EP0000605A1 - Hardeners for aqueous dispersions of epoxy resins, their preparation and use - Google Patents

Abstract

Hardening agent which is a reaction product of a) at least one polyepoxide compound, b) at least one polyalkylene polyether polyol and c) at least one polyamine, with d) unsaturated compounds capable of addition being added to the reactive groups of the polyamine, a process for the preparation of the Hardening agent, the adduct of components a) and b), prepared in the presence of a BF3-amine complex as catalyst, either with c) an amine compound from group c1) at least one polyamine and c2) an adduct of c1) with d) an unsaturated one Component of the formula HC (R1) = C (R2) -X, where R1 = H, -CH3, -C2H5, R2 = H, -CH3 and X = -CN, -COOH, -COOCH3, -COOC2H5, -COOC3H7, -COOC4H9, -CONH2, means, is reacted, or the reaction product of components a), b) and c1) is reacted with d) an unsaturated compound of the formula HC (R1) = C (R2) -X and the use of the curing agents together with polyfunctional epoxy compounds a) with Wa for the production of curable dispersions as coating or coating agents.

Description

It is known that polyamidoamines containing free amino groups and made from alkylene polyamines and polymerized unsaturated natural fatty acids can be used to cure epoxy resins. (Compare epoxy compounds and epoxy resins by Dr. Alfred Paquin, Springer-Verlag Berlin / Göttingen / Heidelberg 1958, pages 511 to 516 and Lee & Neville "Handbook of Epoxy Resins" McGraw-Hill Book Co., New York, 1967, 10, 1 - 10.12) ..

The curing of epoxy resins with adducts, which are formed from polyamidoamines and polyepoxides, in the absence of water is also known from US Pat. No. 3,280,054. Although it was mentioned in German Offenlegungsschrift 15 20 918 to prepare curable, aqueous dispersions from these adducts and epoxy resins, the results obtained are often unsatisfactory, as our own tests have shown. In some cases, the adducts, especially those made from aromatic polyepoxides, are semi-solid and not completely in an aqueous environment. dispersible, while aqueous dispersions containing an aromatic epoxy resin and an adduct made from an aliphatic polyepoxide often have undesirable thixotropic behavior.

In U.S. Patent 3,383,347, phenol modified amines, which may be reaction products of a primary amino group of an aliphatic polyamine with a phenol or reaction products of an aliphatic polyamine with a phenol and an aldehyde, are used as curing agents. However, these hardeners lead to epoxy resin hardener emulsions with insufficient processing time, which form very brittle coatings and which also have undesirable rust-brown discoloration in the presence of iron.

German Offenlegungsschrift 19 25 941 describes epoxy resin hardener emulsions which contain, as hardener component, an amino amide adduct which is an amino amide of a fatty acid and an alkylene polyamine and which contains the reaction product of the amino amide with 10 to 40 percent by weight (based on the weight the highly volatile aminoamide adduct components) is monoepoxide, which consists of an aliphatic monoepoxide having 2 to 12 carbon atoms or of a monoepoxide substituted by a phenyl radical.

These epoxy resin hardener emulsions have a relatively high instability and excrete water within the processing time. The coatings produced with them remain relatively soft and highly sensitive to mechanical influences, so that they cannot be used to produce sufficiently stable protective coatings.

worin der Alkylenrest der Äthylen-, Propylen-, Butylen-, Pentylen oder Hexylenrest sein kann, n eine ganze Zahl größer als Null bedeutet, und einem Mischpolymerisat einer konjugiert ungesättigten Fettsäure oder eines amidbildenden Säurederivates mit einer aromatischen Vinylverbindung, erhältlich ist.In the Swiss patent specification 487 955 _. Described curable, aqueous dispersions which contain a hardener for the epoxy resin which is liquid at room temperature, the hydrogen being bound directly to the nitrogen in the hardener, which by addition of non-aliphatic epoxide which contains only one terminal 1,2-epoxide group per molecule, or aliphatic epoxy, which contains on average one or more than one terminal 1,2-epoxy group per molecule, and a stoichiometric excess of a poly (aminoamide) condensation product which consists of an alkylene polyamine of the formula

wherein the alkylene radical can be the ethylene, propylene, butylene, pentylene or hexylene radical, n is an integer greater than zero, and a copolymer of a conjugated unsaturated fatty acid or an amide-forming acid derivative with an aromatic vinyl compound is obtainable.

In der DT-OS 23 32 177 werden Härtungsmittel für wässerige Epoxydharz-Dispersionen beschrieben, die Assoziate sind, aufgebaut aus:

• (1.) Polyamidoamin-Epoxyd-Addukten (1) mit einem stöchiometrischen Überschuß eines Polyamidoamins (1a) aus einem Polyalkylenpolyamin (worin der Alkylenrest aus dem Äthylen-, Propylen-, Butylen-, Pentylen- oder Hexylenrest besteht) und mono-, di- und/oder trimerisierten Fettsäuren oder einem Mischpolymerisat konjugiert ungesättigter Fettsäuren oder amidbildender Fettsäurederivate (worin die Fettsäuren bzw. Fettsäurederivate in der monomeren Form 8 bis 24 Kohlenstoffatome enthalten) davon mit einer aromatischen Vinylverbindung und 5 bis 35 Gew.-%, bezogen auf das eingesetzte Polyamidoamin, einer aliphatischen Epoxydverbindung (1b) mit mehr als 2 endständigen, jedoch höchstens 6 Epoxydgruppen und
• (2.) 5 bis 30 Gew.-%, bezogen auf das eingesetzte Polyamidoamin, eines Phenol-Formaldehyd-Polyamin-Kondensationsproduktes (2) (wobei das aliphatische, araliphatische, cycloaliphatische oder heterocyclische Polyamin mindestens 2, jedoch höchstens 8 direkt am Stickstoff gebundene Wasserstoffatome enthält) besteht.

These aqueous dispersions preferably also contain an accelerator for curing. These accelerators are compounds containing at least one tertiary amino nitrogen atom and one phenolic hydroxyl group. The dispersions also contain orthophosphoric acid or a liquid aliphatic monocarboxylic acid, e.g. B. acetic acid. These epoxy hardener dispersions also have insufficient stability and only provide relatively soft and mechanically sensitive protective coatings. Furthermore, the presence of the dissociating acids leads to instability of the dispersion, since the acid anion (A-) can react with the epoxy group according to the following scheme and consumes epoxy groups:

DT-OS 23 32 177 describes curing agents for aqueous epoxy resin dispersions, which are associates, composed of:

• (1.) Polyamidoamine-epoxy adducts (1) with a stoichiometric excess of a polyamidoamine (1a) from a polyalkylene polyamine (in which the alkylene radical consists of the ethylene, propylene, butylene, pentylene or hexylene radical) and mono-, di - and / or trimerized fatty acids or a copolymer of conjugated unsaturated fatty acids or amide-forming fatty acid derivatives (in which the fatty acids or fatty acid derivatives in the monomeric form contain 8 to 24 carbon atoms) thereof with an aromatic vinyl compound and 5 to 35% by weight, based on the amount used Polyamidoamine, an aliphatic epoxy compound (1b) with more than 2 terminal but not more than 6 epoxy groups and
• (2.) 5 to 30% by weight, based on the polyamidoamine used, of a phenol-formaldehyde-polyamine condensation product (2) (the aliphatic, araliphatic, cycloaliphatic or heterocyclic polyamine being bound to nitrogen at least 2, but not more than 8) Contains hydrogen atoms).

