batch mode, preferably after a semi-continuous process. The ones to be polymerized can Monomers continuously, including step or gradient way, the polymerization approach.

In addition to the seed-free production method, a defined polymer particle size according to the emulsion polymerization the seed latex process or in the presence of in situ seed latex. Methods for this are known and can can be taken from the prior art (see EP-B 40419, EP-A-614 922, EP-A-567 812 and literature cited therein and "En cyclopedia of Polymer Science and Technology ", Vol. 5, John Wiley & Sons Inc., New York 1966, p. 847).

The polymerization is preferably carried out in the presence of 0.01 to 3% by weight and in particular 0.05 to 1.5% by weight of a seed latex (Solids content of the seed latex, based on the total amount of monomer), preferably with seed latex (master seed) leads. The latex usually has a weight-average part size from 10 to 300 nm and in particular 20 to 100 nm. Its constituent monomers are, for example, styrene, Me thyl methacrylate, n-butyl acrylate and mixtures thereof, the Seed latex to a lesser extent also monomers M3, preferably less than 10% by weight based on the total weight of the polymer Risk particles in the seed latex that can be copolymerized.

Polymerization pressure and polymerization temperature are of un secondary importance. Generally one works at Tempera structures between room temperature and 120 ° C, preferably at temperature  temperatures of 40 to 95 ° C and particularly preferably between 50 and 90 ° C.

Following the actual polymerization reaction it is if necessary, the aqueous dispersions of Copo lymeren P largely free of odorants, such as residual monomers and other organic volatile components. This can be done physically by distilla in a manner known per se tive removal (especially by steam distillation) or can be achieved by stripping with an inert gas. The Ab Reduction of the residual monomers can continue chemically through radicals post-polymerization, especially under the influence of redo xinitiator systems, such as z. B. in DE-A 44 35 423 and literature cited there are carried out. Prefers is the post-polymerization with a redox initiator system at least one organic peroxide and one organic weld field connection carried out.

In this way, aqueous dispersions of the copolymer P are included Polymer contents up to 80% by weight, based on the total weight the dispersion, accessible. For practical reasons preferably dispersions with polymer contents in the range from 30 to 70 wt .-%, in particular 40 to 65 wt .-%, used.

In addition to the copolymers P, the preparations according to the invention contain at least one crosslinking substance A which has at least one primary and / or secondary amino group AM. One embodiment of the present invention relates to preparations which contain, as crosslinking substance A, compounds A1 which have at least two primary and / or secondary amino groups, in particular primary amino groups per molecule. These are preferably compounds of the general formula I.

wherein
R ¹ , R ² , R ³ and R ⁴ independently of one another represent hydrogen or functional groups of the general formula Alk-NR ⁵ R ⁶ , in which
Alk represents C ₁ -C ₄ alkylene and
R ⁵ , R ⁶ independently of one another are hydrogen or a functional group Alk-NR ⁷ R ⁸ , in which R ⁷ and R ⁸ independently of one another have one of the meanings given for R ¹ to R ⁴ , and
B is C ₂ -C ₂₄ alkylene which can be interrupted by one or more oxygen atoms, cycloalkylene groups or groups NR ⁹ or substituted by one or more groups -Alk-NR ⁵ R ⁶ , where R ^{9 is} one of those for R ¹ to R ⁴ indicated meanings, or C ₁ -C ₁₀ alkyl, for arylene or
represents a remainder 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,
where the cycloaliphatic radicals can also be substituted by 1, 2 or 3 C ₁ -C ₁₀ alkyl radicals.

In the compounds of the general formula I naturally at least two groups NR ¹ R ³ , NR ² R ⁴ , NR ⁵ R ⁶ , NR ⁷ R ^{8 represent} a primary or secondary amino group.

Here and below, C ₁ -C ₁₀ alkyl represents linear or branched alkyl groups which have 1 to 10 carbon atoms and can be interrupted by one or more non-adjacent oxygen atoms. Examples of C ₁ -C ₁₀ alkyl are methyl, ethyl, n- or isopropyl, n-butyl, 2-butyl, isobutyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl and n-decyl, furthermore 3-oxa-1-butyl, 3-oxa-1-pentyl, 3-oxa-1-hexyl, 4-oxo-1-pentyl, 4-oxa-1-hexyl, 5-oxa-1-hexyl, 3, 6-dioxa-1-heptyl, 3,6-dioxa-1-octyl, 4,8-dioxa-1-nonyl etc.

