ADDUCT OF ALKYLATED DIAMIN AND NOVOLAK EPOXY RESIN

Description

Technical field

[0001] The invention relates to amine-functional adducts of monoalkylated diamines and novolac epoxy resins and their use as hardeners for epoxy resin compositions, which are particularly suitable as corrosion protection coatings. State of the art

[0002] Epoxy resin-based coatings or paints for the corrosion protection of steel components are widely used in industry and construction. They consist of liquid resin and hardener components, which are mixed before application and cure to a solid coating at ambient temperatures ranging from approximately 5 to 40 °C. These coatings should have low viscosity, cure quickly and without defects, and form a smooth, tack-free surface without cloudiness, stains, or deposits, even under damp, cold conditions. Furthermore, they should exhibit good interlayer adhesion in multi-layer applications, which is often lacking when surface defects such as blushing occur, and be particularly robust against corrosive conditions, especially moisture in combination with heat and / or salts.For visually demanding applications, the coatings should also have the lowest possible tendency to yellow under the influence of light.

[0003] Novolak epoxy resins are particularly hydrophobic and allow for a high degree of crosslinking. They are therefore especially suitable for use in corrosion protection coatings. In the hardener component, they can be used in the form of adducts with polyamines. However, the amine-functional adducts of novolak epoxy resins known from the prior art are very highly viscous and usually have to be significantly diluted for processing at ambient temperatures, typically with thinners such as xylene or benzyl alcohol and / or high amounts of excess polyamine during adduction.

[0004] Since thinners are not incorporated into the resin matrix during curing, they can be released into the environment through evaporation or diffusion. However, low-emission products with a low content of releasable substances after curing are increasingly desired. Therefore, thinners such as xylene or benzyl alcohol should only be used in small quantities or not at all. Furthermore, high amounts of excess polyamine during adduction lead to increased blushing and result in a reduced concentration of novolac in the hardener, thus diminishing the effect of this hydrophobic component.

[0005] US 4,348,505 discloses adducts of polyalkyleneamines such as diethylenetriamine (DETA) or primary diamines such as 1,2-diaminocyclohexane with novolac epoxy resins. The manufactured adducts contain significant amounts of xylene and / or benzyl alcohol.

[0006] US 2019 / 0382524 discloses adducts of bis(6-aminohexyl)amine or triethylenetetramine (TETA) with novolac epoxy resins produced with a high amine excess.

[0007] EP 2,151,461 discloses a mixture of benzylated DETA and TETA and, in Example 21, an adduct thereof with a novolac epoxy resin with a high xylene content.

[0008] WO 2017 / 046293 discloses adducts of N-benzyl-1,2-propanediamine or N-benzyl-1,2-ethanediamine with diepoxides, in particular bisphenol A diglycidyl ether. Such adducts are significantly less highly functional and hydrophobic compared to adducts of novolac epoxy resins. Description of the invention

[0009] The object of the present invention is therefore to provide an amine-functional adduct which is liquid and easy to handle at room temperature even without diluents such as xylene or benzyl alcohol and without a high excess of amine, enables a particularly high crosslinking density and is therefore particularly suitable for use in corrosion protection coatings.

[0010] Surprisingly, the amine-functional adduct resulting from the reaction of at least one amine of formula (I) with at least one novolac epoxy resin according to claim 1 solves this problem. Despite the high functionality of the novolac epoxy resin, the adduct according to the invention is surprisingly low-viscosity. It is particularly low-odor and can be handled as a liquid at room temperature without a high excess of amines or a thinner. This enables the production of low-odor, low-emission epoxy resin products with a high novolac epoxy resin content in the hardener, whereby further amines and / or a thinner can be flexibly added during subsequent use, depending on the application and requirements. The adduct according to the invention enables the production of epoxy resin coatings that are easy to process at ambient temperatures, cure surprisingly quickly, and form a smooth, defect-free surface with a low tendency to yellow.Such coatings are aesthetically pleasing, particularly robust against moisture, even in combination with heat and / or salts, and exhibit exceptionally good adhesion between layers (interlayer adhesion) in multi-layer applications. Furthermore, these coatings possess high thermal shock resistance, withstanding multiple shock-like temperature changes between ice water and 200 °C without cracking, even in thin layers of, for example, 250 µm on steel. This is particularly surprising given the high functionality of the novolac epoxy resin underlying the adduct.

[0011] Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are the subject of dependent claims. Ways to implement the invention

[0012] The invention relates to an amine-functional adduct resulting from the reaction of at least one amine of formula (I), Z-NH-A-NH-CH2-Y (I) where A represents a divalent alkylene, cycloalkylene or arylalkylene residue with 2 to 15 C atoms, Z represents H or ---CH2-Y, and Y represents H or an alkyl, cycloalkyl, aralkyl or aryl residue with 1 to 11 C atoms, wherein the two nitrogen atoms to which the residue A is bonded are separated from each other by at least two C atoms and the amine of formula (I) contains a total of at least 8 C atoms, with at least one novolac epoxy resin having a medium functionality in the range of 2.5 to 4.

[0013] The "average functionality" of an epoxy resin is defined as the average number of epoxy groups per molecule.

[0014] The term "epoxy liquid resin" refers to a technical polyepoxide with a glass transition temperature below 25°C.

[0015] Substance names beginning with "Poly", such as polyamine or polyepoxide, denote substances that formally contain two or more of the functional groups appearing in their name per molecule.

[0016] A "primary amino group" is an amino group bonded to a single organic residue and bearing two hydrogen atoms; a "secondary amino group" is an amino group bonded to two organic residues, which may also be part of a ring together, and bearing one hydrogen atom; and a "tertiary amino group" is an amino group bonded to three organic residues, which may also be part of one or more rings in pairs or groups of three, and bearing no hydrogen atom.

[0017] The hydrogen atoms of primary and secondary amino groups are referred to as "amine hydrogen".

[0018] The "hydrogen amine equivalent weight" refers to the mass of an amine or an amine-containing composition that contains one mole equivalent of hydrogen amine. It is expressed in the unit "g / eq".

[0019] The term "epoxide equivalent weight" refers to the mass of a compound or composition containing epoxy groups that contains one mole equivalent of epoxy groups. It is expressed in the unit "g / eq".

[0020] A "thinner" is a substance that is soluble in an epoxy resin and reduces its viscosity, but which is not chemically incorporated into the epoxy resin polymer during curing.

[0021] The term "molecular weight" refers to the molar mass (in grams per mole) of a molecule. The term "mean molecular weight" refers to the number mean Mn of a polydisperse mixture of oligomeric or polymeric molecules, which is usually determined by gel permeation chromatography (GPC) against polystyrene as a standard.

[0022] The term "gelling time" refers to the period from the mixing of the components of an epoxy resin composition until it gels.

[0023] A dashed line in the formulas represents the bond between a substituent and the corresponding molecular residue.

[0024] A temperature of 23 °C is referred to as "room temperature".

[0025] All industry standards and norms mentioned in this document refer to the versions valid at the time of the initial application. Weight percent (wt%), abbreviated wt%, denotes the mass fraction of a component of a composition or molecule, relative to the entire composition or molecule, unless otherwise specified. The terms "mass" and "weight" are used synonymously in this document.

[0026] In the amine of formula (I), A is preferably selected from the group consisting of 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,3-butylene, 2-methyl-1,2-propylene, 1,3-pentylene, 1,5-pentylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene, 2-methyl-1,5-pentylene, 1,7-heptylene, 1,8-octylene, 2,5-dimethyl-1,6-hexylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 4(2)-methyl-1,3-cyclohexylene, 1,3-Cyclohexylene bis(methylene) and 1,4-Cyclohexylene bis(methylene).

[0027] Of these, 1,2-ethylene or 1,2-propylene is preferred.

[0028] A is particularly preferred for 1,2-ethylene. These amines of formula (I) enable low-viscosity adducts with particularly fast curing.

[0029] In the amine of formula (I), Y is preferably selected from the group consisting of H, Methyl, Ethyl, Propyl, Isopropyl, Butyl, Pentyl, Heptyl, Hept-2-yl, Phenyl, 4-Methylphenyl, 1-Naphthyl and Cyclohexyl.