For the production of coatings, however, it is necessary to add organic water-dilutable solvents to the mixture of epoxy resin prepolymer and curing agent in order to reduce the viscosity of the composition and to make it easier to use. Although these organic solvents facilitate the application of the compositions and produce films with good properties, they offer a number of serious problems. The solvents are expensive and are usually toxic or flammable. Contamination from the solvent during manufacture, storage, transportation and ultimate use of the Bulk, solvent vapors, solvent waste from cleaning systems, and solvent spills are other problems that are often difficult and costly to solve. These disadvantages place considerable restrictions on the use of the known epoxy coating compositions, especially when they are to be used in connection with the handling or production of foods. In addition, the cleaning of a plant that has been in contact with such coatings is accompanied by considerable difficulties.

The object of the present invention is to provide a solvent-free curing agent for aqueous epoxy resin dispersions which does not have the disadvantages mentioned and which provides surprisingly resistant protective coatings in conjunction with aqueous epoxy resin dispersions.

The absence of organic solvents eliminates the problems caused by smell, toxicity and flammability; Furthermore, all systems that come into contact with epoxy resins can be cleaned by washing with water.

• a) einer Polyepoxydverbindung,
• b) einem Polyalkylenpolyätherpolyol.und
• c) einem Polyamin

ist, vorzugsweise ist a) wasserunlöslich und b) wasserlöslich.The invention relates to curing agents for aqueous epoxy resin dispersions, the curing agent consisting of a reaction product

• a) a polyepoxide compound,
• b) a Polyalkylenpolyätherpolyol.und
• c) a polyamine

is preferably a) water-insoluble and b) water-soluble.

• a) 2 bis 4 Äquivalenten einer Polyepoxydverbindung und
• b) 0,2 bis 1,5 Äquivalenten eines Polyalkylenpolyätherpolyols durch Umsetzung mit 80 bis 20 Gew.-% der Komponente c), eines aliphatischen, cycloaliphatischen und/oder heterocyclischen Polyamins oder Polyamingemisches, wobei die eingesetzte Aminmenge in einem 2 bis 10-fachen Überschuß, bezogen auf die zur Umsetzung befähigten Epoxydgruppen und die am Stickstoff befindlichen H-Atome verwendet wurde, erhalten worden ist. Vorzugsweise werden 50 bis 70 Gew.-% eines Adduktes aus a) 2,3 - 3,0 Äquivalenten einer Polyepoxydverbindung und b) 0,3 bis 0,8 Äquivalenten eines Polyalkylenpolyätherpolyols mit 50-30 Gew.-% der Komponente c) eines aliphatischen, cycloaliphatischen und/oder heterocyclischen Polyamins oder Polyamingemisches, wobei die eingesetzte Aminmenge in einem 5 bis 8-fachen Überschuß, bezogen auf die zur Umsetzung befähigten Epoxyd- und Aminwasserstoffgruppen, umgesetzt.

One embodiment of the invention is characterized in that the curing agent consists of a reaction product which consists of 20 to 80% by weight of an adduct

• a) 2 to 4 equivalents of a polyepoxide compound and
• b) 0.2 to 1.5 equivalents of a polyalkylene polyether polyol by reaction with 80 to 20% by weight of component c), an aliphatic, cycloaliphatic and / or heterocyclic polyamine or polyamine mixture, the amount of amine used being obtained in a 2 to 10-fold excess, based on the epoxy groups capable of reaction and the H atoms on the nitrogen, used. 50 to 70% by weight of an adduct of a) 2.3-3.0 equivalents of a polyepoxide compound and b) 0.3 to 0.8 equivalents of a polyalkylene polyether polyol with 50-30% by weight of component c) are preferably one aliphatic, cycloaliphatic and / or heterocyclic polyamines or polyamine mixtures, the amount of amine used being reacted in a 5 to 8-fold excess, based on the epoxy and amine hydrogen groups capable of reaction.

wobei R₁=H,-CH₃, -C₂H₅, R₂=H, CH₃ und X=-CN, -COOH, -COOCH₃, -OOO₂H₅, -OOOC₃H₇, -COOC₄H₉, -CONH₂, -CONHCH₃ oder -CCN(CH₃)₂ bedeutet, weiter umgesetzt worden ist.A further embodiment of the invention is characterized in that unsaturated compounds capable of addition are added to the reactive groups of the polyamine c), d), the component c) per or on the nitrogen atom being present before or after the reaction with the adduct components a) and b) with up to 0.5, preferably 0.1-0.3 equivalents of an unsaturated compound d) of the type - capable of addition

where R ₁ = H, -CH ₃ , -C ₂ H ₅ , R ₂ = H, CH ₃ and X = -CN, -COOH, -COOCH ₃ , -OOO ₂ H ₅ , -OOOC ₃ H ₇ , -COOC ₄ H ₉ , -CONH ₂ , -CONHCH ₃ or -CCN (CH ₃ ) ₂ means has been further implemented.

Another object of the invention is also a process for the preparation of the hardening agents as described in claims 6 to 8. The hydroxyl groups of the polyalkylene polyether polyol are preferably reacted with the epoxy groups at 20 to 204 ° C.

The invention also relates to the use of the curing agents obtained by the abovementioned processes together with polyfunctional epoxy compounds a) and water and, if appropriate, emulsifiers for the preparation of curable, if appropriate film-forming, dispersions as coating or coating agents