C ₁ -C ₄ alkylene is preferably 1,2-ethylene, 1,2-propylene, 1,3-propylene and 1,4-butylene.

C ₂ -C ₂₄ alkylene represents linear or branched alkylene which has 2 to 24 carbon atoms. Examples of C ₂ -C ₂₄ alkylene are 1,2-ethylene, 1,2- and 1,3-propylene, 1,2, -, 1,3- and 1,4-butylene, 2-methyl-1 , 3-propylene, 2,2-dimethyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 1,6-hexylene, 2-methyl-1,6-hexylene, 2,2-dimethyl-1,6-hexylene, 2,2,4-trimethyl-1,6-hexylene, β, ω-octylene, β, ω-decylene, β, ω-dodecylene. Examples of alkylene which is interrupted by oxygen atoms are: 3-oxa-1,5-pentylene, 3,6-dioxa-1,8-octylene, 3,6,9-trioxa-1,11-undecylene, 4- Oxa-1,7-heptylene, 4,7-dioxa-1,11-undecylene and 4,8, 12-trioxa-1,15-penta decylene etc. Examples of alkylene which is interrupted by groups NR ⁹ -alkylene, are 3-imino-1,5-pentylene, 3,6-bisimino-1,8-octylene, 3,6,9-trisimino-1,1-undecylene, 4-imino-1,7-heptylene etc.

Arylene is, for example, 1,2-, 1,3- or 1,4-phenylene, where the phenyl group may have 1 or 2 C ₁ -C ₁₀ -alkyl groups or ethoxylated -OH as substituents. Arylene also includes atomic groups of the following formula:

wherein
u and w independently of one another represent 0 or 1,
v = 0, 1 or 2, and
-T- for a single bond, linear or branched C ₁ -C ₄ alkyl or for -O-, -S-, -S (O) -, -S (O) ₂ -, -C (O) -, -OC (O) -, -NH-C (O) - or -NH-C (O) -NH-.

Examples of compounds of the formula I are aliphatic or cycloaliphatic diamines such as 1,2-ethylenediamine, 1,2- and 1,3-diaminopropane, 1,3- and 1,5-diaminopentane, 2-methyl-1,5-dia minopentane, 2-ethyl-2-butyl-1,5-diaminopentane, 2,2-dime thyl-1,3-diaminopropane, 1, 3-diamino-2-methylpropane, 2-Me ethyl-1,6-diaminohexane, 3-methyl-1,6-diaminohexane, 2,2,4-trime thyl-1,6-diaminohexane, isophoronediamine, bis (4-aminocyclohe xyl) methane, bis (4-amino-3-methylcyclohexyl) methane and 2,2-bis (4-aminocyclohexyl) propane and aromatic diamines,  e.g. B. 1,2-, 1,3- and 1,4-xylylenediamine, bis (4-aminophenyl) me than sulfone, sulfide, 2,2-bis (4-aminophenyl) propane and 2,2-bis (4-aminophenyl) ether. This also includes alkylenediamines, wherein the alkylene unit by one or more NH groups or is interrupted by oxygen atoms, for example N- (2-Ami noethyl) -1,2-diaminoethane (= diethylenetriamine), N- (3-aminopro pyl) -1,2-diaminoethane, N, N'-bis (3-aminopropyl) ethylenediamine, Triethylene tetramine, tetraethylene pentamine, 1,5-diamino-3,6,9-tri oxaundecane, 1,10-diamino-4,7-dioxadecane, 1,12-diamino-4,9-dioxa dodecane, 1,14-diamino-4,11-dioxatetradecane and 1,13-dia mino-4,7,10-trioxatridecan, also polyoxyalkylenediamines, the un sold under the name Jeffamine® by Huntsman be, e.g. B. Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, Jeffamine ED-600, Jeffamine ED-900, Jeffamine ED-2001 and Jeffamine EDR-148.

