Amine-epoxy resin adduct

Abstract

The subject of the invention is an amine-functional adduct resulting from the reaction of an amine mixture with at least one diepoxide in a stoichiometric ratio of at least 1.2 moles of diamine of formula (I) per 1 molar equivalent of epoxy groups, said amine mixture comprising at least one diamine of formula (I) and at least one diamine of formula (II) in a weight ratio in the range of 65 / 35 to 95 / 5. The adduct is liquid at room temperature without a diluent even in the case of only a small excess of diamine and is surprisingly of low viscosity. Furthermore, it is particularly cost-effective since it can be obtained from an amine mixture that can be prepared technically simply. The adduct enables epoxy resin coatings with low or no emissions, which have surprisingly good processability and surprisingly rapid curing, have a very high hardness and a low tendency to yellowing and hardly tend to have defects caused by hazing even under wet and cold conditions.

Description

Field of the Invention

[0001] The present invention relates to amine-functional adducts of diamines and diepoxides and their use as curing agents for epoxy resin compositions which are particularly suitable as floor coatings. Prior Art

[0002] Epoxy resin-based coatings are widely used in the construction industry. They consist of a liquid resin and a curing agent component which are mixed before application and subsequently cured at ambient temperature in the range of about 5 - 35 °C. When applied, the viscosity of the coating should be as low as possible so that they level well at ambient temperature. After application, they should also cure as quickly as possible and without defects, even under wet and cold conditions, and form a defect-free surface without haze, spots, tackiness or craters. After curing, they should have high hardness as well as low brittleness and a high glass transition temperature in order to withstand mechanical stress as well as possible. For applications with high visual requirements, such as top coverings of floors, they should also have a high gloss and a minimal tendency to yellow under the influence of light.

[0003] However, such epoxy resin coatings often have surface defects such as haze, spots, roughness or a tendency to become tacky, which is also referred to as "blushing". Blushing is caused by the formation of salts of amines present in the curing agent component with carbon dioxide from the air and occurs especially at high humidity and low temperature. Many curing agents for epoxy resin coatings contain adducts of diamines and epoxy resins. This reduces the blushing effect and also allows faster curing. However, diamine-epoxy resin adducts are significantly more viscous than free diamines. To limit the viscosity, the diamine is used in a large stoichiometric excess relative to the epoxy resin. The content of unreacted diamine and the distribution of the various adduct molecules vary according to the level of stoichiometric amount or excess diamine in the production of the adduct. Adducts prepared using a low excess of diamine contain less unreacted diamine and more higher molecular weight adduct molecules with two, three or more diepoxide units. Such adducts are themselves advantageous. They have a low odor, a particularly low tendency to blush, and allow the adduct to be used in large amounts and / or in combination with other amines. However, adducts produced with a low excess of diamine are very highly viscous or even solid and can therefore only be processed at room temperature with a considerable amount of diluent such as benzyl alcohol. The diluent does not incorporate into the resin matrix during curing and can be released into the environment by evaporation or diffusion processes. However, there is now an increasing desire for low-emission products with a low content of releasable substances after curing. Therefore, for low-emission or emission-free epoxy resin compositions, such diluents can only be used in small amounts or not at all.

[0004] WO 2017 / 046293 discloses adducts of N-benzyl-1,2-propanediamine or N-benzyl-1,2-ethanediamine purified by distillation with bisphenol A-diglycidyl ether, which enable coatings with good surfaces. These adducts are prepared using a greatly excessive amount of diamine, thereby severely limiting the freedom when combining them with other amines.

[0005] Adducts of alkylated diamines and epoxides are also known as components of curing agents for aqueous epoxy resin products, for example from EP1956034. The adducts contain polyether chains and are diluted with unreacted diamine and a large amount of water after the reaction. Summary of the Invention

[0007] Accordingly, it is an object of the present invention to provide diamine-epoxy resin adducts which are liquid at room temperature and have as low a viscosity as possible without the addition of diluents even in the case of a very low excess of diamine during the production process, and which, when used as curing agents for epoxy resin coatings, allow good processability, rapid curing and a defect-free glossy surface, even under wet and cold conditions.

[0008] This object is achieved by the adducts described below. The adducts are obtained by reacting an amine mixture comprising a monoalkylated diamine and a dialkylated diamine with a dicyclic epoxide in a stoichiometric ratio of at least 1.2 moles of monoalkylated diamine to 1 mole equivalent of epoxy groups.

[0009] Despite the very low excess amount of diamine, the adducts of the present invention are liquid at room temperature and have a surprisingly low viscosity. Even when the content of the dialkylated diamine is very low, the viscosity of the adducts is much lower than that of the corresponding adducts prepared in the absence of the dialkylated diamine. Surprisingly, when the adducts are used as curing agents for epoxy resins, the dialkylated diamine neither has any significant adverse effect on the curing rate nor has any significant adverse effect on the final hardness. The much lower viscosity of the adducts is very advantageous and unexpected based on the prior art.

[0010] The adducts of the present invention are particularly cost-effective because they can be obtained from amine mixtures that are technically easy to produce.

[0011] The adducts of the present invention enable low-emission or emission-free epoxy resin coatings, and they have surprisingly good processing properties and surprisingly rapid curing, with high hardness and a low tendency to yellowing, and even hardly tend to have defects caused by cloudiness even under wet and cold conditions. Detailed Description of the Invention

[0013] The present invention provides an amine-functional adduct resulting from the reaction of the following substances in a stoichiometric ratio of at least 1.2 moles of diamine of formula (I) per 1 molar equivalent of epoxy groups:

[0014] (i) an amine mixture comprising at least one diamine of formula (I) and at least one diamine of formula (II) in a weight ratio in the range of 65 / 35 to 95 / 5,

[0015]

[0016] wherein

[0017] A is an alkylene, cycloalkylene or aralkylene group having 2 - 12 carbon atoms, and

[0018] R is an alkyl, cycloalkyl or aralkyl group having 1 - 12 carbon atoms,

[0019] wherein the two nitrogen atoms in the diamines of formula (I) and (II) are each separated from one another by at least two carbon atoms in each case, and the diamine of formula (I) has a total of 8 - 15 carbon atoms, and

[0020] (ii) at least one diepoxide.

[0021] “Primary amino group” means an amino group that is attached to a single organic group and carries two hydrogen atoms; “secondary amino group” means an amino group that is attached to two organic groups and carries one hydrogen atom, where the organic groups can also together be part of a ring; and “tertiary amino group” means an amino group that is attached to three organic groups and does not carry any hydrogen atoms, two or three of which can also be part of one or more rings.

[0022] “Amine hydrogen” means the hydrogen atoms of primary and secondary amino groups.

[0023] “Amine hydrogen equivalent” means the mass of an amine or amine-containing composition that contains one molar equivalent of amine hydrogen. It is expressed in the mass unit “g / Eq”.

[0024] “Epoxy equivalent” means the mass of an epoxy group-containing compound or composition that contains one molar equivalent of epoxy groups. It is expressed in the mass unit “g / Eq”.

[0025] Substance names starting with “poly( )”, such as polyamine or polyepoxide, mean substances that formally contain two or more of the functional groups appearing in their name per molecule.

[0026] “Diluent” means a substance that is soluble in an epoxy resin and reduces its viscosity, and that does not chemically bond to the epoxy resin polymer during the curing process.

[0027] "Molecular weight" means the molar mass of a molecule (grams / mole). "Average molecular weight" means the number average molecular weight Mn of a polydisperse mixture of oligomer or polymer molecules, which is typically determined by gel permeation chromatography (GPC) using polystyrene as a standard. n , which is typically determined by gel permeation chromatography (GPC) using polystyrene as a standard.

[0028] "Gel time" is the time period from mixing the components of the epoxy resin composition until it gels.

[0029] "Room temperature" means a temperature of 23 °C.