• Die Epoxyde mehrfach-ungesättigter Kohlenwasserstoffe (Vinylcyclohexen, Dicyclopentadien, Cyclohexadien, Cyclododecadien, Cyclododecatrien, Isopren, 1,5-Hexadien, Butadien, Polybutadiene, Divinylbenzole und dergleichen), Oligomere des Epichlorhydrins und ähnliche, Epoxyäther mehrwertiger Alkohole (Äthylen-, Propylen- und Butylenglykole, Polyglykole, Thiodiglykole, Glycerin, Pentaerythrit, Sorbit, Polyvinylalkohol, Polyallylalkohol und ähnliche), Epoxyäther mehrwertiger Phenole -(Resorcin, Hydrochinon, Bis-(4-hydrpxyphenyl)-methan, Bis-(4-hy- droxy-3-methylphenyl)-methan, Bis-(4-hydroxy-3,5-dibromphenyl)-methan, Bis-(4-hydroxy-3,5-difluorphenyl)-methan, 1,1-Bis-(4-hydroxyphenyl)-äthan, 2,2-Bis-(4-hydroxyphenyl) -propan, 2,2-Bis-(4-hydroxy-3-methylphenyl)-propan, 2,2-Bis-(4-hydroxy-3-chlorphenyl)-propan, 2,2-Bis-(4-hydrcxy-3,5-dichlorphenyl)-propan, 2,2-Bis-(4-hydroxy-3,5-dichlorphenyl)-propan, Bis-(4-hydroxyphenyl)-phenylmethan, Bis-(4-hydroxyphenyl)-diphenylmethan, Bis-(4-hydroxyphenyl)-4'-methylphenylmethan, 1,1-Bis-(4-hydroxyphenyl)-2,2,2-trichloräthan, Bis-(4-hydroxyphenyl)-(4-chlorphenyl)-methan, 1,1-Bis-(4-hydroxyphenyl)-cyclohexan, Bis-(4-hydroxyphenyl)-cyclohexylmethan, 4,4'-Dihydroxydiphenyl, 2,2'-Dihydroxydiphenyl, 4,4'-Dihydroxydiphenylsulfon sowie deren Hydroxyäthyläther, Phenol-Formaledhyd-Kondensationsprodukte, wie Phenolalkohole, Phenolaldehydharze und ähnliche, S- und N-haltige Epoxyde, (N,N-Diglycidylanilin, N,N'-Dimethyldiglycidyl-4,4-Diaminodiphenylmethan) sowie Epoxyde, welche nach üblichen Verfahren aus mehrfach ungesättigten Carbonsäuren oder einfach ungesättigten Carbonsäureestern ungesättigter Alkohole hergestellt worden sind, Glycidylestern, Polyglycidylester, die durch Polymerisation oder Mischpolymerisation von Glycidylestern ungesättigter Säuren gewonnen werden können oder aus anderen sauren Verbindungen (Cyanursäure, Diglycidylsulfid, cyclischem Trimethylentrisulfon bzw. deren Derivaten und anderen) erhältlich sind.

From the large number of polyfunctional epoxy compounds a) which contain more than one 1,2-epoxy group in the molecule, are preferably water-insoluble and which, according to the invention, are used to form adducts with polyalkenyl polyether polyols and amines to form the curing agents according to the invention and which likewise together with the curing agents according to the invention can be used to prepare dispersions, include:

• The epoxies of polyunsaturated hydrocarbons (vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene, isoprene, 1,5-hexadiene, butadiene, polybutadienes, divinylbenzenes and the like), oligomers of epichlorohydrin and the like, epoxy ethers and polyhydric alcohols Butylene glycols, polyglycols, thiodiglycols, glycerin, pentaerythritol, sorbitol, polyvinyl alcohol, polyallyl alcohol and the like), epoxy ether of polyhydric phenols - (resorcinol, hydroquinone, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxyphenyl-3-methyl ) -methane, bis- (4-hydroxy-3,5-dibromophenyl) -methane, bis- (4-hydroxy-3,5-difluorophenyl) -methane, 1,1-bis- (4-hydroxyphenyl) -ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, bis (4-hydroxyphenyl) phenylmethane, Bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl ) -4'-methylphenylmethane, 1,1-bis- (4-hydroxyphenyl) -2,2,2-trichloroethane, bis- (4-hydroxyphenyl) - (4-chlorophenyl) methane, 1,1-bis- ( 4-hydroxyphenyl) cyclohexane, bis- (4-hy hydroxyphenyl) -cyclohexylmethane, 4,4'-dihydroxydiphenyl, 2,2'-dihydroxydiphenyl, 4,4'-dihydroxydiphenylsulfone and their hydroxyethyl ether, phenol-formaldehyde condensation products, such as phenol alcohols, phenol aldehyde resins and similar, S- and N-containing epoxides, (N, N-diglycidylaniline, N, N'-dimethyldiglycidyl-4,4-diaminodiphenylmethane) and epoxides, which have been prepared by conventional processes from polyunsaturated carboxylic acids or monounsaturated carboxylic esters of unsaturated alcohols, glycidyl esters, polyglycidyl esters, by polymerization or mixed polymerization can be obtained from glycidyl esters of unsaturated acids or can be obtained from other acidic compounds (cyanuric acid, diglycidyl sulfide, cyclic trimethylene trisulfone or their derivatives and others).

The above polyfunctional epoxy compounds, this expression also includes the term epoxy resin, can be reacted individually or in a mixture, if appropriate in the presence of solvents or plasticizers, by the present process or used to prepare dispersions. They can also be used in mixtures with monoepoxides. For example, the following monoepoxides are used in a mixture with the aforementioned epoxy compounds: epoxidized unsaturated hydrocarbons (butylene, cyclohexene, styrene oxide and others), halogen-containing epoxides, such as. B. epichlorohydrin, epoxy ether of monohydric alcohols (methyl, ethyl, butyl, 2-ethylhexyl, dodecyl alcohol and others), epoxy ether of monohydric phenols (phenol, cresol and other phenols substituted in the o- or p-position), glycidyl esters of unsaturated carboxylic acids , epoxidized esters of unsaturated alcohols or unsaturated carboxylic acids and the acetals of glycidaldehyde.

The preferred polyhydric phenols are: resorcinol and various bisphenols, which can be obtained by condensing phenol with aldehydes and ketones such as, for. _B. Formaldehyde, acetaldehyde, acetone, methyl ethyl ketone and others. Resins of this type are described in U.S. Patents 2,855,159 and 2,589,245.

bzw. das Analogon auf Basis von Bisphenol F:

einzeln oder im Gemisch mit Bisphenol A, worin n 0 oder eine ganze Zahl bis 10 bedeutet. Normalerweise ist n nicht größer als 2 oder 3 und vorzugsweise 1 oder weniger. Das Epoxydharz hat ein Epoxyd-Äquivalent von 160 - 500.Particularly preferred epoxy resins are polyphenol glycidyl ether, e.g. B. the reaction product of epichlorohydrin and 2,2-bis (4-hydroxyphenyl) propane (= _B isphenol A), which epoxy resin has the following theoretical structural formula:

or the analog based on bisphenol F:

individually or in a mixture with bisphenol A, in which n denotes 0 or an integer up to 10. Typically, n is not greater than 2 or 3, and preferably 1 or less. The epoxy resin has an epoxy equivalent of 160 - 500.