[0030] Y is particularly preferred for phenyl or cyclohexyl, especially for phenyl. Such an amine of formula (I) enables low-viscosity adducts with particularly fast and trouble-free curing.

[0031] In the amine of formula (I), Z preferentially represents H, or the amine of formula (I) is a mixture containing an amine of formula (I) with Z = H and an amine of formula (I) with Z = ---CH₂-Y. In both amines, Y preferentially represents the same residue.

[0032] Preferably a mixture containing amine of formula (I) with Z = H and amine of formula (I) with Z = ---CH 2 -Y contains at most 35 wt%, preferably at most 30 wt%, amine of formula (I) with Z = ---CH 2 -Y based on the sum of the two amines.

[0033] Z is particularly preferred as H. In particular, in such an amine of formula (I), the content of amine of formula (I) with Z = ---CH₂-Y is less than 5 wt%. Such an adduct enables particularly rapid curing.

[0034] Preferably the amine of formula (I) is selected from the group consisting of N-benzyl-1,2-ethanediamine, N,N'-dibenzyl-1,2-ethanediamine, N-(4-methylbenzyl)-1,2-ethanediamine, N,N'-bis(4-methylbenzyl)-1,2-ethanediamine, N-(1-naphthylmethyl)-1,2-ethanediamine, N,N'-bis(1-naphthylmethyl)-1,2-ethanediamine, N-cyclohexylmethyl-1,2-ethanediamine, N,N'-dicyclohexylmethyl-1,2-ethanediamine, N-benzyl-1,2-propanediamine and N,N'-dibenzyl-1,2-propanediamine.

[0035] The most preferred amino acids are A for 1,2-ethylene and Y for phenyl. Such an amine of formula (I) enables adducts with particularly low viscosity and particularly fast and trouble-free curing.

[0036] The amine of formula (I) is particularly preferred N-benzyl-1,2-ethanediamine.

[0037] The amine of formula (I) is further preferably a mixture of N-benzyl-1,2-ethanediamine and N,N'-dibenzyl-1,2-ethanediamine in a weight ratio in the range of 65 / 35 to 95 / 5, preferably 70 / 30 to 90 / 10.

[0038] The amine of formula (I) is preferably prepared by partial alkylation of at least one amine of the formula H₂NA-NH₂ with at least one alkylating agent. Preferably, the alkylation is a reductive alkylation, wherein an aldehyde of the formula Y-CH=O and hydrogen are used as the alkylating agent. Particularly preferably, a molar excess of the amine of the formula H₂NA-NH₂ is reductively alkylated with an aldehyde of the formula Y-CH=O, and the excess amine of the formula H₂NA-NH₂ is removed from the reaction product by distillation. This preparation is particularly preferred for small residues A such as 1,2-ethylene.

[0039] The amine of formula (I) with Z = H can then be freed by distillation from the corresponding dialkylated amine of formula (I) with Z = ---CH 2 -Y.

[0040] Preferably, the amine of formula (I) contains only a small amount of dialkylated amine of formula (I) with Z = ---CH 2 -Y, in particular at most 35 wt%, preferably at most 30 wt%, based on the sum of the two amines.

[0041] Particularly preferably, the amine of formula (I) with Z = H contains less than 5 wt% of the corresponding dialkylated amine of formula (I) with Z = ---CH 2 -Y. Such an adduct enables particularly rapid curing.

[0042] The Novolak epoxy resin is preferably liquid at room temperature.

[0043] The Novolak epoxy resin preferably has a medium functionality in the range of 2.7 to 3.7.

[0044] Preferably, the novolac epoxy resin is a phenol-formaldehyde novolac glycidyl ether. In particular, it has formula (II), where n on average represents a value in the range of 0.5 to 2, preferably 0.7 to 1.7.

[0045] Preferably, the Novolak epoxy resin has a mean epoxy equivalent weight in the range of 165 to 210 g / eq, in particular 170 to 185 g / eq.

[0046] Suitable novolac epoxy resins include, in particular, commercially available technical phenol-formaldehyde novolac glycidyl ethers, such as Epilox® < N 18-10 (from Leuna Harze), DEN 431, DEN 438 or DEN 439 (all from Olin), Araldite® < EPN 1179 or Araldite® < EPN 1180 (all from Huntsman), Epalloy® < 8250, Epalloy® < 8330 or Epalloy® < 8350 (all from Huntsman), or Epon® < Resin 154 or Epon® < Resin 160 (from Momentive).

[0047] Preferably, the reaction between the amine of formula (I) and the novolac epoxy resin takes place in a stoichiometric ratio of less than 3 mol, preferably less than 2.6 mol, amine of formula (I) to 1 mol equivalent of epoxy groups, particularly in the range of 1.3 to 2.5 mol, preferably 1.4 to 2.1 mol, amine of formula (I) to 1 mol equivalent of epoxy groups.

[0048] Such an adduct contains very little unreacted amine of formula (I) and a high content of adduct molecules. It is particularly low in odor and surprisingly low in viscosity. It allows for particularly rapid curing and exceptional flexibility in combination with other amines.

[0049] In the case of a novolac epoxy resin with high functionality in the range of 3 to 4, the stoichiometric ratio during the reaction is preferably in the range of 1.6 to 2.5 mol, in particular 1.8 to 2.1 mol, amine of formula (I) to 1 mol equivalent of epoxy groups.

[0050] Preferably, the temperature during the reaction is in the range of 40 to 120 °C, particularly 60 to 100 °C.

[0051] Preferably, the amine of formula (I) is initially prepared and, in particular, heated to a temperature in the range of 40 to 100 °C before the novolac epoxy resin is added and mixed in. Preferably, the novolac epoxy resin is added at a temperature in the range of 20 to 100 °C, particularly 50 to 100 °C. Preferably, the addition is carried out at such a rate that the reaction mixture does not exceed a temperature of 120 °C, preferably 100 °C.

[0052] After the reaction, unreacted amine of formula (I) is preferably not removed from the adduct, but remains in it and is a component of the adduct.

[0053] The resulting adduct is stored in a dry place. It is low-odor, liquid at room temperature, and surprisingly low-viscosity, making it very easy to handle.

[0054] In particular, the adduct contains oligomeric compounds of formula (III), where n on average stands for a value in the range of 0.5 to 2, preferably 0.7 to 1.7, G 1< and G 2< stand for Z with the proviso that at least one of the two stands for ---CH 2 -Y, and Y and A have the meanings already mentioned.

[0055] Furthermore, the adduct contains higher adducted fractions in which more than one amine hydrogen of one or more amines of formula (I) has been reacted.

[0056] Preferably the adduct contains less than 10 wt%, preferably less than 5 wt%, in particular less than 1 wt%, diluent.

[0057] Preferably, the adduct contains less than 1% by weight of water.

[0058] Preferably, the adduct has a viscosity at 20 °C in the range of 5 to 500 Pa·s, preferably 10 to 350 Pa·s, measured using a cone-plate viscometer at a shear rate of 10 s -1< .

[0059] The adduct according to the invention is particularly suitable for curing an epoxy resin.

[0060] Another object of the invention is a hardener for epoxy resins, comprising the adduct according to the invention and at least one further component selected from the group consisting of further amines, accelerators and thinners.

[0061] The hardener preferably contains 10 to 80 wt%, preferably 15 to 70 wt%, in particular 20 to 60 wt%, of the adduct according to the invention.

[0062] The hardener for epoxy resins is preferably non-water-based. It contains, in particular, less than 15% by weight, preferably less than 10% by weight, water. Such a hardener is suitable for non-aqueous epoxy resin products.

[0063] Preferably, the hardener contains at least one further amine with aliphatic amino groups and at least three hydrogen amines, which was not present in the preparation of the adduct. This further amine may be the same amine of formula (I) as the one used to prepare the adduct, or a different amine.