The compounds A1 of the general formula I also include Ver bonds with more than 2 amino groups, e.g. B. 4-amino-ethyl-1,8- diaminooctane, also known as "dendrimer" polyamines can be described by the general formulas Ia and Ib nen.

In formulas Ia and Ib, B has one of the meanings given above for B in formula I. In formula Ib, R 'is -CH ₂ -CH ₂ -CH ₂ -NH ₂ , and some of the radicals R' can also be hydrogen. Dendrimer polyamines of the general formula Ia are based on aliphatic or cycloaliphatic diamines, for example the above-mentioned diamines and in particular 1,2-ethylenediamine, by reaction with up to 4 moles of acrylonitrile per mole of diamino compound in the sense of a Michael reaction and subsequent catalytic Hydrogenation accessible. An example of this is the hydrogenated adduct of 4 moles of acrylonitrile with ethylenediamine. This results in a hexamine with 4 primary amino groups of the general formula Ia, in which B is 1,2-ethylene. This compound is also known as N-6 amine. The N-6-amine thus obtained can in turn now be reacted with up to 8 mol of acrylonitrile and then hydrogenated again. In extreme cases, this results in the N-14-amine (compound Ib, in which B is 1,2-ethylene and all radicals R 'are 3-aminopropyl). Instead of ethylenediamine, other aliphatic diamines or triamines can of course also be used for the dendrimer synthesis. The preparation of the dendrimer polyamines is described in WO 93/14 147, to which full reference is made here.

The preparations according to the invention can, as crosslinking substance A, also aminosiloxanes of the general formula II

R ^a HN-X-Si (OR ^b ) ₃ (II)

contain what
R ^{a represents} hydrogen, C ₁ -C ₁₀ alkyl, aryl or aralkyl,
R ^{b is} C ₁ -C ₁₀ alkyl and
X is C ₂ -C ₂₄ alkylene, which can be interrupted by one or more oxygen atoms or groups NR ^c , in which Rc is hydrogen or C ₁ -C ₁₀ alkyl, or is arylene.

Preferred aminosiloxanes of the general formula II are compounds in which R ^{a is} hydrogen. R ^b is preferably C ₁ -C ₄ alkyl and X is preferably C ₁ -C ₄ alkylene. Examples of compounds II are 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

Amino alcohols can also be used as the cross-linking substance. Here and below, amino alcohols are understood to mean compounds A3 which contain at least one OH group bonded to an sp ³ carbon atom and at least one primary or secondary amino group, preferably also bound to an sp ³ -C atom. Examples of suitable amino alcohols A3 are 2-aminoethanol, 2- or 3-aminopropanol, 2- (2-aminoethoxy) ethanol, N- (2-aminoethyl) ethanolamine, N-methyl- and N-ethylethanolamine, diethanolamine and 3- (2-Hydroxyethylamino -) - 1-propanol.

The preparations according to the invention can also contain, as crosslinking substance A, instead of or together with the compounds A1, A2 or A3, one or more amino groups having polyamines AP. The distinction between compounds A1 and polymers AP is of a purely formal nature and relates to the molecular weight, the compounds A generally having a molecular weight <800 and the polymers AP generally having a weight-average molecular weight M _w <800. However, this limit is fluid. The weight average molecular weight M _{w of} the polymers AP is preferably in the range from 1000 to 50,000 daltons. The polymers AP have several terminally and / or laterally arranged, optionally via C ₁ -C ₄ -alkylene, for. B. methylene, bound, primary and / or secondary amino groups AM. The number of amino groups AM in the polymer is generally in the range from 0.5 to 20 mmol and preferably in the range from 1 to 10 mmol of amino groups per gram of polymer. This corresponds to an amine number in the range from 20 to 1200 and preferably in the range from 60 to 600 mg KOH / g polymer. Examples of suitable polymers AP containing amino groups are the hydrogenation products of homo- and copolymers of acrylonitrile and / or methacrylonitrile with, for example, styrene and / or butadiene.