[0030] The amine mixture for the adducts of the present invention preferably contains essentially no or only small amounts of other amines that do not correspond to formulas (I) and (II). The amine mixture preferably has a purity of at least 95 wt%, especially at least 97 wt%, based on the sum of the diamines of formula (I) and the diamines of formula (II).

[0031] The amine mixture for preparing the adduct preferably has a diamine content of formula H2N-A-NH2 of not more than 5 wt%, preferably not more than 3 wt%, more preferably not more than 2 wt%, especially not more than 1 wt%, where A is as defined above. Such an amine mixture has a particularly low odor and enables a low-viscosity adduct, and when used as a curing agent for epoxy resins, this low-viscosity adduct hardly causes cloudiness.

[0032] A is preferably selected from 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, 1,9-nonylene, 2,2(4),4-trimethyl-1,6-hexylene, 1,10-decylene, 1,11-undecylene, 2-butyl-2-ethyl-1,5-pentylene, 1,12-dodecylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, (1,5,5-trimethylcyclohexan-1-yl)methane-1,3, 4(2)-methyl-1,3-cyclohexylene, 1,3-cyclohexylenebis(methylene), 1,4-cyclohexylenebis(methylene), 1,3-phenylenebis(methylene) and 1,4-phenylenebis(methylene). These diamines of formulas (I) and (II) are derived from commercially available primary diamines.

[0033] A is especially selected from 1,2-ethylene, 1,2-propylene, 2-methyl-1,2-propylene, 1,3-pentylene, 1,2-cyclohexylene, 1,4-cyclohexylene, 4(2)-methyl-1,3-cyclohexylene, 1,3-cyclohexylenebis(methylene), 1,4-cyclohexylenebis(methylene), 1,3-phenylenebis(methylene) and 1,4-phenylenebis(methylene).

[0034] A is most preferably 1,2-ethylene. These diamines of formula (I) and (II) allow adducts with particularly low viscosities and particularly high reactivities and allow a particularly low tendency to yellowing.

[0035] R is preferably selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, 3-methylbutan-2-yl, hexyl, 4-methylpentan-2-yl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, and optionally substituted 1-phenylethyl, 2-phenylethyl, benzyl, naphthylmethyl, cyclohexylmethyl and 2-cyclohexylethyl.

[0036] Preferred are groups R having 6 to 12 carbon atoms, especially 6 to 8 carbon atoms.

[0037] R is particularly preferably selected from 2-ethylhexyl, 2-phenylethyl, benzyl, 1-naphthylmethyl and cyclohexylmethyl.

[0038] Most preferably, R is benzyl. These diamines of formula (I) and (II) allow adducts with particularly low viscosities and high reactivities, as well as particularly low clouding effects and yellowing tendencies, especially when combined with group A which does not contain an aromatic group.

[0039] The diamines of formula (I) are particularly preferably selected from N-benzyl-1,2-ethanediamine, N-(1-naphthylmethyl)-1,2-ethanediamine, N-cyclohexylmethyl-1,2-ethanediamine, N-benzyl-1,2-propanediamine and N-(2-ethylhexyl)-bis(aminomethyl)-1,3-benzene.

[0040] The most preferred diamine of formula (I) is N-benzyl-1,2-ethanediamine. This diamine allows adducts with particularly low viscosities and reactivities.

[0041] Groups A and R in the diamines of formula (I) and (II) are preferably the same group. Such amine mixtures are particularly easily obtained as reaction products of alkylation.

[0042] Particularly preferably, the diamine of formula (I) is N-benzyl-1,2-ethanediamine and the diamine of formula (II) is N,N'-dibenzyl-1,2-ethanediamine.

[0043] The weight ratio of the diamine of formula (I) to the diamine of formula (II) is preferably in the range of 70 / 30 - 95 / 5, more preferably 80 / 20 - 90 / 10. This adduct is particularly reactive and enables high hardness.

[0044] The diamine of formula (I) and the diamine of formula (II) are preferably prepared by partially alkylating at least one amine of formula H2N - A - NH2 with at least one alkylating agent.

[0045] The alkylation is preferably reductive alkylation using an aldehyde or a ketone as the alkylating agent and hydrogen.

[0046] The reductive alkylation is preferably carried out in the presence of a suitable catalyst. Preferred catalysts are palladium on carbon (Pd / C), platinum on carbon (Pt / C), Adams catalyst or Raney nickel, especially palladium on carbon or Raney nickel.

[0047] When using molecular hydrogen, the reductive alkylation is preferably carried out in a pressure device at a hydrogen pressure of 5 - 150 bar, especially 10 - 100 bar. This can be carried out in a batch process or preferably in a continuous process.

[0048] The reductive alkylation is preferably carried out at a temperature of 40 - 120 °C, especially 60 - 100 °C.

[0049] In the case of small volatile amines such as especially 1,2 - ethylenediamine or 1,2 - propylenediamine, they are preferably used in a stoichiometric excess relative to the aldehyde or ketone, and after alkylation, the unreacted amine is partially or completely removed from the reaction mixture, especially by distillation or stripping.

[0050] If A and R in the diamines of formula (I) and (II) are the same group, the resulting reaction product can be used in the form of an amine mixture without further purification.

[0051] However, the diamine of formula (I) and the diamine of formula (II) can also be prepared separately and mixed to form an amine mixture. For this purpose, it is preferred to further purify the reaction mixture from the reductive alkylation, especially by distillation.

[0052] The reaction mixture is preferably not further purified, but contains the diamine of formula (I) and the diamine of formula (II) in the proportions according to the invention. This reaction mixture is particularly cost - effective.

[0053] The amine mixture comprising at least one diamine of formula (I) and at least one diamine of formula (II) is preferably the reaction product of reductive alkylation of at least one amine of formula H2N - A - NH2 with at least one aldehyde or ketone and hydrogen.

[0054] As aldehydes or ketones, preference is given to formaldehyde, acetaldehyde, 1-propanal, acetone, 1-butyraldehyde, isobutyraldehyde, methyl ethyl ketone, 1-pentanal, methyl isopropyl ketone, 1-hexanal, methyl isobutyl ketone, 2-ethylhexanal, 1-octanal, 1-nonanal, 1-decanal, 1-undecanal, 1-dodecanal, methyl phenyl ketone, benzaldehyde, 1-naphthaldehyde or cyclohexanecarbaldehyde.

[0055] Particular preference is given to 2-ethylhexanal, benzaldehyde, 1-naphthaldehyde or cyclohexanecarbaldehyde, especially benzaldehyde.

[0056] Particularly preferred as the amine of the formula H2N-A-NH2 is 1,2-ethylenediamine.

[0057] The bicyclic epoxide is preferably an aromatic bicyclic epoxide. If the bicyclic epoxide contains at least one aromatic ring, it is called "aromatic".

[0058] The aromatic bicyclic epoxide preferably does not contain a polyether chain. Such an aromatic bicyclic epoxide is particularly suitable as a curing agent for non-aqueous epoxy resin products and is particularly stable to the influence of climate.

[0059] The aromatic bicyclic epoxide is preferably selected from bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, a mixture of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, bis(4-hydroxy-3-methylphenyl)methane diglycidyl ether, 2,2-bis(4-hydroxy-3-methylphenyl)propane diglycidyl ether, bis(3,5-dimethyl-4-hydroxyphenyl)methane diglycidyl ether, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane diglycidyl ether, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane diglycidyl ether, 2,2-bis(4-hydroxyphenyl)butane diglycidyl ether, 3,3-bis(4-hydroxyphenyl)pentane diglycidyl ether, 3,4-bis(4-hydroxyphenyl)hexane diglycidyl ether, 4,4-bis(4-hydroxyphenyl)heptane diglycidyl ether, 2,4-bis(4-hydroxyphenyl)-2-methylbutane diglycidyl ether and 4,4'-dihydroxydiphenyl diglycidyl ether.