[0064] Other suitable amines include, in particular, N-benzyl-1,2-ethanediamine, N-benzyl-1,2-propanediamine, N-benzyl-1,3-bis(aminomethyl)benzene, N-(2-ethylhexyl)-1,3-bis(aminomethyl)benzene, 2,2-dimethyl-1,3-propanediamine, 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),4-trimethyl-1,6-hexanediamine (TMD), 1,7-heptanediamine, and 1,8-octanediamine. 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, Bis(4-aminocyclohexyl)methane, 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, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 2(4)-methyl-1,3-diaminocyclohexane, 2,5(2,6)-Bis(aminomethyl)bicyclo[2.2.1]heptane (NBDA), 3(4),8(9)-Bis(aminomethyl)tricyclo[5.2.1.0 2,6< ]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, 1,3-bis(aminomethyl)benzene (MXDA), 1,4-bis(aminomethyl)benzene, 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, 4,7,10-Trioxatridecan-1,13-diamine or higher oligomers of these diamines, bis(3-aminopropyl)polytetrahydrofurans or other polytetrahydrofurandiamines, polyoxyalkylenediamines or triamines, especially polyoxypropylenediamines or polyoxypropylenetriamines such as Jeffamine® < D-230, Jeffamine® < D-400 or Jeffamine® < T-403 (all from Huntsman), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), dipropylenetriamine (DPTA), N-(2-aminoethyl)-1,3-propanediamine (N3-amine), N,N'-bis(3-aminopropyl)ethylenediamine (N4-amine), N,N'-bis(3-aminopropyl)-1,4-Diaminobutane, N5-(3-Aminopropyl)-2-methyl-1,5-pentanediamine, N3-(3-Aminopentyl)-1,3-pentanediamine, N5-(3-Amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine, N,N'-Bis(3-amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine, 3-(2-Aminoethyl)aminopropylamine, Bis(hexamethylene)triamine (BHMT), N-Aminoethylpiperazine, 3-Dimethylaminopropylamine (DMAPA), 3-(3-(Dimethylamino)propylamino)propylamine (DMAPAPA), amine-functional adducts of the aforementioned amines with epoxides or a mixture of two or more of these amines.

[0065] The hardener particularly preferably contains at least one further amine selected from the group consisting of N-benzyl-1,2-ethanediamine, N,N'-dibenzyl-1,2-ethanediamine, MPMD, TMD, 1,2-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, IPDA, 2(4)-methyl-1,3-diaminocyclohexane, MXDA, DETA, TETA, TEPA, N3-amine, N4-amine, DPTA, BHMT, polyoxypropylenediamines with an average molecular weight M n in the range of 200 to 500 g / mol and polyoxypropylenetriamines with an average molecular weight M n in the range of 300 to 500 g / mol.

[0066] Of these, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, especially 1,3-bis(aminomethyl)cyclohexane, is preferred. This enables particularly rapid curing.

[0067] IPDA remains the preferred option. It achieves particularly high glass transition temperatures, resulting in exceptional robustness against high operating temperatures.

[0068] MXDA remains the preferred option. It achieves high curing speeds and particularly high strengths, and especially exceptional thermal shock resistance.

[0069] N-Benzyl-1,2-ethanediamine remains the preferred compound. It yields particularly low-viscosity epoxy resin products with exceptionally attractive surfaces.

[0070] Preferably, the hardener contains such an amount of further amines that 5 to 70%, preferably 7 to 55%, particularly 10 to 40% of all amine hydrogens present originate from the adduct according to the invention.

[0071] Suitable accelerators are in particular acids or compounds hydrolyzable to acids, especially 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 acid esters, other organic or inorganic acids such as phosphoric acid, or mixtures of the aforementioned acids and acid esters; nitrates such as calcium nitrate; tertiary amines such as in particular 1,4-diazabicyclo[2.2.2]octane, benzyldimethylamine, α-methylbenzyldimethylamine, triethanolamine, dimethylaminopropylamine, imidazoles such as in particular N-methylimidazole, N-vinylimidazole or 1,2-dimethylimidazole, salts of such tertiary amines, quaternary ammonium salts such as in particular benzyltrimethylammonium chloride, amidines such as in particular 1,8-diazabicyclo[5.4.0]-undec-7-ene, guanidines such as in particular 1,1,3,3-tetramethylguanidine, phenols, in particular bisphenols, phenol resins or Mannich bases such as in particular 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol or polymers of phenol, formaldehyde and N,N-dimethyl-1,3-propanediamine, phosphites such as in particular di- or triphenyl phosphites, or compounds containing mercapto groups.

[0072] Preferred accelerators are acids, nitrates, tertiary amines or Mannich bases, in particular salicylic acid, calcium nitrate or 2,4,6-tris(dimethylaminomethyl)phenol, or a combination of these accelerators.

[0073] Suitable thinners include in particular n-propanol, isopropanol, n-butanol, isobutanol, tert.Butanol, 1-Pentanol, 2-Pentanol, 3-Pentanol, 2-Methyl-1-butanol, 3-Methyl-1-butanol, 3-Methyl-2-butanol n-Hexanol, 2-Ethylhexanol, Xylol, 2-Methoxyethanol, Dimethoxyethanol, 2-Ethoxyethanol, 2-Propoxyethanol, 2-Isopropoxyethanol, 2-Butoxyethanol, 2-Phenoxyethanol, 2-Benzyloxyethanol, Benzylalkohol, Ethylenglykol, Ethylenglykoldimethylether, Ethylenglykoldiethylether, Ethylenglykoldibutylether, Ethylenglykoldiphenylether, Diethylenglykol, Diethylenglykolmonomethylether, Diethylenglykolmonoethylether, Diethylenglykolmono-n-butylether, Diethylenglykoldimethylether, Diethylenglykoldiethylether, Diethylenglykoldi-n-butylylether, Propylenglykolbutylether, Propylenglykolphenylether, Dipropylenglykol, Dipropylenglykolmonomethylether, Dipropylenglykoldimethylether, Dipropylenglykoldi-n-butylether, 2,2,4-Trimethyl-1,3-pentandiolmonoisobutyrat, Diphenylmethan, Diisopropylnaphthalin, Erdölfraktionen wie zum Beispiel Solvesso ®< -Typen (von Exxon), Alkylphenole wie tert.Butylphenol, nonylphenol, dodecylphenol, cardanol, styrolated phenol, bisphenols, aromatic hydrocarbon resins, especially phenol-containing types, alkoxylated phenol, especially ethoxylated or propoxylated phenol, especially 2-phenoxyethanol, adipates, sebacates, phthalates, benzoates, organic phosphoric or sulfonic acid esters or sulfonamides.

[0074] Preferred thinners include those with a boiling point above 200 °C, in particular benzyl alcohol, styrolated phenol, ethoxylated phenol, aromatic hydrocarbon resins containing phenol groups such as, in particular, the Novares® types LS 500, LX 200, LA 300 or LA 700 (from Rütgers), diisopropylnaphthalene or Cardanol, especially benzyl alcohol.

[0075] Thinners containing phenol groups also act as accelerators.

[0076] Of these, low-toxicity, low-odor thinners with a boiling point in the range of 90 to 150 °C are still preferred, in particular n-butanol, 1-pentanol, 3-pentanol, 3-methyl-1-butanol, or 3-methyl-2-butanol. Such thinners enable low-odor, easily workable corrosion protection coatings, in which the thinner evaporates in a relatively short time and can hardly penetrate any insulation applied over the corrosion protection coating and damage it.

[0077] Aromatic thinners with a particularly high thinning effect, especially xylene, are still preferred.

[0078] The hardener may contain other components, in particular the following: Other adducts, in particular adducts of MPMD or 1,2-ethanediamine or 1,2-propanediamine with cresyl glycidyl ether, in which unreacted MPMD, 1,2-ethanediamine or 1,2-propanediamine was removed by distillation after the reaction; monoamines such as, in particular, benzylamine or furfurylamine; polyamidoamines, in particular reaction products of a mono- or polyhydric carboxylic acid or its ester or anhydride, in particular a dimer fatty acid, with a polyamine used in stoichiometric excess, in particular DETA or TETA; Mannich bases, in particular phenalkamines, i.e., reaction products of phenols, in particular cardanol, with aldehydes, in particular formaldehyde, and polyamines; aromatic polyamines such as in particular 4,4'-, 2,4' and / or 2,2'-diaminodiphenylmethane, 2,4(6)-toluenediamine, 3,5-dimethylthio-2,4(6)-toluenediamine or 3,5-diethyl-2,4(6)-toluenediamine;Compounds containing mercapto groups, in particular liquid mercaptan-terminated polysulfide polymers, mercaptan-terminated polyoxyalkylene ethers, mercaptan-terminated polyoxyalkylene derivatives, polyesters of thiocarboxylic acids, 2,4,6-trimercapto-1,3,5-triazine, triethylene glycol dimercaptan or ethanedithiol.

