Indian Patents. 279695:WATER-SOLUBLE AMINE AND COMPOSITION THEREOF

Title of Invention	WATER-SOLUBLE AMINE AND COMPOSITION THEREOF
Abstract	The present invention relates to novel compounds VB of the formula (I) or (II), said compounds being particularly suitable as curing agents for epoxide resins. The compounds can be produced easily and rapidly. They can be used in the form of aqueous curing agents and form stabile aqueous emulsions in particular. This facilitates the formulation of ECC compounds for use primarily as coatings.

Full Text	WATER-SOLUBLE AMINE AND USES THEREOF Technical Field The present invention relates to the field of water- dilutable amines and the use thereof as hardeners for epoxy resins. State of the Art Amine hardeners for aqueous epoxy resin dispersions are known. They typically contain an adduct formed from polyamines and polyepoxides, which is free of epoxy groups and contains secondary and possibly primary amino groups. Often, primary amino groups present in such an adduct are converted further, since there is otherwise the disadvantage that the adduct tends to form carbonate and carbamate salts with carbon dioxide gas from the air, which can impair the quality of a hardened film in respect of esthetic and mechanical properties such as clarity, shine, surface properties, hardness and toughness. EP 0 000 605 A1 discloses hardening compositions for aqueous epoxy resin dispersions in the form of adducts formed from polyepoxides, polyalkylene polyether polyols and polyamines. Primary amino groups of the adducts have been converted to secondary amino groups by addition onto unsaturated compounds such as acrylonitrile. These hardening compositions have the disadvantage that they tend to coagulate at temperatures in the region of 50°C, i.e. are not storage-stable. EP 0 567 831 Al discloses hardening compositions for aqueous epoxy resin dispersions, which are storage- stable at 50°C. The emulsifier and coemulsifier described are each adducts formed from polyamines and polyepoxides. Primary amino groups of the adducts are alkylated reductively by means of aldehydes and formic acid and are in the form of secondary amino groups. However, the hardeners described have disadvantages. Firstly, the preparation thereof is complicated, especially owing to the slowness of the reduction process used, and they secondly tend to form an esthetically unsatisfactory, hazy film when applied in a thick layer, for example as an anticorrosion coating. EP 0 024 915 Al discloses two-pack aqueous epoxy resin systems, the hardeners of which are present in the form of polyamine-polyepoxy resin adducts. Primary amino groups of the adducts are converted by means of monoepoxides. As a result of the reaction with monoepoxides, the preparation of the adducts described takes a very long time. Summary of the Invention It is therefore an object of the present invention to provide compounds which are preparable in a simple rapid process from readily available raw materials, which are usable as hardeners for epoxy resins, especially as a constituent of an aqueous hardener composition for epoxy resin dispersions, and which overcome the disadvantages of the prior art. It has been found that, surprisingly, this object is achieved by compounds as claimed in claim 1. The compounds can . be used highly advantageously as hardeners for epoxy resins. More particularly, it has been found that these compounds have low viscosity, can be prepared in a simple and rapid manner from readily available raw materials and are highly suitable as hardeners for epoxy resins. They are storable substantially unchanged within a broad temperature range, have a low processing and mixing viscosity with the epoxy resin and harden rapidly and completely with the epoxy resin to develop good adhesion to the substrate. They meet the high demands on the quality of a hardened film in respect of esthetic and. mechanical properties such as clarity, shine, surface properties, hardness and toughness. It has particularly been shown that these compounds are highly suitable as aqueous hardeners for epoxy resins. More particularly, they enable the production of storage-stable, low-viscosity aqueous hardener emulsions which are stable especially up to 50°C. Thus, further aspects of the invention are a process as claimed in claim 5 for preparation of the compound and a hardener composition as claimed in claim 10. It has additionally been found that these hardener compositions are highly suitable for two- or three-pack epoxy resin compositions as claimed in claim 16. More particularly, it is also possible to produce ECC (epoxy cement concrete) compositions. The compounds or the aqueous hardener compositions formed therefrom are especially suitable as a constituent of ECC compositions which can be used especially as a coating. Further aspects of the present invention are a hardened composition as claimed in claim 17 and uses as claimed in claims 18 and 19. Preferred embodiments of the invention are the subject of the dependent claims. Ways of Performing the Invention In a first aspect, the present invention relates to a compound VB of the formula (I) or (II) where R1 and R3 are each independently an alkyl, cycloalkyl, aryl or arylalkyl group which has 1 to 12 carbon atoms and optionally has ether groups or halogen atoms, and R2 is a hydrogen atom or an alkyl, cycloalkyl, aryl or arylalkyl group having 1 to 12 carbon atoms, or R2 and R1 together are a divalent hydrocarbon radical which is part of an optionally substituted carbocyclic ring having 5 to 8 and preferably 5 or 6 carbon atoms, and R3 is an alkyl, cycloalkyl, aryl or arylalkyl group which has 1 to 12 carbon atoms and optionally has ether groups or halogen atoms; or R2 and R3 together are a divalent hydrocarbon radical which is part of an optionally substituted carbocyclic ring having 5 to 8 and preferably 5 or 6 carbon atoms, and R1 is an alkyl, cycloalkyl, aryl or arylalkyl group which has 1 to 12 carbon atoms and optionally has ether groups or halogen atoms; R4 and R5 are each independently an alkyl, cycloalkyl, aryl or arylalkyl group which has 1 to 12 carbon atoms and optionally has ether groups or halogen atoms; A is an (a+b)-valent radical of a polyamine-polyepoxide adduct after removal of (a+b) primary amino groups; a is an integer from 0 to 4; and b is an integer from 1 to 4. The following provisos apply here: that the sum of a and b is an integer from 1 to 4, and that the parent polyepoxide of the polyamine- polyepoxide adduct is a polyepoxide E, especially a diepoxide E1, and has an epoxy equivalent weight (EEW) of 65 to 500 g/eq. In the present document, the term "polyamine" refers to compounds having at least two primary or secondary amino groups. In the present document, a "primary" amino group refers to an NH2 group which is bonded to an organic radical, and a "secondary" amino group refers to an NH group which is bonded to two organic radicals which may also together be part of a ring. In the present document, "molecular weight" in the case of oligomers or polymers is always understood to mean the molecular weight average Mn. In the present document, the term "polyepoxide" refers to compounds having at least two epoxy groups. "Diepoxides" . refer to compounds having two epoxy groups. In the present document, "epoxy group" refers to the structural element The bold designations such as VB, E, E1, A1, A2, A3, A4, A11, AD, AE, K1, K2, H1, H2, HW, C1, C2, C3 or the like in the present document serve merely for better readability and identification. The acyl enamino groups of the formula (i) are in an equilibrium with the tautomeric isomers of the formula (ii) and of the formula (iii). Each mention of the acyl enamino groups of the formula (i) likewise means the tautomers of the formula (ii) and of the formula (iii), even though this is not mentioned explicitly in each case. In this document, the broken lines in the formulae each represent the bond between a substituent and the rest of the corresponding molecule. Preferably, R1 and R3 are each a methyl group. Preferably, R2 is a hydrogen atom. Preferably, R4 and R5 are each a methyl group. Preferably, a is 0. Preferably, b is 1. The polyamine-polyepoxide adduct from which A in the formulae (I) and (II) derives is free of epoxy groups and has (a+b) primary amino groups. It is an addition product of at least one polyamine A1 and optionally further amines, preferably at least one further amine A2, with at least one polyepoxide E, especially a diepoxide El. The polyepoxide E has an epoxy equivalent weight of 65 to 500 g/eq. The polyamine Al is preferably a polyamine having two primary amino groups. The amine A2 is preferably an amine having only one primary amino group. The polyepoxide E is preferably a diepoxide E1, more preferably a liquid diglycidyl ether of bisphenols, especially of bisphenol A. The abbreviation "EEW" in the present document stands for "epoxy equivalent weight". In the present document, a "glycidyl ether" refers to an ether of 2,3-epoxy-l-propanol (glycidol). A compound VB of the formula (I) is preferably a compound VB of the formula (1a) or (1b) . A compound VB of the formula (II) is preferably a compound VB of the formula (IIa) or (IIb). In the formulae (Ia), (Ib), (IIa) and (IIb), R1, R2, R3, R4 and R5 are each as already defined, and R6 is an alkyl or cycloalkyl or arylalkyl group which optionally has ether or secondary amino groups; E1 and E2 are each independently the remainder of a diepoxide El having an EEW of 65 to 500 g/eq, after removal of two epoxy groups; x is an integer from 0 to 50; y is an integer from 0 to 100, preferably 10 to 50; z is an integer from 1 to 50; (x+z) is an integer from 1 to 100, preferably 1 to 10; p is 0 or 1; and q is 0, 1, 2 or 3. R6 in the formulae (Ia), (IIa), (Ib) and (IIb) is preferably an alkyl or cycloalkyl or arylalkyl group which has at least 4 carbon atoms, especially 4 to 18 carbon atoms, and optionally has ether or secondary amino groups. The diepoxide E1 is preferably selected from the group consisting of a bisphenol A, bisphenol F and bisphenol A/F diglycidyl ether having an epoxy equivalent weight of 156 to 250 g/eq, N,N-diglycidylaniline and a polyglycol diglycidyl ether having an epoxy equivalent weight of 170 to 340 g/eq. The diepoxide E1 is more preferably a bisphenol A, bisphenol F and bisphenol A/F diglycidyl ether. Thus, E1 in the formulae (Ia) and (IIa) and E2 in the formulae (Ib) and (IIb) are preferably each independently the remainder of a diepoxide E1 which is selected from the group consisting of a bisphenol A, bisphenol F and bisphenol A/F diglycidyl ether having an epoxy equivalent weight of 156 to 250 g/eq, N,N- diglycidylaniline and a polyglycol diglycidyl ether having an epoxy equivalent weight of 170 to 340 g/eq, especially a bisphenol A, bisphenol F and bisphenol A/F diglycidyl ether having an epoxy equivalent weight of 156 to 250 g/eq, after removal of two epoxy groups. The invention further provides a process for preparing a compound VB of the formula (I) or (II) as described above. In this process, (a) at least one polyamine A1 containing at least two primary amino groups, ((3) optionally at least one amine A2 containing only one primary amino group, (y) at least one polyepoxide E having an epoxy equivalent weight (EEW) of 65 to 500 g/eq and (6) at least one diketone K1 of the formula (IV) or K2 of the formula (V) are reacted with one another over more than one stage. In the formulae (IV) and (V), R1, R2, R3, R4 and R5 are each as already defined. The ratio between the number of primary amino groups and epoxy groups is especially 1.25 to 2.0. In addition, the diketone K1 or K2 is used in a ratio to the primary amino groups, which are in excess in relation to the epoxy groups, especially in an amount of 0.25 to 1.0 equivalent. In the case that the index a in the formula (I) or (II) is different than zero, the diketone is used in a substoichiometric ratio to the primary amino groups, which are in excess in relation to the epoxy groups. In the case that the index a in the formula (I) or (II) is zero, the diketone is used in at least a stoichiometric ratio to the primary amino groups, which are in excess in relation to the epoxy groups. The process can be performed in such a way that, in a first stage, the polyamine A1 and optionally the amine A2 are reacted with the polyepoxide E to give an adduct AE of the formula (III), with predominant reaction of primary amino groups with the epoxy groups, while secondary amino groups and hydroxyl groups already present or formed in the course of the reaction react with epoxy groups only in an insignificant portion, if at all, owing to the significantly lower reactivity. In the formula (III), A, a and b are each as already defined. In a second stage, the adduct AE of the formula (III) is subsequently reacted with the diketone K1 or K2 of the formula (IV) or (V) to give a compound VB of the formula (I) or (II), the diketone reacting with primary amino groups to eliminate water. In the case of the diketone Kl of the formula (IV) - a β-diketone, also known as a 1,3-diketone - a compound VB of the formula (I) is formed, releasing one mole of water per mole of diketone Kl converted. This reaction proceeds very rapidly and virtually quantitatively. It is preferably performed at a temperature in the range from 20 to 120°C. In the case of the diketone K2 of the formula (V) - a γ- diketone, also known as a 1,4-diketone - a compound VB of the formula (II) is formed, releasing two moles of water per mole of diketone K2 converted. This reaction is also known by the name "Paal-Knorr pyrrole synthesis". An intermediate (or by-product) which occurs in the formation of the compound VB of the formula (II) is the noncyclized form, as shown in the formula (II') . In the formula (II'), R4, R5, A, a and b are each as already defined. The cyclization to the pyrrole group (condensation reaction) proceeds in a predominant portion when the reaction mixture is stirred, for example, at elevated temperature over a few hours, for example 60 to 120°C. In addition, the process for preparing a compound VB of the formula (I) or (II) can also be performed in such a way that, in a first stage, the polyamine A1 is reacted with the diketone K1 or K2 with elimination of water to form an alkylated polyamine All of the formula (VI) or (VII), in which case the diketones react with primary amino groups in the manner already described. In the formulae (VI) and (VII), Q is the remainder of a polyamine Al after removal of (b+c) primary amino groups; c is 1 or 2, preferably 1; and R1, R2, R3, R4, R5 and b are each as already defined. In a second stage, the alkylated polyamine A11 is subsequently, optionally in the presence of the amine A2, reacted with the polyepoxide E to give a compound VB of the formula (I) or (II), at least as many free primary amino groups as epoxy groups still being present in the reaction mixture. In the processes described, the reaction of primary amino groups with epoxy groups is advantageously performed at a temperature in the range from 60 to 120°C. The processes described can be performed as a one-pot reaction. It is thus unnecessary to purify the intermediate before the 2nd stage is carried out. The water formed in the reaction between the diketone and the primary amino groups need not be removed from the reaction mixture. It can, however, be removed from the reaction mixture if desired, for example by means of application of reduced pressure. It is also possible to prepare a compound VB of the formula (I) by using, instead of a diketone K1 of the formula (IV), a ketone of the formula (IVa). In this case, the primary amino groups are alkylated without elimination of water. In the formula (IVa) , R1 and R3 are each as already defined. The polyamine A1 has at least two primary amino groups. In addition, it may have secondary and/or tertiary amino groups. Suitable polyamines for this purpose are especially the following: - aliphatic, cycloaliphatic or arylaliphatic diamines, especially ethylenediamine, 1,2-propanediamine, 1,3- propanediamine, 2-methyl-1,2-propanediamine, 2,2- dimethyl-1,3-propanediamine, 1,3-butanediamine, 1,4- butanediamine, 1,3-pentanediamine (DAMP), 1,5- pentanediamine, 1,5-diamino-2-methylpentane (MPMD), 2-butyl-2-ethyl-1,5-pentanediamine (C11-neodiamine), 1,6-hexanediamine, 2,5-dimethyl-1, 6-hexanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine (TMD), 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonane- diamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,2-, 1,3- and 1,4- diaminocyclohexane, bis(4-aminocyclohexyl)methane (H12-MDA), bis(4-amino-3-methylcyclohexyl)methane, bis(4-amino-3-ethylcyclohexyl)methane, bis(4-amino- 3,5-dimethylcyclohexyl)methane, bis(4-amino-3-ethyl- 5-methylcyclohexyl)methane (M-MECA), 1-amino-3- aminomethyl-3,5,5-trimethylcyclohexane (= isophorone- diamine or IPDA), 2- and 4-methyl-1,3- diaminocyclohexane and mixtures thereof, 1,3- and 1,4-bis(aminomethyl)cyclohexane, 2,5(2,6)-bis(amino- methyl)bicyclo[2.2.1]heptane (NBDA), 3(4),8 (9)- bis (aminomethyl) tricyclo [5 . 2 .1. 02'6] decane, 1, 4- diamino-2,2,6-trimethylcyclohexane (TMCDA), 1,8- menthanediamine, 3,9-bis(3-aminopropyl)-2,4,8,10- tetraoxaspiro[5.5]undecane, and 1,3- and 1,4- xylylenediamine; - aliphatic diamines containing ether groups, especially bis(2-aminoethyl) ether, 3,6-dioxaoctane- 1,8-diamine, 4,7-dioxadecane-1,10-diamine, 4,7- dioxadecane-2,9-diamine, 4,9-dioxadodecane-1,12- diamine, 5,8-dioxadodecane-3,10-diamine and higher oligomers of these diamines, bis(3- aminopropyl)polytetrahydrofurans and polytetrahydro- furandiamines having molecular weights in the range from, for example, 350 to 5200, and polyoxyalkylenediamines. The latter are typically products from the amination of polyoxyalkylenediols and are obtainable, for example, under the Jeffamine® name (from Huntsman), under the Polyetheramine name (from BASF) or under the PC Amine® name (from Nitroil). Especially suitable polyoxyalkylenediamines are Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-2000, Jeffamine® D-4000, Jeffamine® XTJ-511, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003, Jeffamine® XTJ-568, Jeffamine® XTJ-569, Jeffamine® XTJ-523, Jeffamine® XTJ-536, Jeffamine® XTJ-542, Jeffamine® XTJ-559, Jeffamine® EDR-104, Jeffamine® EDR-14 8, Jeffamine® EDR-17 6; Polyetheramine D 230, Polyetheramine D 400 and Polyetheramine D 2000, PC Amine® DA 250, PC Amine® DA 400, PC Amine® DA 650 and PC Amine® DA 2000; - aliphatic, cycloaliphatic or arylaliphatic triamines, especially 4-aminomethyl-1,8-octanediamine, 1,3,5- tris(aminomethyl)benzene, 1,3,5-tris(aminomethyl)- cyclohexane, tris(2-aminoethyl)amine, tris(2- aminopropyl)amine, tris(3-aminopropyl)amine; - polyoxyalkylene triamines, which are typically products from the amination of polyoxyalkylenetriols and are obtainable, for example, under the Jeffamine® trade name (from Huntsman), under the Polyetheramine name (from BASF) or under the PC Amine® name (from Nitroil), for example Jeffamine® T-403, Jeffamine® T-3000, Jeffamine® T-5000; Polyetheramine T403, Polyetheramine T5000; and PC Amine® TA 403, PC Amine® TA 5000; - polyamines having secondary amino groups, especially what are known as polyalkyleneamines, such as diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and also polyethylenepolyamine having 5 to 7 ethyleneamine units (known as "higher ethylenepolyamine", HEPA), dipropylenetriamine (DPTA), bishexamethylenetriamine (BHMT), 3-(2-aminoethyl)aminopropylamine (N3-amine), N,N'-bis(3-aminopropyl)ethylenediamine (N4-amine), N3- (3-aminopentyl)-1,3-pentanediamine, N5-(3-amino- propyl) -2-methyl-1,5-pentanediamine and N5-(3-amino- 1-ethylpropyl)-2-methyl-1,5-pentanediamine; such polyalkyleneamines are prepared, for example, from 1,2-dichloroethane and ammonia, or from the cyanoethylation or cyanobutylation and subsequent hydrogenation of primary polyamines; - polyamines having tertiary amino groups, especially N,N'-bis(aminopropyl)piperazine, N,N-bis(3-amino- propyl )methylamine, N,N-bis(3-aminopropyl)ethylamine, N,N-bis(3-aminopropyl)propylamine, N,N-bis(3- aminopropyl)cyclohexylamine, N,N-bis(3-aminopropyl)- 2-ethylhexylamine, and also the products from the double cyanoethylation and subsequent reduction of fatty amines derived from natural fatty acids, such as N,N-bis(3-aminopropyl)dodecylamine and N,N-bis(3- aminopropyl)tallowalkylamine, obtainable as Triameen® Y12D and Triameen® YT (from Akzo Nobel). The polyamine Al preferably has two primary amino groups. Particularly preferred polyamines Al are firstly ether- containing diamines of the formula (VIII), especially having a molecular weight of 500 to 5000 g/mol, preferably Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003, and secondly polyalkyleneamines, especially DETA, TETA, TEPA, PEHA, HEPA, N3-amine and N4-amine. In the formula (VIII), x, y and z are each as already defined. A suitable amine A2, as optionally used in part to prepare a compound VB of the formula (I) or (II), has only one primary amino group. In addition, it optionally contains secondary and/or tertiary amino groups. Suitable examples are the following amines: - aliphatic, cycloaliphatic or arylaliphatic monoamines, especially methylamine, ethylamine, 1- propylamine, 2-propylamine, 1-butylamine, 2- butylamine, tert-butylamine, 3-methyl-1-butylamine, 3-methyl-2-butylamine, cyclopentylamine, hexylamine, cyclohexylamine, octylamine, 2-ethyl-1-hexylamine, benzylamine, 1- or 2-phenylethylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, docosylamine, and also fatty amines derived from natural fatty acid mixtures, for example cocoalkylamine, C16-C22- alkylamine, soyaalkylamine, oleylamine and tallowalkylamine, obtainable, for example, under the Armeen® (from Akzo Nobel) or Rofamin® (from Ecogreen Oleochemicals) trade names. Especially suitable fatty amines are Armeen® 12D, Armeen® 18D, Armeen® CD, Armeen® HT, Armeen® M, Armeen® OD, Armeen® OVD and Armeen® TD, and Rofamin® KD, Rofamin® LD, Rofamin® STD, Rofamin® TD, Rofamin® RD, Rofamin® TD4 0, Rofamin® OD80, Rofamin® OD85 and Rofamin® OD90; - aliphatic, cycloaliphatic or arylaliphatic monoamines containing ether groups, especially 2-methoxy- ethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-(2-ethylhexyloxy)propylamine, 3-(2-methoxyethoxy)propylamine, 2(4)-methoxyphenyl- ethylamine and also polyoxyalkylenemonoamines which are obtainable, for example, under the Jeffamine® trade name (from Huntsman) , such as especially Jeffamine® M-600, Jeffamine® M-1000, Jeffamine® M-2005, Jeffamine® M-2070, Jeffamine® XTJ-435, Jeffamine® XTJ-4 36; - aliphatic, cycloaliphatic or arylaliphatic amines having one primary and at least one secondary amino group, especially N-methyl-1,2-ethanediamine, N- ethyl-1,2-ethanediamine, N-butyl-1,2-ethanediamine, N-hexyl-1,2-ethanediamine, N-butyl-1,6-hexanediamine, N-cyclohexyl-1,2-ethanediamine, 4-aminomethyl- piperidine, 3- (4-aminobutyl)piperidine, N-(2-amino- ethyDpiperazine (N-AEP) , N-(2-aminopropyl)- piperazine, diamines from the cyanoethylation or cyanobutylation and subsequent hydrogenation of primary monoamines, for example N-methyl-1, 3- propanediamine, N-ethyl-1,3-propanediamine, N-butyl- 1,3-propanediamine, N-hexyl-1,3-propanediamine, N-(2- ethylhexyl)-1,3-propanediamine, N-dodecyl-1,3- propanediamine, N-cyclohexyl-1,3-propanediamine, 3- me thylamino-1-pentylamine, 3-ethylamino-1-pentyl- amine, 3-butylamino-1-pentylamine, 3-hexylamino-1- pentylamine, 3-(2-ethylhexyl)amino-1-pentylamine, 3- dodecylamino-1-pentylamine, 3-cyclohexylamino-1- pentylamine, and additionally diamines obtainable by cyanoethylation and subsequent reduction of fatty amines, such as N-cocoalkyl-1,3-propanediamine, N- oleyl-1,3-propanediamine, N-soyaalkyl-1,3-propane- diamine, N-tallowalkyl-1,3-propanediamine or N- (Ci6-22-alkyl)-1,3-propanediamine, obtainable, for example, as Duomeen® CD, Duomeen® M, Duomeen® 0, Duomeen® OV and Duomeen® T (Akzo Nobel), and additionally triamines and tetramines derived from fatty amines, such as cocoalkyldipropylenetriamine, oleyldipropylenetriamine, tallowalkyldipropylene- triamine, oleyltripropylenetetramine and tallowalkyltripropylenetetramine, obtainable, for example, as Triameen® C, Triameen® OV, Triameen® T, Tetrameen® OV and Tetrameen® T (Akzo Nobel); - aliphatic, cycloaliphatic or arylaliphatic amines having one primary and at least one tertiary amino group, especially N,N-diethyl-1,2-ethanediamine, N,N- dimethyl-1,3-propanediamine, N,N-diethyl-1,3- propanediamine and N,N-diethyl-1,4-pentanediamine. Preferred amines A2 contain at least 4 carbon atoms, especially 4 to 18 carbon atoms, and optionally have ether or secondary amino groups. Particularly preferred amines A2 are amines which are selected from the group consisting of butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, docosylamine, 2-ethyl-1-hexylamine, benzylamine, 1- or 2-phenylethylamine, N-hexyl-1,2-ethanediamine, N-(2- ethylhexyl)-1, 2-ethanediamine, N-cyclohexyl-1,2- ethanediamine, N-butyl-1,3-propanediamine, N-hexyl-1,3- propanediamine, N-(2-ethylhexyl)-1,3-propanediamine, N- dodecyl-1,3-propanediamine, N-cyclohexyl-1,3- propanediamine, cocoalkylamine, soyaalkylamine, oleylamine, N-cocoalkyl-1,3-propanediamine, N-oleyl- 1,3-propanediamine and N-soyaalkyl-1,3-propanediamine. The polyepoxide E has an epoxy equivalent weight (EEW) of 65 to 500 g/eq. Polyepoxides E can be prepared in a known manner, for example from the oxidation of the corresponding olefins or from the reaction of epichlorohydrin with the corresponding polyols, polyphenols or amines. Especially suitable as polyepoxides E are what are known as polyepoxide liquid resins, referred to hereinafter as "liquid resin". They have a glass transition temperature which is typically below 25 oC, in contrast to solid polyepoxide resins which can be comminuted to powders which are pourable at 25 °C and have a glass transition temperature above 25 °C. Polyepoxides which are known to the person skilled in the art as reactive diluents are also referred to m the present document as liquid resins. In one embodiment, the polyepoxide E is an aromatic polyepoxide. Suitable examples for this purpose are liquid resins of the formula (IX) where R' and R" are each independently a hydrogen atom or a methyl group, and s has an average value of 0 to 1. Preference is given to those liquid resins of the formula (IX) in which the index s has an average value of less than 0.2. The liquid resins of the formula (IX) are diglycidyl ethers of bisphenol A, bisphenol F and bisphenol A/F, where A represents acetone and F formaldehyde, which serve as reactants for preparation of these bisphenols. A bisphenol A liquid resin accordingly has methyl groups, a bisphenol F liquid resin hydrogen atoms, and a bisphenol A/F liquid resin both methyl groups and hydrogen atoms, as R' and R" in formula (IX) . In the case of bisphenol F, it is also possible for positional isomers to be present, especially derived from 2,4'- and 2,2'-hydroxyphenylmethane. Such liquid resins are commercially available, for example as Araldite® GY 204, Araldite® GY 250, Araldite® GY 260, Araldite® GY 281, Araldite® GY 282, Araldite® GY 285, Araldite® PY 304, Araldite® PY 720 (from Huntsman); D.E.R.® 330, D.E.R.® 331, D.E.R.® 332, D.E.R.® 336, D.E.R.® 354, D.E.R.® 351, D.E.R.® 352, D.E.R.