[0060] The bicyclic epoxide is particularly preferably bisphenol A diglycidyl ether, bisphenol F diglycidyl ether or bisphenol A / F diglycidyl ether, especially bisphenol A diglycidyl ether.

[0061] The diglycidyl ether is preferably used in industrial grade quality.

[0062] Particularly preferred are commercially available liquid resins, such as especially GY 240, GY250, GY 281, GY 282, GY 285, PY 304 or PY 720 (all from Huntsman), or 330, 331, 332, 336, 351, 352, 354 or 356 (all from Dow).

[0063] The diepoxide preferably has an epoxy equivalent in the range of 110 to 260 g / Eq, preferably 156 to 200 g / Eq.

[0064] The amine mixture is preferably used in the adduct of the present invention in such an amount that the stoichiometric ratio is 1.3 - 2, especially 1.4 - 1.7 moles of diamine of formula (I) to 1 mole equivalent of epoxy groups of the diepoxide.

[0065] This adduct contains particularly little unreacted diamine and a high content of adduct molecules. It has a particularly low odor and surprisingly low viscosity. It enables particularly rapid curing and high flexibility in combination with other amines.

[0066] Preferably, the temperature during the reaction is in the range of 40 to 120 °C, especially 60 to 100 °C.

[0067] After the reaction, it is preferred not to remove the unreacted diamine of formula (I) and diamine of formula (II) from the adduct, but to leave them therein and they are components of the adduct.

[0068] The adduct contains a so-called 2:1 adduct obtained by the addition of 2 moles of diamine of formula (I) or (II) and 1 mole of diepoxide. In the case of N-benzyl-1,2-ethanediamine as the diamine of formula (I), N,N'-dibenzyl-1,2-ethanediamine as the diamine of formula (II), and bisphenol A diglycidyl ether, the adduct mainly contains the following 2:1 adducts,

[0069]

[0070] Also present therein are those with secondary amino groups added to the epoxy groups as other 2:1 adducts, such as those shown below:

[0071]

[0072]

[0073] The adduct further contains higher adducts, in particular the so-called 3:2 adduct obtained by adding 3 moles of the diamine of formula (I) or (II) and 2 moles of the diepoxide. In the case of N-benzyl-1,2-ethanediamine as the diamine of formula (I) and bisphenol A diglycidyl ether, the following 3:2 adducts are mainly present:

[0074]

[0075] Among them, there are also 3:2 adducts resulting from the reaction with secondary amino groups.

[0076] The adduct also contains other higher adducts, the so-called >3:2 adducts, in particular those obtained by adding 4 moles of the diamine of formula (I) or (II) and 3 moles of the diepoxide or 5 moles of the diamine of formula (I) or (II) and 4 moles of the diepoxide.

[0077] The adduct of the present invention preferably contains 2:1 adduct and higher adducts in a weight ratio of 30 / 70 - 80 / 20, preferably 35 / 65 - 70 / 30. Such an adduct enables a particularly advantageous combination of low viscosity and rapid curing.

[0078] The adduct of the present invention particularly preferably contains 2:1 adduct and higher adducts in a weight ratio of 30 / 70 to 49.9 / 50.1, especially 35 / 65 - 49 / 51. Such an adduct is particularly prepared in a stoichiometric ratio of 1.4 - 1.7 moles of the diamine of formula (I) to 1 molar equivalent of the epoxy groups of the diepoxide. It enables particularly rapid curing.

[0079] The adduct preferably contains less than 1% by weight of diluent or water.

[0080] The adduct preferably has a viscosity of 5 - 500 Pa·s, preferably 10 - 250 Pa·s, especially 20 - 150 Pa·s at 20 °C, and the viscosity is measured using a cone-plate viscometer at a shear rate of 10 s -1 of.

[0081] The adduct of the present invention is particularly suitable for curing epoxy resins.

[0082] The present invention further provides a curing agent for epoxy resins, which comprises the adduct of the present invention and at least one other component selected from other amines, accelerators and diluents.

[0083] The curing agent preferably contains 1 - 80% by weight, preferably 2 - 60% by weight, especially 5 - 50% by weight of the adduct of the present invention.

[0084] The curing agent for the epoxy resin is preferably not water-based. It especially contains less than 15% by weight, preferably less than 10% by weight, of water. This curing agent is suitable for non-aqueous epoxy resin products, especially floor coatings.

[0085] The curing agent preferably contains at least one other amine having an aliphatic amino group and at least three amine hydrogens. Preferably, the additional amine is only incorporated into the adduct after the amine mixture has reacted with the diepoxide. The additional amine can be the same amine as those used as the diamine of formula (I) in the reaction for forming the adduct, or it can be a different amine.

[0086] Suitable other amines are especially N-benzyl-1,2-ethylenediamine, N-benzyl-1,2-propanediamine, N-benzyl-1,3-bis(aminomethyl)benzene, N-(2-ethylhexyl)-bis(aminomethyl)-1,3-benzene or N-(2-phenylethyl)-bis(aminomethyl)-1,3-benzene, and also 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-tetramethyl-1,6-hexanediamine (TMD), 1,7-heptanediamine, 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 2.6Decane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), menthane-1,8-diamine, 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-trioxatridecane-1,13-diamine or higher oligomers of these diamines, bis(3-aminopropyl)polytetrahydrofuran or other polytetrahydrofuran diamines, polyoxyalkylene diamines or -triamines, especially polyoxypropylene diamines or polyoxypropylene triamines, such as D-230, D-400 or T-403 (all from Huntsman), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), dipropylenetriamine (DPTA), N-(2-aminoethyl)propane-1,3-diamine (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) or 3-(3-(dimethylamino)propylamino)propylamine (DMAPAPA).

[0087] It may be advantageous when the curing agent of the present invention comprises a combination of two or more other amines.

[0088] Preferably selected from N-benzyl-1,2-ethylenediamine, N-benzyl-1,2-propanediamine, N-benzyl-bis(aminomethyl)-1,3-benzene, N-(2-ethylhexyl)-bis(aminomethyl)-1,3-benzene, N-(2-phenylethyl)-bis(aminomethyl)-1,3-benzene, TMD, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, IPDA, 2(4)-methyl-1,3-diaminocyclohexane, MXDA, polyoxypropylenediamine with an average molecular weight M n of 200 - 500 g / mol, polyoxypropylenetriamine with an average molecular weight M n of 300 - 500 g / mol, DMAPAPA, BHMT, DETA, TETA, TEPA, PEHA, DPTA, N3-amine and N4-amine.

[0089] The curing agent particularly preferably comprises at least one selected from N-benzyl-1,2-ethylenediamine, TMD, 1,2-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, IPDA, 2(4)-methyl-1,3-diaminocyclohexane, MXDA, polyoxypropylenediamine with an average molecular weight M n of 200 - 500 g / mol and polyoxypropylenetriamine with an average molecular weight M n of 300 - 500 g / mol and other amines.

[0090] Another particularly preferred other amine is N-benzyl-1,2-ethylenediamine. This amine gives the curing agent particularly good processing properties, rapid curing and a tendency towards almost no turbidity effect.

[0091] Another particularly preferred other amine is MXDA, optionally in the form of an amine-functional adduct with an epoxy resin. This amine allows particularly rapid curing.

[0092] Another particularly preferred other amine is IPDA, optionally in the form of an amine-functional adduct with an epoxy resin. This amine enables particularly high glass transition temperatures and final hardness.