[0079] Another object of the present invention is an epoxy resin composition comprising a resin component containing at least one epoxy resin and a hardener component containing at least one adduct according to the invention or the hardener described above.

[0080] Preferably, the hardener component comprises the hardener described above.

[0081] A suitable epoxy resin is obtained in a known manner, in particular from the reaction of epichlorohydrin with polyols, polyphenols or amines.

[0082] Suitable epoxy resins are in particular aromatic epoxy resins, especially the glycidyl ethers of: Bisphenol A, bisphenol F, or bisphenol A / F, where A stands for acetone and F for formaldehyde, which served as starting materials for the production of these bisphenols. In the case of bisphenol F, positional isomers may also be present, in particular derived from 2,4'- or 2,2'-hydroxyphenylmethane; dihydroxybenzene derivatives such as resorcinol, hydroquinone, or catechol; and other 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-hydroxyphenyl)propane, and 2,2-bis(4-hydroxy-3-tert-dibromo-4-hydroxyphenyl)propane.butylphenyl) 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-phenylethane, 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 or Bis(4-hydroxyphenyl)sulfone; novolacs, which are in particular condensation products of phenol or cresols with formaldehyde or...Paraformaldehyde, acetaldehyde, crotonaldehyde, isobutyraldehyde, 2-ethylhexanal, benzaldehyde, or furfural; aromatic amines such as aniline, toluidine, 4-aminophenol, 4,4'-methylenediphenyldiamine, 4,4'-methylenediphenyldi-(N-methyl)amine, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline (bisaniline-P), or 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline (bisaniline-M).

[0083] Other suitable epoxy resins are aliphatic or cycloaliphatic polyepoxides, in particular Glycidyl ethers of saturated or unsaturated, branched or unbranched, cyclic or open-chain di-, tri- or tetrafunctional C2 to C30 alcohols, in particular ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, polypropylene glycols, dimethylolcyclohexane, neopentyl glycol, dibromoneopentyl glycol, castor oil, trimethylolpropane, trimethylolethane, pentaerythrole, sorbitol or glycerol, or alkoxylated glycerol or alkoxylated trimethylolpropane; a hydrogenated bisphenol A, F or A / F liquid resin, or the glycidylation products of hydrogenated bisphenol A, F or A / F; an N-glycidyl derivative of amides or heterocyclic nitrogenous bases, such as triglycidyl cyanurate or triglycidyl isocyanurate, or reaction products of epichlorohydrin with hydantoin.

[0084] Preferably, the epoxy resin is a liquid resin or a mixture containing two or more liquid epoxy resins.

[0085] The term "epoxy liquid resin" refers to a technical polyepoxide with a glass transition temperature below 25°C.

[0086] The resin component may also contain additional amounts of epoxy solid resin.

[0087] The epoxy resin is in particular a liquid resin based on a bisphenol or novolacs, especially with a mean epoxy equivalent weight in the range of 156 to 210 g / eq.

[0088] Particularly suitable are bisphenol-A diglycidyl ethers and / or bisphenol-F diglycidyl ethers, such as those commercially available from Olin, Huntsman, or Momentive. These liquid resins have a low viscosity for epoxy resins and allow for rapid curing and high hardness. They may contain proportions of bisphenol-A solid resin or novolac epoxy resins.

[0089] Furthermore, a novolac epoxy resin is particularly suitable, especially a phenol-formaldehyde novolac glycidyl ether, particularly with a medium functionality in the range of 2.3 to 4, preferably 2.5 to 3. This results in coatings with particularly good corrosion protection properties. They may contain components of other epoxy resins, especially bisphenol A diglycidyl ether or bisphenol F diglycidyl ether.

[0090] The resin component may contain a reactive diluent.

[0091] Preferred reactive diluents are epoxy group-containing reactive diluents, in particular butanediol diglycidyl ethers, hexanediol diglycidyl ethers, trimethylolpropane di- or triglycidyl ethers, phenyl glycidyl ethers, cresyl glycidyl ethers, guaiacol glycidyl ethers, 4-methoxyphenyl glycidyl ethers, pn-butylphenyl glycidyl ethers, p-tert-butylphenyl glycidyl ethers, 4-nonylphenyl glycidyl ethers, 4-dodecylphenyl glycidyl ethers, cardanol glycidyl ethers, benzyl glycidyl ethers, allyl glycidyl ethers, butyl glycidyl ethers, hexyl glycidyl ethers, 2-ethylhexyl glycidyl ethers, or glycidyl ethers of natural alcohols such as, in particular, C8 to C10, C12 to C14, or C13 to C15 alkyl glycidyl ethers.

[0092] Preferably, the epoxy resin composition contains at least one further component selected from the group consisting of thinners, accelerators, pigments and fillers.

[0093] Those already mentioned are particularly suitable as accelerators.

[0094] The thinners already mentioned are particularly suitable.

[0095] Suitable pigments include, in particular, corrosion protection pigments, titanium dioxides, iron oxides, chromium(III) oxides, organic pigments or carbon black, especially corrosion protection pigments and / or titanium dioxides.

[0096] Suitable corrosion protection pigments are, in particular, phosphorus-containing corrosion protection pigments, especially phosphates, orthophosphates, or polyphosphates, which contain chromium, zinc, aluminum, calcium, strontium, or a combination of these metals as a counterion. Zinc orthophosphate, zinc-aluminum orthophosphate, calcium phosphate, zinc polyphosphate, zinc-aluminum polyphosphate, or strontium-aluminum polyphosphate are particularly suitable, especially an organically modified basic zinc orthophosphate hydrate.

[0097] Suitable fillers include, in particular, ground or precipitated calcium carbonate, optionally coated with fatty acids, especially stearates; barite (barytes); talc; quartz flour; quartz sand; silicon carbide; micaceous iron oxide; dolomite; wollastonite; kaolin; mica (potassium aluminum silicate); molecular sieves; aluminum oxide; zinc oxide; aluminum-doped zinc oxide; aluminum hydroxide; magnesium hydroxide; silica; cement; gypsum; fly ash; carbon black; graphite; metal powders such as aluminum, copper, iron, zinc, silver, or steel; PVC powder; or hollow spheres. Calcium carbonate, barite, quartz flour, talc, aluminum powder, or a combination thereof are preferred.

[0098] The epoxy resin composition may contain further auxiliary and additive substances, in particular the following: Reactive diluents, in particular those already mentioned, or epoxidized soybean oil or linseed oil, compounds containing acetoacetate groups, in particular acetoacetylated polyols, butyrolactone, carbonates, aldehydes, isocyanates or silicones containing reactive groups; polymers, in particular polyamides, polysulfides, polyvinyl formal (PVF), polyvinyl butyral (PVB), polyurethanes (PUR), polymers with carboxyl groups, polyamides, butadiene-acrylonitrile copolymers, styrene-acrylonitrile copolymers, butadiene-styrene copolymers, homo- or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl(meth)acrylates, in particular chlorosulfonated polyethylenes or fluorine-containing polymers or sulfonamide-modified melamines; Fibers, in particular glass fibers, carbon fibers, metal fibers, ceramic fibers or plastic fibers such as polyamide fibers or polyethylene fibers; nanofillers,especially carbon nanotubes; rheology modifiers, especially thickeners or anti-settling agents; adhesion promoters, especially organoalkoxysilanes; Flame-retardant substances, in particular the fillers already mentioned: aluminum hydroxide or magnesium hydroxide, antimony trioxide, antimony pentoxide, boric acid (B(OH) 3), zinc borate, zinc phosphate, melamine borate, melamine cyanurate, ammonium polyphosphate, melamine phosphate, melamine pyrophosphate, polybrominated diphenyl oxides or diphenyl ethers, phosphates such as, in particular, diphenyl cresyl phosphate, resorcinol bis(diphenyl phosphate), resorcinol diphosphate oligomer, tetraphenyl resorcinol diphosphite, ethylenediamine diphosphate, bisphenol A bis(diphenyl phosphate), tris(chloroethyl) phosphate, tris(chloropropyl) phosphate, tris(dichloroisopropyl) phosphate, tris[3-bromo-2,2-bis(bromomethyl)-propyl] phosphate, tetrabromobisphenol A, bis(2,3-dibromopropyl ether) of bisphenol A, brominated epoxy resins, Ethylene bis(tetrabromophthalimide),Ethylene bis(dibromonorbornane dicarboximide), 1,2-bis(tribromophenoxy)ethane, tris(2,3-dibromopropyl)isocyanurate, tribromophenol, hexabromocyclododecane, bis(hexachlorocyclopentadieno)cyclooctane or chlorinated paraffins; or additives, in particular defoamers, deaerants, wetting agents, dispersants, leveling agents, dispersed paraffin wax, stabilizers against oxidation, heat, light or UV radiation or biocides.