Suitable polyalkylene polyether polyols b) for the preparation of the curing agents according to the invention can be used and are preferably water-soluble include, for example, the adducts of an alkylene oxide or an alkylene oxide with a polyhydric alcohol. Suitable alkylene oxides are, for example, ethylene oxide, propylene oxide, butylene oxide, amylene oxide and hetero- or block copolymers of these oxides, but preferably ethylene oxide. As polyhydric alcohols, both aliphatic and aromatic alcohols are suitable individually or in a mixture, for. B. ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,4-pentanediol, 1,3- Pentanediol, 1,6-hexanediol, 1,7-heptanediol glycerin, 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, hexane-1,2,6-triol, α-methylglucoside, pentaerythritol and sorbitol.

The polyalkylene polyether polyols can also be prepared from other starting materials, for. B. from tetrahydrofuran and alkylene oxide-tetrahydrofuran copolymers; Epihalohydrins, e.g. B. epichlorohydrin and aralkylene oxides, e.g. B. styrene oxide.

The polyalkylene polyether polyols may have either primary or secondary hydroxyl groups and are preferably polyethers made from alkylene oxides having 2 to 6 carbon atoms, e.g. Polyethylene ether glycols, polypropylene ether glycols and polybutylene ether glycols. The polyalkylene polyether polyols can be prepared by any known method, e.g. B. by the method specified by Wurtz 1859 and in Encyclopedia of Chemical Technology, Vol. 7, pp. 257 to 262, Interscience Publishers, Inc (1951) or in the USA. - Patent specification 1922 459 is described. The average molar mass of component b) is 200 to 10,000, preferably 800 to 1,200.

According to the invention, aliphatic, cycloaliphatic, araliphatic amines or mixtures thereof as component c) can be reacted with the epoxy-polyalkylene polyether polyol adducts.

• aliphatische, gesättigte oder ungesättigte, bifunktionelle Amine, z. B. niedere aliphatische Alkylen-Polyamine, wie z. B. Äthylendiamin, 1,2-Propylendiamin; 1,3-Propylendiamin, 1,4-Butylendiamin, Hexamethylendiamin, 2,2,4-(2,4,4-)Trimethylhexamethylendiamin oder Polyalkylen-Polyamine, z. B. homologe Polyäthylen-Polyamine, wie Diäthylentriamin, Triäthylentetramin, Tetraäthylenpentamin oder analoge Polypropylen-Polyamine, wie z. B. Dipropylentriamin, oder Polyoxypropylenpolyamine und Diamine der allgemeinen Formel ^H ₂ ^N.CH₂-X-CH₂.NH₂, wobei X die zweiwertigen Reste bedeutet.
  

Examples include:

• aliphatic, saturated or unsaturated, bifunctional amines, e.g. B. lower aliphatic alkylene polyamines such. B. ethylenediamine, 1,2-propylenediamine; 1,3-propylene diamine, 1,4-butylene diamine, hexamethylene diamine, 2,2,4- (2,4,4-) trimethyl hexamethylene diamine or polyalkylene polyamines, e.g. B. homologous polyethylene-polyamines, such as diethylenetriamine, triethylene tetramine, tetraethylene pentamine or analogous polypropylene polyamines, such as. B. dipropylenetriamine, or polyoxypropylene polyamines and diamines of the general formula ^H ₂ ^N. CH ₂ -X-CH ₂ .NH ₂ , where X is the divalent radicals.
  

In particular, 1,2-, 1,3- and 1,4-bis (aminomethyl) benzene, or mixtures of the isomers, 1,2-, 1,3- and 1,4-bis (aminomethyl) cyclohexane or mixtures of the isomers mentioned. Isophoronediamine (= 1-amino -3-aminomethyl-3,5,5-trimethylcyclohexane) and N-aminoethylpiperazine can also be used. However, preferred compounds of component c) are xylylenediamine 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 2,2,4- (2,4,4, -) - trimethylhexamethylene diamine or polyoxypropylene polyamine and mixtures thereof. It is possible. lent, all the amines mentioned before the reaction with the epoxy-polyalkylene polyether polyol adduct with the monounsaturated compound d) of the type

to convert to so-called cyanoethylated amines and then use them instead of the pure polyamines. However, the route described below is more common. Before the reaction product consisting of polyamines and the epoxy-polyalkylene polyether polyol adduct is reacted with the monounsaturated compound, it may be diluted with water to a solids content of 50.0 to 90% by weight.

The reaction with the monounsaturated compound is carried out by adding z. B. acrylonitrile at 20 to 70 ° C, wherein after the addition a residence time at elevated temperature, preferably 50 to 70 ° C is appropriate.

Acrylonitrile or methacrylonitrile form the preferred compounds of component d).

• n-Amylamin (10,63), Anilin (4,63), B-Phenylalanin = 2-Aminoäthylbenzol (9,84), 2-Äthylbenzimidazol (6,18), Benzylamin (9,33), trans-Bornylamin (10,17), 1-Amino-3-Methylbutan (10,60), 1,4-Diaminobutan (11,15), n-Butylamin (10,77), t.-Butylamin (10, 83), n-Butylcyclohexylamin (11,23), Cyclohexylamin (10,66), n-Decylamin (10,64) Diäthylamin (10,49), Düsobutylamin (10, 91), Diisopropyl- amin (10,96), Dimethylamin (10,73), n-Dodecanamin = Laurylamin (10,63), 2-Aminoäthanol (9,50), Äthylamin (10,81), Hexadecanamin (10,63), 1-Aminoheptan (10,66), 2-Aminoheptan (10,88), n-Hexylamin (10,56), 2,4-Dimethylimidazol (8,36), Morpholin (8,33), Methylamin (10,66), n-Nonylamin (10,64), Octadecanamin (10,60), Octylamin (10,65), 3-Aminopentan (10,59), 3-Amino-3-Methylpentan (11,01), n-Pentadecylamin (10,61), Piperazin (9,83), Propylamin (10,71), Pyrrolidin (11,27), Tetradecanamin = Myristylamin (10,62), Tridecanamin (10,63), Triäthylamin (11,01), Trimethylamin (9,81).

Suitable BF ₃ amine complexes are, for example, those which are formed from the following amines (pK _b values in brackets) and BF ₃ :

• n-amylamine (10.63), aniline (4.63), B-phenylalanine = 2-aminoethylbenzene (9.84), 2-ethylbenzimidazole (6.18), benzylamine (9.33), trans-bornylamine (10 , 17), 1-amino-3-methylbutane (10.60), 1,4-diaminobutane (11.15), n-butylamine (10.77), t-butylamine (10, 83), n-butylcyclohexylamine (11.23), cyclohexylamine (10.66), n-decylamine (10.64) diethylamine (10.49), diisobutylamine (10, 91), diisopropylamine (10.96), dimethylamine (10.73) , n-dodecanamine = laurylamine (10.63), 2-aminoethanol (9.50), ethylamine (10.81), hexadecanamine (10.63), 1-aminoheptane (10.66), 2-aminoheptane (10, 88), n-hexylamine (10.56), 2,4-dimethylimidazole (8.36), morpholine (8.33), methylamine (10.66), n-nonylamine (10.64), octadecanamine (10, 60), octylamine (10.65), 3-aminopentane (10.59), 3-amino-3-methylpentane (11.01), n-pentadecylamine (10.61), piperazine (9.83), propylamine ( 10.71), pyrrolidine (11.27), tetradecanamine = myristylamine (10.62), tridecanamine (10.63), triethyl amine (11.01), trimethylamine (9.81).