Preferred examples of such polymers AP are the hydrie tion products of copolymers consisting of 5 to 50 wt .-%, in particular 10 to 30% by weight of acrylonitrile and / or methacrylonitrile and 50 up to 95% by weight, in particular 70 to 90% by weight of butadiene and / or Isoprene are built up.

A special example of this are the hydrogenation products from Copolymers consisting of approximately 18% by weight acrylonitrile, approximately 79.6% by weight Butadiene and about 2.4 wt .-% carboxylate end groups are, wherein in the hydrogenation product about 50 to 95% of Ni Trilgruppen were hydrogenated to the amine. The molecular weight of this special hydrogenation products is in the range of 2000 to 10,000 daltons and the amine number in the range of 100 to 200 mg KOH / g polymer. Process for the preparation of the hydrogenated copoly mers are for example from US-A-2,456,428, the US-A-2,585,583, US-A-3,122,526, the earlier German application P 196 43 126.3 and P 197 02 103.4 are known. In particular the latter writings are hereby made in their entirety Referred.

Such amino groups are also suitable according to the invention the polymers AP, which by radical homo- or copolymerisa tion of hydrolyzable N-vinylamides such as N-vinylformamide, N-vinyl acetamide, N-vinyl propionamide, N-vinyl succinimide or N-Vi  nylphthalimide and subsequent hydrolysis of the resultant Homo- or copolymers are available. Such homo or copo polymers and their hydrolyzates are known from the prior art known or can be produced in an analogous manner (see e.g. B. Römpp, chemical lexicon, vinylamine polymers and cited therein. Li temperature and EP-A-71 050).

Derivatives of polyvinyl alcohols also come in as polymers AP Question, in which part or all of the OH groups by aminating Hy Dration were converted into primary amino groups. As out transition materials serve commercially available polyvinyl alcohols, such as from Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., Vol 21A, pp. 743-747 are known, wherein Poly vinyl alcohols with a molecular weight in the range from 2000 to 50,000 are preferred. These are made using known methods (see, for example, DE-A-44 28 004, EP-A-382 049 and litera cited therein tur) with hydrogen and ammonia at temperatures in the range of 80 to 250 ° C and pressures up to 400 bar at oxidic transition meters tall catalysts, for example Cu oxide, Ni oxide, Co oxide, Ru oxide catalysts, mixed oxide catalysts of the aforementioned transition metals, which may also contain oxides of molybdenum, Va Contain nadium, zircon, aluminum or silicon, e.g. B. Zr-Cu Ni-Mo oxide catalysts implemented. This results in an amino group Pen-containing polymers with KOH numbers in the range of 50 to 500 mg KOH / g polymer.

Polymers AP which are suitable according to the invention are also polyalkyleneimines such as polyethyleneimine. Such poly ethyleneimines are generally known. Polyethyleneimines with molecular weights M _w in the range from 400 to 2,000,000 are available, for example, under the name Lupasol® from BASF Aktiengesellschaft. Polyethyleneimines usually consist of branched polymer chains and therefore contain primary, secondary and tertiary amino groups. Their ratio is usually 1: 2: 1. At lower molecular weights, which are preferred according to the invention, higher proportions of primary amino groups are found. Largely linear polyethyleneimines, which are accessible via special production processes, are also preferred for the preparations according to the invention. Particularly preferred alkylene imines have a number average molecular weight M _n in the range from 400 to 1400 daltons. Examples of these are polyethyleneimines of the general formula H ₂ N - (CH ₂ -CH ₂ -NH-) _k CH ₂ -CH ₂ -NH ₂ , where k is a number in the range from 8 to 30. Polymeric alkylene mines with primary and / or secondary amino groups are described for example in "Encyclopedia of Polymer Science and Engineering", H. Mark (ed.), Rev. ed., Vol. 1, pp. 680-739, John Wiley & Sons Inc. New York, 1985.