[0099] Preferably, the epoxy resin composition contains further auxiliary and additive substances, in particular pigments, wetting agents, leveling agents and / or defoamers.

[0100] Preferably, the epoxy resin composition contains only a small amount of thinner. Preferably, it contains less than 35% by weight, more preferably less than 20% by weight, and particularly less than 15% by weight, thinner.

[0101] Preferably, the epoxy resin composition contains only a small amount of water, preferably less than 5% by weight, and in particular less than 1% by weight.

[0102] The resin and hardener components of the epoxy resin composition are stored in separate containers. Other components of the epoxy resin composition may be present as part of either the resin or the hardener component, with reactive components towards epoxy groups preferably being part of the hardener component. It is also possible that other components are present as separate, additional components.

[0103] Suitable containers for storing the resin or hardener components include, in particular, a drum, a pail, a bag, a bucket, a can, a cartridge, or a tube. The components are storable, meaning they can be stored for several months up to a year or longer before use without their respective properties changing to an extent relevant to their application.

[0104] The resin and hardener components are mixed shortly before or during application. The mixing ratio is preferably chosen such that the molar ratio of the epoxy-reactive groups to the epoxy groups is in the range of 0.5 to 1.5, particularly 0.7 to 1.2. In parts by weight, the mixing ratio between the resin and hardener components is typically in the range of 1:2 to 20:1, preferably 1:1 to 20:1. The components are mixed continuously or batchwise using a suitable method, taking care to ensure that the time between mixing and application is not too long and that the application takes place within the pot life. Mixing and application are carried out, in particular, at ambient temperature, which is typically in the range of about 5 to 40°C, preferably about 10 to 35°C.

[0105] The curing of the epoxy resin composition begins with the mixing of the components through a chemical reaction. Primary and secondary amino groups, and any other groups reactive towards epoxy groups, react with the epoxy groups, opening their rings. As a result of these reactions, the composition polymerizes and thus hardens.

[0106] The curing process typically extends over several hours to several days. The duration depends on factors such as temperature, the reactivity of the components, their stoichiometry, and the presence or quantity of accelerators.

[0107] In its freshly mixed state, the epoxy resin composition has a low viscosity. Preferably, the viscosity 5 minutes after mixing the resin and hardener components at 20 °C is in the range of 0.3 to 20 Pa·s, more preferably 0.3 to 10 Pa·s, particularly preferably 0.3 to 5 Pa·s, and especially 0.3 to 2 Pa·s, measured using a cone-plate viscometer at a shear rate of 10 s⁻¹.

[0108] The epoxy resin composition is applied to at least one substrate, the following being particularly suitable: Glass, glass ceramics, concrete, mortar, cement screed, fiber cement, brick, tile, gypsum or natural stone such as granite or marble; repair or leveling compounds based on PCC (polymer-modified cement mortar) or ECC (epoxy-modified cement mortar); metals or alloys such as aluminum, iron, steel, copper, other non-ferrous metals, including surface-treated metals or alloys such as galvanized or chrome-plated metals; asphalt or bitumen; leather, textiles, paper, wood, with resins, for example phenolic, melamine or epoxy resins, bonded wood-based materials, resin-textile composites or other so-called polymer composites; Plastics such as rigid and flexible PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM or EPDM, either untreated or surface-treated, for example by means of plasma, corona or flames;Fiber-reinforced plastics, such as carbon fiber-reinforced plastics (CFRP), glass fiber-reinforced plastics (GFRP) and sheet molding compounds (SMC); insulating foams, in particular made of EPS, XPS, PUR, PIR, rock wool, glass wool or foamed glass (Foamglas); coated or painted substrates, in particular painted tiles, painted concrete, powder-coated metals or alloys or painted sheets; coatings, paints or varnishes, in particular coated floors which are covered with a further floor covering layer.

[0109] The substrates can be pretreated before application if necessary, in particular by physical and / or chemical cleaning processes or by applying an activator or a primer.

[0110] Metals or alloys, especially steel, are particularly preferred as substrates. Such a substrate is especially well protected against corrosion by the adduct in the epoxy resin composition.

[0111] The curing of the epoxy resin composition results in a hardened composition.

[0112] The epoxy resin composition is preferably used as a coating, primer, adhesive, sealant, potting compound, casting resin, impregnating resin or as a matrix for fiber-reinforced composites such as CFRP or GFRP.

[0113] Epoxy resin compositions are particularly preferred for use as coatings. Coatings are understood to be coverings of all kinds applied to a surface, in particular floor coverings, paints, varnishes, sealants, primers, or protective coatings, especially corrosion protection coatings for light or heavy corrosion protection.

[0114] The epoxy resin composition is particularly suitable as a floor covering or floor coating for interior spaces such as offices, industrial halls, gymnasiums or cold storage rooms, or for exterior use on balconies, terraces, parking decks, bridges or roofs, as a protective coating for concrete, cement, metals, plastics or wood, for example for surface sealing of wooden structures, vehicles, loading areas, tanks, silos, shafts, pipes, pipelines, machines, vessels or steel structures, for example of ships, piers, offshore platforms, lock gates, hydroelectric power plants, river structures, swimming pools, wind turbines, bridges, chimneys, cranes or sheet pile walls, or as a primer, adhesion primer, corrosion protection primer or for hydrophobing surfaces.

[0115] The epoxy resin composition is particularly suitable as a corrosion protection coating, especially for insulated steel pipes or vessels, and is particularly well-suited as a protective coating against corrosion under insulation (CUI). It has been shown that the epoxy resin composition according to the invention possesses high thermal shock resistance in accordance with DIN EN ISO 19277. At a layer thickness of 250 µm on steel, it withstands multiple sudden temperature changes between ice water and 200 °C without cracking.

[0116] For use as a coating, the epoxy resin composition preferably exhibits a particularly low viscosity and good flow properties. Within the pot life, the mixed composition is typically applied as a thin film with a thickness of approximately 50 µm to approximately 5 mm to a substrate, typically at ambient temperature. Application is carried out in particular by pouring the resin onto the substrate to be coated and then spreading it evenly using, for example, a doctor blade or notched trowel, or by brush or roller, or by spraying. During curing, the resin typically forms largely homogeneous, glossy, and non-sticky films of high hardness, which exhibit good adhesion to a wide variety of substrates.

[0117] The epoxy resin composition is used in particular in a coating process, comprising the following steps: (i) Applying the mixed epoxy resin composition to a substrate within the pot life, followed by curing of the composition, (ii) optionally applying a further layer of the mixed epoxy resin composition to the cured layer within the pot life, (iii) optionally repeating step (ii), and (iv) optionally applying a further composition to the cured layer, which may be another epoxy resin composition or another material, in particular a polyurethane or polyurea coating.

[0118] In the event that the epoxy resin composition is used as a multi-layer coating, it has particularly good interlayer adhesion.

[0119] Furthermore, the epoxy resin composition is particularly preferred for use as an adhesive. Typically, when used as an adhesive, the epoxy resin composition exhibits a pasty consistency with shear-thinning properties after mixing the components. During application, the mixed adhesive is applied to at least one of the substrates to be bonded within its pot life, and the two substrates are joined within the open time of the adhesive.