BF ₃ -benzylamine, BF ₃ -monoethylamine, BF ₃ -propylamine and BF ₃ -n-butylamine are preferably used. For a g equivalent of a hydroxyl group to be reacted with a g equivalent of an epoxy group, 100 to 1, preferably 15 to 2 mmol, of the BF ₃ -amine complex are used. The reaction of the hydroxyl groups with the epoxy groups can be carried out in the temperature range from 20 to 200 ° C. The reaction temperature depends on the respective BF ₃ amine complex. For example, the reaction temperature when using BF ₃ -monoethylamine or BF ₃ -benzylamine is around 130 ° C. The mixtures of hydroxyl groups and epoxide group-containing compounds to be reacted are therefore expediently heated to the temperature at which the reaction proceeds at a sufficient rate, ie in 30 minutes to 15 hours. The implementation is appropriately followed _; on the increase in epoxy equivalent, which indicates a decrease in epoxy groups.

The reaction can be stopped by cooling below the reaction temperature.

Part of the BF ₃ amine complex is consumed during the reaction by incorporating the fluoride ions into the reaction product. Any excess of the BF ₃ amine complex can be rendered harmless after the reaction has ended by adding basic-acting substances such as bleaching earth, calcium oxide, calcium hydroxide, barium oxide and barium hydroxide to the complex. The basic substances are removed together with the products resulting from them and the BF ₃ amine complexes by filtration. The reaction of the adduct, which still contains reactive epoxy groups, with the polyamine or the adduct of polyamine and component d) is carried out at 20 to 100 ° C., preferably 20 to 40 ° C. This is followed by a holding time at elevated temperature, preferably 50 to 80 ° C., with stirring applied for 1 to 3 hours.

The curing agents according to the invention are used, optionally together with emulsifiers, for the preparation of aqueous curable epoxy resin dispersions which are used as coating or coating agents.

The epoxy resins curable with the curing agents according to the invention can contain further additives, such as, for. B. wetting agents. Preferred wetting agents are the commercially available, non-ionic wetting agents based on modified alkylphenol, such as. B. alkylphenoxypoly (ethyleneoxy) ethanol, a condensate of nonylphenol and ethylene oxide, containing 9-10 moles of ethylene oxide per mole of nonylphenol, etc.

The epoxy resins, if appropriate mixed with diluents and / or wetting agents, are generally introduced into water, so that the dispersion preferably contains up to 50% by weight of water. If a combination of epoxy resin and curing agent according to the invention is used as block filler or if pigments are present, the water content can even be 90% by weight.

If colored coating mixtures are produced from epoxy resins and curing agents according to the invention, various additives can be added to the dispersion of epoxy resin and the curing agent according to the invention. These include pigments such as titanium dioxide, iron oxide, fillers such as asbestos, talc, mortar and other cementitious substances, pigment dispersants and other conventional coloring and coating aids.

bekannten Weise verwendet werden. Geeignete Methoden schließen ein: Bürstenanwendung, Rollen, Sprühen, Gießüberziehen, Eintauchen, Rakel, Pressen, Spachteln, Elektroabscheidung, Siebdruck usw.The dispersion of epoxy resins and water-based hardening agents according to the invention can be used in any

known way can be used. Suitable methods include: brushing, rolling, spraying, pouring, dipping, squeegees, pressing, filling, electrodeposition, screen printing, etc.

The dispersion of epoxy resins and the invention

Hardening agents can be used as a base coat, filler, clear sealer, protective coating, coatings, seals, thin mortar, mortar etc. They are particularly useful where corrosion resistance is required. The dispersions can also be used with epoxy resin / thermoplastic mixtures such as coal tar, vinyl polymers, etc. It can be used as a binder for pressed carbon, conductive floor coverings and fillers, as an adhesive for wood, fabric, leather and metal and for various types of substrates such as cemented floors, walls, swimming pools, glass, glazed bricks etc. Furthermore, the epoxy resin dispersion can be mixed with mortar or cement, the water being used as an emulsion to make the cement pasty. Conversely, the water in the cement mixture can be used as a solvent for the epoxy resin dispersion. Addition of the hardening agent according to the invention enables uniform mixing of cement and epoxy resin hardener dispersion. It is thus possible to obtain epoxy resin hardener dispersion hardened cement.

Examples Manufacture of curing agents

• 1 A) 300 g polyethylene glycol, average molecular weight 1000 (≙ 0.6 Vale),
  • 470 g bisphenol A diglycidyl ether / bisphenol F diglycidyl ether - mixture in a ratio of 60:40 parts by weight with an EV value of 180 (≙ 2.6 Vale) and
  • 2 ^{g of} BF ₃ amine complex (e.g. Anchor 1040) are weighed into a 2 1 three-necked flask equipped with a thermometer and stirrer. The piston is connected to a cooler via a separator. With nitrogen as the inert gas, the mixture is heated to 80 ° C. in 30 minutes, a homogeneous mixture being formed.
  Then heat to 170 ° C and keep this temperature until the theoretical EV value of 385 ± 10 is reached. After a holding time of 5 hours at 170 ° C., an EV value of 378 was obtained. The viscosity of the product at 25 ° C., measured in a Höppler falling ball viscometer, is 9600 m Pas. This product is used as a preliminary product for the production of the curing agents according to the invention.
• 1 B) 272 g of xylylenediamine (4 Vale) are placed in a 1 1 three-necked flask, nitrogen becomes; transferred and at room temperature 378 g (1 eq) of the preliminary product according to Example 1A in 15 to 30 'are added. After the addition has ended, the mixture is stirred for a further 1 hour, the temperature rising to about 60 ° C. After the temperature has dropped, the mixture is heated to 80 ° C. and held there for 1 hour. The hydrogen equivalent weight (HAV) is 93. This product is 80% diluted with water, the HAV is now 116.
• 1 C) 813 g of this 80% aqueous solution contain 7 active amine hydrogen atoms. At 60 ° C., 74 g of acrylonitrile are added by dropwise addition in 30 ', this corresponds to 0.2 vale of acrylonitrile per hydrogen amine. After the addition has ended, the mixture is kept at 60 ° C. for 1 hour. The curing agent obtained is now 82% i ^g , has an HAV of 159 and a viscosity at 25 ° C., measured in a falling ball viscometer according to Höppler, of 2330 m Pas.
• 2 B) 272 g of xylylenediamine (4 vale) are placed in a 2 1 three-necked flask, nitrogen is passed over and, at room temperature, 173 g (1.25 vale) of precursor according to Be match 1 A in 15 to 30 'added. After the addition has ended, the mixture is stirred for a further 1 hour, the temperature rising to about 60 ° C. After the temperature has dropped, the mixture is heated to 80 ° C. and held there for 1 hour. The HAV is 111. This product is 80% diluted with water, the HAV is now 138.
• 2 C) 932 g of this 80% aqueous solution contain 6.75 active amine hydrogen atoms. At 60 ° C., 71.5 g of acrylonitrile is added by dropwise addition in 30 ', this corresponds to 0.2 vale of acrylonitrile per hydrogen amine. After the addition has ended, the mixture is kept at 60 ° C. for 1 hour. The curing agent obtained is now 81%, has an HAV of 186 and a viscosity, measured in a falling ball viscometer according to Höppler, of 5150 m Pas.
• 3A) Example 1A was repeated. After a 4.5 hour hold time at 170 ° C, an EV value of 391 was obtained.
• 3 B) 136 g of xylylenediamine (2 Vale) and 170 g of 1-amino-3-aminomethyl -3,5,5-trimethylcyclohexane (2 Vale) are placed in a 2 1 three-necked flask, nitrogen is passed over and at room temperature are stirred 489 g (1.25 Vale) of precursor according to Example 3A in 15 'to 30' added. After the addition has ended, the mixture is stirred for a further 1 hour, the temperature rising to about 60 ° C. After the temperature has dropped, the mixture is heated to 80 ° C. and held there for 1 hour. The HAV is 118. This product is 80% diluted with water, the HAV is 147.
• 3 C) 994 g of this 80% aqueous solution contain 6.75 active amine hydrogen atoms. At 60 ° C., 71.5 g of acrylonitrile is added by dropwise addition in 30 ', this corresponds to 0.2 vale of acrylonitrile per hydrogen amine. After the addition stops one more hour at 60 ° C.