[0093] Suitable accelerators are especially acids or compounds that can be hydrolyzed into 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, especially phosphoric acid for example, or mixtures of the above acids and acid esters; nitrates, especially calcium nitrate; tertiary amines, for example especially 1,4-diazabicyclo[2.2.2]octane, benzyldimethylamine, α-methylbenzyldimethylamine, triethanolamine, dimethylaminopropylamine, imidazoles such as especially N-methylimidazole, N-vinylimidazole or 1,2-dimethylimidazole, salts of these tertiary amines, quaternary ammonium salts, especially benzyltrimethylammonium chloride for example, amidines, especially 1,8-diazabicyclo[5.4.0]undec-7-ene for example, guanidines such as especially 1,1,3,3-tetramethylguanidine, phenols especially bisphenols, phenolic resins or Mannich bases, especially 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol or polymers prepared from phenol, formaldehyde and N,N-dimethyl-1,3-propanediamine for example, phosphites, especially diphenyl or triphenyl phosphite for example, or compounds having a mercapto group.

[0094] Preferred are acids, nitrates, tertiary amines or Mannich bases, especially salicylic acid, calcium nitrate or 2,4,6-tris(dimethylaminomethyl)phenol, or combinations of these accelerators.

[0095] Suitable diluents are especially xylene, 2-methoxyethanol, dimethoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, benzyl alcohol, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol diphenyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monon-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol butyl ether, propylene glycol phenyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol dibutyl ether, diphenylmethane, diisopropylnaphthalene, mineral oil fractions, for example grades (from Exxon), alkylphenols such as tert-butylphenol, nonylphenol, dodecylphenol, cardanol (from cashew nut shell liquid, mainly containing 3-(8,11-pentadecadienyl)phenol), styrenated phenol, bisphenols, aromatic hydrocarbon resins, especially of the type containing phenolic groups, alkoxylated phenols, especially ethoxylated or propoxylated phenols, especially 2-phenoxyethanol, adipic acid esters, sebacic acid esters, phthalic acid esters, benzoic acid esters, organic phosphoric acid esters or sulfonic acid esters or sulfonamides.

[0096] Preferred diluents have a boiling point above 200 °C.

[0097] The diluent is preferably selected from benzyl alcohol, styrenated phenol, ethoxylated phenol, aromatic resins containing phenolic groups, especially products LS 500, LX 200, LA 300 or LA 700 (from Rütgers), diisopropylnaphthalene and cardanol.

[0098] Particularly preferred is benzyl alcohol.

[0099] Diluents containing phenolic groups can also function effectively as accelerators.

[0100] The curing agent may contain other components, especially the following:

[0101] - other adducts, especially adducts of IPDA, MXDA, DETA, TETA or TEPA with bisphenol A, F or A / F diglycidyl ethers, or adducts of MPMD or 1,2-ethylenediamine or 1,2-propylenediamine with tolyl glycidyl ether, wherein the unreacted MPMD, 1,2-ethylenediamine or 1,2-propylenediamine is removed by distillation after the reaction;

[0102] - primary amines, such as especially benzylamine or furfurylamine;

[0103] - polyamidoamines, especially reaction products of mono- or polycarboxylic acids or their esters or acid anhydrides, especially dimer fatty acids with polyamines used in stoichiometric excess, especially DETA or TETA;

[0104] - Mannich bases, especially phenolic alkylamines, i.e., reaction products of phenols (especially cardanol) with aldehydes (especially formaldehyde) and polyamines.

[0105] - aromatic polyamines, such as especially 4,4'-, 2,4'- and / or 2,2'-diaminodiphenylmethane, 2,4- and / or 2,6-toluenediamine, 3,5-dimethylthio-2,4-toluenediamine and / or 3,5-dimethylthio-2,6-toluenediamine, 3,5-diethyl-2,4-toluenediamine and / or 3,5-diethyl-2,6-toluenediamine;

[0106] - compounds having a mercapto group, especially liquid thiol-terminated polysulfide polymers, thiol-terminated polyoxyalkylene ethers, thiol-terminated polyoxyalkylene derivatives, polyesters of thioacids, 2,4,6-trimercapto-1,3,5-triazine, triethylene glycol dithiol or ethylene dithiol.

[0107] The present invention further provides an epoxy resin composition comprising

[0108] - a resin component comprising at least one epoxy resin, and

[0109] - a curing agent component comprising the adduct of the present invention.

[0110] The curing agent component preferably contains the above-mentioned curing agent.

[0111] Suitable epoxy resins can be obtained in a known manner, in particular by reacting epichlorohydrin with polyols, polyphenols or amines.

[0112] Suitable epoxy resins are especially aromatic epoxy resins, in particular glycidyl ethers of the following substances:

[0113] - Bisphenol A, bisphenol F or bisphenol A / F, where A represents acetone and F represents formaldehyde, which are used as reactants in the preparation of these bisphenols. In the case of bisphenol F, positional isomers may also be present, more particularly positional isomers derived from 2,4'- or 2,2'-hydroxyphenylmethane.

[0114] - Dihydroxybenzene derivatives, such as resorcinol, hydroquinone or catechol;

[0115] - 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-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-tert-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), 1,5-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (bisphenol-M), 4,4'-dihydroxybiphenyl (DOD), 4,4'-dihydroxybenzophenone, bis(2-hydroxynaphthalen-1-yl)methane, bis(4-hydroxynaphthalen-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;

[0116] - Novolacs, which are especially condensation products of phenol or cresol with formaldehyde or paraformaldehyde or acetaldehyde or crotonaldehyde or isobutyraldehyde or 2-ethylhexaldehyde or benzaldehyde or furfural;

[0117] - Aromatic amines, such as aniline, toluidine, 4-aminophenol, 4,4'-methylenediphenyldiamine, 4,4'-methylenediphenylbis(N-methyl)amine, 4,4'-[1,4-phenylenebis(1-methylethylidene)]diphenylamine (diphenylamine-P) or 4,4'-[1,3-phenylenebis(1-methylethylidene)]diphenylamine (diphenylamine-M).

[0118] Other suitable epoxy resins are aliphatic or cycloaliphatic polyepoxides, especially

[0119] - Glycidyl ethers of saturated or unsaturated, branched or unbranched, cyclic or open-chain di-, tri- or tetra-functional C2-C 30 alcohols, especially ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, octylene glycol, polypropylene glycol, dimethylolcyclohexane, neopentyl glycol, dibromoneopentyl glycol, castor oil, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol or glycerol, or glycidyl ethers of alkoxylated glycerol or alkoxylated trimethylolpropane;

[0120] - Hydrogenated bisphenol A, F or A / F liquid resins or glycidylated products of hydrogenated bisphenol A, F or A / F;

[0121] - N-glycidyl derivatives of amides or heterocyclic nitrogen bases, such as triglycidyl cyanurate or triglycidyl isocyanurate, or reaction products of epichlorohydrin and hydantoin.

[0122] The epoxy resin is preferably a liquid resin or a mixture comprising two or more liquid epoxy resins.

[0123] "Liquid epoxy resin" means an industrial polyepoxide having a glass transition temperature below 25 °C.

[0124] The resin component may optionally additionally contain a certain proportion of solid epoxy resin.

[0125] The epoxy resin is especially a bisphenol-based liquid resin, especially bisphenol A diglycidyl ether and / or bisphenol F diglycidyl ether, 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 a certain proportion of solid bisphenol A resin or novolac glycidyl ether.

[0126] The resin component may contain a reactive diluent.

[0127] Preferred reactive diluents are epoxy group-containing reactive diluents, especially butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether or triglycidyl ether, phenyl glycidyl ether, tolyl glycidyl ether, guaiacol glycidyl ether, 4-methoxyphenyl glycidyl ether, p-n-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, 4-nonylphenyl glycidyl ether, 4-dodecylphenyl glycidyl ether, cardanol glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, or glycidyl ethers of natural alcohols, such as especially C8-C 10 or C 12 -C 14 or C 13 -C 15 alkyl glycidyl ethers.

[0128] The epoxy resin composition preferably contains at least one other component selected from diluents, accelerators and fillers.

[0129] Suitable accelerators are those already mentioned, especially salicylic acid, calcium nitrate or 2,4,6-tris(dimethylaminomethyl)phenol or combinations thereof.