® 356 (from Dow); Epikote® 162, Epikote® 827, Epikote® 828, Epikote® 158, Epikote® 862, Epikote® 169, Epikote® 144, Epikote® 238, Epikote® 232, Epikote® 235 (from Hexion), Epalloy® 7190, Epalloy® 8220, Epalloy® 8230, Epalloy® 7138, Epalloy® 7170, Epalloy® 9237-70 (from CVC), Chem Res® E 20, Chem Res® E 30 (from Cognis), Beckopox® EP 116, Beckopox® EP 140 (from Cytec). Further suitable aromatic polyepoxides E are the glycidylization products of - dihydroxybenzene derivatives such as resorcinol, hydroquinone and catechol; - further bisphenols or polyphenols such as bis (4- hydroxy-3-methylphenyl)methane, 2, 2-bis(4-hydroxy-3- methylphenyl)propane (bisphenol C), bis(3,5-dimethyl- 4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4- hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxy- phenyl)propane, 2,2-bis(4-hydroxy-3-tert-butyl- phenyl)propane, 2,2-bis(4-hydroxyphenyl)butane (bisphenol B) , 3,3-bis(4-hydroxyphenyl)pentane, 3,4- bis(4-hydroxyphenyl)hexane, 4,4-bis(4-hydroxyphenyl)- heptane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z) , 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC), 1,1-bis(4-hydroxyphenyl)-1-phenyl- ethane, 1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene) (bisphenol P), 1,3-bis[2-(4-hydroxyphenyl)-2- propyl]benzene) (bisphenol M), 4,4'-dihydroxydiphenyl (DOD), 4,4'-dihydroxybenzophenone, bis(2- hydroxynaphth-1-yl)methane, bis(4-hydroxynaphth-1- yl)methane, 1,5-dihydroxynaphthalene, tris(4- hydroxyphenyl)methane, 1,1,2,2-tetrakis(4- hydroxyphenyl)ethane, bis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl) sulfone; - condensation products of phenols with formaldehyde, which are obtained under acidic conditions, such as phenol novolacs or cresol novolacs; - aromatic amines, such as aniline, toluidine, 4- aminophenol, 4,4'-methylenediphenyldiamine (MDA), 4,4'-methylenediphenyldi(N-methyl)amine, 4,4'-[1,4- phenylenebis(1-methylethylidene)]bisaniline (bisaniline P), 4,4'-[1,3-phenylenebis(1- methylethylidene)]bisaniline (bisaniline M). Commercially available epoxy novolacs are, for example, Araldite® EPN 1179, Araldite® GY 289, Araldite® PY 307-1 (from Huntsman), D.E.N.® 425 and D.E.N.® 431 (from Dow), Epalloy® 8240 and Erisys® RF50 (from CVC); a commercially available N,N-diglycidylaniline is, for example, Epikote® Resin 4 93 (from Hexion); a commercially available resorcinol diglycidyl ether is, for example, Erisys® RDGE (from CVC). In a further embodiment, the polyepoxide E is an aliphatic or cycloaliphatic polyepoxide, for example - diglycidyl ether; - a glycidyl ether of a saturated or unsaturated, branched or unbranched, cyclic or open-chain C2 to C30 diol, for example ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, a polypropylene glycol, dimethylolcyclohexane, neopentyl glycol; - a glycidyl ether of a tri- or tetrafunctional, saturated or unsaturated, branched or unbranched, cyclic or open-chain polyol such as castor oil, trimethylolpropane, trimethylolethane, penta- erythritol, sorbitol or glycerol, and alkoxylated glycerol or alkoxylated trimethylolpropane; - a hydrogenated bisphenol A, F or A/F liquid resin, or the glycidylization products of hydrogenated bisphenol A, F or A/F; - an N-glycidyl derivative of amides or heterocyclic nitrogen bases, such as triglycidyl cyanurate and triglycidyl isocyanurate, and reaction products of epichlorohydrin and hydantoin. Aliphatic or cycloaliphatic liquid resins are, for example, commercially available as Araldite® DY-C, Araldite® DY-F, Araldite® DY-H, Araldite® DY-T, Araldite® DY 0397, Araldite® DY 3601 (from Huntsman), D.E.R.® 732, D.E.R.® 736 (from Dow); Heloxy® BD, Heloxy® HD, Heloxy® TP, Epikote® 877 (from Hexion), Beckopox® EP 075 (from Cytec). In a further embodiment, the polyepoxide E is a polyepoxide which has been prepared from the oxidation of olefins, for example from the oxidation of vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene, isoprene, 1,5- hexadiene, butadiene, polybutadiene or divinylbenzene. The polyepoxide E is preferably a diepoxide El. The diepoxide E1 is more preferably selected from the group consisting of a bisphenol A, bisphenol F and bisphenol A/F diglycidyl ether having an epoxy equivalent weight of 156 to 250 g/eq, especially Araldite® GY 250, Araldite® PY 304, Araldite® GY 282 (from Huntsman); D.E.R.® 331, D.E.R.® 330 (from Dow); Epikote® 828, Epikote® 862 (from Hexion), N,N- diglycidylaniline and a polyglycol diglycidyl ether having an epoxy equivalent weight of 170 to 340 g/eq, especially D.E.R.® 732 and D.E.R.® 736 (from Dow). Suitable diketones K1 of the formula (IV) are especially 2,4-pentanedione (= acetylacetone), 3- alkylated 2,4-pentanedione, i.e. especially 3-methyl-, 3-ethyl-, 3-propyl-, 3-isopropyl-, 3-butyl-, 3-tert- butyl-, 3-cyclohexyl- and 3-phenyl-2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5,5,5- hexafluoro-2,4-pentanedione, 3,5-heptanedione, 3,5- octanedione, 2,4-octanedione, 6-methyl-3,5- heptanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 2,2,4,6,6-pentamethyl-3,5-heptanedione, 1-phenyl-1,3- butanedione, 2-acetylcyclopentanone, 2-acetylcyclo- hexanone, 2-benzoylcyclopentanone and 2- benzoylcyclohexanone. Preferred diketones K1 are selected from the group consisting of 2,4-pentanedione, 3-methyl-, 3-ethyl-, 3- propyl-, 3-isopropyl-, 3-butyl-, 3-tert-butyl-, 3- cyclohexyl- and 3-phenyl-2,4-pentanedione, 3,5- heptanedione, 6-methyl-3,5-heptanedione, 2,2,6,6- tetramethyl-3, 5-heptanedione, 2,2,4,6,6-pentamethyl- 3,5-heptanedione, 2-acetylcyclopentanone and 2- acetylcyclohexanone. A particularly preferred diketone Kl is 2,4- pentanedione. Suitable diketones K2 of the formula (V) are especially diketones selected from the group consisting of 2,5- hexanedione (= acetonylacetone), 3,4-dimethyl-2,5- hexanedione, 1,2-dibenzoylethane, 1,4-bis(2-furyl)-1,4- butanedione and 2-(2-oxopropyl)cyclopentanone. A preferred diketone K2 is 2,5-hexanedione. A preferred process for preparing a compound VB of the formula (I) or (II) is characterized in that (a) at least one polyamine A1 having two primary amino groups, (P) at least one amine A2, (γ) at least one diepoxide E1 and (5) at least one diketone K1 of the formula (IV) or K2 of the formula (V) are reacted with one another in a molar ratio of 1:(0.8 to 1.2): (0.8 to 1.2): (0.8 to 1.2), especially 1:1:1:1, in one of the sequences already described, i.e. via an intermediate of the formula (III), or via an intermediate of the formula (VI) or (VII). In a first particularly preferred process, at least one polyamine Al in the form of a polyoxyalkylenediamine, at least one amine A2 and at least one diepoxide E1 are reacted in a molar ratio of 1:(0.8 to 1.2): (0.8 to 1.2), especially 1:1:1, to give an adduct AE, and the latter is subsequently reacted in a molar ratio of 1:(0.8 to 1.2), especially 1:1, with at least one diketone K1 of the formula (IV) or K2 of the formula (V) to give a compound VB of the formula (1a) or (IIa). In a second particularly preferred process, at least one polyamine A1 in the form of a polyalkyleneamine and at least one diketone Kl of the formula (IV) or K2 of the formula (V) are reacted in a molar ratio of 1: (0.8 to 1.2), especially 1:1, to give an alkylated polyamine All, and the latter is subsequently reacted in a molar ratio of 1:(0.8 to 1.2): (0.8 to 1.2), especially 1:1:1, with at least one amine A2 and at least one diepoxide E1 to give a compound VB of the formula (Ib) or (IIb). It is also possible to initially charge a compound VB of the formula (Ia) or (IIa) and to prepare a compound VB of the formula (Ib) or (IIb) therein - effectively in a solvent. In this way, it is possible in a one-pot process to prepare a mixture of at least one compound VB of the formula (Ia) or (IIa) and at least one compound VB of the formula (Ib) or (IIb). The compound VB of the formula (I) or (II) is preparable in a simple process from readily available raw materials. It preferably has at least two NH hydrogen atoms which are active toward epoxy groups and at least some of which are in the form of secondary amino groups. Secondary amino groups have formed more particularly from the reaction of primary amino groups with epoxy groups. The compound VB, or the A radical, preferably does not have any primary amino groups. If it nevertheless has primary amino groups, the number thereof is preferably 1 or 2. As a result, it barely reacts, if at all, with carbon dioxide gas from the air and as a result forms a low level of carbonate and/or carbamate salts, if any. The absence of such salt formation is very advantageous especially in the case of use of the compound VB as a hardener for epoxy resins, since this means that there cannot be any salt- related optical and/or mechanical defects in the curing of the epoxy resin, such as more particularly the film opacity known as "blushing". The acylenamino groups of the formula (i) from the reaction with the diketone K1 of the formula (IV) - or the pyrrole groups from the reaction with the diketone K2 of the formula (V) - of the compound VB are stable, even in the presence of water and at elevated temperature, for example at 60oC. Even in the presence of moisture, they do not react to any significant degree with epoxy groups, in spite of the enamine nitrogen in the acylenamino group; the latter is a vinylogous amido group in which the hydrogen atom of the enamine nitrogen can enter into a stable intramolecular hydrogen bond with the carbonyl oxygen. The compound VB has a comparatively low viscosity for polyepoxide-polyamine adducts. The compound VB of the formula (I) or (II) can be used as a reactant for substances which have groups reactive toward NH and OH groups. Groups reactive toward NH and OH groups are, for example, isocyanate, isothiocyanate, cyclocarbonate, epoxide, episulfide, aziridine, acryloyl, methacryloyl, 1-ethynylcarbonyl, 1- propynylcarbonyl, maleimide, citraconimide, vinyl, isopropenyl or allyl groups. The compound VB can advantageously be used as a hardener for substances which have at least two of the aforementioned reactive groups, especially as a hardener for polyisocyanates and polyepoxides. The compound VB is especially suitable as a hardener for epoxy resins. The compound VB is advantageously used as a constituent of a mixture which comprises further substances suitable as hardeners for epoxy resins. The compound VB of the formula (I) or (II) is most suitable as a constituent of a water-dilutable hardener for aqueous epoxy resin dispersions. The present invention further provides a hardener composition comprising at least one compound VB of the formula (I) or (II), preferably at least one compound VB of the formula (Ia) or (IIa) and at least one compound VB of the formula (Ib) or (IIb), as described above. A hardener composition comprising at least one compound VB of the formula (Ia) or (IIa) and at least one compound VB of the formula (Ib) or (IIb) is also referred to hereinafter as hardener composition H1. A hardener composition H1 is of similar composition to the mixture of an emulsifier and a coemulsifier described in EP 0 567 831 A1. The difference from the emulsifier-coemulsifier mixture described in EP 0 567 831 Al is that the primary amino groups have been converted or capped in another way, namely by means of at least one diketone K1 of the formula (IV) or a diketone K2 of the formula (V) instead of by reductive alkylation by means of aldehyde and formic acid. The capping of primary amino groups by means of reductive alkylation forms secondary amino groups, whereas the reaction with a diketone K1 or K2 caps the primary amino groups such that they no longer have any reactivity toward epoxy groups. Surprisingly, the hardener compositions H1 described, however, are nevertheless just as suitable as hardeners in epoxy resin compositions as the emulsifier-coemulsifier mixtures described in EP 0 567 831 A1. The capping of the primary amino groups by means of a diketone K1 or K2 has a series of advantages over the reductive alkylation described in EP 0 567 831 A1. One is that the reaction with diketone is substantially more rapid, which means a greatly shortened production time for a corresponding water-dilutable hardener. In addition, the reaction with diketone does not form CO2, which can form troublesome carbonate and carbamate salts with primary amino groups, as is the case in the reductive alkylation in EP 0 567 831 A1. The water obtained in the reaction with the diketones K1 or K2 is not disruptive in the case of use as a water-dilutable hardener. The hardener composition, especially the hardener composition H1, preferably comprises, in addition to at least one compound VB of the formula (I) or (II), (b) at least one adduct AD formed from at least one polyamine A3 having at least two amino groups in the form of primary or secondary amino groups and at least one polyepoxide E having an epoxy eguivalent weight (EEW) of 65 to 500 g/eq, where the adduct AD has terminal primary and/or secondary amino groups, Cc) optionally at least one polyamine A4 having at least two amino groups in the form of primary or secondary amino groups, and (d) optionally water. Such a preferred hardener composition is referred to hereinafter as hardener composition H2. The hardener composition H2 preferably comprises a mixture of a compound VB of the formula (Ia) or (IIa) and a compound VB of the formula (Ib) or (IIb), as described above. Such a mixture can display self- emulsifying action in the hardener composition when mixed with water. The compound VB of the formula (Ia) or (IIa) is present advantageously in an amount of 0.5 to 1.5 parts by weight, based on 1 part by weight of the compound VB of the formula (Ib) or (IIb). In addition, an adduct AD is present in the hardener composition H2. In one embodiment, suitable polyamines A3 for preparation of a suitable adduct AD are the same polyamines as already mentioned above as polyamines Al having at least two primary amino groups. In a further embodiment, suitable polyamines A3 are the same polyamines as already mentioned as amines A2 having one primary and at least one secondary amino group. In a further embodiment, suitable polyamines A3 are polyamines having at least two secondary amino groups, especially N,N' -dibutylethylenediamine; N,N'-di-tert- butylethylenediamine, N, N' -diethyl-1,6-hexanediamine, 1-(1-methylethylamino)-3-(1-methylethylaminomethyl)- 3,5,5-trimethylcyclohexane (Jefflink® 754 from Huntsman), N4-cyclohexyl-2-methyl-N2-(2-methylpropyl)- 2, 4-pentanediamine, N,N'-dialkyl-1,3-xylylenediamine, bis(4-(N-alkylamino)cyclohexyl)methane, 4,4'- trimethylenedipiperidine, N-alkylated polyetheramines, for example the Jeffamine® products SD-231, SD-401, SD-404 and SD-2001 (from Huntsman). Preferred polyamines A3 for preparation of an adduct AD are those selected from the group consisting of firstly polyoxyalkylenediamines of the formula (VIII) having a molecular weight of at most 1000 g/mol, preferably Jeffamine® D-230, Jeffamine® D-4 00, Jeffamine® XTJ-511, Jeffamine® EDR-104, Jeffamine® EDR-148, Jeffamine® EDR-176; Polyetheramine D 230, Polyetheramine D 400, PC /Amine® DA 250, PC Amine® DA 4 00 or PC Amine® DA 650, and secondly isophoronediamine (IPDA), 2,2,4- and 2, 4, 4-trimethylhexamethylenediamine (TMD), 1,3- xylylenediamine (meta-xylylenediamine or MXDA), 2- butyl-2-ethyl-1,5-pentanediamine (C11-neodiamine), N- ethyl-1,3-propanediamine and N-cyclohexyl-1,3- propanediamine. Suitable and also preferred polyepoxides E for preparation of a suitable adduct AD are the same polyepoxides as already described for preparation of a compound VB of the formula (I) or (II), especially the diepoxides E1 mentioned. A particularly suitable adduct AD is the adduct of two moles of polyamine A3 having two amino groups in the form of primary or secondary amino groups and one mole of diepoxide E1. The adduct AD is present in the hardener composition H2 advantageously in an amount of 0.5 to 1.5 parts by weight, based on 1 part by weight of the compound VB of the formula (I) or (II). Suitable polyamines A4 are the same polyamines as already mentioned as polyamines A3 for preparation of an adduct AD, and additionally what are known as polyamidoamines. A polyamidoamine is the reaction product of a mono- or polybasic carboxylic acid, or the esters or anhydrides thereof, and an aliphatic, cycloaliphatic or aromatic polyamine, the polyamine being used in a stoichiometric excess. A polybasic carboxylic acid used is typically what is known as a dimer fatty acid, and the polyamine used is typically a polyalkyleneamine, for example TETA. Commercially available polyamidoamines are, for example, Versamid® 100, 125, 140 and 150 (from Cognis), Aradur® 223, 250 and 848 (from Huntsman), Euretek® 3607, Euretek® 530 (from Huntsman), Beckopox® EH 651, EH 654, EH 655, EH 661 and EH 663 (from Cytec). The polyamine A4 present may be the same polyamine as the polyamine A3 used to prepare an adduct AD, for example by virtue of an excess of polyamine A3 having been used in the reaction with the polyepoxide E, such that unreacted polyamine A3 is still present after the reaction of all epoxy groups. Preferred polyamines A4 are relatively hydrophobic polyamines, especially selected from the group consisting of isophoronediamine, bis(4-aminocyclo- hexyl)methane, (Hi2-MDA), bis(4-amino-3-methylcyclo- hexyl)methane, 2,2,4- and 2,4,4-trimethylhexa- methylenediamine (TMD), 1,3-xylylenediamine (meta- xylylenediamine or MXDA) and 2-butyl-2-ethyl-1,5- pentanediamine (C11-neodiamine). The polyamine A4 is present in the hardener composition H2 advantageously in an amount of 0.01 to 0.5 part by weight, based on 1 part by weight of the sum of the compound VB of the formula (I) or (II) and of the adduct AD. The hardener composition H2 preferably comprises water, especially in an amount of 20 to 90% by weight, based on the overall hardener composition. The hardener composition H2 more preferably comprises at least one compound VB of the formula (Ia) or (IIa) , at least one compound VB of the formula (Ib) or (IIb), at least one adduct AD, at least one polyamine A4 and water. A hardener composition H2 can be prepared in any desired sequence. In a preferred preparation process, a one-pot process, at least one compound VB of the formula (I) or (II) is initially charged, and the adduct AD is prepared therein - effectively in a solvent. The adduct AD is advantageously prepared at elevated temperature, fox example at a temperature in the range from 60 to 120oC. Subsequently, a polyamine A4 is added to the reaction mixture. And finally, the reaction mixture is diluted with water until the desired solids content is attained, for example a solids content in the range from 10 to 80% by weight. Compared to a hardening composition as described in EP 0 567 831 A1, the hardener composition described here has the great advantage that the preparation of the compound VB of the formula (I) or (II) is significantly more rapid than the preparation of the emulsifier and coemulsifier described in EP 0 567 831 Al. The hardener composition H2 may comprise further substances in the form of assistants and additives. The hardener composition H2 preferably comprises water and has a solids content in the range from 10 to 80% by weight. Such a hardener composition is referred to hereinafter as aqueous hardener composition HW. An aqueous hardener composition HW is in the form of an emulsion. The compound VB of the formula (I) or (II) may have an emulsifying effect, especially when at least one compound VB of the formula (Ia) or (IIa) and at least one compound VB of the formula (Ib) or (IIb) is present. The appearance of the emulsion depends on the fineness of the emulsion droplets. Fine emulsions (microemulsions) are clear or slightly opalescent and typically have the Tyndall effect, whereas coarse emulsions (macroemulsions) have a turbid to milky appearance. Microemulsions have particles which are within the order of magnitude of visible light or smaller. A microemulsion typically has a mean particle size of less than 100 nm. The aqueous hardener composition HW is preferably present as a microemulsion within a broad temperature range, especially in the range between 0 and 50°C. The aqueous hardener composition HW typically has a relatively low viscosity, such that it is easy to handle at room temperature. A preferred aqueous hardener composition HW comprising, as well as water, at least one compound VB of the formula (Ia) or (IIa), at least one compound VB of the formula (Ib) or (IIb), at least one adduct AD and at least one polyamine A4 is in the form of a thermodynamically stable emulsion and has a clear to slightly turbid appearance. Such an aqueous hardener composition HW can be diluted further by simply stirring water in. Such an aqueous hardener composition is typically storage-stable up to a temperature of 50°C. "Storage-stable" refers to the property that the aqueous hardener composition does not coalesce in the course of storage, i.e. does not exhibit any phase separation, and remains useable in the manner intended. Storage stability up to 50 °C is an important property which is rarely fulfilled by aqueous epoxy hardeners according to the prior art. One of the hardener compositions described is advantageously used as a constituent of an epoxy resin composition, and acts as a hardener for at least one epoxy resin. The present invention thus further provides a two- or three-pack epoxy resin composition consisting of a hardener component C1 and a resin component C2 and optionally a further component C3. The two- or three-pack epoxy resin composition can be used especially as an adhesive, sealing compound, potting compound, coating, floor covering, paint, varnish, primer or undercoat, preferably as a coating, especially as a floor coating. In a first embodiment, the epoxy resin composition consists of a hardener component C1 and a resin component C2. The hardener component C1 comprises at least one hardener composition as described above. The resin component C2 comprises at least one epoxy resin. Suitable epoxy resins are epoxy resins customary in epoxy chemistry, for example - a polyepoxide E as already specified above; - a bisphenol A, F or A/F solid resin which is of similar composition to the liquid resins of the formula (IX) already specified as the polyepoxide E, but instead of the index s has a value of 2 to 12, and also has a glass transition temperature above 25°C; - one of the epoxy resins mentioned, which has been modified hydrophilically by the reaction with at least one polyoxyalkylenepolyol. Preferred epoxy resins are bisphenol A, F or A/F solid or liquid resins, as available commercially, for example, from Dow, Huntsman and Hexion. The epoxy resin may comprise what is known as a reactive diluent. Suitable reactive diluents are mono- and polyepoxides, for example the glycidyl ethers of mono- or polyhydric phenols and aliphatic or cycloaliphatic alcohols, especially the polyglycidyl ethers of di- or polyols already mentioned as aliphatic or cycloaliphatic polyepoxides E, and additionally especially phenyl glycidyl ether, cresyl glycidyl ether, p-n-butylphenyl glycidyl ether, p-tert- butylphenyl glycidyl ether, nonylphenyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, and glycidyl ethers of natural alcohols, for example C8- to C10-alkyl glycidyl ethers or C12- to C14-alkyl glycidyl ethers, commercially available as Erysis® GE-7 and Erysis® GE-8 (from CVC) . The addition of a reactive diluent to the epoxy resin causes a reduction in the viscosity and - in the hardened state of the epoxy resin composition - a reduction in the glass transition temperature and in the mechanical values. When the hardener composition C1 comprises an aqueous hardener composition HW, the resin component C2 preferably comprises either what is known as an "emulsifiable epoxy resin" or an aqueous epoxy resin dispersion. An epoxy resin dispersion preferably comprises, as well as water, at least one epoxy resin as specified above, and additionally at least one emulsifier, especially a nonionic emulsifier, for example an alkyl or alkylaryl polyglycol ether, especially a polyalkoxylated alkylphenol such as alkylphenoxypoly(ethyleneoxy)ethanol, for example a polyadduct formed from nonylphenol and ethylene oxide, containing up to 30 mol of ethylene oxide per mole of nonylphenol. Commercial epoxy resin dispersions are, for example, Sika® Repair/Sikafloor® EpoCem® Module A (from Sika Schweiz AG), Araldite® PZ 323, Araldite® PZ 756/67, Araldite® PZ 3961 (from Huntsman), XZ 92598.00, XZ 92546.00, XZ 92533.00 (from Dow), Waterpoxy® 1422, Waterpoxy® 1455 (from Cognis), Beckopox® EP 384w, Beckopox® EP 385w, Beckopox® EP 386w, Beckopox® EP 2340w, Beckopox® VEP 2381w (from Cytec). Epoxy resin dispersions typically have a solids content in the range of 40-65% by weight. An emulsifiable epoxy resin preferably contains at least one emulsifier as already mentioned above as a constituent of an epoxy resin dispersion. Commercial emulsifiable epoxy resins are, for example, Araldite® PY 340 and Araldite® PY 340-2 (from Huntsman), Beckopox® 122w and Beckopox® EP 147w (from Cytec). Both the hardener component C1 and the resin component C2 may comprise further assistants and additives, for example - nonreactive diluents, solvents or film-forming assistants, such as toluene, xylene, methyl ethyl ketone, 2-ethoxyethanol, 2-ethoxyethyl acetate or benzyl alcohol, ethylene glycol, diethylene glycol butyl ether, dipropylene glycol butyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, N- methylpyrrolidone, propylene glycol butyl ether, propylene glycol phenyl ether, bisphenols and phenol resins, diphenylmethane, diisopropylnaphthalene, mineral oil fractions, for example Solvesso® products (from Exxon), aromatic hydrocarbon resins, sebacates, phthalates, organic phosphoric and sulfonic esters and sulfonamides; - reactive diluents and extenders, for example reactive diluents containing epoxy groups as already mentioned above, epoxidized soybean oil, butyrolactone, triphenyl phosphite, and additionally polyamides, polymers having carboxyl groups, isocyanates, silicones having reactive groups, polysulfides, butadiene-acrylonitrile copolymers and polyurethanes; - polymers, for example polyamides, polysulfides, polyvinyl formal (PVF), polyvinyl butyral (PVB), polyurethanes (PUR), styrene-butadiene copolymers, homo- or copolymers of unsaturated monomers, especially from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate and alkyl (meth)acrylates, especially chlorosulfonated polyethylenes and fluorinated polymers, sulfonamide-modified melamines; - thermoplastic polymers such as polyether sulfone, polyether imide and bitumen; - inorganic and organic fillers, for example ground or precipitated calcium carbonates, which have optionally been coated with fatty acids, especially stearates, barite (heavy spar), talcs, quartz flours, quartz sand, dolomites, wollastonites, kaolins, mica (potassium aluminum silicate), molecular sieves, aluminum oxides, aluminum hydroxides, silicas, cements, gypsums, fly ashes, carbon black, graphite, metal powders such as aluminum, copper, iron, silver or steel, PVC powders or hollow spheres; - fibers, for example of polymer or glass; - pigments, for example titanium dioxide or iron oxides; - accelerators which accelerate the reaction between amino groups and epoxy groups, for example acids or compounds hydrolyzable to acids, for example organic carboxylic acids such as acetic acid, benzoic acid, salicylic acid, 2-nitrobenzoic acid, lactic acid, organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, sulfonic esters, other organic or inorganic acids, for example phosphoric acid, or mixtures of the aforementioned acids and acid esters; and also tertiary amines such