Amine epoxy resin adduct

Abstract

The present invention relates to an amine-functional adduct obtained by reacting an amine mixture containing at least one diamine of formula (I) and at least one diamine of formula (II) in a weight ratio ranging from 65 / 35 to 95 / 5, with at least one diepoxide, in a stoichiometric ratio of at least 1.2 moles of diamine of formula (I) per mole equivalent of epoxy groups. The adduct is liquid at room temperature without a diluent, even in the presence of a small excess of diamine, and has an unexpectedly low viscosity. In addition, it is particularly cost-effective because it is available from a technically easy-to-prepare amine mixture. The adduct enables low- or no-emission epoxy resin coatings with unexpectedly fast cure and surprisingly good application properties, which coatings have high hardness, low yellowing tendency, and little tendency to blush-related defects, even under low temperature and humid conditions. TIFF2023515315000010.tif18160

Description

[Technical Field]

[0001] This invention relates to amine-functional adducts of diamines and diepoxides and to their use as curing agents for epoxy resin compositions that are particularly suitable as floor coatings. [Background technology]

[0002] Epoxy resin-based coatings are widely used in the construction industry. They consist of a liquid resin and a hardener component, which are mixed before application and then cure at ambient temperatures ranging from about 5 to 35°C. When applied, the coating's viscosity should be as low as possible so that it flows well at ambient temperatures. After application, it should also cure as quickly and flawlessly as possible, even under humid, cold conditions, to form a flawless surface without haze, spots, or craters. Once cured, they should have high hardness combined with low brittleness and a high glass transition temperature to withstand mechanical stress as well as possible. For visually demanding applications, such as floor top coverings, they should also have a high level of gloss and minimal tendency to yellow under the influence of light.

[0003] However, such epoxy resin coatings are often prone to surface defects such as haze, spots, roughness, or stickiness, also known as "blushing." Blush is caused by the amines present in the curing agent component forming salts with carbon dioxide from the air, especially at high humidity and low temperatures. Many curing agents for epoxy resin coatings contain adducts of diamines and epoxy resins. This reduces the blushing effect and also allows for faster curing. However, diamine-epoxy resin adducts are significantly more viscous than free diamines. To limit viscosity, diamines are used in large stoichiometric excess relative to the epoxy resin. The content of unreacted diamine and the distribution of various adduct molecules vary depending on the stoichiometry and diamine excess level used to prepare the adduct. Adducts prepared using a low excess of diamine contain less unreacted diamine and two, three, or higher molecular weight adduct molecules with two, three, or more diepoxide units. Such adducts may be advantageous in their own right. They have low odor and especially low blushing tendency, allowing the adducts to be used in large amounts and / or combined with additional amines. However, adducts prepared with a low excess of diamine are very viscous or even solid, and as a result, they can only be handled at room temperature with a significant amount of a thinner, such as benzyl alcohol. The thinner is not incorporated into the resin matrix during curing and can be released into the environment by evaporation or diffusion processes. Recently, however, there has been an increasing demand for low-emission products with a low content of releasable substances after curing. For low-emission or no-emission epoxy resin compositions, this type of thinner is therefore used only in small amounts or not at all.

[0004] WO 2017 / 046293 discloses adducts of N-benzylpropane-1,2-diamine or N-benzylethane-1,2-diamine with bisphenol A diglycidyl ether, which are purified by distillation and allow coatings with good surfaces. These adducts are produced using a large excess of diamine, which severely limits the freedom to combine them with additional amines.

[0005] Adducts of alkylated diamines with epoxides are also known as components of hardeners for water-based epoxy resin products, for example from EP 1 956 034. The adducts contain polyether chains and are diluted after the reaction with unadducted diamine and a large amount of water. Summary of the Invention [Means for solving the problem]

[0006] It is therefore an object of the present invention to provide a diamine-epoxy resin adduct that is liquid at room temperature, has the lowest possible viscosity, even with a small excess of diamine during preparation without the addition of a thinner, and when used as a curing agent for epoxy resin coatings, allows good processability, fast cure, and a defect-free, glossy surface, even under humid and low temperature conditions.

[0007] This object is achieved with an adduct as claimed in claim 1. It is obtained by reacting an amine mixture comprising mono- and di-alkylated diamines with a diepoxide in a stoichiometric ratio of at least 1.2 moles of mono- and di-alkylated diamines per mole equivalent of epoxy groups.