[0130] Suitable diluents are those already mentioned, especially those with a boiling point greater than 200 °C.

[0131] The diluent is preferably selected from benzyl alcohol, styrenated phenol, ethoxylated phenol, aromatic resins containing phenolic groups, especially LS 500, LX 200, LA 300 or LA 700 products (from Rütgers), diisopropylnaphthalene and cardanol.

[0132] Particularly preferred is benzyl alcohol.

[0133] Suitable fillers are especially ground or precipitated calcium carbonate, optionally coated with fatty acids, especially stearic acid, stearates, barite (Schwerspat), talc, quartz powder, quartz sand, silicon carbide, iron mica, dolomite, wollastonite, kaolin, mica (potassium aluminosilicate), molecular sieves, alumina, 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 beads.

[0134] Preferred are calcium carbonate, quartz powder, quartz sand or combinations thereof.

[0135] The epoxy resin composition may optionally contain other auxiliaries and additives, especially the following:

[0136] - Reactive diluents, especially those already mentioned, or epoxidized soybean oil or linseed oil, compounds containing acetoacetate groups, especially acetylated polyols, butyrolactones, carbonates, aldehydes, isocyanates or organosilicons with reactive groups;

[0137] - Polymers, especially polyamides, polysulfides, polyvinyl formal (PVF), polyvinyl butyral (PVB), polyurethanes (PUR), polymers with carboxyl groups, polyamides, butadiene-acrylonitrile copolymers, styrene-acrylonitrile copolymers, butadiene-styrene copolymers, homopolymers or copolymers of unsaturated monomers, especially selected from ethylene, propylene, butene, isobutene, isoprene, vinyl acetate or alkyl (meth)acrylates, especially chlorosulfonated polyethylene or fluoropolymers or sulfonamide-modified melamine;

[0138] - Fibers, especially glass fibers, carbon fibers, metal fibers, ceramic fibers or polymer fibers, such as polyamide fibers or polyethylene fibers;

[0139] – Pigments, especially titanium dioxide, iron oxide or chromium(III) oxide;

[0140] – Rheological modifiers, especially thickeners or anti-settling agents;

[0141] – Adhesion improvers, especially organoalkoxysilanes;

[0142] - Flame retardants, especially the fillers aluminum hydroxide or magnesium hydroxide already mentioned, 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, phosphate esters such as especially diphenyltolyl phosphate, resorcinol bis(diphenyl phosphate), resorcinol bisphosphate oligomers, tetraphenyl resorcinol bisphosphite, ethylenediamine bisphosphate, bisphenol A-bis(diphenyl phosphate), tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, tris(2,3-dichloropropyl) phosphate, tris[3-bromo-2,2-

[0143] bis(bromomethyl)propyl] phosphate, tetrabromobisphenol A, bis(2,3-dibromopropyl ether) of bisphenol A, brominated epoxy resins, ethylenebis(tetrabromophthalimide), ethylenebis(dibromonorbornanedicarboximide), 1,2-bis(tribromophenoxy)ethane, tris(2,3-dibromopropyl) isocyanurate, tribromophenol, hexabromocyclododecane, bis(hexachlorocyclopentadiene) cyclooctane or chlorinated paraffin; or

[0144] - Additives, in particular paraffin wax dispersants, film-forming aids, wetting agents, leveling agents, defoamers, degassing agents, stabilizers against oxidation, heat, light or UV radiation, or biocides.

[0145] The epoxy resin composition preferably contains other auxiliaries and additives, in particular pigments, wetting agents, leveling agents and / or defoamers.

[0146] The epoxy resin composition preferably has only a low content of diluent. It preferably contains less than 20% by weight, more preferably less than 15% by weight, in particular less than 10% by weight of diluent. This enables low-emission or emission-free epoxy resin products.

[0147] The epoxy resin composition preferably has only a low content of water, preferably less than 5% by weight, in particular less than 1% by weight of water.

[0148] In the epoxy resin composition, the ratio of the number of groups reactive to epoxy groups to the number of epoxy groups is preferably in the range of 0.5 to 1.5, especially 0.7 to 1.2.

[0149] The primary and secondary amino groups present in the epoxy resin composition and optionally other groups reactive to epoxy groups react with the epoxy groups, causing their ring opening (addition reaction). Due mainly to this reaction, the composition polymerizes and thus cures.

[0150] The resin component and the curing agent component of the epoxy resin composition are stored in separate containers. Other components of the epoxy resin composition can be present as components of the resin component or the curing agent component, wherein other components reactive to epoxy groups are preferably components of the curing agent component. Similarly, other components can be present as separate additional components.

[0151] Suitable containers for storing the resin component or the curing agent component are in particular drums, barrels, bags, sachets, cans, cartridges or tubes. The components are storable, which means that they can be stored for several months to one year or longer before use, without any change in their respective properties to the extent relevant to their use. For the use of the epoxy resin composition, the components are mixed with each other shortly before or during application. The mixing ratio between the resin component and the curing agent component is preferably selected such that the groups reactive to epoxy groups of the curing agent component and the epoxy groups of the resin component have a suitable ratio, as described above. By weight, the mixing ratio between the resin component and the curing agent component is usually in the range of 1:10 to 10:1.

[0152] Mix the components by a suitable method; the mixing can be carried out continuously or batchwise. If the mixing is not carried out immediately before application, it must be ensured that there is no excessive time lapse between mixing the components and applying the components, and the application is carried out within the pot life. The mixing is carried out especially at ambient temperature, which is generally in the range of about 5 - 40°C, preferably about 10 - 35°C.

[0153] As described above, the curing by chemical reaction starts with the mixing of the two components. The curing is generally carried out at a temperature in the range of 0 to 150°C. It is preferably carried out at ambient temperature and generally continues for several days to several weeks. The duration depends especially on the temperature, the reactivity of the components, their stoichiometric ratio, and on the presence of a promoter.

[0154] In the freshly mixed state, the epoxy resin composition has a low viscosity. The viscosity at 20°C, 10 minutes after mixing the resin component and the curing agent component, is preferably in the range of 300 - 4000 mPa·s, more preferably 300 - 3000 mPa·s, particularly preferably 300 - 2000 mPa·s, measured using a cone - plate viscometer at a shear rate of 10 s -1 of shear rate.

[0155] Apply the epoxy resin composition to at least one substrate, and the following substrates are particularly suitable:

[0156] - glass, glass - ceramics, concrete, mortar, cement screed, fibre - cement, bricks, tiles, gypsum or natural stone, such as granite or marble;

[0157] - repair or levelling materials based on PCC (polymer - modified cement mortar) or ECC (epoxy - resin - modified cement mortar);

[0158] - metals or alloys, such as aluminium, iron, steel, copper, other non - ferrous metals, including surface - refined metals or alloys, such as galvanized or chrome - plated metals;

[0159] - tar or asphalt;

[0160] - leather, fabric, paper, wood, wood materials bonded with resins (such as phenolic resin, melamine resin or epoxy resin), resin - fabric composites or other so - called polymer composites;

[0161] - plastics, such as rigid and flexible PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resin, phenolic resin, PUR, POM, TPO, PE, PP, EPM or EPDM, each being untreated or surface - treated, for example, by plasma, corona or flame;

[0162] - Fiber-reinforced plastics, such as carbon fiber-reinforced plastics (CFK), glass fiber-reinforced plastics (GFK), and sheet molding compounds (SMC);

[0163] - Insulating foams, especially those made of EPS, XPS, PUR, PIR, rock wool, glass wool, or foam glass (foamed glass);

[0164] - Coated or painted substrates, especially painted tiles, coated concrete, powder-coated metals or alloys, or painted metal sheets;

[0165] - Coatings, paints, or varnishes, especially coated floors that have been overlaid with another floor covering.

[0166] If required, the substrate can be pretreated before application, especially by physical and / or chemical cleaning methods or by applying an activator or primer.