• 4 A) Es wurde das Produkt aus Beispiel 3 A eingesetzt.
• 4 B) In einen 2 1-Dreihalskolben werden 489 g (1,25 Vale) Vorprodukt nach Beispiel 3 A vorgelegt, Stickstoff wird übergeleitet und bei Raumtemperatur'werden unter Rühren nacheinander 136 g Xylylendiamin (2 Vale) und 170 g 1-Amino -3-aminomethyl- 3,5,5-trimethylcyclohexan (2 Vale) in 10 - 15 Minuten zugesetzt. Nach Beendigung der Zugabe wird noch 1 Stunde verrührt, wobei die Temperatur auf ca. 65 °C ansteigt. Nach Äbfallen der Temperatur wird auf 60 °C geheizt und 1 Stunde dort gehalten. Das HAV beträgt 118. Dieses Produkt wird mit Wasser 80%ig verdünnt, das HAV beträgt 147.
• 4 C) Es wurde wie unter Beispiel 3 C beschrieben verfahren. Das erhaltene Härtungsmittel ist 81,5%ig, hat einen HAV von 197 und eine Viskosität, gemessen im Kugelfallviskosimeter nach Höppler, von 13120 m Pas.

The curing agent obtained is now 81.5%, has an HAV of 197 and a viscosity, measured in the Höppler falling ball viscometer, of 13,450 m Pas.

• 4 A) The product from Example 3 A was used.
• 4 B) 489 g (1.25 Vale) of preliminary product according to Example 3A are placed in a 2 1 three-necked flask, nitrogen is passed over and 136 g of xylylenediamine (2 Vale) and 170 g of 1-amino are successively stirred at room temperature. 3-aminomethyl-3,5,5-trimethylcyclohexane (2 Vale) added in 10-15 minutes. After the addition has ended, the mixture is stirred for a further 1 hour, the temperature rising to about 65.degree. After the temperature has dropped, the mixture is heated to 60 ° C. and held there for 1 hour. The HAV is 118. This product is 80% diluted with water, the HAV is 147.
• 4 C) The procedure was as described in Example 3 C. The curing agent obtained is 81.5% pure, has an HAV of 197 and a viscosity, measured in a falling ball viscometer according to Höppler, of 13120 m Pas.

5 A and B) Example 3 A + B were repeated.

25 5 C) 882 g of the 80% solution, as described under Example 3 B, contain 6.0 active amine hydrogen atoms. At 60 ° C., 79.5 g of acrylonitrile are added dropwise in 30 minutes, which corresponds to 0.25 vale of acrylonitrile per hydrogen amine. After the addition has ended, the mixture is kept at 70 ° C. for 1 hour. The curing agent obtained is now 82%, has an HAV of 216 and a viscosity, measured in a falling ball viscometer according to Höppler, of 14520 m Pas.

6 A and B) Example 1 A + B were repeated.

6 C) 696 g of the 80% solution, as described under Example 1 _B , contain 6.0 active amine hydrogen atoms. At 50 ° C., 79.5 g of acrylonitrile are added dropwise in 30 minutes, which corresponds to 0.25 vale of acrylonitrile per hydrogen amine. After the addition has ended, the mixture is kept at 70 ° C. for a further 1.5 hours. The curing agent obtained is now 82%, has an HAV of 175 and a viscosity, measured in a falling ball viscometer according to Höppler, of 3150 m Pas.

7 C) 932 g of the 80% solution, as described in Example 2 B, are reacted with 89.5 g of acrylonitrile (0.25 Vale per hydrogen amine), as described in Example 5 C. The curing agent obtained is now 82%, has an HAV of 202 and a viscosity of 5900 m Pas.

In Examples 8 C-11 C, the procedure was as in Example 5 C.

• EV-Wert : 388
• Viskosität 25 °C : 13750 m Pas

12 A) 300 g of polyethylene glycol, average molecular weight 1000 (≙ 0.6 Vale), 482 g of bisphenol A diglycidyl ether with an EV value of 185 (viscosity 25 ° C. 9800 m Pas) and 2 g of BF ₃ amine Complex implemented as described in Example 1A. The product had the following characteristics:

• EV value: 388
• Viscosity 25 ° C: 13750 m Pas

12 B) 388 g of this product were reacted with 272 g of xylylenediamine as described in Example 1B. The 80% solution in water has an HAV of 118.

12 C) 590 g of the 80% solution are now reacted with 53 g of acrylonitrile (0.2 Vale per hydrogen amine) as described under Example 1 C. The HAV is now 161, the viscosity at 25 ° C is 3940 m Pas.

Each 1.25 Valse, based on epoxy groups, of the precursors listed under Example 13 A to 19 A were mixed with 136 g xylylenediamine (2 Vale) and 170 g 1-amino -3-aminomethyl -3,5,5-trimethylcyclohexane (2 Vale ) implemented according to Example 3 B.