as 1,4- diazabicyclo[2.2.2]octane, benzyldimethylamine, a- methylbenzyldimethylamine, 2-(dimethylaminomethyl)- phenol or 2,4,6-tris(dimethylaminomethyl)phenol, triethanolamine, dimethylaminopropylamine, salts of such tertiary amines, and quaternary ammonium salts, for example benzyltrimethylammonium chloride; - rheology modifiers, such as especially thickeners, for example sheet silicates such as bentonites, derivatives of castor oil, hydrogenated castor oil, polyamides, polyurethanes, urea compounds, fumed silicas, cellulose ethers and hydrophobically modified polyoxyethylenes; - adhesion improvers, for example organoalkoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-amino- propyltrimethoxysilane, N-(2-aminoethyl)-3-amino- propyltrimethoxysilane, N-(2-aminoethyl)-N'-[3- (trimethoxysilyl)propyl]ethylenediamine, 3-ureido- propyltrimethoxysilane, 3-chloropropyltrimethoxy- silane, vinyltrimethoxysilane, or the corresponding organoalkoxysilanes with ethoxy instead of the methoxy groups; - heat, light or UV stabilizers; - flame-retardant substances; - surface-active substances, for example wetting agents, leveling agents, deaerating agents or defoamers; - biocides, for example algaecides, fungicides or fungal growth inhibitors. The hardener component C1 and the resin component C2 can each be stored in a suitable package or arrangement, for example a drum, a hobbock, a pouch, a bucket, a canister, a cartridge or a tube, over several months up to a year and longer before use thereof, without the particular properties thereof changing to a degree relevant for the use thereof. The mixing ratio between the hardener component C1 and the resin component C2 is preferably selected such that the groups reactive toward epoxy groups in the hardener component C1 are in a suitable ratio to the epoxy groups of the resin component C2. Suitably, 0.7 to 1.5 and preferably 0.9 to 1.1 equivalents of NH hydrogens active toward epoxy groups are present before the curing per equivalent of epoxy groups. In parts by weight, the mixing ratio between the hardener component C1 and the resin component C2 is typically in the range from 1:10 to 10:1. Before or during the application, the two components are mixed with one another by means of a suitable process. The mixing can be effected continuously or batchwise. If the mixing is effected before the application, it must be ensured that the time which passes between the mixing of the components and the application is not too long, since the result may be defects, for example a slowed or incomplete buildup of the adhesion to the solid surface. With the mixing, the hardening reaction begins. The NH hydrogens which are reactive toward epoxy groups and are present in the epoxy resin composition react with epoxy groups present, which ultimately cures the composition. The present invention thus also describes a cured composition which is obtained by mixing the components of a two- or three-pack epoxy resin composition as described above. The application and the hardening are effected advantageously at temperatures in the range from 5 to 50°C. The hardening proceeds rapidly and completely. The hardening rate depends on the ambient temperature and on any accelerators present. The rate of hardening can be determined by means of a Byk Gardner drying time recorder. This involves pulling a needle over a film applied to a glass strip at a defined speed, and, according to the degree of hardening of the film, a "deep trace" is first drawn into the film, then there is a "film tear", which ultimately becomes a "surface trace" before the film is so dry that the needle no longer leaves any visible trace. "Flow" refers to the moment where the applied composition no longer flows together properly, i.e. the start of the deep trace. "Soft gel" refers to the moment where the film begins to tear. "Hard gel" refers to the moment where the film tear becomes the surface trace, and "cured" refers to the moment where the surface trace disappears and the needle no longer leaves any visible trace. The hardening of the epoxy resin composition described typically gives rise to clear films with a smooth surface and high shine, which have a high hardness and toughness and excellent adhesion on a wide variety of different substrates. The epoxy resin composition can be used as an adhesive, sealing compound, potting compound, coating, floor covering, paint, varnish, primer or undercoat, for which important properties may be properties such as watertightness, corrosion protection, chemical resistance and/or high hardness and toughness. They may be used, for example, in construction or civil engineering, in the manufacture or repair of industrial goods or consumer goods. In a further embodiment, the epoxy resin composition consists of a hardener component C1, a resin component C2 and a further component C3. In this embodiment, the hardener component C1 preferably comprises at least one aqueous hardener composition HW, the resin component C2 preferably comprises at least one epoxy resin dispersion, and the component C3 comprises at least one hydraulically setting mineral substance. Such an epoxy resin composition is also referred to as ECC composition (ECC stands for "epoxy cement concrete"). Suitable hydraulically setting mineral substances are - substances which are referred to conventionally as hydraulic binders and are hardenable with water, even under water, such as lime and especially cement; - latently hydraulic binders which set with water under the action of additives, such as especially blast furnace slag for fly ash; - substances which react with water only under air, known as nonhydraulic binders, such as especially gypsum, Sorel cement, anhydrite, magnesia binders and white lime. Thus, in the present document, not only cements but especially also calcium sulfate in the form of anhydrite, hemihydrate gypsum or dihydrate gypsum, or blast furnace slags, are referred to as hydraulically setting substances. The hydraulically setting substance is preferably a cement, especially a cement according to European standard EN 197. Preferred cements are portland cements, sulfoaluminate cements and high-alumina cements, especially portland cement. Mixtures of cements can lead to particularly good properties. Particularly suitable are mixtures of at least one portland cement with either at least one sulfoaluminate cement or with at least one high-alumina cement. For rapid hardening, cementitious quick-setting binders in particular are used, which preferably comprise at least one high-alumina cement or another aluminate source, for example aluminate-donating clinker, and optionally calcium sulfate in the form of anhydrite, hemihydrate or dihydrate gypsum and/or calcium hydroxide. Component C3 optionally comprises further substances, for example various sand types or quartz flours, fly ash, pigments, and assistants and additives customary in the cement industry, for example plasticizers or setting accelerators or defoamers. Component C3 of an ECC composition is typically in pulverulent form, whereas the hardener component C1 and the resin component C2 are in liquid form. An ECC composition is typically used as a high-quality coating or mortar, which are moisture-proof, have good mechanical properties, low shrinkage and good adhesion, especially on moist substrates, for example as a floor covering, barrier .layer for sealing from wetness and moisture, as a screed, jointing mortar or tile adhesive, as a leveling, spackling or primer compound, or as a repair mortar. In addition, such ECC compositions are notable for high chemical resistance. The epoxy resin compositions described are applied to at least one substrate, suitable substrates being the following: - glass, glass ceramic, concrete, mortar, brick, tile, gypsum and natural stone, such as granite or marble; - metals or alloys, such as aluminum, steel, iron, nonferrous metals, galvanized metals; - leather, textiles, paper, wood, resin-bonded woodbase materials, resin-textile composite materials and further polymer composites; - polymers such as polyvinyl chloride (rigid and flexible PVC), acrylonitrile-butadiene-styrene copolymers (ABS), SMC (sheet molding compounds), polycarbonate (PC), polyamide (PA), polyester, poly(methyl methacrylate) (PMMA) , polyester, epoxy resins, polyurethanes (PUR), polyoxymethylene (POM), polyolefins (PO), polyethylene (PE) or polypropylene (PP), ethylene/propylene copolymers (EPM) and ethylene-propylene-diene terpolymers (EPDM), and the polymers may preferably be surface-treated by means of plasma, corona or flame; - coated substrates such as powder-coated metals or alloys; and paints and other coating materials. If required, the substrates may be pretreated before the application of the epoxy resin composition. Such pretreatments include especially physical and/or chemical cleaning processes, for example grinding, sand blasting, shot blasting, brushing or the like, dusts which arise advantageously being removed by suction, and also treatment with detergents or solvents, or the application of an adhesion promoter, of an adhesion promoter solution or of a primer. Examples 1. Description of the test methods The viscosity was measured on a Rheotec RC30 cone-plate viscometer (cone diameter 25 mm, cone angle 1°, cone tip-plate distance 0.05 mm, shear rate 50 s-1) . The viscosities measured at 50°C and at 20°C were reported, respectively, as "η50oc" in Table 1 and as "η20oc" in Table 2. 2. Raw materials used Jeffamine® ED-2003 (Huntsman) Polyoxyalkylenediamine based on propoxylated polyethylene glycol, mean molecular weight = 2000 g/mol Armeen® CD (Akzo Nobel) Cocoalkylamine (C12 fatty amine), mean molecular weight = 200 g/mol Araldite® GY 250 (Huntsman) Bisphenol A diglycidyl ether, EEW = 187 g/eq, mean molecular weight thus approx. 37 5 g/mol N4-Amine (BASF) N,N'-Bis(3- aminopropyl)ethylenediamine, molecular weight = 174 g/mol Tetraethylenepentamine Technical-grade, molecular (Delamine) ("TEPA") weight = 18 9 g/mol Benzylamine Molecular weight = 107 g/mol 2,5-Hexanedione (Wacker) Molecular weight = 114 g/mol 2,4-Pentanedione (Wacker) Molecular weight = 100 g/mol 2-Ethylhexylamine Molecular weight = 129 g/mol Dimethylacrylamide Molecular weight = 99 g/mol Butylene oxide Molecular weight = 72 g/mol Jeffamine® D-230 (Huntsman) Polypropylene glycol diamine, mean molecular weight = 240 g/mol Isophoronediamine (Evonik) l-Amino-3-aminomethyl-3,5,5- ("IPDA") trimethylcyclohexane, molecular weight =17 0 g/mol meta-Xylylenediamine (Mitsubishi 1,3-Bis(aminomethyl)benzene, Gas Chem.) ("MXDA") molecular weight = 136 g/mol 3. Preparation of hardener compositions of the H1 type Example 1 A round-bottom flask under a nitrogen atmosphere was initially charged with 200.0 g of Jeffamine® ED-2003 and 20.0 g of Armeen® CD at a temperature of 90°C. With good stirring, 37.5 g of Araldite® GY 250 were added slowly, in the course of which it was ensured that the temperature did not rise above 105oC, and the reaction mixture was subsequently stirred further at 90°C over the course of 2 hours. Then 11.4 g of 2,5-hexanedione were added and stirred in at 90 °C over the course of 15 nain. Then 52.2 g of N4-Amine, then a further 34.2 g of 2,5-hexanedione, were added to the reaction mixture and stirred in at 90 °C over the course of 15 min. Then a further 60.0 g of Armeen® CD, then a further 112.5 g of Araldite® GY 250, were added, in the course of which it was ensured that the temperature did not rise above 105°C. Finally, the reaction mixture was stirred at 90'C for a further 2 hours and then cooled. A yellowish, waxy material which was solid at room temperature was obtained. The viscosity thereof at 50oC and the (calculated) NH equivalent weight are reported in Table 1. In the present document, the NH equivalent weight refers to the equivalent weight per hydrogen atom bonded to an amine nitrogen. Examples 2 to 7 and Comparative examples 8 and 9 Examples 2 to 7 and comparative example 8 were prepared analogously to example 1, using the ingredients according to the information in Table 1 in the sequence specified. The amounts are reported in grams. In comparative example 8, after the addition of dimethylacrylamide, a reaction time of 1 hour instead of 15 minutes was observed in each case before a further addition. In comparative example 9, after the first addition of butylene oxide, a reaction time of 14 hours at 60°C instead of 15 minutes at 90°C was observed, and, after the second addition of butylene oxide, a reaction time of 3 hours at 60 °C and then 90 minutes at 90°C was observed, before the further addition in each case. All hardener compositions of examples 1 to 7 and of comparative examples 8 and 9 were in the form of yellowish, solid, waxy materials at room temperature. In the molten state, they were dilutable with water by simple stirring with a spatula to obtain an almost clear liquid in each case. The preparation time of comparative example 9 is significantly longer than the preparation times of the hardener compositions of examples 1 to 7. 4. Production of hardener compositions of the H2 or HW type Example 10 A round-bottom flask under a nitrogen atmosphere was initially charged with 200 g of the hardener composition from example 1, to which 126.5 g of Jeffamine® D-230 were added, and the reaction mixture was heated to 90 °C while stirring. Then, with good stirring, 98.5 g of Araldite® GY 250 were added gradually, in the course of which it was ensured that the temperature did not rise above 105oC. Finally, the reaction mixture was stirred at 90 °C for a further 90 min, then 75 g of isophoronediamine and 489.1 g of water were stirred in successively, and the mixture was cooled. A yellowish, clear liquid was obtained. The viscosity at 20°C, the (calculated) NH equivalent weight, the water content (incl. water formed, in % by weight) and the storage stability at 50°C are reported in Table 2. Examples 11 to 17 and comparative examples 18 and 19 Examples 11 to 17 and comparative examples 18 and 19 were prepared analogously to example 10, using the ingredients according to the information in Table 2. The amounts are reported in grams. In all examples apart from comparative examples 18 and 19, a clear liquid was obtained in each case. The appearance was assessed visually and reported in Table 2. For the assessment of storage stability ("storage stabso'c") i the hardener compositions were heated to 50°C over the course of 4 weeks. When no coalescence occurred within this time, the composition was designated stable or "ok", and otherwise as unstable or "no". 5. Production of epoxy resin compositions Examples 20 to 27 and comparative examples 28 and 29 The hardener compositions of the H2 or HW type from examples 10 to 17 and the hardener compositions from comparative examples 18 and 19 were mixed in the proportions by weight specified in Table 3 with 50 parts by weight of the epoxy resin dispersion Sika® Repair/Sikafloor® EpoCem® Module A (EEW = 288.7 g/eq, solids content = 62% by weight; Sika Schweiz AG) . For each mixed composition, a film with a layer thickness of 76 um was drawn down onto a glass plate, and a film with a layer thickness of 500 um onto a further glass plate. The following tests were carried out thereon: The hardening rate was determined on a freshly applied film in a layer thickness of 76 una on glass by means of a BYK-Gardner drying time recorder (Beck-Koller method): in Table 3, the start of the deep trace ("flow") was designated "tflow, the start of film tearing ("soft gel") "tsoft gel", the start of the surface trace ("hard gel") "thard gel", and the end of the surface trace ("cured") "tcured". The hardness was determined as the Buchholz hardness on a film drawn down onto a glass plate in a layer thickness of 500 µm, after a hardening time of 30 days at 23°C and 50% relative humidity (r.H.), by means of a PIG universal instrument from Byk-Gardner. The adhesion was determined on glass on a film drawn down onto a glass plate in a layer thickness of 500 um. To test the adhesion, the film was repeatedly incized down to the glass plate with a blade, and attempts were made to detach the film from the glass plate with the blade. If this was impossible, the adhesion was designated "good". The appearance was assessed on two films each on glass with layer thicknesses of 76 µm and 500 µm, and designated in Table 3 as appearance (76 yua) and as appearance (500 µm) . The appearances were designated clear ("clear"), hazy ("hazy"), impeccable ("imp.") and structured ("struc") . Impeccable films are considered to be those which are clear, shiny and tack-free, and have no surface structure whatsoever. Structured films are considered to be those whose surface is not completely smooth but has a slight orange-like skin. The results of the tests are reported in Table 3. 6. Preparation of ECC compositions Example 30 7.2 parts by weight of the hardener composition from example 10 were mixed with 17.6 parts by weight of water and 0.19 part by weight of defoamer (BYK®-023, BYK-Chemie) (= hardener component) . To this were added 10 parts by weight of Sika® Repair/Sikafloor® EpoCem® Module A (EEW = 288.7 g/eq, solids content = 62% by weight; Sika Schweiz AG) (= resin component) and 150 parts by weight of Sikafloor®-81 EpoCem® component C (Sika Schweiz AG) (=cementitious powder), and- everything was mixed thoroughly. The ECC composition obtained was used to determine the solidification time to EN 480-2, the slump to EN 1015-3 and the compressive strength and the flexural tensile strength on prisms of dimensions 40x40x160 mm to EN 13892-2, the tensile adhesive strength to EN 13892-8 and the shrinkage (change in length) of prisms of dimensions 40x40x160 mm to DIN 52450 after storage under standard climatic conditions (23oC, 50% relative humidity) for different durations. The results are reported in Table 4. Example 31 In the same way as described for example 30, the hardener composition from example 13 was used to produce an ECC mortar, and it was tested. The results are reported in Table 4. The ECC compositions of examples 30 and 31 have exceptionally good processability, have very good mechanical properties and harden with impeccable surface appearance. Claims 1. A compound VB of the formula (I) or (II) where R1 and R3 are each independently an alkyl, cycloalkyl, aryl or arylalkyl group which has 1 to 12 carbon atoms and optionally has ether groups or halogen atoms, and R2 is a hydrogen atom or an alkyl, cycloalkyl, aryl or arylalkyl group having 1 to 12 carbon atoms, or R2 and R1 together are a divalent hydrocarbon radical which is part of an optionally substituted carbocyclic ring having 5 to 8 and preferably 5 or 6 carbon atoms, and R3 is an alkyl, cycloalkyl, aryl or arylalkyl group which has 1 to 12 carbon atoms and optionally has ether groups or halogen atoms; or R2 and R3 together are a divalent hydrocarbon radical which is part of an optionally substituted carbocyclic ring having 5 to 8 and preferably 5 or 6 carbon atoms, and R1 is an alkyl, cycloalkyl, aryl or arylalkyl group which has 1 to 12 carbon atoms and optionally has ether groups or halogen atoms; R4 and R5 are each independently an alkyl, cycloalkyl, aryl or arylalkyl group which has 1 to 12 carbon atoms and optionally has ether groups or halogen atoms; A is an (a+b)-valent radical of a polyamine-polyepoxide adduct after removal of (a+b) primary amino groups; a is an integer from 0 to 4; and b is an integer from 1 to 4; with the provisos that the sum of a and b is an integer from 1 to 4, and that the parent polyepoxide of the polyamine-polyepoxide adduct is a polyepoxide E, especially a diepoxide E1, and has an epoxy equivalent weight (EEW) of 65 to 500 g/eq. 2. A compound VB as claimed in claim 1, characterized in that it has the formula (Ia) or (Ib) where R6 is an alkyl or cycloalkyl or arylalkyl group which optionally has ether or secondary amino groups; E1 and E2 are each independently the remainder of a diepoxide E1 having an epoxy equivalent weight (EEW) of 65 to 500 g/eq, after removal of two epoxy groups; x is an integer from 0 to 50; y is an integer from 0 to 100, preferably 10 to 50; z is an integer from 1 to 50; (x+z) is an integer from 1 to 100, preferably 1 to 10; p is 0 or 1; and q is 0, 1, 2 or 3. 3. A compound VB as claimed in claim 1, characterized in that it has the formula (IIa) or (IIb) where R6 is an alkyl or cycloalkyl or arylalkyl group which optionally has ether or secondary amino groups; E1 and E2 are each independently the remainder of a diepoxide El having an epoxy equivalent weight (EEW) of 65 to 500 g/eq, after removal of two epoxy groups; x is an integer from 0 to 50; y is an integer from 0 to 100, preferably 10 to 50; z is an integer from 1 "to 50; (x+z) is an integer from 1 to 100, preferably 1 to 10; p is 0 or 1; and q is 0, 1, 2 or 3. 4. A compound VB as claimed in any of the preceding claims, characterized in that the diepoxide E1 is selected from the group consisting of a bisphenol A, bisphenol F and bisphenol A/F diglycidyl ether having an epoxy equivalent weight of 156 to 250 g/eq, N,N- diglycidylaniline and a polyglycol diglycidyl ether having an epoxy equivalent weight of 170 to 340 g/eq. 5. A process for preparing a compound VB as claimed in any of claims 1 to 4, characterized in that (a) at least one polyamine Al containing at least two primary amino groups, (β) optionally at least one amine A2 containing only one primary amino group, (γ) at least one polyepoxide E having an epoxy equivalent weight (EEW) of 65 to 500 g/eq and (δ) at least one diketone K1 of the formula (IV) or K2 of the formula (V) are reacted with one another over more than one stage, where the ratio between the number of primary amino groups and epoxy groups is especially 1.25 to 2.0, and where the diketone Kl or K2 is used in a ratio to the primary amino groups, which are in excess in relation to the epoxy groups, especially in an amount of 0.25 to 1.0 equivalent. 6. The process as claimed in claim 5, characterized in that the diketone Kl is selected from the group consisting of 2,4-pentanedione, 3-methyl-, 3-ethyl-, 3- propyl-, 3-isopropyl-, 3-butyl-, 3-tert-butyl-, 3- cyclohexyl-, and 3-phenyl-2,4-pentanedione, 3,5- heptanedione, 6-methyl-3,5-heptanedione, 2,2,6,6- tetramethyl-3,5-heptanedione, 2,2,4,6,6-pentamethyl- 3,5-heptanedione, 2-acetylcyclopentanone and 2- acetylcyclohexanone, and is preferably 2,4- pentanedione. 7. The process as claimed in claim 5 or 6, characterized in that the polyamine A1 is selected from the group consisting of ether-containing diamines of weight of 500 to 5000 g/mol, and polyalkyleneamines, especially diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), polyethylenepolyamine having 5 to 7 ethyleneamine units (known as "higher ethylenepolyamine", HEPA), 3-(2- aminoethyl)aminopropylamine (N3-amine) and N,N'-bis(3- aminopropyl)ethylenediamine (N4-amine). 8. The process as claimed in any of claims 5 to 7, characterized in that the amine A2 is selected from the group consisting of butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, docosylamine, 2-ethyl-1- hexylamine, benzylamine, 1- or 2-phenylethylamine, N- hexyl-1,2-ethanediamine, N-(2-ethylhexyl)-1,2- ethanediamine, N-cyclohexyl-1,2-ethanediamine, N-butyl- 1,3-propanediamine, N-hexyl-1,3-propanediamine, N-(2- ethylhexyl)-1,3-propanediamine, N-dodecyl-1,3- propanediamine, N-cyclohexyl-1,3-propanediamine, cocoalkylamine, soyaalkylamine, oleylamine, N- cocoalkyl-1, 3-propanediamine, N-oleyl-1,3- propanediamine and N-soyaalkyl-1,3-propanediamine. 9. The process as claimed in any of claims 5 to 8, characterized in that the polyepoxide E is a diepoxide E1 which is selected from the group consisting of a bisphenol A, bisphenol F and bisphenol A/F diglycidyl ether having an epoxy equivalent weight of 156 to 250 g/eq, N, N-diglycidylaniline and a polyglycol diglycidyl ether having an epoxy equivalent weight of 170 to 340 g/eq. 10. A hardener composition comprising (a) at least one compound VB of the formula (I) or (II) as claimed in any of claims 1 to 4. 11. The hardener composition as claimed in claim 10, characterized in that it comprises at least one compound VB of the formula (Ia) or (IIa) as claimed in any of claims 2 to 4, and at least one compound VB of the formula (Ib) or (IIb) as claimed in any of claims 2 to 4. 12. The hardener composition as claimed in claim 10 or 11, characterized in that the hardener composition additionally comprises: (b) at least one adduct AD formed from at least one polyamine A3 having at least two amino groups in the form of primary or secondary amino groups and at least one polyepoxide E having an epoxy equivalent weight (EEW) of 65 to 500 g/eq, where the adduct AD has terminal primary and/or secondary amino groups, (c) optionally at least one polyamine A4 having at least two amino groups in the form of primary or secondary amino groups, and (d) optionally water. 13. The hardener composition as claimed in claim 12, characterized in that the polyamine A3 is selected from the group consisting of firstly polyoxyalkylenediamines having a molecular weight of at most 1000 g/mol, and secondly isophoronediamine (IPDA), 2,2,4- and 2,4,4- trimethylhexamethylenediamine (TMD), 1,3-xylylene- diamine (meta-xylylenediamine or MXDA), 2-butyl-2- ethyl-1,5-pentanediamine (Cll-neodiamine), N-ethyl-1,3- propanediamine and N-cyclohexyl-1,3-propanediamine. 14. The hardener composition as claimed in claim 12 or 13, characterized in that the polyamine A4 is selected from the group consisting of isophoronediamine (IPDA), bis(4-aminocyclohexyl)methane (H12-MDA), bis(4-amino-3- methylcyclohexyl)methane, 2,2,4- and 2,4,4- trimethylhexamethylenediamine (TMD), 1,3-xylylene- diamine (meta-xylylenediamine or MXDA) and 2-butyl-2- ethyl-1,5-pentanediamine (C11-neodiamine). 15. The hardener composition as claimed in any of claims 12 to 14, characterized in that the composition contains water, especially in an amount of 20 to 90% by weight, based on the overall hardener composition. 16. A two-pack or three-pack epoxy resin composition' consisting of a hardener component C1 and a resin component C2 and optionally a further component C3, where hardener component C1 comprises or consists of at least one hardener composition as claimed in any of claims 10 to 15; and resin component C2 comprises or consists of at least one epoxy resin; and component C3 comprises or consists of at least one hydraulically setting mineral substance, preferably cement. 17. A hardened composition which is obtained by mixing the components of a two- or three-pack epoxy resin composition as claimed in claim 16. 18. The use of a compound VB as claimed in any of claims 1 to 4 as a hardener for substances which have at least two groups reactive toward NH and OH groups and which are especially selected from the group consisting of isocyanate, isothiocyanate, cyclocarbonate, epoxide, episulfide, aziridine, acryloyl, methacryloyl, 1-ethynylcarbonyl, 1- propynylcarbonyl, maleimide, citraconimide, vinyl, isopropenyl and allyl groups. 19. The use of a two- or three-pack epoxy resin composition as claimed in claim 16 as a coating, especially as a floor coating. The present invention relates to novel compounds VB of the formula (I) or (II), said compounds being particularly suitable as curing agents for epoxide resins. The compounds can be produced easily and rapidly. They can be used in the form of aqueous curing agents and form stabile aqueous emulsions in particular. This facilitates the formulation of ECC compounds for use primarily as coatings.