[0008] Despite a small excess of diamine, the adducts of the present invention are liquid at room temperature and have unexpectedly low viscosities. Even with low levels of dialkylated diamine, the adducts are much less viscous than corresponding adducts prepared in the absence of dialkylated diamine. Surprisingly, when the adducts are used as curing agents for epoxy resins, neither the rate of cure nor the final hardness is adversely affected to any significant extent by the dialkylated diamine. The much lower viscosity of the adducts is highly advantageous and could not have been predicted based on the prior art.

[0009] The adducts of the invention are particularly inexpensive since they can be obtained from amine mixtures which are technically simple to prepare.

[0010] The adducts of the present invention enable low or no emission epoxy resin coatings with unexpectedly good processability and unexpectedly fast cure, having high hardness and low yellowing tendency, and also having low tendency to blush-related defects even under humid and low temperature conditions.

[0011] Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention provides a diamine of formula (I) in a stoichiometric ratio of at least 1.2 moles per mole equivalent of epoxy groups, (i) an amine mixture containing at least one diamine of formula (I) and at least one diamine of formula (II) in a weight ratio ranging from 65 / 35 to 95 / 5; [ka] (In the formula, A is an alkylene group, a cycloalkylene group, or an arylalkylene group having 2 to 12 carbon atoms; R is an alkyl group, a cycloalkyl group, or an arylalkyl group having 1 to 12 carbon atoms; wherein the two nitrogen atoms in the diamines of formulas (I) and (II) are each separated from each other by at least two carbon atoms, and the diamine of formula (I) has a total of 8 to 15 carbon atoms. and (ii) at least one diepoxide to provide an amine-functional adduct from the reaction of

[0013] A "primary amino group" refers to an amino group that is bonded to only one organic group and has two hydrogen atoms; a "secondary amino group" refers to an amino group that is bonded to two organic groups that may together be part of a ring and has one hydrogen atom; and a "tertiary amino group" refers to an amino group that is bonded to three organic groups, two or three of which may also be part of one or more rings, and does not have any hydrogen atoms.

[0014] "Amine hydrogen" refers to the hydrogen atoms of primary and secondary amino groups.

[0015] "Amine hydrogen equivalent" refers to the mass of an amine or amine-containing composition that contains one molar equivalent of an amine hydrogen. It is expressed in units of "g / equivalent."

[0016] "Epoxide equivalent" refers to the mass of an epoxy group-containing compound or composition that contains one molar equivalent of epoxy groups. It is expressed in units of "g / equivalent."

[0017] Substance names beginning with "poly", such as polyamine or polyepoxide, refer to substances that formally contain two or more of the functional groups appearing in their names per molecule.

[0018] "Thinner" refers to a substance that is soluble in epoxy resin, reduces its viscosity, and does not become chemically incorporated into the epoxy resin polymer during the curing process.

[0019] "Molecular weight" refers to the molar mass of a molecule (in grams per molecule). "Average molecular weight" refers to the number average M of a polydisperse mixture of oligomeric or polymeric molecules.n and is usually measured by gel permeation chromatography (GPC) against polystyrene as a standard.

[0020] "Gel time" is the time interval from mixing the components of an epoxy resin composition to its gelation.

[0021] "Room temperature" refers to a temperature of 23°C.

[0022] The amine mixture used for the adduct of the present invention preferably contains only small amounts or no other amines not corresponding to formula (I) and (II). The amine mixture preferably has a purity of at least 95% by weight, in particular at least 97% by weight, based on the sum of the diamines of formula (I) and formula (II).

[0023] The amine mixture used for preparing the adduct preferably has a content of diamine of formula HN-A-NH (where A is as defined above) of 5% by weight or less, preferably 3% by weight or less, more preferably 2% by weight or less, and in particular 1% by weight or less. Such an amine mixture allows for a low-viscosity adduct which has a particularly low odor and causes virtually no blushing when used as a curing agent for epoxy resins.

[0024] A is preferably 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 readily commercially available primary diamines.

[0025] A is selected from the group consisting of, inter alia, 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).

[0026] A is most preferably 1,2-ethylene. These diamines of formula (I) and (II) allow for adducts with particularly low viscosity and particularly high reactivity, and allow for a particularly low tendency to yellow.