[0120] The mixed adhesive is applied, in particular, by means of a brush, roller, spatula, squeegee, trowel, or from a tube, cartridge or dispensing device.

[0121] The adhesive is particularly suitable for use in the construction industry, especially for reinforcing structures with steel lamellae or lamellae made of carbon fiber reinforced plastics (CFRP), for structures containing bonded precast concrete elements, especially bridges or concrete towers for, for example, wind turbines, shafts, pipelines or tunnels, or for structures containing bonded natural stone, ceramic elements or parts made of fiber cement, steel, cast iron, aluminum, wood or polyester, for anchoring dowels or steel rods in boreholes, for fixing, for example, railings, parapets or door frames, for repairs such as, in particular, filling edges, holes or joints in concrete repair, or for bonding films made of polyvinyl chloride (PVC), flexible polyolefin (Combiflex®) or adhesion-modified chlorosulfonated polyethylene (Hypalon®) to concrete or steel.

[0122] Other areas of application include structural bonding in the construction or manufacturing industry, in particular as adhesive mortar, assembly adhesive, reinforcing adhesive such as for bonding CFRP or steel lamellae to concrete, masonry or wood, as element adhesive for bridge elements, sandwich element adhesive, facade element adhesive, reinforcing adhesive, body adhesive or half-shell adhesive for rotor blades of wind turbines.

[0123] The epoxy resin composition is used in particular in a bonding process, comprising the following steps: (i) Mixing the components of the epoxy resin composition, (ii) Applying the mixed composition within the pot life, either to at least one of the substrates to be bonded and joining the substrates to form a bond within the open time, or into a cavity or gap between several substrates and, if necessary, inserting an anchor into the cavity or gap within the open time, followed by the hardening of the mixed composition.

[0124] The term "anchor" refers in particular to a reinforcing bar, a threaded rod, or a bolt. Such an anchor is specifically glued or anchored in a wall, ceiling, or foundation in such a way that part of it is bonded in place and part of it protrudes and can bear structural loads.

[0125] Similar or different substrates can be bonded together.

[0126] The application and curing of the epoxy resin composition will yield an article.

[0127] Another object of the invention is therefore an article obtained from the use of the epoxy resin composition.

[0128] The article is preferably a structure or part thereof, in particular a building or civil engineering structure, an office, an industrial building, a gymnasium, a cold storage room, a silo, a bridge, a roof, a stairwell, a floor, a balcony, a terrace or a parking deck, or an industrial or consumer good, in particular a pier, an offshore platform, a lock gate, a crane, a sheet pile wall, a pipeline, an insulated vessel or a rotor blade of a wind turbine, or a means of transport such as in particular an automobile, a truck, a rail vehicle, a ship, an aircraft or a helicopter, or an attachment thereof.

[0129] The epoxy resin composition according to the invention is readily processable at ambient temperatures, cures surprisingly quickly, and forms smooth, defect-free surfaces with a low tendency to yellow. It is particularly suitable as an aesthetically pleasing, high-quality corrosion protection coating that is robust against moisture, even in combination with heat and / or salts, and exhibits particularly good thermal shock resistance and interlayer adhesion. Examples

[0130] The following are exemplary embodiments intended to further illustrate the described invention. Of course, the invention is not limited to these described embodiments.

[0131] "AHEW" stands for amine hydrogen equivalent weight.

[0132] "EEW" stands for epoxy equivalent weight.

[0133] A temperature of 23±1°C and a relative humidity of 50±5% are referred to as "standard climate" ("NC").

[0134] Unless otherwise stated, the chemicals used were from Sigma-Aldrich Chemie GmbH. Description of the measurement methods:

[0135] The viscosity was measured on a thermostatically controlled cone-plate viscometer Rheotec RC30 (cone diameter 50 mm, cone angle 1°, cone tip-plate distance 0.05 mm, shear rate 10 s -1< ).

[0136] The Amin number was determined by titration (with 0.1N HClO 4 in acetic acid against crystal violet). Substances used and abbreviations:

[0137] DEN®< 431: Phenol-formaldehyde novolac glycidyl ether, EEW approx. 175 g / eq, average functionality approx. 2.8 (from Olin) DEN®< 438: Phenol-formaldehyde novolac glycidyl ether, EEW approx. 180 g / eq, average functionality approx. 3.6 (from Olin) Epilox®< N 18-10: Phenol-formaldehyde novolac glycidyl ether, EEW approx. 175 g / eq, average functionality approx. 2.6 (from Leuna Harze) Araldite®< GY 250: Bisphenol A diglycidyl ether, EEW approx. 187 g / eq (from Huntsman) Araldite®< DY-E: Monoglycidyl ethers of C12 to C14 alcohols, EEW approx. 290 g / eq (from Huntsman) B-EDAN-Benzyl-1,2-ethanediamine, prepared as described below, 150.2 g / mol, AHEW 50.1 g / eq IPDA3-Aminomethyl-3,5,5-trimethylcyclohexylamine, AHEW 42.6 g / eq (Vestamin® < IPD, from Evonik) N-Benzyl-1,2-ethanediamine (B-EDA):

[0138] 180.3 g (3 mol) of 1,2-ethanediamine were placed at room temperature, mixed with a solution of 106.0 g (1 mol) of benzaldehyde in 1200 ml of isopropanol, and stirred for 2 hours. The mixture was then hydrogenated at 80°C, 80 bar hydrogen pressure, and a flow rate of 5 ml / min in a continuous hydrogenation apparatus with a Pd / C fixed-bed catalyst. The hydrogenated solution was concentrated by rotary evaporation at 65°C, removing unreacted 1,2-ethanediamine, water, and isopropanol. The resulting reaction mixture was purified by distillation at 80°C under vacuum. A colorless liquid was obtained with an N-benzyl-1,2-ethanediamine content of > 97%, determined by GC. Production of adducts: Adduct A1:

[0139] 55.0 g of N-benzyl-1,2-ethanediamine (B-EDA, 0.366 mol) were heated to 80 °C and, with good stirring, 33.0 g of DEN®< 438 (0.183 mol EP groups), which had been warmed to 60 °C, were slowly added, maintaining the temperature of the reaction mixture between 70 and 90 °C. The reaction mixture was kept at this temperature for one hour and then cooled. A clear, slightly yellowish liquid with a viscosity at 20 °C of 24.1 Pa·s, an amine number of 460 mg KOH / g, and a calculated AHEW of 96.2 g / eq was obtained. Adduct A2:

[0140] 55.0 g of N-benzyl-1,2-ethanediamine (B-EDA, 0.366 mol) were heated to 80 °C and, with good stirring, 32.0 g of DEN®< 431 (0.183 mol EP groups), which had been warmed to 60 °C, were slowly added, maintaining the temperature of the reaction mixture between 70 and 90 °C. The reaction mixture was kept at this temperature for one hour and then cooled. A clear, slightly yellowish liquid with a viscosity at 20 °C of 8.4 Pa·s, an amine number of 464 mg KOH / g, and a calculated AHEW of 95.1 g / eq was obtained. Adduct A3:

[0141] 55.0 g of N-benzyl-1,2-ethanediamine (B-EDA, 0.366 mol) were heated to 80 °C and, with good stirring, 42.7 g of DEN®< 431 (0.244 mol EP groups), which had been warmed to 60 °C, were slowly added, maintaining the temperature of the reaction mixture between 70 and 90 °C. The reaction mixture was kept at this temperature for one hour and then cooled. A clear, slightly yellowish liquid with a viscosity at 20 °C of 256 Pa·s, an amine number of 404 mg KOH / g, and a calculated AHEW of 114.4 g / eq was obtained. Adduct A4 (Ref.):

[0142] 55.0 g of N-benzyl-1,2-ethanediamine (B-EDA, 0.366 mol) were heated to 80 °C and 45.0 g of Araldite® < GY 250 (0.241 mol EP groups) were slowly added with good stirring, maintaining the temperature of the reaction mixture between 70 and 90 °C. The reaction mixture was kept at this temperature for one hour and then cooled. A clear, slightly yellowish liquid was obtained with a viscosity at 20 °C of 262 Pa·s, an amine number of 408 mg KOH / g, and a calculated AHEW of 116.3 g / eq. Adduct A5 (Ref.):