Full Text

WATER-SOLUBLE AMINE AND USES THEREOF
Technical Field
The present invention relates to the field of water-
dilutable amines and the use thereof as hardeners for
epoxy resins.
State of the Art
Amine hardeners for aqueous epoxy resin dispersions are
known. They typically contain an adduct formed from
polyamines and polyepoxides, which is free of epoxy
groups and contains secondary and possibly primary
amino groups. Often, primary amino groups present in
such an adduct are converted further, since there is
otherwise the disadvantage that the adduct tends to
form carbonate and carbamate salts with carbon dioxide
gas from the air, which can impair the quality of a
hardened film in respect of esthetic and mechanical
properties such as clarity, shine, surface properties,
hardness and toughness.
EP 0 000 605 A1 discloses hardening compositions for
aqueous epoxy resin dispersions in the form of adducts
formed from polyepoxides, polyalkylene polyether
polyols and polyamines. Primary amino groups of the
adducts have been converted to secondary amino groups
by addition onto unsaturated compounds such as
acrylonitrile. These hardening compositions have the
disadvantage that they tend to coagulate at
temperatures in the region of 50°C, i.e. are not
storage-stable.
EP 0 567 831 Al discloses hardening compositions for
aqueous epoxy resin dispersions, which are storage-
stable at 50°C. The emulsifier and coemulsifier
described are each adducts formed from polyamines and
polyepoxides. Primary amino groups of the adducts are
alkylated reductively by means of aldehydes and formic

acid and are in the form of secondary amino groups.
However, the hardeners described have disadvantages.
Firstly, the preparation thereof is complicated,
especially owing to the slowness of the reduction
process used, and they secondly tend to form an
esthetically unsatisfactory, hazy film when applied in
a thick layer, for example as an anticorrosion coating.
EP 0 024 915 Al discloses two-pack aqueous epoxy resin
systems, the hardeners of which are present in the form
of polyamine-polyepoxy resin adducts. Primary amino
groups of the adducts are converted by means of
monoepoxides. As a result of the reaction with
monoepoxides, the preparation of the adducts described
takes a very long time.
Summary of the Invention
It is therefore an object of the present invention to
provide compounds which are preparable in a simple
rapid process from readily available raw materials,
which are usable as hardeners for epoxy resins,
especially as a constituent of an aqueous hardener
composition for epoxy resin dispersions, and which
overcome the disadvantages of the prior art.
It has been found that, surprisingly, this object is
achieved by compounds as claimed in claim 1. The
compounds can . be used highly advantageously as
hardeners for epoxy resins. More particularly, it has
been found that these compounds have low viscosity, can
be prepared in a simple and rapid manner from readily
available raw materials and are highly suitable as
hardeners for epoxy resins. They are storable
substantially unchanged within a broad temperature
range, have a low processing and mixing viscosity with
the epoxy resin and harden rapidly and completely with
the epoxy resin to develop good adhesion to the
substrate. They meet the high demands on the quality of