[0027] R is preferably selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, 3-methyl-but-2-yl, hexyl, 4-methylpent-2-yl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, and optionally substituted 1-phenylethyl, 2-phenylethyl, benzyl, naphthylmethyl, cyclohexylmethyl, and 2-cyclohexylethyl groups.

[0028] Groups R having 6 to 12 carbon atoms, especially 6 to 8 carbon atoms, are preferred.

[0029] R is particularly preferably selected from the group consisting of 2-ethylhexyl, 2-phenylethyl, benzyl, 1-naphthylmethyl, and cyclohexylmethyl.

[0030] Most preferably, R is benzyl. These diamines of formula (I) and (II), especially when combined with a group A that does not contain an aromatic group, allow for adducts with particularly low viscosity and high reactivity, as well as particularly low tendency to fog effect and low tendency to yellowing.

[0031] The diamine of formula (I) is particularly preferably selected from the group consisting of N-benzylethane-1,2-diamine, N-(1-naphthylmethyl)ethane-1,2-diamine, N-cyclohexylmethylethane-1,2-diamine, N-benzylpropane-1,2-diamine, and N-(2-ethylhexyl)-1,3-bis(aminomethyl)benzene.

[0032] The most preferred diamine of formula (I) is N-benzylethane-1,2-diamine, which allows for particularly low viscosity and highly reactive adducts.

[0033] The groups A and R in the diamines of formulae (I) and (II) are preferably identical groups. Such amine mixtures are particularly readily available as reaction products of alkylations.

[0034] Particularly preferably, the diamine of formula (I) is N-benzylethane-1,2-diamine and the diamine of formula (II) is N,N'-dibenzylethane-1,2-diamine.

[0035] The weight ratio of the diamine of formula (I) to the diamine of formula (II) is preferably in the range of 70 / 30 to 95 / 5, more preferably 80 / 20 to 90 / 10. Such an adduct is particularly highly reactive and enables high hardness.

[0036] The diamines of formula (I) and (II) are preferably prepared by partial alkylation of at least one amine of formula H2N-A-NH2 with at least one alkylating agent.

[0037] The alkylation is preferably a reductive alkylation using an aldehyde or ketone as the alkylating agent and hydrogen.

[0038] The reductive alkylation is preferably carried out in the presence of a suitable catalyst, preferred catalysts being palladium on charcoal (Pd / C), platinum on charcoal (Pt / C), Adams' catalyst or Raney nickel, especially palladium on charcoal or Raney nickel.

[0039] If molecular hydrogen is used, the reductive alkylation is preferably carried out in a pressure apparatus at a hydrogen pressure of 5 to 150 bar, in particular 10 to 100 bar. It can be carried out in a batchwise or, preferably, continuous process.

[0040] The reductive alkylation is preferably carried out at a temperature in the range of 40 to 120°C, especially 60 to 100°C.

[0041] In the case of small volatile amines, such as ethane-1,2-diamine or propane-1,2-diamine in particular, this is preferably used in stoichiometric excess relative to the aldehyde or ketone, and after alkylation some or all of the unreacted amine is removed from the reaction mixture, especially by distillation or stripping.

[0042] When A and R in the diamines of formulae (I) and (II) are the same group, the resulting reaction product can be used as an amine mixture without further purification.

[0043] However, it is also possible that the diamine of formula (I) and the diamine of formula (II) are each prepared separately and mixed to form the amine mixture, for which purpose the reaction mixture from the reductive alkylation is preferably further purified, especially by distillation.

[0044] The reaction mixture is preferably not further purified, but instead contains the diamine of formula (I) and the diamine of formula (II) in the ratio according to the invention. Such a reaction mixture is particularly inexpensive.

[0045] The amine mixture comprising at least one diamine of formula (I) and at least one diamine of formula (II) is preferably a reaction product from at least one aldehyde or ketone and the reduction alkylation of at least one amine of formula HN-A-NH with hydrogen.

[0046] As the aldehyde or ketone, formaldehyde, acetaldehyde, 1-propanal, acetone, 1-butanal, isobutyroaldehyde, 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 cyclohexylcarbaldehyde is preferred.

[0047] 2-Ethylhexanal, benzaldehyde, 1-naphthaldehyde or cyclohexanecarbaldehyde, especially benzaldehyde, are particularly preferred.