Products 13 B to 19 B were reacted according to Example 3 C.

einen 2 1 -Dreihalskolben werden 136 g Xylylendi-

(3 Vale) und 170 g 1-Amino-3-aminomethyl-3,5,5-trimethylcyclohexan (2 Vale) vorgelegt und Stickstoff wird Ubergeleitet. Bei 60 °C'addiert man durch Zu-

in 30' 71,5 g Acrylnitril. Nach Zugabeende hält man noch 1 Std. bei 60 °C.

a 2 1 three-necked flask, 136 g of xylylenedi

(3 vale) and 170 g of 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (2 vale) and nitrogen is passed over. At 60 ° C 'add by

in 30 '71.5 g acrylonitrile. After the end of the encore hold at 60 ° C for 1 hour.

489 g (1.25 Vale) of precursor according to Example 3A in 15 'to 30' are added to this cyanoethylated polyamine mixture at room temperature with stirring. After the addition has ended, the mixture is stirred for a further 1 hour, the temperature rising to about 60.degree. After the temperature has dropped, the mixture is heated to 80 ° C. and held there for 1 hour. The mixture is then diluted to 81.5% solids with water. The curing agent obtained has a HAV of 197 and a viscosity, measured in a falling ball viscometer according to Höppler, of 13300 m Pas.

Production of the epoxy resin dispersions

• österreichische Patentschrift 286 647 (=Britische Patentschrift 1.244.424) und Japanische Patentschrift 29.625/71, sowie die Schweizerische Patentschrift 603 738.

Epoxy resin dispersions, which can be combined with the adducts according to the invention as curing agents, are described, inter alia, in the following patents:

• Austrian patent specification 286 647 (= British patent specification 1.244.424) and Japanese patent specification 29.625 / 71, as well as Swiss patent specification 603 738.

• 21) Epoxydharz A (EV-Wert ca. 195)
  • 72 g eines Epoxydharz-Emulgatorgemisches, bestehend aus
  • 66 g einer Mischung aus 88 Gew.-% eines Epoxyd- harzes auf Basis von Bisphenol A und Epichlorhydrin mit einem Epoxydäquivalent von ca. 186 und einer Viskosität von 9000 m Pas, gemessen bei 25 °C, und 12 Gew.-% 2-Äthylhexylglycidyläther, wurde in der Wärme mit
  • 6 g eines Emulgatorgemisches, bestehend aus
  • 2,67g eines Anlagerungsproduktes von 25 - 30 Molen Äthylenoxyd an 1 Mol Abietinsäure,
  • 1 g eines Anlagerungsproduktes von 30 Molen Äthylenoxyd an 1 Mol p-Nonylphenol
  • 1 g eines Anlagerungsproduktes von 10 Molen Äthylenoxyd an 1 Mol p-Nonylphenol
  1,33 g n-Dodecylalkohol vermischt (Diese Mischung entspricht dem Epcxydharz-Emulgator-Gemisch aus Beispiel 7 der schweizerischen Patentschrift 603 738.
• 22) Epoxydharz B (EV-Wert ca. 185)
  • 80 g eines Epoxydharz-Emulgatogemisches, bestehend aus
  • 75,2 g einer Mischung aus 60 Gew.-% eines Epoxydharzes auf Basis Bisphenol A und Epichlorhydrin und 40 Gew.-% eines Epoxydharzes auf Basis Roh-Bisphenol F und Epichlorhydrin mit einem Misch-Epoxydäquivalent von ca. 180 und einer Viskosität von 6500 m Pas, gemessen bei 25 ΦC, wurde in der Wärme mit
  • 4,8 g eines Emulgatorgemisches,bestehend aus
  • 2,14 g eines Anlagerungsproduktes von 25 - 30 Molen Äthylenoxyd an 1 Mol Abietinsäure,
  • 0,8 g eines Anlagerungsproduktes von 4 Molen Äthylenoxyd an 1_Mol p-Nonylphenol
  • 0,8 g eines Anlagerungsproduktes von 10 Molen- Äthylenoxyd an 1 Mol p-Nonylphenol
  • 1,06 g n-Dodecylalkohol vermischt
• 23) Epoxydharz C
  • 100 g einer Mischung bestehend aus 60 Gew.-% eines Epoxydharzes auf Basis Bisphenol A und Epichlorhydrin und 40 Gew.-% eines Epoxydharzes auf Basis Roh-Bisphenol F und Epichlorhydrin mit einem Misch-Epoxydäquivalent von ca. 180 und einer Viskosität von 6500 m Pas gemessen bei 25 °C.
• 24) Epoxydharz D
  Epoxydharz auf Basis von Bisphenol A und Epichlorhydrin mit einem Epoxydäquivalent von ca. 185 und einer Viskosität von 9000 m Pas gemessen bei 25 °C.
• 25) Je 100 g der bevorzugt eingesetzten Epoxydharze A,B,C und D wurden mit Hilfe eines Rührers mit den erfindungsgemäßen Härtungsmitteln der Beispiele 1 C bis 19 C, 20 und 1 B bis 3 B äquivalent vermischt. Es wurde soviel Wasser zugesetzt, bis die Dispersionen 60%ig waren. Die Mengen sind der nachfolgenden Tabelle zu entnehmen.
  
  

The following epoxy resins were preferably used:

• 21) Epoxy resin A (EV value approx. 195)
  • 72 g of an epoxy resin-emulsifier mixture consisting of
  • 66 g of a mixture of 88% by weight of an epoxy resin based on bisphenol A and epichlorohydrin with an epoxy equivalent of approx. 186 and a viscosity of 9000 m Pas, measured at 25 ° C., and 12% by weight of 2- Ethylhexylglycidyl ether, was in the warmth with
  • 6 g of an emulsifier mixture consisting of
  • 2.67 g of an adduct of 25-30 moles of ethylene oxide with 1 mole of abietic acid,
  • 1 g of an adduct of 30 moles of ethylene oxide with 1 mole of p-nonylphenol
  • 1 g of an adduct of 10 moles of ethylene oxide with 1 mole of p-nonylphenol
  1.33 g of n-dodecyl alcohol mixed (this mixture corresponds to the epoxy resin-emulsifier mixture from Example 7 of the Swiss patent 603 738.
• 22) Epoxy resin B (EV value approx. 185)
  • 80 g of an epoxy resin-emulsifier mixture consisting of
  • 75.2 g of a mixture of 60% by weight of an epoxy resin based on bisphenol A and epichlorohydrin and 40% by weight of an epoxy resin based on crude bisphenol F and epichlorohydrin with a mixed epoxy equivalent of approx. 180 and a viscosity of 6500 m Pas, measured at 25 ΦC, was in the warm with
  • 4.8 g of an emulsifier mixture consisting of
  • 2.14 g of an adduct of 25-30 moles of ethylene oxide with 1 mole of abietic acid,
  • 0.8 g of an adduct of 4 moles of ethylene oxide with 1 mole of p-nonylphenol
  • 0.8 g of an adduct of 10 moles of ethylene oxide and 1 mole of p-nonylphenol
  • 1.06 g of n-dodecyl alcohol mixed
• 23) epoxy resin C
  • 100 g of a mixture consisting of 60% by weight of an epoxy resin based on bisphenol A and epichlorohydrin and 40% by weight of an epoxy resin based on crude bisphenol F and epichlorohydrin with a mixed epoxy equivalent of approx. 180 and a viscosity of 6500 m Pas measured at 25 ° C.
• 24) epoxy resin D
  Epoxy resin based on bisphenol A and epichlorohydrin with an epoxy equivalent of approx. 185 and a viscosity of 9000 m Pas measured at 25 ° C.
• 25) 100 g each of the preferred epoxy resins A, B, C and D were mixed with the aid of a stirrer with the curing agents according to the invention of Examples 1 C to 19 C, 20 and 1 B to 3 B equivalent. So much water was added until the dispersions were 60%. The quantities are shown in the table below.
  