a hardened film in respect of esthetic and. mechanical
properties such as clarity, shine, surface properties,
hardness and toughness.
It has particularly been shown that these compounds are
highly suitable as aqueous hardeners for epoxy resins.
More particularly, they enable the production of
storage-stable, low-viscosity aqueous hardener
emulsions which are stable especially up to 50°C. Thus,
further aspects of the invention are a process as
claimed in claim 5 for preparation of the compound and
a hardener composition as claimed in claim 10.
It has additionally been found that these hardener
compositions are highly suitable for two- or three-pack
epoxy resin compositions as claimed in claim 16. More
particularly, it is also possible to produce ECC (epoxy
cement concrete) compositions. The compounds or the
aqueous hardener compositions formed therefrom are
especially suitable as a constituent of ECC
compositions which can be used especially as a coating.
Further aspects of the present invention are a hardened
composition as claimed in claim 17 and uses as claimed
in claims 18 and 19.
Preferred embodiments of the invention are the subject
of the dependent claims.
Ways of Performing the Invention
In a first aspect, the present invention relates to a
compound VB of the formula (I) or (II)

where
R1 and R3 are each independently an alkyl, cycloalkyl,
aryl or arylalkyl group which has 1 to 12 carbon atoms
and optionally has ether groups or halogen atoms, and
R2 is a hydrogen atom or an alkyl, cycloalkyl, aryl or
arylalkyl group having 1 to 12 carbon atoms,
or
R2 and R1 together are a divalent hydrocarbon radical
which is part of an optionally substituted carbocyclic
ring having 5 to 8 and preferably 5 or 6 carbon atoms,
and R3 is an alkyl, cycloalkyl, aryl or arylalkyl group
which has 1 to 12 carbon atoms and optionally has ether
groups or halogen atoms;
or
R2 and R3 together are a divalent hydrocarbon radical
which is part of an optionally substituted carbocyclic
ring having 5 to 8 and preferably 5 or 6 carbon atoms,
and R1 is an alkyl, cycloalkyl, aryl or arylalkyl group
which has 1 to 12 carbon atoms and optionally has ether
groups or halogen atoms;
R4 and R5 are each independently an alkyl, cycloalkyl,
aryl or arylalkyl group which has 1 to 12 carbon atoms
and optionally has ether groups or halogen atoms;
A is an (a+b)-valent radical of a polyamine-polyepoxide
adduct after removal of (a+b) primary amino groups;
a is an integer from 0 to 4; and

b is an integer from 1 to 4.
The following provisos apply here:
that the sum of a and b is an integer from 1 to 4, and
that the parent polyepoxide of the polyamine-
polyepoxide adduct is a polyepoxide E, especially a
diepoxide E1, and has an epoxy equivalent weight (EEW)
of 65 to 500 g/eq.
In the present document, the term "polyamine" refers to
compounds having at least two primary or secondary
amino groups.
In the present document, a "primary" amino group refers
to an NH2 group which is bonded to an organic radical,
and a "secondary" amino group refers to an NH group
which is bonded to two organic radicals which may also
together be part of a ring.
In the present document, "molecular weight" in the case
of oligomers or polymers is always understood to mean
the molecular weight average Mn.
In the present document, the term "polyepoxide" refers
to compounds having at least two epoxy groups.
"Diepoxides" . refer to compounds having two epoxy
groups.
In the present document, "epoxy group" refers to the
structural element
The bold designations such as VB, E, E1, A1, A2, A3,
A4, A11, AD, AE, K1, K2, H1, H2, HW, C1, C2, C3 or the
like in the present document serve merely for better
readability and identification.
The acyl enamino groups of the formula (i) are in an
equilibrium with the tautomeric isomers of the formula

(ii) and of the formula (iii). Each mention of the acyl
enamino groups of the formula (i) likewise means the
tautomers of the formula (ii) and of the formula (iii),
even though this is not mentioned explicitly in each
case.

In this document, the broken lines in the formulae each
represent the bond between a substituent and the rest
of the corresponding molecule.
Preferably, R1 and R3 are each a methyl group.
Preferably, R2 is a hydrogen atom.
Preferably, R4 and R5 are each a methyl group.
Preferably, a is 0.
Preferably, b is 1.
The polyamine-polyepoxide adduct from which A in the
formulae (I) and (II) derives is free of epoxy groups
and has (a+b) primary amino groups. It is an addition
product of at least one polyamine A1 and optionally
further amines, preferably at least one further amine
A2, with at least one polyepoxide E, especially a
diepoxide El. The polyepoxide E has an epoxy equivalent
weight of 65 to 500 g/eq. The polyamine Al is
preferably a polyamine having two primary amino groups.
The amine A2 is preferably an amine having only one
primary amino group. The polyepoxide E is preferably a
diepoxide E1, more preferably a liquid diglycidyl ether
of bisphenols, especially of bisphenol A.
The abbreviation "EEW" in the present document stands
for "epoxy equivalent weight".

In the present document, a "glycidyl ether" refers to
an ether of 2,3-epoxy-l-propanol (glycidol).
A compound VB of the formula (I) is preferably a
compound VB of the formula (1a) or (1b) . A compound VB
of the formula (II) is preferably a compound VB of the
formula (IIa) or (IIb).

In the formulae (Ia), (Ib), (IIa) and (IIb), R1, R2, R3,
R4 and R5 are each as already defined, and
R6 is an alkyl or cycloalkyl or arylalkyl group which
optionally has ether or secondary amino groups;
E1 and E2 are each independently the remainder of a
diepoxide El having an EEW of 65 to 500 g/eq, after
removal of two epoxy groups;
x is an integer from 0 to 50;
y is an integer from 0 to 100, preferably 10 to 50;
z is an integer from 1 to 50;
(x+z) is an integer from 1 to 100, preferably 1 to 10;
p is 0 or 1; and

q is 0, 1, 2 or 3.
R6 in the formulae (Ia), (IIa), (Ib) and (IIb) is
preferably an alkyl or cycloalkyl or arylalkyl group
which has at least 4 carbon atoms, especially 4 to 18
carbon atoms, and optionally has ether or secondary
amino groups.
The diepoxide E1 is preferably selected from the group
consisting of a bisphenol A, bisphenol F and bisphenol
A/F diglycidyl ether having an epoxy equivalent weight
of 156 to 250 g/eq, N,N-diglycidylaniline and a
polyglycol diglycidyl ether having an epoxy equivalent
weight of 170 to 340 g/eq.
The diepoxide E1 is more preferably a bisphenol A,
bisphenol F and bisphenol A/F diglycidyl ether.
Thus, E1 in the formulae (Ia) and (IIa) and E2 in the
formulae (Ib) and (IIb) are preferably each
independently the remainder of a diepoxide E1 which is
selected from the group consisting of a bisphenol A,
bisphenol F and bisphenol A/F diglycidyl ether having
an epoxy equivalent weight of 156 to 250 g/eq, N,N-
diglycidylaniline and a polyglycol diglycidyl ether
having an epoxy equivalent weight of 170 to 340 g/eq,
especially a bisphenol A, bisphenol F and bisphenol A/F
diglycidyl ether having an epoxy equivalent weight of
156 to 250 g/eq, after removal of two epoxy groups.
The invention further provides a process for preparing
a compound VB of the formula (I) or (II) as described
above. In this process, (a) at least one polyamine A1
containing at least two primary amino groups,
((3) optionally at least one amine A2 containing only
one primary amino group, (y) at least one polyepoxide E
having an epoxy equivalent weight (EEW) of 65 to
500 g/eq and (6) at least one diketone K1 of the

formula (IV) or K2 of the formula (V) are reacted with
one another over more than one stage.

In the formulae (IV) and (V), R1, R2, R3, R4 and R5 are
each as already defined.
The ratio between the number of primary amino groups
and epoxy groups is especially 1.25 to 2.0. In
addition, the diketone K1 or K2 is used in a ratio to
the primary amino groups, which are in excess in
relation to the epoxy groups, especially in an amount
of 0.25 to 1.0 equivalent.
In the case that the index a in the formula (I) or (II)
is different than zero, the diketone is used in a
substoichiometric ratio to the primary amino groups,
which are in excess in relation to the epoxy groups.
In the case that the index a in the formula (I) or (II)
is zero, the diketone is used in at least a
stoichiometric ratio to the primary amino groups, which
are in excess in relation to the epoxy groups.
The process can be performed in such a way that, in a
first stage, the polyamine A1 and optionally the amine
A2 are reacted with the polyepoxide E to give an adduct
AE of the formula (III), with predominant reaction of
primary amino groups with the epoxy groups, while
secondary amino groups and hydroxyl groups already

present or formed in the course of the reaction react
with epoxy groups only in an insignificant portion, if
at all, owing to the significantly lower reactivity.

In the formula (III), A, a and b are each as already
defined.
In a second stage, the adduct AE of the formula (III)
is subsequently reacted with the diketone K1 or K2 of
the formula (IV) or (V) to give a compound VB of the
formula (I) or (II), the diketone reacting with primary
amino groups to eliminate water.
In the case of the diketone Kl of the formula (IV) - a
β-diketone, also known as a 1,3-diketone - a compound
VB of the formula (I) is formed, releasing one mole of
water per mole of diketone Kl converted. This reaction
proceeds very rapidly and virtually quantitatively. It
is preferably performed at a temperature in the range
from 20 to 120°C.
In the case of the diketone K2 of the formula (V) - a γ-
diketone, also known as a 1,4-diketone - a compound VB
of the formula (II) is formed, releasing two moles of
water per mole of diketone K2 converted. This reaction
is also known by the name "Paal-Knorr pyrrole
synthesis". An intermediate (or by-product) which
occurs in the formation of the compound VB of the
formula (II) is the noncyclized form, as shown in the
formula (II') .

In the formula (II'), R4, R5, A, a and b are each as
already defined.
The cyclization to the pyrrole group (condensation
reaction) proceeds in a predominant portion when the
reaction mixture is stirred, for example, at elevated
temperature over a few hours, for example 60 to 120°C.
In addition, the process for preparing a compound VB of
the formula (I) or (II) can also be performed in such a
way that, in a first stage, the polyamine A1 is reacted
with the diketone K1 or K2 with elimination of water to
form an alkylated polyamine All of the formula (VI) or
(VII), in which case the diketones react with primary
amino groups in the manner already described.

In the formulae (VI) and (VII),
Q is the remainder of a polyamine Al after removal of
(b+c) primary amino groups;
c is 1 or 2, preferably 1;

and R1, R2, R3, R4, R5 and b are each as already defined.
In a second stage, the alkylated polyamine A11 is
subsequently, optionally in the presence of the amine
A2, reacted with the polyepoxide E to give a compound
VB of the formula (I) or (II), at least as many free
primary amino groups as epoxy groups still being
present in the reaction mixture.
In the processes described, the reaction of primary
amino groups with epoxy groups is advantageously
performed at a temperature in the range from 60 to
120°C.
The processes described can be performed as a one-pot
reaction. It is thus unnecessary to purify the
intermediate before the 2nd stage is carried out. The
water formed in the reaction between the diketone and
the primary amino groups need not be removed from the
reaction mixture. It can, however, be removed from the
reaction mixture if desired, for example by means of
application of reduced pressure.
It is also possible to prepare a compound VB of the
formula (I) by using, instead of a diketone K1 of the
formula (IV), a ketone of the formula (IVa). In this
case, the primary amino groups are alkylated without
elimination of water.

In the formula (IVa) , R1 and R3 are each as already
defined.

The polyamine A1 has at least two primary amino groups.
In addition, it may have secondary and/or tertiary
amino groups. Suitable polyamines for this purpose are
especially the following:
- aliphatic, cycloaliphatic or arylaliphatic diamines,
especially ethylenediamine, 1,2-propanediamine, 1,3-
propanediamine, 2-methyl-1,2-propanediamine, 2,2-
dimethyl-1,3-propanediamine, 1,3-butanediamine, 1,4-
butanediamine, 1,3-pentanediamine (DAMP), 1,5-
pentanediamine, 1,5-diamino-2-methylpentane (MPMD),
2-butyl-2-ethyl-1,5-pentanediamine (C11-neodiamine),
1,6-hexanediamine, 2,5-dimethyl-1, 6-hexanediamine,
2,2,4- and 2,4,4-trimethylhexamethylenediamine (TMD),
1,7-heptanediamine, 1,8-octanediamine, 1,9-nonane-
diamine, 1,10-decanediamine, 1,11-undecanediamine,
1,12-dodecanediamine, 1,2-, 1,3- and 1,4-
diaminocyclohexane, bis(4-aminocyclohexyl)methane
(H12-MDA), bis(4-amino-3-methylcyclohexyl)methane,
bis(4-amino-3-ethylcyclohexyl)methane, bis(4-amino-
3,5-dimethylcyclohexyl)methane, bis(4-amino-3-ethyl-
5-methylcyclohexyl)methane (M-MECA), 1-amino-3-
aminomethyl-3,5,5-trimethylcyclohexane (= isophorone-
diamine or IPDA), 2- and 4-methyl-1,3-
diaminocyclohexane and mixtures thereof, 1,3- and
1,4-bis(aminomethyl)cyclohexane, 2,5(2,6)-bis(amino-
methyl)bicyclo[2.2.1]heptane (NBDA), 3(4),8 (9)-
bis (aminomethyl) tricyclo [5 . 2 .1. 02'6] decane, 1, 4-
diamino-2,2,6-trimethylcyclohexane (TMCDA), 1,8-
menthanediamine, 3,9-bis(3-aminopropyl)-2,4,8,10-
tetraoxaspiro[5.5]undecane, and 1,3- and 1,4-
xylylenediamine;
- aliphatic diamines containing ether groups,
especially bis(2-aminoethyl) ether, 3,6-dioxaoctane-
1,8-diamine, 4,7-dioxadecane-1,10-diamine, 4,7-
dioxadecane-2,9-diamine, 4,9-dioxadodecane-1,12-
diamine, 5,8-dioxadodecane-3,10-diamine and higher
oligomers of these diamines, bis(3-
aminopropyl)polytetrahydrofurans and polytetrahydro-

furandiamines having molecular weights in the range
from, for example, 350 to 5200, and
polyoxyalkylenediamines. The latter are typically
products from the amination of polyoxyalkylenediols
and are obtainable, for example, under the Jeffamine®
name (from Huntsman), under the Polyetheramine name
(from BASF) or under the PC Amine® name (from
Nitroil). Especially suitable polyoxyalkylenediamines
are Jeffamine® D-230, Jeffamine® D-400, Jeffamine®
D-2000, Jeffamine® D-4000, Jeffamine® XTJ-511,
Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine®
ED-2003, Jeffamine® XTJ-568, Jeffamine® XTJ-569,
Jeffamine® XTJ-523, Jeffamine® XTJ-536, Jeffamine®
XTJ-542, Jeffamine® XTJ-559, Jeffamine® EDR-104,
Jeffamine® EDR-14 8, Jeffamine® EDR-17 6;
Polyetheramine D 230, Polyetheramine D 400 and
Polyetheramine D 2000, PC Amine® DA 250, PC Amine®
DA 400, PC Amine® DA 650 and PC Amine® DA 2000;
- aliphatic, cycloaliphatic or arylaliphatic triamines,
especially 4-aminomethyl-1,8-octanediamine, 1,3,5-
tris(aminomethyl)benzene, 1,3,5-tris(aminomethyl)-
cyclohexane, tris(2-aminoethyl)amine, tris(2-
aminopropyl)amine, tris(3-aminopropyl)amine;
- polyoxyalkylene triamines, which are typically
products from the amination of polyoxyalkylenetriols
and are obtainable, for example, under the Jeffamine®
trade name (from Huntsman), under the Polyetheramine
name (from BASF) or under the PC Amine® name (from
Nitroil), for example Jeffamine® T-403, Jeffamine®
T-3000, Jeffamine® T-5000; Polyetheramine T403,
Polyetheramine T5000; and PC Amine® TA 403, PC Amine®
TA 5000;
- polyamines having secondary amino groups, especially
what are known as polyalkyleneamines, such as
diethylenetriamine (DETA), triethylenetetramine
(TETA), tetraethylenepentamine (TEPA),
pentaethylenehexamine (PEHA), and also
polyethylenepolyamine having 5 to 7 ethyleneamine

units (known as "higher ethylenepolyamine", HEPA),
dipropylenetriamine (DPTA), bishexamethylenetriamine
(BHMT), 3-(2-aminoethyl)aminopropylamine (N3-amine),
N,N'-bis(3-aminopropyl)ethylenediamine (N4-amine),
N3- (3-aminopentyl)-1,3-pentanediamine, N5-(3-amino-
propyl) -2-methyl-1,5-pentanediamine and N5-(3-amino-
1-ethylpropyl)-2-methyl-1,5-pentanediamine; such
polyalkyleneamines are prepared, for example, from
1,2-dichloroethane and ammonia, or from the
cyanoethylation or cyanobutylation and subsequent
hydrogenation of primary polyamines;
- polyamines having tertiary amino groups, especially
N,N'-bis(aminopropyl)piperazine, N,N-bis(3-amino-
propyl )methylamine, N,N-bis(3-aminopropyl)ethylamine,
N,N-bis(3-aminopropyl)propylamine, N,N-bis(3-
aminopropyl)cyclohexylamine, N,N-bis(3-aminopropyl)-
2-ethylhexylamine, and also the products from the
double cyanoethylation and subsequent reduction of
fatty amines derived from natural fatty acids, such
as N,N-bis(3-aminopropyl)dodecylamine and N,N-bis(3-
aminopropyl)tallowalkylamine, obtainable as Triameen®
Y12D and Triameen® YT (from Akzo Nobel).
The polyamine Al preferably has two primary amino
groups.
Particularly preferred polyamines Al are firstly ether-
containing diamines of the formula (VIII), especially
having a molecular weight of 500 to 5000 g/mol,
preferably Jeffamine® ED-600, Jeffamine® ED-900,
Jeffamine® ED-2003, and secondly polyalkyleneamines,
especially DETA, TETA, TEPA, PEHA, HEPA, N3-amine and
N4-amine.