[0143] 47.7 g of 1,2-diaminocyclohexane (Dytek® < DCH-99, from Invista, 0.42 mol) were placed in the solution and heated to 60 °C. With good stirring, 37.6 g of DEN® < 438 (0.21 mol EP groups), preheated to 60 °C, were slowly added, maintaining the temperature of the reaction mixture between 70 and 90 °C. The reaction mixture was kept at this temperature for one hour and then cooled. A clear, slightly yellowish, highly viscous liquid was obtained with a viscosity at 50 °C of 98 Pa·s, an amine number of 532 mg KOH / g, and a calculated AHEW of 58.3 g / eq. Adduct A6 (Ref.):

[0144] 90.0 g of bis(6-aminohexyl)amine (Dytek® < BHMT-HP, from Invista, 0.42 mol) were placed in the solution and heated to 60 °C. With good stirring, 37.6 g of DEN® < 438 (0.21 mol EP groups), preheated to 60 °C, were slowly added, maintaining the temperature of the reaction mixture between 70 and 90 °C. The reaction mixture was kept at this temperature for one hour and then cooled. A clear, slightly yellowish liquid was obtained with a viscosity of 22.5 Pa·s at 20 °C, an amine number of 529 mg KOH / g, and a calculated AHEW of 67.9 g / eq. Production of epoxy resin coatings: Examples 1 to 11:

[0145] For each example, the ingredients of the resin component listed in Tables 1 and 2 were mixed in the specified amounts (in parts by weight) using a centrifugal mixer (SpeedMixer™< DAC 150, FlackTek Inc.) and stored in the absence of moisture.

[0146] The ingredients of the hardener component listed in Tables 1 and 2 were also processed and stored.

[0147] Subsequently, the two components of each composition were processed into a homogeneous liquid using a centrifugal mixer and immediately tested as follows: viscosity The measurement was taken 5 minutes after mixing the resin and hardener components as described, at a temperature of 20 °C.

[0148] The Gelling time was determined by moving a freshly mixed quantity of approximately 3 g under standard climate conditions with a spatula at regular intervals until the mass gelled.

[0149] The Shore D Hardness was determined according to DIN 53505 on two cylindrical test specimens (diameter 20 mm, thickness 5 mm), one of which was stored in standard climate and the other at 8°C and 80% relative humidity, with the hardness measured after 1 day and after 2 days.

[0150] The Aspect (NK) The quality was determined on a film that was applied to a glass plate in a layer thickness of 500 µm and stored for 14 days under standard climatic conditions. A film was considered "beautiful" if it had a glossy and non-sticky surface without any structure. "Structure" was defined as any kind of drawing or pattern on the surface.

[0151] The Aspect (8° / 80%)A film was applied to a glass plate in a thickness of 500 µm and stored for 7 days at 8°C and 80% relative humidity, followed by 7 days under standard climate conditions. Twenty-four hours after application, a polypropylene bottle cap was placed on the film, with a moist sponge underneath. After another 24 hours, the sponge and cap were removed and placed at a new location on the film, where they were again removed and repositioned after 24 hours, a total of four times. The appearance of this film was then assessed as described for the aspect (NK). "Blushing" The number of white stains caused by the damp sponge was recorded. A faint, slightly white stain was designated as "(1)".

[0152] Some films also had the King's hardness(King's pendulum hardness, measured according to DIN EN ISO 1522). For this purpose, a first film with a layer thickness of 500 µm was applied to a glass plate, stored under standard climate conditions, and the King's hardness was determined after 1 day ("King's hardness (1d NK)"), after 2 days ("King's hardness (2d NK)"), after 7 days ("King's hardness (7d NK)"), and after 14 days ("King's hardness (14d NK)"). Furthermore, a second film with a thickness of 500 µm was applied to a glass plate and stored immediately after application for 7 days at 8°C and 80% relative humidity and subsequently for 2 weeks under standard climate conditions, whereby the hardness was measured after 7 days at 8°C and 80% relative humidity ("King's hardness (7d 8° / 80%)") and then after a further 2 days under standard climate conditions ("King's hardness (+2d NK)") or 7 days under standard climate conditions ("King's hardness (+7d NK)") or 14 days under standard climate conditions ("King's hardness (+14d NK)").

[0153] As a measure of yellowing, the color change after exposure to a weathering tester was also determined. (Q-Sun (72h)). For this purpose, another film with a thickness of 500 µm was applied to a glass plate and stored under standard climate conditions for 14 days. Subsequently, it was subjected to a Q-Sun Xenon Xe-1 weathering tester with a Q-SUN Daylight-Q optical filter and a xenon lamp with a luminous intensity of 0.51 W / m² at 340 nm at a temperature of 65°C for 72 hours. The color difference was then measured. ΔE of the contaminated film in comparison to a corresponding uncontaminated film using a colorimeter NH310 from Shenzhen 3NH Technology Co. LTD, equipped with Silicon Photoelectric Diode Detector, Light Source A, Color Space Measurement Interface CIE L*a*b*C*H*.

[0154] The results are given in Tables 1 and 2.

[0155] The examples marked "(Ref.)" are comparative examples. Table 1: Composition and properties of examples 1 to 6. Example 1 2 3 4 (Ref.) 5 (Ref.) 6 (Ref.) Resin component: Araldite® < GY 250: 167.2 167.2 167.2 167.2 167.2 167.2 Araldite® < DY-E: 31.8 31.8 31.8 31.8 31.8 31.8 Hardener component: Adduct A1 96.2 - - - - - Adduct A2 - 95.1 - - - - Adduct A3 - - 114.4 - - - Adduct A4 - - - 116.3 - - Adduct A5 - - - - 58.3 - Adduct A6 - - - - - 67.9 Viscosity (5') [Pa·s] 5.9 4.2 19.4 15.0 nb 1< 2.0 Gelling time (h:min) 2:30 2:40 2:20 2:40 nb 1< 3:30 Shore D (1d NK) 82 81 82 78 nm 2< 67 (2d NK) 82 82 82 78 45 72 Shore D (1d 8° / 80%) 74 74 74 74 nm 2< 16 (2d 8° / 80%) 78 78 78 75 nm 2< 44 Aspect (NK) nice nice nice nice structure murky Aspect (8° / 80%) nice nice nice nice sticky, liquid nm 3< cloudy, uneven nm 3< Blushing 0 (1) (1) (1) Q-Sun (72h) ΔE 2.5 3.0 3.5 2.1 nb nb 1 < not determined (very high viscosity) 2 < not measurable (too soft) 3 < not measurable (surface too inhomogeneous for assessment) "nb" stands for "not determined" Table 2: Composition and properties of examples 7 to 11. Example 7 8 9 (Ref.) 10 (Ref.) 11 (Ref.) Resin component: Araldite® < GY 250: 167.2 167.2 167.2 167.2 167.2 Araldite® < DY-E: 31.8 31.8 31.8 31.8 31.8 Hardener component: Adduct A1 38.5 - - - - Adduct A3 - 38.0 - - - Adduct A4 - - 46.5 - - Adduct A5 - - - 23.3 - Adduct A6 - - - - 27.2 IPDA 25.8 25.8 25.8 25.8 25.8 Benzyl alcohol 25.0 25.0 25.0 25.0 25.0 Viscosity (5') [Pa·s] 1.12 1.45 1.46 1.07 0.91 Gelling time (h:min) 3:25 3:20 3:30 4:15 3:20 Shore D (1d NK) 66 67 65 68 68 (2d NK) 78 78 78 78 76 Shore D (1d 8° / 80%) 16 18 15 nm 2< 22 (2d 8° / 80%) 65 67 63 39 65 King's hardness [s] (1d NK) 52 51 45 36 36 (2d NK) 99 93 95 115 99 (7d NK) 153 151 155 164 148 (14d NK) 161 158 160 176 151 King's hardness [s] (7d 8° / 80%) 31 38 22 28 18 (+2d NK) 115 122 115 87 52 (+7d NK) 152 153 151 105 97 (+14d NK) 163 164 161 110 123 aspect ( NK ) nice nice nice nice (Structure) Aspect (8° / 80%) Blushing beautiful (1) beautiful (1) beautiful (1) Structure 4 Structure 4 Q-Sun (72h) ΔE 2.1 1.7 2.5 nb nb 2 < not measurable (too soft); "nb" stands for "not determined" Examples 12 to 13:

[0156] For each example, the ingredients of the resin component listed in Table 3 were mixed in the specified amounts (in parts by weight) using a centrifugal mixer (SpeedMixer™< DAC 150, FlackTek Inc.) and stored in the absence of moisture.