  

The dispersions showed excellent stability within the processing time (i.e. until the start of the crosslinking reaction between the resin and hardener components), which was 30 minutes to 5 hours.

The aqueous dispersions using epoxy resin A were applied in a layer thickness of approximately 200 μm to phosphated iron sheets and asbestos-cement plates.

The application results are summarized in Table 5 below, the numbering of the dispersions being identical to the labeling of the curing agents. Drying is the point in time at which no more surface stickiness can be determined when touched with the finger.

The dispersions produced with the epoxy resins B, C and D and the films produced therefrom gave properties similar to those with epoxy resin A.

26) 100 g each of the preferred epoxy resins A and C were rubbed on a roller with 150 g non-chalking titanium dioxide of the rutile type and 5 g of highly disperse silica. With the aid of a stirrer, equivalent amounts of the curing agents according to Example 1 C to 12 C and 1 B to 3 B and sufficient water were added to give 55% dispersions. The amounts are shown in Table 6 below.

The dispersions showed excellent stability within the processing time (ie until the start of the crosslinking reaction between the resin and hardener components), which was 30 minutes to 3 hours.

The aqueous emulsion paints using the epoxy resin C were applied in a layer thickness of approximately 100 u to phosphated iron sheets and asbestos-cement plates. The application results are summarized in Table 7 below:

The emulsion paint produced with epoxy resin A and the films produced therefrom showed test results similar to those with epoxy resin C.

The term "pot life" was used to refer to the time which elapsed until a dispersion of 50 g of the epoxy resin, 50 g of water and an equivalent amount of the particular curing agent according to the invention, Example 1 C to 19 C and 1 B to 3 B, gelled or until the viscosity of the dispersion has risen so much that it is no longer possible to process it properly.

27) A mixture consisting of 80 g of fine-grained quartz sand (grain size 0.5 mm), 160 g of coarse-grained quartz sand, 80 g of cement, 11 g of epoxy resin B and 11.7 g of the curing agent according to Example 3 C according to the invention were homogeneous in a mixer mixed and mixed with 80 g water to a pasty consistency. This mass was processed with a squeegee to an approximately 5 mm thick concrete floor covering, which after curing had excellent oil and water resistance. The tensile, compressive and flexural strengths of the concrete mixture are improved by approximately 20% by adding the epoxy resin hardener dispersion.

Claims (9)

1. Hardening agent for aqueous epoxy resin dispersions, characterized in that the hardening agent is a reaction product a) at least one polyepoxide compound, b) at least one polyalkenyl polyether polyol and c) at least one polyamine is. 2. Hardening agent according to claim 1, characterized in that the hardening agent is a reaction product a) at least one water-insoluble polyepoxide compound, b) at least one water-soluble polyalkylene polyether polyol and c) at least one polyamine is. 3. Hardening agent according to claim 1 or 2, characterized in that it consists of a reaction product consisting of 20 to 80 wt .-% of an adduct a) 2 to 4 equivalents of at least one polyepoxide compound and b) 0.2 to 1.5 equivalents of at least one polyalkylene polyether polyol by reaction with 80 to 20 wt .-% of Kömponente c) an aliphatic, cycloaliphatic and / or heterocyelischen polyamine - or polyamine, wherein the amount of amine used poxydgruppen in a 2- to 10-fold excess, based on the groups capable of reacting _E and the most Nitrogen atoms, has been used. 4. Hardening agent according to one of claims 1 to 3, characterized in that unsaturated compounds capable of addition are added to the reactive groups of the polyamine c) or d). 5. Hardening agent according to claim 4, characterized in that to component c) before or after the reaction with the adduct of components a) and b) per nitrogen atom up to 0.5 equivalents of an unsaturated unsaturated capable Compound d) of type

where R _{1 =} H, -CH ₃ , -C ₂ H ₅ , R ₂ = H, -CH ₃ and X = -CN, -COOH, -COOCH ₃ , -COOC ₂ H ₅ , -COOC ₃ H ₇ , - COOC ₄ H ₉ , -CONH ₂ , means are added. 6.Process for the preparation of hardening agents, characterized in that I) in the 1st stage, an adduct of a) at least one polyepoxide compound and b) at least one polyalkylene polyether polyol with an average molecular weight of 200 to 10,000 in the presence of a BF ₃ amine complex as a catalyst and this is then prepared with c) an amine compound the group c ₁ ) at least one polyamine and c ₂ ) an adduct of c ₁ ) with d) an unsaturated component of the formula HC (R ₁ ) = C (R ₂ ) -X, where R ₁ , R ₂ and X are the above have the meaning mentioned, is implemented or II) the reaction product of components a), b) and c ₁ ) with d) an unsaturated compound of the formula HC (R ₁ ) = C (R ₂ ) -X _i in which R ₁ , ^R ₂ and X have the meaning given above _{i is} implemented the reactions when using component d) are carried out at a temperature between 20 and 70 ° C. 7. The method according to claim 6, characterized in that a) 2 to 4 equivalents of at least one polyepoxide compound and b) 0.2 to 1.5 equivalents of at least one polyalkylene polyether polyol in the presence of a BF ₃ amine complex as a catalyst at a temperature of 20 to 200 ° C and the reaction with c) an amine compound of group c ₁ ) at least one aliphatic, cyclcaliphatic or heterocyclic polyamine or c ₂ ) an adduct of c _l ) with d) at a temperature of 20 to 100 ° C. is used, the amount of amine used in a 2 to 10-fold excess, based on the epoxy groups capable of reaction and the nitrogen atoms on the nitrogen. 8. The method according to claim 6 or 7, characterized in that as component a) polyphenol glycidyl ether are reacted with a polyalkylene polyether polyol. 9. Use of the curing agent according to claim 1 to 5, together with polyfunctional epoxy compounds a) and water for the preparation of curable dispersions as coating or coating agents.