In the preparations according to the invention, the quantitative ver Ratio of crosslinking substance A to copolymers P the desired degree of crosslinking. This has to be taken into account realize that crosslinking is primarily due to the molar ratio of the amino groups AM in the crosslinking substance A. the anhydride groups copolymerized into copolymers P AH be is true. It should also be borne in mind that with polyamino Connections, e.g. B. in the dendrimer polyamines, and also in the polymers AP containing amino groups do not all amino groups pen can react. Therefore, in low molecular weight ren diamino compounds or in the case of amino alcohols or aminosilo xanen a comparable networking effect already with a ge achieved a lower molar ratio AM / AH than with polyamino ver polymers or amino-containing polymers AP.

As a rule, the molar ratio of the amino groups AM in the Substance A to the anhydride groups AH in the copolymer P in the range from 100: 1 to 1:20 and preferably in the range from 50: 1 to 1:10 lie. In the case of low-molecular diamino compounds, the mo lare ratio AM / AH preferably in the range from 5: 1 to 1:20 and in particular in the range from 2: 1 to 1: 10. The same applies for amino alcohols and aminosiloxanes. For dendrimer polyamines the molar ratio AM / AH is preferably selected in the range from 10: 1 to 1:15 and in particular in the range from 5: 1 to 1:10 Use according to the invention of polymers containing amino groups AP, the molar ratio AM / AH is preferably selected in the range from 100: 1 to 1:10 and in particular in the range from 50: 1 to 1: 2.

Depending on the content of copolymerized anhydride groups in the copolymer P and the amine number of substance A are chosen in the Invention formulations a weight ratio of copolymer P to sub punch A in the range from 2000: 1 to 1:10, especially in the range from 1000: 1 to 1: 5 and particularly preferably in the range from 500: 1 to 1: 2. When using compounds containing amino groups A1, A2 or A3 as the crosslinker is the weight ratio of Copo lymer P to compound A1, A2 or A3 preferably in the range of 2000: 1 to 5: 1, especially in the range of 1000: 1 to 10: 1 The use of polymer AP as a crosslinking agent lies in the weight ratio from copolymer P to polymer AP in the range from 50: 1 to 1:10 preferably in the range from 20: 1 to 1: 5 and in particular in the range from 10: 1 to 1: 2.  

For the stability of the preparations according to the invention, it is fundamentally advantageous if the preparations according to the invention contain at least one quaternary, non-polymerizable ammonium salt. These are usually salts of the general formula III

wherein R ^a , R ^b , R ^c and R ^d independently of one another are C ₁ -C ₁₈ alkyl, aryl or aralkyl and X⁻ is an anion equivalent.

C ₁ -C ₁₈ alkyl is understood to mean linear or branched alkyl, which may also have OH groups or halide groups. Examples of C ₁ -C ₁₈ alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-decyl, lauryl and stearyl. Aryl is preferably understood to mean phenyl or naphthyl, optionally with C ₁ -C ₄ alkyl or halide, for. B. chloride, may be substituted. Aryl can also be substituted with ethoxylated OH. Aralkyl is aryl which has a C ₁ -C ₄ alkylene unit, e.g. B. methylene, 1,2-ethylene, 1,1-ethylene, 1,3-propylene. Preferred aralkyl is phenylmethyl (= benzyl) and phenylethyl, where the phenyl radical can also be substituted in the manner described above. Preference is given to those salts of the general formula III in which at most one of the radicals R ^a to R ^d and in particular none of these radicals is aryl or aralkyl. It is further preferred if the radicals R ^a to R ^{d are selected} from C ₁ -C ₁₂ alkyl and in particular from C ₂ -C ₈ alkyl.

In formula III, X⁻ is preferably selected from organic anions such as acetate, toluenesulfonate, benzenesulfonate, and inorganic anions such as halide, 1/2 SO ₄ ^2- , 1/3 PO ₄ ^3- , HSO _4- , ClO _4- , BF _4- or OH⁻. X⁻ preferably represents an inorganic anion, in particular halide and particularly preferably chloride or bromide. Examples of particularly preferred salts of the general formula III are benzyltriethylamonium salts, tetra n-butylamonium salts, tetraethylamonium salts, e.g. B. the chlorides, bromides, sulfates, hydrogen sulfates and perchlorates.

If desired, the preparations according to the invention contain preferably 0.1 to 10% by weight, in particular 0.2 to 5% by weight, based on the total weight of the preparation, at least one quaternary, non-polymerizable ammonium salt.