[0157] The ingredients of the hardener component listed in Table 3 were also processed and stored.

[0158] Subsequently, the two components of each composition were processed into a homogeneous liquid using a centrifugal mixer and immediately tested as follows: To assess the Aspect and the Interim liabilityA test specimen of each coating was produced by spraying a 180 µm wet film layer onto a 150x100x3mm steel sheet using a gravity-feed spray gun. This was then stored for 24 hours under standard climate conditions, followed by the application of a second 180 µm wet film layer using the same spray gun. After a storage period of 14 days under standard climate conditions, the surface of the coating was assessed (aspect). A smooth, non-sticky, glossy surface without any structure, deposits, or other defects was considered "good." To measure interlayer adhesion, a pull-off test according to ISO 4624 was then performed at a test speed of 1 MPa / s. A stamp affixed to the coating was pulled vertically upwards. Interlayer adhesion was rated as "poor" if the pull-off value was less than 5 MPa and an adhesive fracture pattern was observed between the two layers of the test specimen.Otherwise, the interim liability was rated as "good" as a measure for the . Thermal shock resistanceA 150×100×3 mm steel sheet (blasted SA 2.5, surface roughness 60-80 µm) was coated by applying two coats of 220 µm wet film (equivalent to two coats of approximately 150 µm dry film, totaling approximately 300 µm dry film) using a gravity-feed spray gun, with a 24-hour waiting period between coats. The resulting test specimens were stored for 7 days under standard climate conditions and then subjected to 20 cycles according to DIN EN ISO 19277 between a convection oven at 204 °C and ice water. During each cycle, the specimens were stored in the convection oven at 204 °C, immersed directly from the oven into a bucket of ice water for 1 minute every 24 hours, and then immediately returned to the convection oven. The specimens were stored in the convection oven over the weekend.After 20 cycles, the test specimens were cooled to room temperature and visually assessed using a magnifying glass to determine whether the coating was intact or damaged, and whether there were any cracks or chips in the coating or corrosion on the steel sheet.

[0159] As a measure for the Corrosion resistance A test specimen, manufactured as for the intermediate adhesion test, was used with 720 h Condensation water The specimen was subjected to a load test according to ISO 6270-1 and subsequently a tensile adhesion test according to ISO 4624 was performed at a test speed of 1 MPa / s. If the specimen showed no signs of corrosion and the tensile adhesion value was greater than 6 MPa, the test was rated as "very good". Another identically manufactured specimen was subjected to a neutral load test for 1440 h. Salt spray mistThe material was subjected to a load according to ISO 9227 and subsequently a tensile adhesion test was performed according to ISO 4624 at a test speed of 1MPa / s, with the evaluation being carried out as described for the load with condensation water.

[0160] The results are shown in Table 3. 12 13. Table 3: Composition and properties of the examples up to Example 12 13 Resin component: Epilox® < N 18-10 21.0 21.0 Xylene 10.0 10.0 Zinc pigment 10.0 10.0 Talk 39.0 39.0 Pigment paste 10.0 10.0 n-Butanol 10.0 10.0 Hardener component: Adduct A1 11.5 - Adduct A2 - 11.5 aspect nice nice Interim liability good good Thermal shock resistance: passed passed Corrosion resistance: Condensation water: very good very good Salt spray mist: very good very good

Claims

1. Amine-functional adduct from the reaction of - at least one amine of the formula (I),         Z-NH-A-NH-CH2-Y     (I) where A is a divalent alkylene, cycloalkylene or arylalkylene radical having 2 to 15 carbon atoms, Z is H or ---CH2-Y, and Y is H or an alkyl, cycloalkyl, aralkyl or aryl radical having 1 to 11 carbon atoms, wherein the two nitrogen atoms to which the A radical is attached are separated from one another by at least two carbon atoms and the amine of the formula (I) contains a total of at least 8 carbon atoms, - with at least one novolak epoxy resin having an average functionality in the range from 2.5 to 4.

2. Adduct according to Claim 1, characterized in that A is selected from the group consisting of 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,3-butylene, 2-methyl-1,2-propylene, 1,3-pentylene, 1,5-pentylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene, 2-methyl-1,5-pentylene, 1,7-heptylene, 1,8-octylene, 2,5-dimethyl-1,6-hexylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 4(2)-methyl-1,3-cyclohexylene, 1,3-cyclohexylene bis(methylene), and 1,4-cyclohexylenebis(methylene).

3. Adduct according to either of Claims 1 and 2, characterized in that Y is selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, pentyl, heptyl, hept-2-yl, phenyl, 4-methylphenyl, 1-naphthyl, and cyclohexyl.

4. Adduct according to any of Claims 1 to 3, characterized in that Z is H, or in that the amine of the formula (I) is a mixture comprising an amine of the formula (I) where Z = H and an amine of the formula (I) where Z = ---CH2-Y.

5. Adduct according to any of Claims 1 to 4, characterized in that A is 1,2-ethylene and Y is phenyl.

6. Adduct according to any of Claims 1 to 5, characterized in that the novolak epoxy resin is a phenol-formaldehyde novolak glycidyl ether.

7. Adduct according to any of Claims 1 to 6, characterized in that the reaction takes place in a stoichiometric ratio of less than 3 mol, preferably less than 2.6 mol, of amine of the formula (I) to 1 molar equivalent of epoxy groups, especially in the range from 1.3 to 2.5 mol, preferably 1.4 to 2.1 mol, of amine of the formula (I) to 1 molar equivalent of epoxy groups.

8. Adduct according to any of Claims 1 to 7, characterized in that it contains oligomeric compounds of the formula (III), where n on average has a value in the range from 0.5 to 3, preferably 0.7 to 2.7, and G1 and G2 are Z, with the proviso that at least one of the two is ---CH2-Y.

9. Adduct according to any of Claims 1 to 8, characterized in that it has a viscosity at 20°C in the range from 5 to 500 Pa·s, measured using a cone-plate viscometer at a shear rate of 10 s-1.

10. Curing agent for epoxy resins comprising at least one adduct according to any of Claims 1 to 9 and at least one further constituent selected from the group consisting of further amines, accelerators, and thinners.

11. Curing agent according to Claim 10, characterized in that at least one further amine selected from the group consisting of N-benzylethane-1,2-diamine, N,N'-dibenzylethane-1,2-diamine, 1,5-diamino-2-methylpentane, 2,2(4),4-trimethylhexane-1,6-diamine, 1,2-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl) methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 2(4)-methyl-1,3-diaminocyclohexane, 1,3-bis(aminomethyl)benzene, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N-(2-aminoethyl)propane-1,3-diamine, N,N'-bis(3-aminopropyl)ethylenediamine, dipropylenetriamine, bis(hexamethylene)triamine, polyoxypropylene diamines having an average molecular weight Mn in the range from 200 to 500 g / mol, and polyoxypropylene triamines having an average molecular weight Mn in the range from 300 to 500 g / mol is present, where the average molecular weight is determined by gel-permeation chromatography against polystyrene as standard.

12. Curing agent according to either of Claims 10 and 11, characterized in that 5 to 70%, preferably 7 to 55%, especially 10 to 40%, of all amine hydrogens present originate from the adduct according to any of Claims 1 to 9.

13. Epoxy resin composition comprising - a resin component comprising at least one epoxy resin and - a curing agent component comprising at least one adduct according to any of Claims 1 to 9 or a curing agent according to any of Claims 10 to 12.

14. Use of an epoxy resin composition according to Claim 13 as coating, primer, adhesive, sealant, potting compound, casting resin, impregnating resin or as matrix for fiber composites.

15. Article obtained from the use according to Claim 14.