In the formula (VIII), x, y and z are each as already
defined.
A suitable amine A2, as optionally used in part to
prepare a compound VB of the formula (I) or (II), has
only one primary amino group. In addition, it
optionally contains secondary and/or tertiary amino
groups. Suitable examples are the following amines:
- aliphatic, cycloaliphatic or arylaliphatic
monoamines, especially methylamine, ethylamine, 1-
propylamine, 2-propylamine, 1-butylamine, 2-
butylamine, tert-butylamine, 3-methyl-1-butylamine,
3-methyl-2-butylamine, cyclopentylamine, hexylamine,
cyclohexylamine, octylamine, 2-ethyl-1-hexylamine,
benzylamine, 1- or 2-phenylethylamine, decylamine,
dodecylamine, tetradecylamine, hexadecylamine,
octadecylamine, eicosylamine, docosylamine, and also
fatty amines derived from natural fatty acid
mixtures, for example cocoalkylamine, C16-C22-
alkylamine, soyaalkylamine, oleylamine and
tallowalkylamine, obtainable, for example, under the
Armeen® (from Akzo Nobel) or Rofamin® (from Ecogreen
Oleochemicals) trade names. Especially suitable fatty
amines are Armeen® 12D, Armeen® 18D, Armeen® CD,
Armeen® HT, Armeen® M, Armeen® OD, Armeen® OVD and
Armeen® TD, and Rofamin® KD, Rofamin® LD, Rofamin®
STD, Rofamin® TD, Rofamin® RD, Rofamin® TD4 0,
Rofamin® OD80, Rofamin® OD85 and Rofamin® OD90;
- aliphatic, cycloaliphatic or arylaliphatic monoamines
containing ether groups, especially 2-methoxy-
ethylamine, 2-ethoxyethylamine, 3-methoxypropylamine,
3-ethoxypropylamine, 3-(2-ethylhexyloxy)propylamine,
3-(2-methoxyethoxy)propylamine, 2(4)-methoxyphenyl-
ethylamine and also polyoxyalkylenemonoamines which
are obtainable, for example, under the Jeffamine®
trade name (from Huntsman) , such as especially
Jeffamine® M-600, Jeffamine® M-1000, Jeffamine®

M-2005, Jeffamine® M-2070, Jeffamine® XTJ-435,
Jeffamine® XTJ-4 36;
- aliphatic, cycloaliphatic or arylaliphatic amines
having one primary and at least one secondary amino
group, especially N-methyl-1,2-ethanediamine, N-
ethyl-1,2-ethanediamine, N-butyl-1,2-ethanediamine,
N-hexyl-1,2-ethanediamine, N-butyl-1,6-hexanediamine,
N-cyclohexyl-1,2-ethanediamine, 4-aminomethyl-
piperidine, 3- (4-aminobutyl)piperidine, N-(2-amino-
ethyDpiperazine (N-AEP) , N-(2-aminopropyl)-
piperazine, diamines from the cyanoethylation or
cyanobutylation and subsequent hydrogenation of
primary monoamines, for example N-methyl-1, 3-
propanediamine, N-ethyl-1,3-propanediamine, N-butyl-
1,3-propanediamine, N-hexyl-1,3-propanediamine, N-(2-
ethylhexyl)-1,3-propanediamine, N-dodecyl-1,3-
propanediamine, N-cyclohexyl-1,3-propanediamine, 3-
me thylamino-1-pentylamine, 3-ethylamino-1-pentyl-
amine, 3-butylamino-1-pentylamine, 3-hexylamino-1-
pentylamine, 3-(2-ethylhexyl)amino-1-pentylamine, 3-
dodecylamino-1-pentylamine, 3-cyclohexylamino-1-
pentylamine, and additionally diamines obtainable by
cyanoethylation and subsequent reduction of fatty
amines, such as N-cocoalkyl-1,3-propanediamine, N-
oleyl-1,3-propanediamine, N-soyaalkyl-1,3-propane-
diamine, N-tallowalkyl-1,3-propanediamine or N-
(Ci6-22-alkyl)-1,3-propanediamine, obtainable, for
example, as Duomeen® CD, Duomeen® M, Duomeen® 0,
Duomeen® OV and Duomeen® T (Akzo Nobel), and
additionally triamines and tetramines derived from
fatty amines, such as cocoalkyldipropylenetriamine,
oleyldipropylenetriamine, tallowalkyldipropylene-
triamine, oleyltripropylenetetramine and
tallowalkyltripropylenetetramine, obtainable, for
example, as Triameen® C, Triameen® OV, Triameen® T,
Tetrameen® OV and Tetrameen® T (Akzo Nobel);
- aliphatic, cycloaliphatic or arylaliphatic amines
having one primary and at least one tertiary amino

group, especially N,N-diethyl-1,2-ethanediamine, N,N-
dimethyl-1,3-propanediamine, N,N-diethyl-1,3-
propanediamine and N,N-diethyl-1,4-pentanediamine.
Preferred amines A2 contain at least 4 carbon atoms,
especially 4 to 18 carbon atoms, and optionally have
ether or secondary amino groups.
Particularly preferred amines A2 are amines which are
selected from the group consisting of butylamine,
pentylamine, hexylamine, cyclohexylamine, octylamine,
decylamine, dodecylamine, tetradecylamine,
hexadecylamine, octadecylamine, eicosylamine,
docosylamine, 2-ethyl-1-hexylamine, benzylamine, 1- or
2-phenylethylamine, N-hexyl-1,2-ethanediamine, N-(2-
ethylhexyl)-1, 2-ethanediamine, N-cyclohexyl-1,2-
ethanediamine, N-butyl-1,3-propanediamine, N-hexyl-1,3-
propanediamine, N-(2-ethylhexyl)-1,3-propanediamine, N-
dodecyl-1,3-propanediamine, N-cyclohexyl-1,3-
propanediamine, cocoalkylamine, soyaalkylamine,
oleylamine, N-cocoalkyl-1,3-propanediamine, N-oleyl-
1,3-propanediamine and N-soyaalkyl-1,3-propanediamine.
The polyepoxide E has an epoxy equivalent weight (EEW)
of 65 to 500 g/eq. Polyepoxides E can be prepared in a
known manner, for example from the oxidation of the
corresponding olefins or from the reaction of
epichlorohydrin with the corresponding polyols,
polyphenols or amines.
Especially suitable as polyepoxides E are what are
known as polyepoxide liquid resins, referred to
hereinafter as "liquid resin". They have a glass
transition temperature which is typically below 25 oC,
in contrast to solid polyepoxide resins which can be
comminuted to powders which are pourable at 25 °C and
have a glass transition temperature above 25 °C.
Polyepoxides which are known to the person skilled in

the art as reactive diluents are also referred to m
the present document as liquid resins.
In one embodiment, the polyepoxide E is an aromatic
polyepoxide. Suitable examples for this purpose are
liquid resins of the formula (IX)

where R' and R" are each independently a hydrogen atom
or a methyl group, and s has an average value of 0 to
1. Preference is given to those liquid resins of the
formula (IX) in which the index s has an average value
of less than 0.2.
The liquid resins of the formula (IX) are diglycidyl
ethers of bisphenol A, bisphenol F and bisphenol A/F,
where A represents acetone and F formaldehyde, which
serve as reactants for preparation of these bisphenols.
A bisphenol A liquid resin accordingly has methyl
groups, a bisphenol F liquid resin hydrogen atoms, and
a bisphenol A/F liquid resin both methyl groups and
hydrogen atoms, as R' and R" in formula (IX) . In the
case of bisphenol F, it is also possible for positional
isomers to be present, especially derived from 2,4'-
and 2,2'-hydroxyphenylmethane.
Such liquid resins are commercially available, for
example as Araldite® GY 204, Araldite® GY 250,
Araldite® GY 260, Araldite® GY 281, Araldite® GY 282,
Araldite® GY 285, Araldite® PY 304, Araldite® PY 720
(from Huntsman); D.E.R.® 330, D.E.R.® 331, D.E.R.® 332,
D.E.R.® 336, D.E.R.® 354, D.E.R.® 351, D.E.R.® 352,
D.E.R.® 356 (from Dow); Epikote® 162, Epikote® 827,

Epikote® 828, Epikote® 158, Epikote® 862, Epikote® 169,
Epikote® 144, Epikote® 238, Epikote® 232, Epikote® 235
(from Hexion), Epalloy® 7190, Epalloy® 8220, Epalloy®
8230, Epalloy® 7138, Epalloy® 7170, Epalloy® 9237-70
(from CVC), Chem Res® E 20, Chem Res® E 30 (from
Cognis), Beckopox® EP 116, Beckopox® EP 140 (from
Cytec).
Further suitable aromatic polyepoxides E are the
glycidylization products of
- dihydroxybenzene derivatives such as resorcinol,
hydroquinone and catechol;
- further bisphenols or polyphenols such as bis (4-
hydroxy-3-methylphenyl)methane, 2, 2-bis(4-hydroxy-3-
methylphenyl)propane (bisphenol C), bis(3,5-dimethyl-
4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-
hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxy-
phenyl)propane, 2,2-bis(4-hydroxy-3-tert-butyl-
phenyl)propane, 2,2-bis(4-hydroxyphenyl)butane
(bisphenol B) , 3,3-bis(4-hydroxyphenyl)pentane, 3,4-
bis(4-hydroxyphenyl)hexane, 4,4-bis(4-hydroxyphenyl)-
heptane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane,
2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane,
1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z) ,
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane
(bisphenol TMC), 1,1-bis(4-hydroxyphenyl)-1-phenyl-
ethane, 1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene)
(bisphenol P), 1,3-bis[2-(4-hydroxyphenyl)-2-
propyl]benzene) (bisphenol M), 4,4'-dihydroxydiphenyl
(DOD), 4,4'-dihydroxybenzophenone, bis(2-
hydroxynaphth-1-yl)methane, bis(4-hydroxynaphth-1-
yl)methane, 1,5-dihydroxynaphthalene, tris(4-
hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-
hydroxyphenyl)ethane, bis(4-hydroxyphenyl) ether,
bis(4-hydroxyphenyl) sulfone;
- condensation products of phenols with formaldehyde,
which are obtained under acidic conditions, such as
phenol novolacs or cresol novolacs;

- aromatic amines, such as aniline, toluidine, 4-
aminophenol, 4,4'-methylenediphenyldiamine (MDA),
4,4'-methylenediphenyldi(N-methyl)amine, 4,4'-[1,4-
phenylenebis(1-methylethylidene)]bisaniline
(bisaniline P), 4,4'-[1,3-phenylenebis(1-
methylethylidene)]bisaniline (bisaniline M).
Commercially available epoxy novolacs are, for example,
Araldite® EPN 1179, Araldite® GY 289, Araldite®
PY 307-1 (from Huntsman), D.E.N.® 425 and D.E.N.® 431
(from Dow), Epalloy® 8240 and Erisys® RF50 (from CVC);
a commercially available N,N-diglycidylaniline is, for
example, Epikote® Resin 4 93 (from Hexion); a
commercially available resorcinol diglycidyl ether is,
for example, Erisys® RDGE (from CVC).
In a further embodiment, the polyepoxide E is an
aliphatic or cycloaliphatic polyepoxide, for example
- diglycidyl ether;
- a glycidyl ether of a saturated or unsaturated,
branched or unbranched, cyclic or open-chain C2 to C30
diol, for example ethylene glycol, propylene glycol,
butylene glycol, hexanediol, octanediol, a
polypropylene glycol, dimethylolcyclohexane,
neopentyl glycol;
- a glycidyl ether of a tri- or tetrafunctional,
saturated or unsaturated, branched or unbranched,
cyclic or open-chain polyol such as castor oil,
trimethylolpropane, trimethylolethane, penta-
erythritol, sorbitol or glycerol, and alkoxylated
glycerol or alkoxylated trimethylolpropane;
- a hydrogenated bisphenol A, F or A/F liquid resin, or
the glycidylization products of hydrogenated
bisphenol A, F or A/F;
- an N-glycidyl derivative of amides or heterocyclic
nitrogen bases, such as triglycidyl cyanurate and
triglycidyl isocyanurate, and reaction products of
epichlorohydrin and hydantoin.

Aliphatic or cycloaliphatic liquid resins are, for
example, commercially available as Araldite® DY-C,
Araldite® DY-F, Araldite® DY-H, Araldite® DY-T,
Araldite® DY 0397, Araldite® DY 3601 (from Huntsman),
D.E.R.® 732, D.E.R.® 736 (from Dow); Heloxy® BD,
Heloxy® HD, Heloxy® TP, Epikote® 877 (from Hexion),
Beckopox® EP 075 (from Cytec).
In a further embodiment, the polyepoxide E is a
polyepoxide which has been prepared from the oxidation
of olefins, for example from the oxidation of
vinylcyclohexene, dicyclopentadiene, cyclohexadiene,
cyclododecadiene, cyclododecatriene, isoprene, 1,5-
hexadiene, butadiene, polybutadiene or divinylbenzene.
The polyepoxide E is preferably a diepoxide El.
The diepoxide E1 is more preferably selected from the
group consisting of a bisphenol A, bisphenol F and
bisphenol A/F diglycidyl ether having an epoxy
equivalent weight of 156 to 250 g/eq, especially
Araldite® GY 250, Araldite® PY 304, Araldite® GY 282
(from Huntsman); D.E.R.® 331, D.E.R.® 330 (from Dow);
Epikote® 828, Epikote® 862 (from Hexion), N,N-
diglycidylaniline and a polyglycol diglycidyl ether
having an epoxy equivalent weight of 170 to 340 g/eq,
especially D.E.R.® 732 and D.E.R.® 736 (from Dow).
Suitable diketones K1 of the formula (IV) are
especially 2,4-pentanedione (= acetylacetone), 3-
alkylated 2,4-pentanedione, i.e. especially 3-methyl-,
3-ethyl-, 3-propyl-, 3-isopropyl-, 3-butyl-, 3-tert-
butyl-, 3-cyclohexyl- and 3-phenyl-2,4-pentanedione,
1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5,5,5-
hexafluoro-2,4-pentanedione, 3,5-heptanedione, 3,5-
octanedione, 2,4-octanedione, 6-methyl-3,5-
heptanedione, 2,2,6,6-tetramethyl-3,5-heptanedione,

2,2,4,6,6-pentamethyl-3,5-heptanedione, 1-phenyl-1,3-
butanedione, 2-acetylcyclopentanone, 2-acetylcyclo-
hexanone, 2-benzoylcyclopentanone and 2-
benzoylcyclohexanone.
Preferred diketones K1 are selected from the group
consisting of 2,4-pentanedione, 3-methyl-, 3-ethyl-, 3-
propyl-, 3-isopropyl-, 3-butyl-, 3-tert-butyl-, 3-
cyclohexyl- and 3-phenyl-2,4-pentanedione, 3,5-
heptanedione, 6-methyl-3,5-heptanedione, 2,2,6,6-
tetramethyl-3, 5-heptanedione, 2,2,4,6,6-pentamethyl-
3,5-heptanedione, 2-acetylcyclopentanone and 2-
acetylcyclohexanone.
A particularly preferred diketone Kl is 2,4-
pentanedione.
Suitable diketones K2 of the formula (V) are especially
diketones selected from the group consisting of 2,5-
hexanedione (= acetonylacetone), 3,4-dimethyl-2,5-
hexanedione, 1,2-dibenzoylethane, 1,4-bis(2-furyl)-1,4-
butanedione and 2-(2-oxopropyl)cyclopentanone. A
preferred diketone K2 is 2,5-hexanedione.
A preferred process for preparing a compound VB of the
formula (I) or (II) is characterized in that (a) at
least one polyamine A1 having two primary amino groups,
(P) at least one amine A2, (γ) at least one diepoxide E1
and (5) at least one diketone K1 of the formula (IV) or
K2 of the formula (V) are reacted with one another in a
molar ratio of 1:(0.8 to 1.2): (0.8 to 1.2): (0.8 to
1.2), especially 1:1:1:1, in one of the sequences
already described, i.e. via an intermediate of the
formula (III), or via an intermediate of the formula
(VI) or (VII).
In a first particularly preferred process, at least one
polyamine Al in the form of a polyoxyalkylenediamine,

at least one amine A2 and at least one diepoxide E1 are
reacted in a molar ratio of 1:(0.8 to 1.2): (0.8 to
1.2), especially 1:1:1, to give an adduct AE, and the
latter is subsequently reacted in a molar ratio of
1:(0.8 to 1.2), especially 1:1, with at least one
diketone K1 of the formula (IV) or K2 of the formula
(V) to give a compound VB of the formula (1a) or (IIa).
In a second particularly preferred process, at least
one polyamine A1 in the form of a polyalkyleneamine and
at least one diketone Kl of the formula (IV) or K2 of
the formula (V) are reacted in a molar ratio of 1: (0.8
to 1.2), especially 1:1, to give an alkylated polyamine
All, and the latter is subsequently reacted in a molar
ratio of 1:(0.8 to 1.2): (0.8 to 1.2), especially 1:1:1,
with at least one amine A2 and at least one diepoxide
E1 to give a compound VB of the formula (Ib) or (IIb).
It is also possible to initially charge a compound VB
of the formula (Ia) or (IIa) and to prepare a compound
VB of the formula (Ib) or (IIb) therein - effectively
in a solvent. In this way, it is possible in a one-pot
process to prepare a mixture of at least one compound
VB of the formula (Ia) or (IIa) and at least one
compound VB of the formula (Ib) or (IIb).
The compound VB of the formula (I) or (II) is
preparable in a simple process from readily available
raw materials. It preferably has at least two NH
hydrogen atoms which are active toward epoxy groups and
at least some of which are in the form of secondary
amino groups. Secondary amino groups have formed more
particularly from the reaction of primary amino groups
with epoxy groups. The compound VB, or the A radical,
preferably does not have any primary amino groups. If
it nevertheless has primary amino groups, the number
thereof is preferably 1 or 2. As a result, it barely
reacts, if at all, with carbon dioxide gas from the air

and as a result forms a low level of carbonate and/or
carbamate salts, if any. The absence of such salt
formation is very advantageous especially in the case
of use of the compound VB as a hardener for epoxy
resins, since this means that there cannot be any salt-
related optical and/or mechanical defects in the curing
of the epoxy resin, such as more particularly the film
opacity known as "blushing". The acylenamino groups of
the formula (i) from the reaction with the diketone K1
of the formula (IV) - or the pyrrole groups from the
reaction with the diketone K2 of the formula (V) - of
the compound VB are stable, even in the presence of
water and at elevated temperature, for example at 60oC.
Even in the presence of moisture, they do not react to
any significant degree with epoxy groups, in spite of
the enamine nitrogen in the acylenamino group; the
latter is a vinylogous amido group in which the
hydrogen atom of the enamine nitrogen can enter into a
stable intramolecular hydrogen bond with the carbonyl
oxygen.
The compound VB has a comparatively low viscosity for
polyepoxide-polyamine adducts.
The compound VB of the formula (I) or (II) can be used
as a reactant for substances which have groups reactive
toward NH and OH groups. Groups reactive toward NH and
OH groups are, for example, isocyanate, isothiocyanate,
cyclocarbonate, epoxide, episulfide, aziridine,
acryloyl, methacryloyl, 1-ethynylcarbonyl, 1-
propynylcarbonyl, maleimide, citraconimide, vinyl,
isopropenyl or allyl groups. The compound VB can
advantageously be used as a hardener for substances
which have at least two of the aforementioned reactive
groups, especially as a hardener for polyisocyanates
and polyepoxides. The compound VB is especially
suitable as a hardener for epoxy resins. The compound
VB is advantageously used as a constituent of a mixture

which comprises further substances suitable as
hardeners for epoxy resins.
The compound VB of the formula (I) or (II) is most
suitable as a constituent of a water-dilutable hardener
for aqueous epoxy resin dispersions.
The present invention further provides a hardener
composition comprising at least one compound VB of the
formula (I) or (II), preferably at least one compound
VB of the formula (Ia) or (IIa) and at least one
compound VB of the formula (Ib) or (IIb), as described
above.
A hardener composition comprising at least one compound
VB of the formula (Ia) or (IIa) and at least one
compound VB of the formula (Ib) or (IIb) is also
referred to hereinafter as hardener composition H1.
A hardener composition H1 is of similar composition to
the mixture of an emulsifier and a coemulsifier
described in EP 0 567 831 A1. The difference from the
emulsifier-coemulsifier mixture described in
EP 0 567 831 Al is that the primary amino groups have
been converted or capped in another way, namely by
means of at least one diketone K1 of the formula (IV)
or a diketone K2 of the formula (V) instead of by
reductive alkylation by means of aldehyde and formic
acid. The capping of primary amino groups by means of
reductive alkylation forms secondary amino groups,
whereas the reaction with a diketone K1 or K2 caps the
primary amino groups such that they no longer have any
reactivity toward epoxy groups. Surprisingly, the
hardener compositions H1 described, however, are
nevertheless just as suitable as hardeners in epoxy
resin compositions as the emulsifier-coemulsifier
mixtures described in EP 0 567 831 A1. The capping of
the primary amino groups by means of a diketone K1 or

K2 has a series of advantages over the reductive
alkylation described in EP 0 567 831 A1. One is that
the reaction with diketone is substantially more rapid,
which means a greatly shortened production time for a
corresponding water-dilutable hardener. In addition,
the reaction with diketone does not form CO2, which can
form troublesome carbonate and carbamate salts with
primary amino groups, as is the case in the reductive
alkylation in EP 0 567 831 A1. The water obtained in
the reaction with the diketones K1 or K2 is not
disruptive in the case of use as a water-dilutable
hardener.
The hardener composition, especially the hardener
composition H1, preferably comprises, in addition to at
least one compound VB of the formula (I) or (II),
(b) at least one adduct AD formed from at least one
polyamine A3 having at least two amino groups in the
form of primary or secondary amino groups and at least
one polyepoxide E having an epoxy eguivalent weight
(EEW) of 65 to 500 g/eq, where the adduct AD has
terminal primary and/or secondary amino groups,
Cc) optionally at least one polyamine A4 having at
least two amino groups in the form of primary or
secondary amino groups, and
(d) optionally water.
Such a preferred hardener composition is referred to
hereinafter as hardener composition H2.
The hardener composition H2 preferably comprises a
mixture of a compound VB of the formula (Ia) or (IIa)
and a compound VB of the formula (Ib) or (IIb), as
described above. Such a mixture can display self-
emulsifying action in the hardener composition when
mixed with water.