The preparations according to the invention can also be subordinate Contain neter amount of organic solvents. Type and amount of On the one hand, solvents are based on the desired use purpose of preparation. On the other hand, the fiction Preparations ent also solvents due to manufacturing hold (see below). Suitable solvents are those that no reaction with the anhydride unit of the copolymer P. hen. These include both water-miscible solvents such as cyclic ethers, e.g. B. tetrahydrofuran, dioxane, amides such as acet amide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrro lidon, dialkyl ether of diethylene glycol, triethylene glycol or Tetraethylene glycol, e.g. B. Diethylene glycol bismethyl ether. For this count also water-immiscible solvents, for example as hydrocarbons or hydrocarbon mixtures, e.g. B. Toluene, hexane, cyclohexane, white spirit, also aliphatic ethers, e.g. B. diethyl ether, t-butyl methyl ether etc. Preferably contains the aqueous preparation according to the invention no more than 50 wt .-%, in particular not more than 20 wt .-%, especially be preferably not more than 10% by weight and very particularly preferably not more than 5% by weight of organic solvent, based on the total amount of water and organic solvent.

The preparations according to the invention are produced in usually by mixing the individual components at room temperature temperature or elevated temperature, but preferably below 50 ° C. Preferably the aqueous dispersion of the copolymer P, which often has an acidic pH due to the manufacturing process, before mixing with a base, e.g. B. sodium bicarbonate, Sodium carbonate, potassium hydrogen carbonate or potassium carbonate, new tralized. The pH of the dispersion of the copolymer P is available the addition of the crosslinking substance preferably in the loading range from pH 5 to pH 9. Of course, others can Bases are used for neutralization. Preferably be no amines used for neutralization.

It is preferable to proceed in the production in such a way that the Substance A containing amino groups or the polymer AP to the submitted, neutralized, aqueous dispersion of the copolyme ren P there. Substances A can be either as a solid or Liquid, dissolved in water or in an organic solution medium, or as an aqueous dispersion to the dispersion of the copo lymeren P be given. The quaternary ammonium salt is provided  desirable, preferably before adding substance A to the given aqueous dispersion of the copolymer P. Usually will the quaternary ammonium salt in the form of an aqueous solution or dis persion admitted.

The preparations according to the invention are aqueous dispersions, which are stable in storage over a longer period of time. Excoc The formation of coagulum is not observed. A Crosslinking takes place only when drying, i.e. H. when removing the Water or the solvent instead. The network joins riding at low temperatures, for example under usual Drying conditions, e.g. B. a room temperature. An application elevated temperature is not necessary. Furthermore, the Crosslinking no volatile substances released.

The preparations according to the invention are suitable for a large number of Suitable applications, for example as a binder for Be layering and sealing compounds, as binders for dispersers sion colors, as a binder for fiber composite materials and as Adhesives and as adhesive raw materials. Accordingly, this concerns ing invention also the use of the aforementioned preparation conditions for the aforementioned applications.

The examples listed below are intended to ver the invention clear, but without restricting them.

Examples I Preparation of the AP polymers 1. Preparation of the hydrogenated acrylonitrile / butadiene copolymer AP1

The production was based on DE 197 02 103.4. In an autoclave, 100 g of a solution of 15 g of a Copolymers of 18% by weight copolymerized acrylonitrile, 79.6% by weight of polymerized butadiene and 2.4% by weight, each because of the total weight of the polymer, carbo xylate end groups with an average molecular weight of about 4000 daltons, placed in 85 g of tetrahydrofuran and with 60 ml of a saturated solution of ammonia in tetrahydrofu ran and 15 g of catalyst were added. Then you asked a hydrogen pressure of 250 bar and a temperature of 180 ° C and kept the temperature for 10 h. Subsequently the solvent was removed in vacuo. The Po received lymer had an amine number of about 120 mg KOH / g.  