[0167] The cured composition is obtained by curing the epoxy resin composition.

[0168] The epoxy resin composition is preferably used as a coating, primer, adhesive, sealant, casting resin, casting resin, impregnating resin, or as a matrix for fiber composites, especially for example, the matrix of CFK or GFK.

[0169] The epoxy resin composition is particularly preferably used as a coating. Here, coatings are understood to mean all kinds of flat-applied coverings, especially floor coverings, paints, varnishes, sealants, undercoats, primers, or protective coatings, especially those also used for heavy corrosion protection.

[0170] The epoxy resin composition is particularly suitable as an indoor floor covering or floor coating, such as in offices, industrial workshops, gymnasiums, or cold storages, or for outdoor areas such as balconies, terraces, parking lots, bridges, or roofs, as a protective coating for concrete, cement, metal, plastic, or wood, such as for surface sealing of wooden structures, vehicles, loading areas, tanks, silos, shafts, pipes, machines, or steel structures, such as for surface sealing of ships, bridge piers, offshore platforms, gates, hydropower stations, hydraulic structures, swimming pools, wind turbines, bridges, chimneys, cranes, or sheet pile walls, or as an undercoat, adhesion paint, or anticorrosive primer, or for hydrophobization of surfaces.

[0171] The epoxy resin composition is particularly advantageously used for low-emission coatings with environmentally friendly quality seals, such as those meeting the requirements of Emicode (EC1Plus), AgBB, DIBt, Blue Angel (Der Blaue Engel), AFSSET, RTS (M1), and the US Green Building Council (LEED).

[0172] For use as a coating, the epoxy resin composition advantageously has a liquid consistency with low viscosity and good leveling properties. Usually at ambient temperature, within its pot life, the mixed composition is applied planar in the form of a film with a layer thickness of about 50 μm to about 5 mm to a substrate. In particular, it is applied by pouring onto the substrate to be coated and then spreading it evenly, for example, using a doctor blade or a toothed trowel. It can also be applied with a brush or a roller or in the form of spraying, for example, as an anti-corrosion coating on steel. Curing generally produces a substantially uniform, glossy and non-sticky high-hardness film which has good adhesion to a variety of different substrates.

[0173] Here, the epoxy resin composition is particularly used in a coating method comprising the following steps:

[0174] (i) Mixing the components of the epoxy resin composition,

[0175] (ii) Applying the mixed composition to a substrate within its pot life,

[0176] Subsequently curing the mixed composition.

[0177] An additional coating can be applied to the fully or partially cured composition. In this case, the additional layer can likewise be an epoxy resin composition or another material, in particular a polyurethane or polyurea coating.

[0178] It is also particularly preferred to use the epoxy resin composition as an adhesive. When used as an adhesive, the epoxy resin composition generally has a pasty consistency and structural tackiness after mixing of the components. During application, the mixed adhesive is applied to at least one of the substrates to be joined within its pot life, and the two substrates are joined within the open time of the adhesive to form a bonded assembly.

[0179] The mixed adhesive is applied or coated in particular by means of a brush, a roller, a doctor blade or a trowel, or from a tube, a cartridge or a metering device.

[0180] This adhesive is particularly suitable for the construction industry, especially for strengthening building structures with thin steel sheets or sheets made of carbon fiber-reinforced composite plastics (CFK), for buildings containing bonded precast concrete components, especially bridges or concrete towers, such as for wind turbines, shafts, pipelines or tunnels, or for buildings containing bonded natural stones, ceramic elements or components made of fiber cement, steel, cast iron, aluminum, wood or polyester, for anchoring dowels or steel bars in drill holes, for fixing, for example, handrails, balustrades or door frames, for repairing, for example, filling edges, holes or joints, especially in concrete curing, or for bonding films of polyvinyl chloride (PVC), flexible polyolefins or adhesively modified chlorosulfonated polyethylene to concrete or steel.

[0181] Other application areas relate to structural bonding in the construction or manufacturing industry, especially as bonding mortars, assembly adhesives, reinforcing adhesives, for example, particularly for bonding CFK or steel sheets to concrete, masonry or wood, as component adhesives, for example, for bridge components, sandwich component adhesives, facade component adhesives, reinforcing adhesives, body adhesives or semi-shell adhesives for wind turbine rotor blades.

[0182] This epoxy resin adhesive is also suitable for filling cavities, such as gaps, cracks or drill holes, where the adhesive is filled or injected into the cavity and, after curing, fills the cavity and adhesively bonds or adheres the sides of the cavity to each other in a force-locking manner.

[0183] Here, the epoxy resin composition is particularly used in a bonding method comprising the following steps:

[0184] (i) Mixing the components of the epoxy resin composition,

[0185] (ii) Applying the mixed composition

[0186] - to at least one substrate to be bonded and connecting the substrates during the open time to form a bonded body,

[0187] - or into a cavity or gap between a plurality of substrates and optionally inserting an anchor during the open time into the cavity or gap,

[0188] Subsequently curing the mixed composition.

[0189] "Anchor" more specifically refers here to reinforcing bars, screws or bolts. Thus, such an anchor is in particular adhesively bonded or anchored in a wall, wall, ceiling or foundation such that a part thereof is adhesively bonded in a force-locking manner and a part thereof projects and is able to withstand structural loads.

[0190] Identical or different substrates can be bonded.

[0191] Articles are obtained by applying and curing the epoxy resin composition.

[0192] Accordingly, the present invention also provides an article obtained by applying the epoxy resin composition.

[0193] The article is preferably a building or a part thereof, in particular a building above or below ground, an office, an industrial workshop, a gymnasium, a cold storage, a silo, a bridge, a roof, a stairwell, a floor, a balcony, a terrace or a parking floor, or an industrial or consumer product, in particular a dock, an offshore platform, a gate, a crane, a bulkhead, a pipeline or a rotor blade of a wind turbine, or a means of transport, such as in particular a car, a truck, a rail vehicle, a ship, an aircraft or a helicopter, or an installable part thereof.

[0194] The epoxy resin composition is characterized by advantageous properties. It can also be formulated with little or no diluent, and this formulation has a low viscosity and good processability, and cures reliably and rapidly, especially even under wet and cold conditions. This results in a high mechanical quality and a coating with a high surface quality. This epoxy resin product is particularly suitable as a coating, especially for floors. The amine-functional adduct present in the epoxy resin composition allows for high flexibility when combined with other amines and diluents, and allows for particularly rapid curing. Optionally additionally included IPDA enables a higher glass transition temperature. Examples

[0195] Specific examples will be described below, which are intended to further clarify the described invention. The invention is of course not limited to these described specific examples.

[0196] "AHEW" stands for amine hydrogen equivalent.

[0197] "EEW" stands for epoxy equivalent.

[0198] "Standard climatic conditions" ("NK") means a temperature of 23 ± 1 °C and a relative air humidity of 50 ± 5%.

[0199] Unless otherwise stated, the chemicals used are products of Sigma-Aldrich Chemie GmbH.

[0200] Description of the measuring method:

[0201] The viscosity was measured on a Rheotec RC30 cone-plate viscometer at a constant temperature (cone diameter 50 mm, cone angle 1°, cone tip - plate distance 0.05 mm, shear rate 10 s -1 )

[0202] The amine value was determined by titration (with a solution of 0.1 N HClO4 in acetic acid against crystal violet).

[0203] Liquid chromatography (UHPLC) was carried out to quantitatively determine N-benzyl-1,2-ethylenediamine after derivatization with phenyl isocyanate under external calibration.

[0204] Gel permeation chromatography (GPC) was carried out to determine the weight ratios of the 2:1 adduct, 3:2 adduct, and >3:2 adduct relative to polystyrene standards.