The compound VB of the formula (Ia) or (IIa) is present
advantageously in an amount of 0.5 to 1.5 parts by
weight, based on 1 part by weight of the compound VB of
the formula (Ib) or (IIb).
In addition, an adduct AD is present in the hardener
composition H2. In one embodiment, suitable polyamines
A3 for preparation of a suitable adduct AD are the same
polyamines as already mentioned above as polyamines Al
having at least two primary amino groups. In a further
embodiment, suitable polyamines A3 are the same
polyamines as already mentioned as amines A2 having one
primary and at least one secondary amino group. In a
further embodiment, suitable polyamines A3 are
polyamines having at least two secondary amino groups,
especially N,N' -dibutylethylenediamine; N,N'-di-tert-
butylethylenediamine, N, N' -diethyl-1,6-hexanediamine,
1-(1-methylethylamino)-3-(1-methylethylaminomethyl)-
3,5,5-trimethylcyclohexane (Jefflink® 754 from
Huntsman), N4-cyclohexyl-2-methyl-N2-(2-methylpropyl)-
2, 4-pentanediamine, N,N'-dialkyl-1,3-xylylenediamine,
bis(4-(N-alkylamino)cyclohexyl)methane, 4,4'-
trimethylenedipiperidine, N-alkylated polyetheramines,
for example the Jeffamine® products SD-231, SD-401,
SD-404 and SD-2001 (from Huntsman).
Preferred polyamines A3 for preparation of an adduct AD
are those selected from the group consisting of firstly
polyoxyalkylenediamines of the formula (VIII) having a
molecular weight of at most 1000 g/mol, preferably
Jeffamine® D-230, Jeffamine® D-4 00, Jeffamine® XTJ-511,
Jeffamine® EDR-104, Jeffamine® EDR-148, Jeffamine®
EDR-176; Polyetheramine D 230, Polyetheramine D 400, PC
/Amine® DA 250, PC Amine® DA 4 00 or PC Amine® DA 650,
and secondly isophoronediamine (IPDA), 2,2,4- and
2, 4, 4-trimethylhexamethylenediamine (TMD), 1,3-
xylylenediamine (meta-xylylenediamine or MXDA), 2-
butyl-2-ethyl-1,5-pentanediamine (C11-neodiamine), N-

ethyl-1,3-propanediamine and N-cyclohexyl-1,3-
propanediamine.
Suitable and also preferred polyepoxides E for
preparation of a suitable adduct AD are the same
polyepoxides as already described for preparation of a
compound VB of the formula (I) or (II), especially the
diepoxides E1 mentioned.
A particularly suitable adduct AD is the adduct of two
moles of polyamine A3 having two amino groups in the
form of primary or secondary amino groups and one mole
of diepoxide E1.
The adduct AD is present in the hardener composition H2
advantageously in an amount of 0.5 to 1.5 parts by
weight, based on 1 part by weight of the compound VB of
the formula (I) or (II).
Suitable polyamines A4 are the same polyamines as
already mentioned as polyamines A3 for preparation of
an adduct AD, and additionally what are known as
polyamidoamines. A polyamidoamine is the reaction
product of a mono- or polybasic carboxylic acid, or the
esters or anhydrides thereof, and an aliphatic,
cycloaliphatic or aromatic polyamine, the polyamine
being used in a stoichiometric excess. A polybasic
carboxylic acid used is typically what is known as a
dimer fatty acid, and the polyamine used is typically a
polyalkyleneamine, for example TETA. Commercially
available polyamidoamines are, for example, Versamid®
100, 125, 140 and 150 (from Cognis), Aradur® 223, 250
and 848 (from Huntsman), Euretek® 3607, Euretek® 530
(from Huntsman), Beckopox® EH 651, EH 654, EH 655,
EH 661 and EH 663 (from Cytec).
The polyamine A4 present may be the same polyamine as
the polyamine A3 used to prepare an adduct AD, for

example by virtue of an excess of polyamine A3 having
been used in the reaction with the polyepoxide E, such
that unreacted polyamine A3 is still present after the
reaction of all epoxy groups.
Preferred polyamines A4 are relatively hydrophobic
polyamines, especially selected from the group
consisting of isophoronediamine, bis(4-aminocyclo-
hexyl)methane, (Hi2-MDA), bis(4-amino-3-methylcyclo-
hexyl)methane, 2,2,4- and 2,4,4-trimethylhexa-
methylenediamine (TMD), 1,3-xylylenediamine (meta-
xylylenediamine or MXDA) and 2-butyl-2-ethyl-1,5-
pentanediamine (C11-neodiamine).
The polyamine A4 is present in the hardener composition
H2 advantageously in an amount of 0.01 to 0.5 part by
weight, based on 1 part by weight of the sum of the
compound VB of the formula (I) or (II) and of the
adduct AD.
The hardener composition H2 preferably comprises water,
especially in an amount of 20 to 90% by weight, based
on the overall hardener composition.
The hardener composition H2 more preferably comprises
at least one compound VB of the formula (Ia) or (IIa) ,
at least one compound VB of the formula (Ib) or (IIb),
at least one adduct AD, at least one polyamine A4 and
water.
A hardener composition H2 can be prepared in any
desired sequence.
In a preferred preparation process, a one-pot process,
at least one compound VB of the formula (I) or (II) is
initially charged, and the adduct AD is prepared
therein - effectively in a solvent. The adduct AD is
advantageously prepared at elevated temperature, fox

example at a temperature in the range from 60 to 120oC.
Subsequently, a polyamine A4 is added to the reaction
mixture. And finally, the reaction mixture is diluted
with water until the desired solids content is
attained, for example a solids content in the range
from 10 to 80% by weight.
Compared to a hardening composition as described in
EP 0 567 831 A1, the hardener composition described
here has the great advantage that the preparation of
the compound VB of the formula (I) or (II) is
significantly more rapid than the preparation of the
emulsifier and coemulsifier described in
EP 0 567 831 Al.
The hardener composition H2 may comprise further
substances in the form of assistants and additives.
The hardener composition H2 preferably comprises water
and has a solids content in the range from 10 to 80% by
weight. Such a hardener composition is referred to
hereinafter as aqueous hardener composition HW.
An aqueous hardener composition HW is in the form of an
emulsion. The compound VB of the formula (I) or (II)
may have an emulsifying effect, especially when at
least one compound VB of the formula (Ia) or (IIa) and
at least one compound VB of the formula (Ib) or (IIb)
is present. The appearance of the emulsion depends on
the fineness of the emulsion droplets. Fine emulsions
(microemulsions) are clear or slightly opalescent and
typically have the Tyndall effect, whereas coarse
emulsions (macroemulsions) have a turbid to milky
appearance. Microemulsions have particles which are
within the order of magnitude of visible light or
smaller. A microemulsion typically has a mean particle
size of less than 100 nm.

The aqueous hardener composition HW is preferably
present as a microemulsion within a broad temperature
range, especially in the range between 0 and 50°C.
The aqueous hardener composition HW typically has a
relatively low viscosity, such that it is easy to
handle at room temperature.
A preferred aqueous hardener composition HW comprising,
as well as water, at least one compound VB of the
formula (Ia) or (IIa), at least one compound VB of the
formula (Ib) or (IIb), at least one adduct AD and at
least one polyamine A4 is in the form of a
thermodynamically stable emulsion and has a clear to
slightly turbid appearance. Such an aqueous hardener
composition HW can be diluted further by simply
stirring water in. Such an aqueous hardener composition
is typically storage-stable up to a temperature of
50°C. "Storage-stable" refers to the property that the
aqueous hardener composition does not coalesce in the
course of storage, i.e. does not exhibit any phase
separation, and remains useable in the manner intended.
Storage stability up to 50 °C is an important property
which is rarely fulfilled by aqueous epoxy hardeners
according to the prior art.
One of the hardener compositions described is
advantageously used as a constituent of an epoxy resin
composition, and acts as a hardener for at least one
epoxy resin.
The present invention thus further provides a two- or
three-pack epoxy resin composition consisting of a
hardener component C1 and a resin component C2 and
optionally a further component C3.
The two- or three-pack epoxy resin composition can be
used especially as an adhesive, sealing compound,

potting compound, coating, floor covering, paint,
varnish, primer or undercoat, preferably as a coating,
especially as a floor coating.
In a first embodiment, the epoxy resin composition
consists of a hardener component C1 and a resin
component C2.
The hardener component C1 comprises at least one
hardener composition as described above.
The resin component C2 comprises at least one epoxy
resin.
Suitable epoxy resins are epoxy resins customary in
epoxy chemistry, for example
- a polyepoxide E as already specified above;
- a bisphenol A, F or A/F solid resin which is of
similar composition to the liquid resins of the
formula (IX) already specified as the polyepoxide E,
but instead of the index s has a value of 2 to 12,
and also has a glass transition temperature above
25°C;
- one of the epoxy resins mentioned, which has been
modified hydrophilically by the reaction with at
least one polyoxyalkylenepolyol.
Preferred epoxy resins are bisphenol A, F or A/F solid
or liquid resins, as available commercially, for
example, from Dow, Huntsman and Hexion.
The epoxy resin may comprise what is known as a
reactive diluent. Suitable reactive diluents are mono-
and polyepoxides, for example the glycidyl ethers of
mono- or polyhydric phenols and aliphatic or
cycloaliphatic alcohols, especially the polyglycidyl
ethers of di- or polyols already mentioned as aliphatic
or cycloaliphatic polyepoxides E, and additionally

especially phenyl glycidyl ether, cresyl glycidyl
ether, p-n-butylphenyl glycidyl ether, p-tert-
butylphenyl glycidyl ether, nonylphenyl glycidyl ether,
allyl glycidyl ether, butyl glycidyl ether, hexyl
glycidyl ether, 2-ethylhexyl glycidyl ether, and
glycidyl ethers of natural alcohols, for example C8- to
C10-alkyl glycidyl ethers or C12- to C14-alkyl glycidyl
ethers, commercially available as Erysis® GE-7 and
Erysis® GE-8 (from CVC) . The addition of a reactive
diluent to the epoxy resin causes a reduction in the
viscosity and - in the hardened state of the epoxy
resin composition - a reduction in the glass transition
temperature and in the mechanical values.
When the hardener composition C1 comprises an aqueous
hardener composition HW, the resin component C2
preferably comprises either what is known as an
"emulsifiable epoxy resin" or an aqueous epoxy resin
dispersion. An epoxy resin dispersion preferably
comprises, as well as water, at least one epoxy resin
as specified above, and additionally at least one
emulsifier, especially a nonionic emulsifier, for
example an alkyl or alkylaryl polyglycol ether,
especially a polyalkoxylated alkylphenol such as
alkylphenoxypoly(ethyleneoxy)ethanol, for example a
polyadduct formed from nonylphenol and ethylene oxide,
containing up to 30 mol of ethylene oxide per mole of
nonylphenol.
Commercial epoxy resin dispersions are, for example,
Sika® Repair/Sikafloor® EpoCem® Module A (from Sika
Schweiz AG), Araldite® PZ 323, Araldite® PZ 756/67,
Araldite® PZ 3961 (from Huntsman), XZ 92598.00,
XZ 92546.00, XZ 92533.00 (from Dow), Waterpoxy® 1422,
Waterpoxy® 1455 (from Cognis), Beckopox® EP 384w,
Beckopox® EP 385w, Beckopox® EP 386w, Beckopox®
EP 2340w, Beckopox® VEP 2381w (from Cytec).

Epoxy resin dispersions typically have a solids content
in the range of 40-65% by weight.
An emulsifiable epoxy resin preferably contains at
least one emulsifier as already mentioned above as a
constituent of an epoxy resin dispersion.
Commercial emulsifiable epoxy resins are, for example,
Araldite® PY 340 and Araldite® PY 340-2 (from
Huntsman), Beckopox® 122w and Beckopox® EP 147w (from
Cytec).
Both the hardener component C1 and the resin component
C2 may comprise further assistants and additives, for
example
- nonreactive diluents, solvents or film-forming
assistants, such as toluene, xylene, methyl ethyl
ketone, 2-ethoxyethanol, 2-ethoxyethyl acetate or
benzyl alcohol, ethylene glycol, diethylene glycol
butyl ether, dipropylene glycol butyl ether, ethylene
glycol butyl ether, ethylene glycol phenyl ether, N-
methylpyrrolidone, propylene glycol butyl ether,
propylene glycol phenyl ether, bisphenols and phenol
resins, diphenylmethane, diisopropylnaphthalene,
mineral oil fractions, for example Solvesso® products
(from Exxon), aromatic hydrocarbon resins, sebacates,
phthalates, organic phosphoric and sulfonic esters
and sulfonamides;
- reactive diluents and extenders, for example reactive
diluents containing epoxy groups as already mentioned
above, epoxidized soybean oil, butyrolactone,
triphenyl phosphite, and additionally polyamides,
polymers having carboxyl groups, isocyanates,
silicones having reactive groups, polysulfides,
butadiene-acrylonitrile copolymers and polyurethanes;
- polymers, for example polyamides, polysulfides,
polyvinyl formal (PVF), polyvinyl butyral (PVB),
polyurethanes (PUR), styrene-butadiene copolymers,

homo- or copolymers of unsaturated monomers,
especially from the group comprising ethylene,
propylene, butylene, isobutylene, isoprene, vinyl
acetate and alkyl (meth)acrylates, especially
chlorosulfonated polyethylenes and fluorinated
polymers, sulfonamide-modified melamines;
- thermoplastic polymers such as polyether sulfone,
polyether imide and bitumen;
- inorganic and organic fillers, for example ground or
precipitated calcium carbonates, which have
optionally been coated with fatty acids, especially
stearates, barite (heavy spar), talcs, quartz flours,
quartz sand, dolomites, wollastonites, kaolins, mica
(potassium aluminum silicate), molecular sieves,
aluminum oxides, aluminum hydroxides, silicas,
cements, gypsums, fly ashes, carbon black, graphite,
metal powders such as aluminum, copper, iron, silver
or steel, PVC powders or hollow spheres;
- fibers, for example of polymer or glass;
- pigments, for example titanium dioxide or iron
oxides;
- accelerators which accelerate the reaction between
amino groups and epoxy groups, for example acids or
compounds hydrolyzable to acids, for example organic
carboxylic acids such as acetic acid, benzoic acid,
salicylic acid, 2-nitrobenzoic acid, lactic acid,
organic sulfonic acids such as methanesulfonic acid,
p-toluenesulfonic acid or 4-dodecylbenzenesulfonic
acid, sulfonic esters, other organic or inorganic
acids, for example phosphoric acid, or mixtures of
the aforementioned acids and acid esters; and also
tertiary amines such as 1,4-
diazabicyclo[2.2.2]octane, benzyldimethylamine, a-
methylbenzyldimethylamine, 2-(dimethylaminomethyl)-
phenol or 2,4,6-tris(dimethylaminomethyl)phenol,
triethanolamine, dimethylaminopropylamine, salts of
such tertiary amines, and quaternary ammonium salts,
for example benzyltrimethylammonium chloride;

- rheology modifiers, such as especially thickeners,
for example sheet silicates such as bentonites,
derivatives of castor oil, hydrogenated castor oil,
polyamides, polyurethanes, urea compounds, fumed
silicas, cellulose ethers and hydrophobically
modified polyoxyethylenes;
- adhesion improvers, for example organoalkoxysilanes
such as 3-glycidoxypropyltrimethoxysilane, 3-amino-
propyltrimethoxysilane, N-(2-aminoethyl)-3-amino-
propyltrimethoxysilane, N-(2-aminoethyl)-N'-[3-
(trimethoxysilyl)propyl]ethylenediamine, 3-ureido-
propyltrimethoxysilane, 3-chloropropyltrimethoxy-
silane, vinyltrimethoxysilane, or the corresponding
organoalkoxysilanes with ethoxy instead of the
methoxy groups;
- heat, light or UV stabilizers;
- flame-retardant substances;
- surface-active substances, for example wetting
agents, leveling agents, deaerating agents or
defoamers;
- biocides, for example algaecides, fungicides or
fungal growth inhibitors.
The hardener component C1 and the resin component C2
can each be stored in a suitable package or
arrangement, for example a drum, a hobbock, a pouch, a
bucket, a canister, a cartridge or a tube, over several
months up to a year and longer before use thereof,
without the particular properties thereof changing to a
degree relevant for the use thereof.
The mixing ratio between the hardener component C1 and
the resin component C2 is preferably selected such that
the groups reactive toward epoxy groups in the hardener
component C1 are in a suitable ratio to the epoxy
groups of the resin component C2. Suitably, 0.7 to 1.5
and preferably 0.9 to 1.1 equivalents of NH hydrogens

active toward epoxy groups are present before the
curing per equivalent of epoxy groups.
In parts by weight, the mixing ratio between the
hardener component C1 and the resin component C2 is
typically in the range from 1:10 to 10:1.
Before or during the application, the two components
are mixed with one another by means of a suitable
process. The mixing can be effected continuously or
batchwise. If the mixing is effected before the
application, it must be ensured that the time which
passes between the mixing of the components and the
application is not too long, since the result may be
defects, for example a slowed or incomplete buildup of
the adhesion to the solid surface.
With the mixing, the hardening reaction begins. The NH
hydrogens which are reactive toward epoxy groups and
are present in the epoxy resin composition react with
epoxy groups present, which ultimately cures the
composition. The present invention thus also describes
a cured composition which is obtained by mixing the
components of a two- or three-pack epoxy resin
composition as described above.
The application and the hardening are effected
advantageously at temperatures in the range from 5 to
50°C.
The hardening proceeds rapidly and completely. The
hardening rate depends on the ambient temperature and
on any accelerators present. The rate of hardening can
be determined by means of a Byk Gardner drying time
recorder. This involves pulling a needle over a film
applied to a glass strip at a defined speed, and,
according to the degree of hardening of the film, a
"deep trace" is first drawn into the film, then there

is a "film tear", which ultimately becomes a "surface
trace" before the film is so dry that the needle no
longer leaves any visible trace. "Flow" refers to the
moment where the applied composition no longer flows
together properly, i.e. the start of the deep trace.
"Soft gel" refers to the moment where the film begins
to tear. "Hard gel" refers to the moment where the film
tear becomes the surface trace, and "cured" refers to
the moment where the surface trace disappears and the
needle no longer leaves any visible trace.
The hardening of the epoxy resin composition described
typically gives rise to clear films with a smooth
surface and high shine, which have a high hardness and
toughness and excellent adhesion on a wide variety of
different substrates.
The epoxy resin composition can be used as an adhesive,
sealing compound, potting compound, coating, floor
covering, paint, varnish, primer or undercoat, for
which important properties may be properties such as
watertightness, corrosion protection, chemical
resistance and/or high hardness and toughness. They may
be used, for example, in construction or civil
engineering, in the manufacture or repair of industrial
goods or consumer goods.
In a further embodiment, the epoxy resin composition
consists of a hardener component C1, a resin component
C2 and a further component C3. In this embodiment, the
hardener component C1 preferably comprises at least one
aqueous hardener composition HW, the resin component C2
preferably comprises at least one epoxy resin
dispersion, and the component C3 comprises at least one
hydraulically setting mineral substance. Such an epoxy
resin composition is also referred to as ECC
composition (ECC stands for "epoxy cement concrete").