Ruthenium on aluminum oxide with a ruthenium content of 0.3% by weight, based on the catalyst weight, and a specific ruthenium surface area of 0.4 m ² / g (determined by H ₂ pulse chemisorption) served as the catalyst. The catalyst was obtained by impregnating Al ₂ O ₃ pellets (3 to 6 mm, specific BET surface area 10 m ² / g, pore volume approx. 0.45 ml / g and average pore diameter 0.21 µm) with Ru ( NO ₃ ) ₃ solution and subsequent activation with hydrogen at 200 ° C.

2. Production of the aminatingly hydrogenated polyvinyl alcohol AP2

According to the examples in DE 44 38 001 A1, polyvinyl alcohol with an average molecular weight in the range from 9000 to 10,000 daltons and liquid ammonia was placed in a continuously operated autoclave which was equipped with a catalyst composed of 50% by weight NiO, 17% by weight Cu ₂ O, 1.5% by weight of MoO ₃ and 31.5% by weight of ZrO ₂ (catalyst A of DE-A-44 28 004) had been fed in and fed in at about 200 ° C. and about 250 bar Hydrogenating amine hydrogen pressure. The amine number of the product obtained was about 200 mg KOH / g polymer.

The determination of the amine numbers of AP1 and AP2 was as follows carried out: The respective polymer was in 20 ml dichlorobenzene and 30 ml of glacial acetic acid in a concentration of 0.8 mmol / l. The solution was then treated with a 0.1 M solution of Tri titrated fluoromethanesulfonic acid in glacial acetic acid. The titration curve was determined potentiometrically with a glass electrode.

II. Preparation of the aqueous dispersions of the copolymer P 1. Dispersion D1

375 g of deionized water and 4.5 g of polystyrene seed (33% by weight, average polymer particle diameter 30 nm) were placed in a polymerization reactor and heated to 85.degree. Subsequently, feed 1 was added at a constant flow rate within 2 hours. Starting with feed 1 at the same time, 5% of feed 2 were added within 5 minutes and the rest of feed 2 within 1 hour 55 minutes. After feed 1 and feed 2 had ended, the temperature was maintained for a further half an hour. Then it was cooled to room temperature. The pH of the dispersion was 2.2 and the solids content was 55.3% by weight.

Inlet 1:
654.6 g of deionized water
1125.0 g of n-butyl acrylate
300.0 g methyl methacrylate
30.0 g acrylic acid
45.0 g methacrylic anhydride
30.0 g of a 15% by weight solution of sodium lauryl sulfate in water
25.0 g of a 50% by weight solution of a sodium salt of bis-2-ethylhexyl sulfosuccinate

Inlet 2:
aqueous solution of 4.5 g sodium peroxodisulfate in 175.5 g deionized water.

Dispersion D2

Analogous to dispersion D1 was an aqueous polymer disperser sion D2 manufactured, with the difference that inlet 1 1095 instead of 1125 g n-butyl acrylate and 75 g instead of 45 metha Contained crylic anhydride. The pH of the dispersion was at 2.2, the solids content at 55.3 wt .-%.

III. Preparations according to the invention and examination of the Vernet tongue A. General manufacturing regulations

The dispersions from II were with 15 wt .-%, aqueous Sodium carbonate neutralized (pH = 7 to 8) and then with one part by weight, based on 100 parts by weight of the Disper sion, tetra-n-butylammonium bromide added.

An aqueous dispersion or a solution of the amine or of the Po containing amino groups lymers to the aqueous dispersion. The respective quantities are given in Table 1. The preparation thus prepared gen were filmed at room temperature. For this, the Dis persion on a polyethylene plate in a recess of cast about 3 mm. The sample was then left for 7 days at room temperature and then 2 days at min dry pressure (approx. 500 to 100 mbar). The film pointed a thickness of 1.5 mm. To determine networking the film was weighed and tetra hydrofuran stored for one week. Then the film became the Te Removed trahydrofuran and, after drying, adhering solder drop of solvent weighed immediately. The solvent uptake  of the film in% by weight is given in Table 1 (swelling in %). It is a direct measure of the degree of cross-linking. Here a lower weight gain means a higher net tongue density for the same type of polymer.  

Table 1

4) AP2 Aminatingly hydrogenated polyvinyl alcohol (see 1.2.).