[0205] Substances and abbreviations used:

[0206] GY 250: Bisphenol A diglycidyl ether, EEW 187 g / Eq (from Huntsman)

[0207] DY-E: C 12 -C 14 Mono glycidyl ether of alcohol, EEW approximately 290 g / Eq (from Huntsman)

[0208] B-EDA mixture: An amine mixture containing approximately 85 wt% N-benzyl-1,2-ethylenediamine and approximately 14 wt% N,N'-dibenzyl-1,2-ethylenediamine, prepared as described below, AHEW 55 g / Eq

[0209] B-EDA pure: Purified N-benzyl-1,2-ethylenediamine, prepared as described below, 150.2 g / mol, AHEW 50 g / Eq

[0210] DB-EDA: N,N'-Dibenzyl-1,2-ethylenediamine, 240.4 g / mol, AHEW 120.2 g / Eq (from Sigma Aldrich)

[0211] IPDA: 3-Aminomethyl-3,5,5-trimethylcyclohexylamine, AHEW 42.6 g / Eq (from IPD of Evonik) IPD

[0212] Preparation of diamines of formula (I) and (II):

[0213] Amine mixture containing N-benzyl-1,2-ethylenediamine and N,N'-dibenzyl-1,2-ethylenediamine (B-EDA mixture):

[0214] At room temperature and under a nitrogen atmosphere, 180.3 g (3 mol) of 1,2-ethylenediamine was added to a round-bottom flask. A solution of 106.1 g (1 mol) of benzaldehyde in 1200 ml of isopropanol was slowly added dropwise while stirring well, and stirring was continued for 2 hours. Then, in a continuous hydrogenation apparatus, the reaction mixture was hydrogenated with a Pd / C fixed-bed catalyst at a hydrogen pressure of 80 bar, a temperature of 80 °C, and a flow rate of 5 ml / min. To monitor the reaction, the imine band was checked by IR spectroscopy to see if it was at approximately 1665 cm -1Disappeared at this point. Then the hydrogenated solution was concentrated on a rotary evaporator at 65 °C to remove unreacted 1,2-ethylenediamine, water and isopropanol. The reaction mixture thus obtained was a clear light yellow liquid with an amine value of 678 mg KOH / g and contained approximately 85 wt% of N-benzyl-1,2-ethylenediamine (retention time 8.47 - 8.57 min) and approximately 14 wt% of N,N'-dibenzyl-1,2-ethylenediamine (retention time 14.27 min) as determined by GC. This corresponds to a weight ratio of N-benzyl-1,2-ethylenediamine to N,N'-dibenzyl-1,2-ethylenediamine of 86 / 14.

[0215] N-benzyl-1,2-ethylenediamine (purified, B-EDA pure):

[0216] 50 g of the amine mixture (B-EDA-mixture) containing N-benzyl-1,2-ethylenediamine and N,N'-dibenzyl-1,2-ethylenediamine prepared as described above was distilled under reduced pressure at 80 °C, and 31.3 g of distillate (N-benzyl-1,2-ethylenediamine) was collected at a vapor temperature of 60 - 65 °C and 0.06 mbar. A colorless liquid was obtained, which had a viscosity of 8 mPa·s at 20 °C, an amine value of 750 mg KOH / g and a purity of >97% as determined by GC.

[0217] Preparation of the adduct:

[0218] Adduct A1: (invention example)

[0219] 53.0 g of the amine mixture B-EDA mixture (containing 0.3 mol of N-benzyl-1,2-ethylenediamine and 0.03 mol of N,N'-dibenzyl-1,2-ethylenediamine) prepared as described above was pre-placed under a nitrogen atmosphere and heated to 80 °C. While stirring well, 36.8 g (0.2 mol of epoxy groups) GY 250 was slowly added, and the temperature of the reaction mixture was maintained at 70 - 90 °C by cooling. The reaction mixture was maintained within this temperature range for one hour and then cooled. A transparent light yellow liquid was obtained, which had a viscosity of 74 Pa·s at 20 °C and a calculated AHEW of 117 g / Eq.

[0220] Adduct A1 contained 27.8 wt% of N-benzyl-1,2-ethylenediamine as measured by UHPLC, and the weight ratio of the adduct molecules was 2:1 adduct / 3:2 adduct / >3:2 adduct = 46.5 / 27.2 / 26.3 as measured by GPC.

[0221] Adduct A2: (invention example)

[0222] Under a nitrogen atmosphere, 45.0 g (0.3 mol) of the purified N-benzyl-1,2-ethylenediamine (B-EDA pure) prepared as described above and 11.3 g (0.05 mol) of N,N'-dibenzyl-1,2-ethylenediamine (DB-EDA) were pre-placed, mixed and heated to 80 °C. While stirring well, 36.8 g (0.2 mol of epoxy groups) GY 250 was slowly added, and the temperature of the reaction mixture was maintained at 70 - 90 °C by cooling. The reaction mixture was maintained within this temperature range for one hour and then cooled. A transparent, slightly yellow liquid was obtained, which had a viscosity of 47 Pa·s at 20 °C and a calculated AHEW of 117.3 g / Eq.

[0223] Adduct A3: (Example of the invention)

[0224] Under a nitrogen atmosphere, 45.0 g (0.3 mol) of the purified N-benzyl-1,2-ethylenediamine (B-EDA pure) prepared as described above and 19.3 g (0.08 mol) of N,N'-dibenzyl-1,2-ethylenediamine (DB-EDA) were pre-placed, mixed and heated to 80 °C. While stirring well, 36.8 g (0.2 mol of epoxy groups) GY 250 was slowly added, and the temperature of the reaction mixture was maintained at 70 - 90 °C by cooling. The reaction mixture was maintained within this temperature range for one hour and then cooled. A transparent, slightly yellow liquid was obtained, which had a viscosity of 19 Pa·s at 20 °C and a calculated AHEW of 117.5 g / Eq.

[0225] Adduct A4: (Comparative example)

[0226] Under a nitrogen atmosphere, 45.0 g (0.3 mol) of the purified N-benzyl-1,2-ethylenediamine (B-EDA pure) prepared as described above was pre-placed and heated to 80 °C. While stirring well, 36.8 g (0.2 mol of epoxy groups) GY250 was slowly added, and the temperature of the reaction mixture was maintained at 70 - 90 °C by cooling. The reaction mixture was maintained within this temperature range for one hour and then cooled. A transparent, slightly yellow liquid was obtained, which had a viscosity of 262 Pa·s at 20 °C and a calculated AHEW of 116.3 g / Eq.

[0227] Adduct A4 contains 24.2 wt% of N-benzyl-1,2-ethylenediamine measured by UHPLC, and the weight ratio of the adduct molecules measured by GPC is adduct 2:1 / adduct 3:2 / adduct > 3:2 = 42.5 / 27.0 / 30.5.

[0228] Preparation of the curing agent and the epoxy resin composition:

[0229] Examples 1 - 12:

[0230] For each example, a centrifugal mixer (SpeedMixer TM DAC 150, FlackTek Inc.) was used to mix the components of the resin compositions specified in Tables 1 to 3 in the specified amounts (parts by weight) and stored while excluding moisture.

[0231] The components of the curing agent compositions specified in Tables 1 to 3 were processed and stored in the same manner.

[0232] Then, the two components of each composition were processed into a homogeneous liquid using a centrifugal mixer, and the homogeneous liquid was immediately tested as follows:

[0233] After mixing for 10 minutes, the viscosity was measured at 20 °C (“Viscosity (10')”).

[0234] Under standard climatic conditions, the gelling time was determined by moving the mixed composition (25 g) with a spatula from time to time until it started to gel.

[0235] To determine the Shore D hardness according to DIN 53505, two cylindrical specimens (diameter 20 mm, thickness 5 mm) were prepared in each case. One was stored under standard climatic conditions, and the hardness was measured after 1 day and 2 days (1d NK and 2d NK), while the other sample was stored at 8 °C and 80% relative humidity and the hardness was measured after 1 day and 2 days in the cold state (1d 8° / 80% and 2d 8° / 80%).