Suitable hydraulically setting mineral substances are
- substances which are referred to conventionally as
hydraulic binders and are hardenable with water, even
under water, such as lime and especially cement;
- latently hydraulic binders which set with water under
the action of additives, such as especially blast
furnace slag for fly ash;
- substances which react with water only under air,
known as nonhydraulic binders, such as especially
gypsum, Sorel cement, anhydrite, magnesia binders and
white lime.
Thus, in the present document, not only cements but
especially also calcium sulfate in the form of
anhydrite, hemihydrate gypsum or dihydrate gypsum, or
blast furnace slags, are referred to as hydraulically
setting substances.
The hydraulically setting substance is preferably a
cement, especially a cement according to European
standard EN 197. Preferred cements are portland
cements, sulfoaluminate cements and high-alumina
cements, especially portland cement. Mixtures of
cements can lead to particularly good properties.
Particularly suitable are mixtures of at least one
portland cement with either at least one sulfoaluminate
cement or with at least one high-alumina cement. For
rapid hardening, cementitious quick-setting binders in
particular are used, which preferably comprise at least
one high-alumina cement or another aluminate source,
for example aluminate-donating clinker, and optionally
calcium sulfate in the form of anhydrite, hemihydrate
or dihydrate gypsum and/or calcium hydroxide.
Component C3 optionally comprises further substances,
for example various sand types or quartz flours, fly
ash, pigments, and assistants and additives customary

in the cement industry, for example plasticizers or
setting accelerators or defoamers.
Component C3 of an ECC composition is typically in
pulverulent form, whereas the hardener component C1 and
the resin component C2 are in liquid form.
An ECC composition is typically used as a high-quality
coating or mortar, which are moisture-proof, have good
mechanical properties, low shrinkage and good adhesion,
especially on moist substrates, for example as a floor
covering, barrier .layer for sealing from wetness and
moisture, as a screed, jointing mortar or tile
adhesive, as a leveling, spackling or primer compound,
or as a repair mortar. In addition, such ECC
compositions are notable for high chemical resistance.
The epoxy resin compositions described are applied to
at least one substrate, suitable substrates being the
following:
- glass, glass ceramic, concrete, mortar, brick, tile,
gypsum and natural stone, such as granite or marble;
- metals or alloys, such as aluminum, steel, iron,
nonferrous metals, galvanized metals;
- leather, textiles, paper, wood, resin-bonded woodbase
materials, resin-textile composite materials and
further polymer composites;
- polymers such as polyvinyl chloride (rigid and
flexible PVC), acrylonitrile-butadiene-styrene
copolymers (ABS), SMC (sheet molding compounds),
polycarbonate (PC), polyamide (PA), polyester,
poly(methyl methacrylate) (PMMA) , polyester, epoxy
resins, polyurethanes (PUR), polyoxymethylene (POM),
polyolefins (PO), polyethylene (PE) or polypropylene
(PP), ethylene/propylene copolymers (EPM) and
ethylene-propylene-diene terpolymers (EPDM), and the
polymers may preferably be surface-treated by means
of plasma, corona or flame;

- coated substrates such as powder-coated metals or
alloys; and paints and other coating materials.
If required, the substrates may be pretreated before
the application of the epoxy resin composition. Such
pretreatments include especially physical and/or
chemical cleaning processes, for example grinding, sand
blasting, shot blasting, brushing or the like, dusts
which arise advantageously being removed by suction,
and also treatment with detergents or solvents, or the
application of an adhesion promoter, of an adhesion
promoter solution or of a primer.
Examples
1. Description of the test methods
The viscosity was measured on a Rheotec RC30 cone-plate
viscometer (cone diameter 25 mm, cone angle 1°, cone
tip-plate distance 0.05 mm, shear rate 50 s-1) . The
viscosities measured at 50°C and at 20°C were reported,
respectively, as "η50oc" in Table 1 and as "η20oc" in
Table 2.
2. Raw materials used
Jeffamine® ED-2003 (Huntsman) Polyoxyalkylenediamine based
on propoxylated polyethylene
glycol, mean molecular
weight = 2000 g/mol
Armeen® CD (Akzo Nobel) Cocoalkylamine (C12 fatty
amine), mean molecular
weight = 200 g/mol
Araldite® GY 250 (Huntsman) Bisphenol A diglycidyl
ether, EEW = 187 g/eq, mean
molecular weight thus
approx. 37 5 g/mol
N4-Amine (BASF) N,N'-Bis(3-
aminopropyl)ethylenediamine,
molecular weight = 174 g/mol
Tetraethylenepentamine Technical-grade, molecular
(Delamine) ("TEPA") weight = 18 9 g/mol
Benzylamine Molecular weight = 107 g/mol

2,5-Hexanedione (Wacker) Molecular weight = 114 g/mol
2,4-Pentanedione (Wacker) Molecular weight = 100 g/mol
2-Ethylhexylamine Molecular weight = 129 g/mol
Dimethylacrylamide Molecular weight = 99 g/mol
Butylene oxide Molecular weight = 72 g/mol
Jeffamine® D-230 (Huntsman) Polypropylene glycol
diamine, mean molecular
weight = 240 g/mol
Isophoronediamine (Evonik) l-Amino-3-aminomethyl-3,5,5-
("IPDA") trimethylcyclohexane,
molecular weight =17 0 g/mol
meta-Xylylenediamine (Mitsubishi 1,3-Bis(aminomethyl)benzene,
Gas Chem.) ("MXDA") molecular weight = 136 g/mol
3. Preparation of hardener compositions of the H1
type
Example 1
A round-bottom flask under a nitrogen atmosphere was
initially charged with 200.0 g of Jeffamine® ED-2003
and 20.0 g of Armeen® CD at a temperature of 90°C. With
good stirring, 37.5 g of Araldite® GY 250 were added
slowly, in the course of which it was ensured that the
temperature did not rise above 105oC, and the reaction
mixture was subsequently stirred further at 90°C over
the course of 2 hours. Then 11.4 g of 2,5-hexanedione
were added and stirred in at 90 °C over the course of
15 nain. Then 52.2 g of N4-Amine, then a further 34.2 g
of 2,5-hexanedione, were added to the reaction mixture
and stirred in at 90 °C over the course of 15 min. Then
a further 60.0 g of Armeen® CD, then a further 112.5 g
of Araldite® GY 250, were added, in the course of which
it was ensured that the temperature did not rise above
105°C. Finally, the reaction mixture was stirred at
90'C for a further 2 hours and then cooled.
A yellowish, waxy material which was solid at room
temperature was obtained. The viscosity thereof at 50oC
and the (calculated) NH equivalent weight are reported
in Table 1. In the present document, the NH equivalent

weight refers to the equivalent weight per hydrogen
atom bonded to an amine nitrogen.
Examples 2 to 7 and Comparative examples 8 and 9
Examples 2 to 7 and comparative example 8 were prepared
analogously to example 1, using the ingredients
according to the information in Table 1 in the sequence
specified. The amounts are reported in grams. In
comparative example 8, after the addition of
dimethylacrylamide, a reaction time of 1 hour instead
of 15 minutes was observed in each case before a
further addition. In comparative example 9, after the
first addition of butylene oxide, a reaction time of 14
hours at 60°C instead of 15 minutes at 90°C was
observed, and, after the second addition of butylene
oxide, a reaction time of 3 hours at 60 °C and then 90
minutes at 90°C was observed, before the further
addition in each case.
All hardener compositions of examples 1 to 7 and of
comparative examples 8 and 9 were in the form of
yellowish, solid, waxy materials at room temperature.
In the molten state, they were dilutable with water by
simple stirring with a spatula to obtain an almost
clear liquid in each case. The preparation time of
comparative example 9 is significantly longer than the
preparation times of the hardener compositions of
examples 1 to 7.

4. Production of hardener compositions of the H2 or
HW type
Example 10
A round-bottom flask under a nitrogen atmosphere was
initially charged with 200 g of the hardener
composition from example 1, to which 126.5 g of
Jeffamine® D-230 were added, and the reaction mixture
was heated to 90 °C while stirring. Then, with good
stirring, 98.5 g of Araldite® GY 250 were added
gradually, in the course of which it was ensured that
the temperature did not rise above 105oC. Finally, the
reaction mixture was stirred at 90 °C for a further
90 min, then 75 g of isophoronediamine and 489.1 g of
water were stirred in successively, and the mixture was
cooled.
A yellowish, clear liquid was obtained. The viscosity
at 20°C, the (calculated) NH equivalent weight, the
water content (incl. water formed, in % by weight) and
the storage stability at 50°C are reported in Table 2.
Examples 11 to 17 and comparative examples 18 and 19
Examples 11 to 17 and comparative examples 18 and 19
were prepared analogously to example 10, using the
ingredients according to the information in Table 2.
The amounts are reported in grams.
In all examples apart from comparative examples 18 and
19, a clear liquid was obtained in each case. The
appearance was assessed visually and reported in
Table 2.
For the assessment of storage stability ("storage
stabso'c") i the hardener compositions were heated to 50°C
over the course of 4 weeks. When no coalescence
occurred within this time, the composition was
designated stable or "ok", and otherwise as unstable or
"no".

5. Production of epoxy resin compositions
Examples 20 to 27 and comparative examples 28 and 29
The hardener compositions of the H2 or HW type from
examples 10 to 17 and the hardener compositions from
comparative examples 18 and 19 were mixed in the
proportions by weight specified in Table 3 with 50
parts by weight of the epoxy resin dispersion Sika®
Repair/Sikafloor® EpoCem® Module A (EEW = 288.7 g/eq,
solids content = 62% by weight; Sika Schweiz AG) . For
each mixed composition, a film with a layer thickness
of 76 um was drawn down onto a glass plate, and a film
with a layer thickness of 500 um onto a further glass
plate.
The following tests were carried out thereon:
The hardening rate was determined on a freshly applied
film in a layer thickness of 76 una on glass by means of
a BYK-Gardner drying time recorder (Beck-Koller
method): in Table 3, the start of the deep trace
("flow") was designated "tflow, the start of film
tearing ("soft gel") "tsoft gel", the start of the surface
trace ("hard gel") "thard gel", and the end of the surface
trace ("cured") "tcured".
The hardness was determined as the Buchholz hardness on
a film drawn down onto a glass plate in a layer
thickness of 500 µm, after a hardening time of 30 days
at 23°C and 50% relative humidity (r.H.), by means of a
PIG universal instrument from Byk-Gardner.
The adhesion was determined on glass on a film drawn
down onto a glass plate in a layer thickness of 500 um.
To test the adhesion, the film was repeatedly incized
down to the glass plate with a blade, and attempts were
made to detach the film from the glass plate with the
blade. If this was impossible, the adhesion was
designated "good".

The appearance was assessed on two films each on glass
with layer thicknesses of 76 µm and 500 µm, and
designated in Table 3 as appearance (76 yua) and as
appearance (500 µm) . The appearances were designated
clear ("clear"), hazy ("hazy"), impeccable ("imp.") and
structured ("struc") . Impeccable films are considered
to be those which are clear, shiny and tack-free, and
have no surface structure whatsoever. Structured films
are considered to be those whose surface is not
completely smooth but has a slight orange-like skin.
The results of the tests are reported in Table 3.

6. Preparation of ECC compositions
Example 30
7.2 parts by weight of the hardener composition from
example 10 were mixed with 17.6 parts by weight of
water and 0.19 part by weight of defoamer (BYK®-023,
BYK-Chemie) (= hardener component) . To this were added
10 parts by weight of Sika® Repair/Sikafloor® EpoCem®
Module A (EEW = 288.7 g/eq, solids content = 62% by
weight; Sika Schweiz AG) (= resin component) and 150
parts by weight of Sikafloor®-81 EpoCem® component C
(Sika Schweiz AG) (=cementitious powder), and-
everything was mixed thoroughly. The ECC composition
obtained was used to determine the solidification time
to EN 480-2, the slump to EN 1015-3 and the compressive
strength and the flexural tensile strength on prisms of
dimensions 40x40x160 mm to EN 13892-2, the tensile
adhesive strength to EN 13892-8 and the shrinkage
(change in length) of prisms of dimensions 40x40x160 mm
to DIN 52450 after storage under standard climatic
conditions (23oC, 50% relative humidity) for different
durations. The results are reported in Table 4.
Example 31
In the same way as described for example 30, the
hardener composition from example 13 was used to
produce an ECC mortar, and it was tested. The results
are reported in Table 4.

The ECC compositions of examples 30 and 31 have
exceptionally good processability, have very good
mechanical properties and harden with impeccable
surface appearance.

Claims
1. A compound VB of the formula (I) or (II)

where
R1 and R3 are each independently an alkyl, cycloalkyl,
aryl or arylalkyl group which has 1 to 12 carbon atoms
and optionally has ether groups or halogen atoms, and
R2 is a hydrogen atom or an alkyl, cycloalkyl, aryl or
arylalkyl group having 1 to 12 carbon atoms,
or
R2 and R1 together are a divalent hydrocarbon radical
which is part of an optionally substituted carbocyclic
ring having 5 to 8 and preferably 5 or 6 carbon atoms,
and R3 is an alkyl, cycloalkyl, aryl or arylalkyl group
which has 1 to 12 carbon atoms and optionally has ether
groups or halogen atoms;
or
R2 and R3 together are a divalent hydrocarbon radical
which is part of an optionally substituted carbocyclic
ring having 5 to 8 and preferably 5 or 6 carbon atoms,
and R1 is an alkyl, cycloalkyl, aryl or arylalkyl group
which has 1 to 12 carbon atoms and optionally has ether
groups or halogen atoms;

R4 and R5 are each independently an alkyl, cycloalkyl,
aryl or arylalkyl group which has 1 to 12 carbon atoms
and optionally has ether groups or halogen atoms;
A is an (a+b)-valent radical of a polyamine-polyepoxide
adduct after removal of (a+b) primary amino groups;
a is an integer from 0 to 4; and
b is an integer from 1 to 4;
with the provisos that the sum of a and b is an integer
from 1 to 4, and that the parent polyepoxide of the
polyamine-polyepoxide adduct is a polyepoxide E,
especially a diepoxide E1, and has an epoxy equivalent
weight (EEW) of 65 to 500 g/eq.
2. A compound VB as claimed in claim 1, characterized
in that it has the formula (Ia) or (Ib)

where
R6 is an alkyl or cycloalkyl or arylalkyl group which
optionally has ether or secondary amino groups;
E1 and E2 are each independently the remainder of a
diepoxide E1 having an epoxy equivalent weight (EEW) of
65 to 500 g/eq, after removal of two epoxy groups;
x is an integer from 0 to 50;
y is an integer from 0 to 100, preferably 10 to 50;
z is an integer from 1 to 50;
(x+z) is an integer from 1 to 100, preferably 1 to 10;
p is 0 or 1; and
q is 0, 1, 2 or 3.

3. A compound VB as claimed in claim 1, characterized
in that it has the formula (IIa) or (IIb)

where
R6 is an alkyl or cycloalkyl or arylalkyl group which
optionally has ether or secondary amino groups;
E1 and E2 are each independently the remainder of a
diepoxide El having an epoxy equivalent weight (EEW) of
65 to 500 g/eq, after removal of two epoxy groups;
x is an integer from 0 to 50;
y is an integer from 0 to 100, preferably 10 to 50;
z is an integer from 1 "to 50;
(x+z) is an integer from 1 to 100, preferably 1 to 10;
p is 0 or 1; and
q is 0, 1, 2 or 3.
4. A compound VB as claimed in any of the preceding
claims, characterized in that the diepoxide E1 is
selected from the group consisting of a bisphenol A,
bisphenol F and bisphenol A/F diglycidyl ether having
an epoxy equivalent weight of 156 to 250 g/eq, N,N-
diglycidylaniline and a polyglycol diglycidyl ether
having an epoxy equivalent weight of 170 to 340 g/eq.
5. A process for preparing a compound VB as claimed
in any of claims 1 to 4, characterized in that
(a) at least one polyamine Al containing at least two
primary amino groups,

(β) optionally at least one amine A2 containing only
one primary amino group,
(γ) at least one polyepoxide E having an epoxy
equivalent weight (EEW) of 65 to 500 g/eq and
(δ) at least one diketone K1 of the formula (IV) or K2
of the formula (V)

are reacted with one another over more than one stage,
where the ratio between the number of primary amino
groups and epoxy groups is especially 1.25 to 2.0,
and where the diketone Kl or K2 is used in a ratio to
the primary amino groups, which are in excess in
relation to the epoxy groups, especially in an amount
of 0.25 to 1.0 equivalent.
6. The process as claimed in claim 5, characterized
in that the diketone Kl is selected from the group
consisting of 2,4-pentanedione, 3-methyl-, 3-ethyl-, 3-
propyl-, 3-isopropyl-, 3-butyl-, 3-tert-butyl-, 3-
cyclohexyl-, and 3-phenyl-2,4-pentanedione, 3,5-
heptanedione, 6-methyl-3,5-heptanedione, 2,2,6,6-
tetramethyl-3,5-heptanedione, 2,2,4,6,6-pentamethyl-
3,5-heptanedione, 2-acetylcyclopentanone and 2-
acetylcyclohexanone, and is preferably 2,4-
pentanedione.
7. The process as claimed in claim 5 or 6,
characterized in that the polyamine A1 is selected from
the group consisting of ether-containing diamines of

weight of 500 to 5000 g/mol, and polyalkyleneamines,
especially diethylenetriamine (DETA),
triethylenetetramine (TETA), tetraethylenepentamine
(TEPA), pentaethylenehexamine (PEHA),
polyethylenepolyamine having 5 to 7 ethyleneamine units
(known as "higher ethylenepolyamine", HEPA), 3-(2-
aminoethyl)aminopropylamine (N3-amine) and N,N'-bis(3-
aminopropyl)ethylenediamine (N4-amine).

8. The process as claimed in any of claims 5 to 7,
characterized in that the amine A2 is selected from the
group consisting of butylamine, pentylamine,
hexylamine, cyclohexylamine, octylamine, decylamine,
dodecylamine, tetradecylamine, hexadecylamine,
octadecylamine, eicosylamine, docosylamine, 2-ethyl-1-
hexylamine, benzylamine, 1- or 2-phenylethylamine, N-
hexyl-1,2-ethanediamine, N-(2-ethylhexyl)-1,2-
ethanediamine, N-cyclohexyl-1,2-ethanediamine, N-butyl-
1,3-propanediamine, N-hexyl-1,3-propanediamine, N-(2-
ethylhexyl)-1,3-propanediamine, N-dodecyl-1,3-
propanediamine, N-cyclohexyl-1,3-propanediamine,
cocoalkylamine, soyaalkylamine, oleylamine, N-
cocoalkyl-1, 3-propanediamine, N-oleyl-1,3-
propanediamine and N-soyaalkyl-1,3-propanediamine.
9. The process as claimed in any of claims 5 to 8,
characterized in that the polyepoxide E is a diepoxide
E1 which is selected from the group consisting of a
bisphenol A, bisphenol F and bisphenol A/F diglycidyl
ether having an epoxy equivalent weight of 156 to
250 g/eq, N, N-diglycidylaniline and a polyglycol
diglycidyl ether having an epoxy equivalent weight of
170 to 340 g/eq.

10. A hardener composition comprising
(a) at least one compound VB of the formula (I) or
(II) as claimed in any of claims 1 to 4.
11. The hardener composition as claimed in claim 10,
characterized in that it comprises at least one
compound VB of the formula (Ia) or (IIa) as claimed in
any of claims 2 to 4, and at least one compound VB of
the formula (Ib) or (IIb) as claimed in any of claims 2
to 4.
12. The hardener composition as claimed in claim 10 or
11, characterized in that the hardener composition
additionally comprises:
(b) at least one adduct AD formed from at least one
polyamine A3 having at least two amino groups in the
form of primary or secondary amino groups and at least
one polyepoxide E having an epoxy equivalent weight
(EEW) of 65 to 500 g/eq, where the adduct AD has
terminal primary and/or secondary amino groups,
(c) optionally at least one polyamine A4 having at
least two amino groups in the form of primary or
secondary amino groups, and
(d) optionally water.
13. The hardener composition as claimed in claim 12,
characterized in that the polyamine A3 is selected from
the group consisting of firstly polyoxyalkylenediamines
having a molecular weight of at most 1000 g/mol, and
secondly isophoronediamine (IPDA), 2,2,4- and 2,4,4-
trimethylhexamethylenediamine (TMD), 1,3-xylylene-
diamine (meta-xylylenediamine or MXDA), 2-butyl-2-
ethyl-1,5-pentanediamine (Cll-neodiamine), N-ethyl-1,3-
propanediamine and N-cyclohexyl-1,3-propanediamine.
14. The hardener composition as claimed in claim 12 or
13, characterized in that the polyamine A4 is selected
from the group consisting of isophoronediamine (IPDA),

bis(4-aminocyclohexyl)methane (H12-MDA), bis(4-amino-3-
methylcyclohexyl)methane, 2,2,4- and 2,4,4-
trimethylhexamethylenediamine (TMD), 1,3-xylylene-
diamine (meta-xylylenediamine or MXDA) and 2-butyl-2-
ethyl-1,5-pentanediamine (C11-neodiamine).
15. The hardener composition as claimed in any of
claims 12 to 14, characterized in that the composition
contains water, especially in an amount of 20 to 90% by
weight, based on the overall hardener composition.
16. A two-pack or three-pack epoxy resin composition'
consisting of a hardener component C1 and a resin
component C2 and optionally a further component C3,
where
hardener component C1 comprises or consists of at least
one hardener composition as claimed in any of claims 10
to 15;
and resin component C2 comprises or consists of at
least one epoxy resin;
and component C3 comprises or consists of at least one
hydraulically setting mineral substance, preferably
cement.
17. A hardened composition which is obtained by mixing
the components of a two- or three-pack epoxy resin
composition as claimed in claim 16.
18. The use of a compound VB as claimed in any of
claims 1 to 4 as a hardener for substances which have
at least two groups reactive toward NH and OH groups
and which are especially selected from the group
consisting of isocyanate, isothiocyanate,
cyclocarbonate, epoxide, episulfide, aziridine,
acryloyl, methacryloyl, 1-ethynylcarbonyl, 1-
propynylcarbonyl, maleimide, citraconimide, vinyl,
isopropenyl and allyl groups.

19. The use of a two- or three-pack epoxy resin
composition as claimed in claim 16 as a coating,
especially as a floor coating.

The present invention relates to novel compounds VB of the formula (I) or (II), said compounds being particularly
suitable as curing agents for epoxide resins. The compounds can be produced easily and rapidly. They can be used in the form of
aqueous curing agents and form stabile aqueous emulsions in particular. This facilitates the formulation of ECC compounds for
use primarily as coatings.

Documents:

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Patent Number

279695

Indian Patent Application Number

4048/KOLNP/2010

PG Journal Number

05/2017

Publication Date

03-Feb-2017

Grant Date

30-Jan-2017

Date of Filing

28-Oct-2010

Name of Patentee

SIKA TECHNOLOGY AG

Applicant Address

ZUGERSTRASSE 50, CH-6340 BAAR SWITZERLAND

Inventors:

#	Inventor's Name	Inventor's Address
1	BÜTIKOFER, PIERRE-ANDRÉ	ROSENBERGSTRASSE 7, CH-8304 WALLISELLEN SWITZERLAND

PCT International Classification Number

C08G 59/40

PCT International Application Number

PCT/EP2009/057258

PCT International Filing date

2009-06-12

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	08158211.6	2008-06-13	EUROPEAN UNION