Claims (11)

1. Self-crosslinking aqueous preparations containing

• i) at least one copolymer P having anhydride groups AH in the form of an aqueous dispersion, obtainable by free radical aqueous emulsion polymerization of ethylenically unsaturated monomers M, where the monomers M have at least one ethylenically unsaturated monomer M1, selected from the anhydrides of monoethylenically unsaturated carboxylic acids having 3 to 8 C. -Atoms, and at least one copolymerizable with the monomers M1, different monomer M2 comprise, and
• ii) at least one crosslinking substance A with at least one primary and / or secondary amino group AM, selected from
  Compounds A1 which have at least two primary and / or secondary amino groups AM per molecule,
  Compounds A2 which have at least one primary or secondary amino group AM and one siloxane group,
  Amino alcohols (compounds A3) and
  Polymer AP with several primary and / or secondary amino groups AM.

2. Preparations according to claim 1, wherein the monomers M, based to their total weight, comprises 0.1 to 30% by weight of monomers M1 sen. 3. Preparations according to claim 1 or 2, wherein the monomer M1 is selected from methacrylic anhydride, Acrylsäureanhy drid and itaconic anhydride. 4. Preparations according to one of the preceding claims, wherein the monomers M additionally 0.01 to 10 wt .-%, based on it Total weight, at least one copolymerizable, of which Monomers M1 and M2 different monomers M3 with a what water solubility <60 g / l (at 25 ° C and 1 bar). 5. Preparations according to one of the preceding claims, wherein the compound A1 is selected from compounds of the general formula I.
wherein
R ¹ , R ² , R ³ and R ⁴ independently of one another represent hydrogen or functional groups of the general formula Alk-NR ⁵ R ⁶ , in which
Alk represents C ₁ -C ₄ alkylene and
R ⁵ , R ⁶ independently of one another represent hydrogen or a functional group Alk-NR ⁷ R ⁸ , in which R ⁷ and R ⁸ independently of one another have one of the meanings given for R ¹ to R ⁴ , and
B is C ₂ -C ₂₄ -alkylene which can be interrupted by one or more oxygen atoms or groups NR ⁹ or substituted by one or more groups -Alk-NR ⁵ R ⁶ , where R ^{9 is} one of R ¹ to R ⁴ has the meanings given, or denotes C ₁ -C ₁₀ -alkyl,
for aryls or
represents a remainder 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 stands for 0.1 or 2,
where the cycloaliphatic radicals can also be substituted by 1, 2 or 3 C ₁ -C ₁₀ alkyl radicals. 6. Preparation according to one of claims 1 to 4, wherein the compound A2 is selected from aminosiloxanes of the general formula II
R ^a HN-X-Si (OR ^b ) ₃ (II)
wherein
R ^{a represents} hydrogen, alkyl, aryl or arylalkyl,
R ^{b is} C ₁ -C ₁₀ alkyl and
X is C ₂ -C ₂₄ alkylene, which can be interrupted by one or more oxygen atoms or groups NR ^c , in which R ^{c is} hydrogen or C ₁ -C ₁₀ alkyl, or is arylene. 7. Preparations according to one of claims 1 to 4, wherein the polymer AP has an amine number in the range from 20 to 1200 mg KOH / g and a number average molecular weight M _n in the range from 1000 to 50,000 D. 8. Preparations according to one of the preceding claims, wherein the quantitative ratio of copolymer P to substance A so ge is chosen that the molar ratio of the amino groups AM in the Substance A to the anhydride groups AH in the copolymer P in the Be ranges from 100: 1 to 1:20. 9. Preparation according to one of the preceding claims, including additionally at least one quaternary, not polymerized ammonium salt. 10. Process for the preparation of the self-crosslinking aqueous Preparations according to one of claims 1 to 8, characterized ge indicates that an aqueous dispersion of the copolyme ren P with substance A, optionally in dissolved or dispersed form, mixed. 11. Use of the aqueous preparations according to one of the An Proverbs 1 to 9 as a binder for coating and you tion masses, as a binder for fiber composite materials, as Binder for paints, as adhesives or adhesive raw fabrics and for leather finishing.