[0236] The first coating film was applied to a glass plate with a layer thickness of 500 μm and stored / cured under standard climatic conditions. After 1 day (“ Hardness (1d NK)”), 2 days (“ Hardness (2d NK)”), 4 days (“ Hardness (4d NK)”), 7 days (“ Hardness (7d NK)”) and 14 days (“ Hardness (14d NK)”), the hardness ( pendulum hardness, measured according to DIN EN ISO 1522) of the film was determined. Once a value greater than 200 s was obtained, the hardness was no longer determined. After 14 days, the appearance of the film was evaluated (referred to as “Appearance (NK)” in the table). If the film had a shiny, non - sticky surface and no structure, it was called “good”. “Structure” refers to any kind of mark or pattern on the surface.

[0237] The second coating film was applied to a glass plate with a layer thickness of 500 μm and stored / cured at 8 °C and 80% relative humidity for 7 days immediately after application, and then stored / cured under standard climatic conditions for 2 weeks. After 24 hours of application, a polypropylene bottle cap was placed on the film, and a wet sponge was placed under the cap. After another 24 hours, the sponge and the bottle cap were removed and placed at a new position on the film, and they were removed from the new position and repositioned in turn after 24 hours, which was carried out 4 times in total. Then, the appearance of the film was evaluated in the same manner as described for Appearance (NK) (named "Appearance (8° / 80%)" in the table). In each case, the number and nature of the visible marks formed in the film due to the wet sponge or the placed bottle cap were also reported. As "cloudiness", the number of white spots was reported. The faintly white discolored spots were denoted as "(1)". If there was a circular imprint due to sinking within the first 24 hours after the placed cap was applied, it was reported as "ring". Such a circular imprint indicates that the coating is not yet walkable. The hardness was measured again on the film cured in this way, specifically after 7 days at 8 °C and 80% relative humidity (" Hardness (7d 8° / 80%)"), and then after another 2 days under NK (" Hardness (+2d NK)"), after 7 days under NK (" Hardness (+7d NK)"), or after 14 days under NK (" Hardness (+14d NK)"). Once a value greater than 190 s was reached, the hardness was no longer measured.

[0238] As a measure of yellowing, the change in color after loading in a weathering test machine was also measured. For this purpose, a coating film with a layer thickness of 500 μm was applied again on a glass plate, stored / cured under standard climatic conditions for 2 weeks, and then loaded at a temperature of 65 °C for 72 hours (Q-Sun (72h)) in a Q-Sun Xenon Xe-1 type aging tester with a Q-SUN daylight-Q filter and a xenon lamp with a light intensity of 0.51 W / m 2 ² at 340 nm. Then, the color difference ΔE of the film loaded in this way compared to the corresponding unloaded film was measured using an NH310 colorimeter from Shenzen 3NH Technology Co., LTD, which is equipped with a silicon photodiode detector, a light source A, and a color space measurement interface CIE L*a*b*C*H*. A ΔE value of up to 5 indicates slight yellowing.

[0239] The results are reported in Tables 1 to 3.

[0240] The examples designated as "(Ref.)" are comparative examples.

[0241]

[0242] Table 1: Compositions and properties of Examples 1 - 4 "n.b." means "not determined"

[0243]

[0244] Table 2: Compositions and properties of Examples 5 - 8 "n.b." means "not determined"

[0245]

[0246] Table 3: Compositions and properties of Examples 9 - 12 "n.b." means "not measured"

Claims

1. An amine-functional adduct obtained from the reaction of the following substances in a stoichiometric ratio of at least 1.2 moles of diamine of formula (I) to 1 molar equivalent of epoxy groups: (i) An amine mixture comprising at least one diamine of formula (I) and at least one diamine of formula (II) in a weight ratio in the range of 65 / 35 to 95 / 5 and having a purity of at least 95% by weight based on the sum of the diamine of formula (I) and the diamine of formula (II), wherein A is an alkylene, cycloalkylene or arylalkylene having 2 - 12 carbon atoms, and R is an alkyl, cycloalkyl or arylalkyl having 1 - 12 carbon atoms, wherein in each case the two nitrogen atoms in the diamines of formula (I) and (II) are separated from each other by at least two carbon atoms, and the diamine of formula (I) has a total of 8 - 15 carbon atoms, and (ii) At least one diepoxide.

2. The adduct according to claim 1, wherein The amine mixture for preparing the adduct has a diamine content of formula H2N - A - NH2 of not more than 3% by weight.

3. The adduct according to claim 1, characterized in that The amine mixture for preparing the adduct has a diamine content of formula H2N - A - NH2 of not more than 2% by weight.

4. The adduct according to claim 1, wherein The amine mixture for preparing the adduct has a diamine content of formula H2N - A - NH2 of not more than 1% by weight.

5. The adduct according to any one of claims 1 to 4, characterized in that The groups A and R in the diamines of formula (I) and (II) are the same groups.

6. The adduct according to any one of claims 1 to 4, characterized in that, The diamine of formula (I) is N - benzyl - 1,2 - ethanediamine, and the diamine of formula (II) is N,N' - dibenzyl - 1,2 - ethanediamine.

7. The adduct according to any one of claims 1 to 4, characterized in that The weight ratio between the diamine of formula (I) and the diamine of formula (II) is in the range of 70 / 30 to 95 / 5.

8. The adduct according to any one of claims 1 to 4, characterized in that The weight ratio between the diamine of formula (I) and the diamine of formula (II) is in the range of 80 / 20 to 90 / 10.

9. The adduct according to any one of claims 1 to 4, characterized in that The amine mixture is the reaction product of at least one amine of formula H2N - A - NH2 with at least one aldehyde or ketone and hydrogen by reductive alkylation.

10. The adduct according to any one of claims 1 to 4, characterized in that The diepoxide is an aromatic diepoxide.

11. The adduct according to any one of claims 1 to 4, characterized in that The stoichiometric ratio is 1.3 to 2 moles of diamine of formula (I) to 1 molar equivalent of epoxy groups of the diepoxide.

12. The adduct according to any one of claims 1 to 4, characterized in that The stoichiometric ratio is 1.4 to 1.7 moles of diamine of formula (I) to 1 molar equivalent of epoxy groups of the diepoxide.

13. The adduct according to claim 11, wherein It contains 2:1 adduct and higher adducts in a weight ratio of 30 / 70 - 80 / 20.

14. The adduct according to any one of claims 1 to 4, characterized in that It contains less than 1% by weight of diluent or water.

15. A curing agent for epoxy resins, comprising the adduct as described in any one of claims 1 to 14 and at least one other component selected from other amines, accelerators and diluents.

16. The curing agent for epoxy resin according to claim 15, characterized in that, Comprising at least one other amine having an aliphatic amino group and at least three amine hydrogens, and the other amine is not added during the preparation of the adduct.

17. The curing agent for epoxy resin according to claim 15 or 16, characterized in that, The other amines are selected from N-benzyl-1,2-ethylenediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 1,2-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 2-methyl-1,3-diaminocyclohexane, 4-methyl-1,3-diaminocyclohexane, 1,3-bis(aminomethyl)benzene, polyoxypropylenediamine with an average molecular weight M n of 200-500 g / mol and polyoxypropylenetriamine with an average molecular weight M n of 300-500 g / mol.

18. An epoxy resin composition, comprising - A resin component comprising at least one epoxy resin, and - A curing agent component comprising the adduct as described in any one of claims 1 - 13 or the curing agent as described in any one of claims 15 - 17.

19. Use of the epoxy resin composition as described in claim 18 as a coating, adhesive, sealant, casting, casting resin, impregnating resin or as a matrix for fiber composites.

20. Use of the epoxy resin composition according to claim 18 as a primer.

21. An article obtained by the use according to claim 19 or 20.

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