[0048] The amine of formula H2N-A-NH2 is particularly preferably ethane-1,2-diamine.

[0049] The diepoxide is preferably an aromatic diepoxide. A diepoxide is said to be "aromatic" if it contains at least one aromatic ring.

[0050] The aromatic diepoxide preferably does not contain polyether chains. Such aromatic diepoxides are particularly suitable as curing agents for non-aqueous epoxy resin products, which are particularly stable against weathering effects.

[0051] The diepoxide is preferably 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)methane diglycidyl ether, 2,2-bis(4-hydroxyphenyl)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'-dihydroxybiphenyl diglycidyl ether.

[0052] The diepoxide is particularly preferably bisphenol A diglycidyl ether, bisphenol F diglycidyl ether or bisphenol A / F diglycidyl ether, especially bisphenol A diglycidyl ether.

[0053] The diglycidyl ethers are preferably used in technical grade quality.

[0054] Particular preference is given to commercially available liquid resins such as, in particular, Araldite® GY 240, Araldite® GY 250, Araldite® GY 281, Araldite® GY 282, Araldite® GY 285, Araldite® PY 304 or Araldite® PY 720 (all from Huntsman), or DER® 330, DER® 331, DER® 332, DER® 336, DER® 351, DER® 352, DER® 354 or DER® 356 (all from Dow).

[0055] The diepoxide preferably has an epoxide equivalent weight in the range of 110 to 260 g / equivalent, preferably 156 to 200 g / equivalent.

[0056] The amine mixture is preferably used in the reaction to give the adduct of the present invention in an amount such that the stoichiometric ratio is in the range of 1.3 to 2, especially 1.4 to 1.7 moles of diamine of formula (I) per mole equivalent of epoxy groups of the diepoxide.

[0057] Such adducts contain particularly little unreacted diamine and a high content of adduct molecules. They have particularly low odor and surprisingly low viscosity. They allow particularly fast curing and high flexibility for combining with additional amines.

[0058] Preferably, the temperature during the reaction is in the range of 40 to 120°C, particularly 60 to 100°C.

[0059] After the reaction, the unreacted diamine of formula (I) and diamine of formula (II) are preferably not removed from the adduct but remain there and are constituents of the adduct.

[0060] The adduct contains the so-called 2:1 adduct from the addition of two moles of diamine of formula (I) or (II) with one mole of diepoxide. In the case of N-benzylethane-1,2-diamine as the diamine of formula (I) or N,N'-dibenzylethane-1,2-diamine as the diamine of formula (II) with bisphenol A diglycidyl ether, the adduct mainly contains the following 2:1 adduct: [ka] However, there are also additional 2:1 adducts formed by addition of a secondary amino group to an epoxy group, such as those shown below. [ka]

[0061] The adduct also contains higher order adducts, in particular the so-called 3:2 adducts from the addition of 3 moles of diamine of formula (I) or (II) with 2 moles of diepoxide. In the case of N-benzylethane-1,2-diamine as formula (I) with bisphenol A diglycidyl ether, it is mainly the following 3:2 adduct that is present together with the 3:2 adduct from the reaction with secondary amino groups: [ka]

[0062] The adducts also contain higher order adducts, so-called 3:2 superadducts, in particular those resulting from the addition of 4 moles of a diamine of formula (I) or (II) with 3 moles of a diepoxide or 5 moles of a diamine of formula (I) or (II) with 4 moles of a diepoxide.

[0063] The adducts of the present invention preferably contain the 2:1 adduct and the higher order adduct in a weight ratio ranging from 30 / 70 to 80 / 20, preferably from 35 / 65 to 70 / 30. Such adducts allow a particularly advantageous combination of low viscosity and fast cure.

[0064] The adducts of the present invention particularly preferably contain the 2:1 adduct and higher adducts in a weight ratio ranging from 30 / 70 to 49.9 / 50.1, especially 35 / 65 to 49 / 51. Such adducts are typically prepared in a stoichiometric ratio ranging from 1.4 to 1.7 moles of diamine of formula (I) per mole equivalent of epoxy groups of diepoxide, which allows for particularly fast curing.

[0065] The adduct preferably contains less than 1% by weight of thinner or water.

[0066] The adduct is preferably 10s -1 The viscosity at 20°C, measured using a cone-plate viscometer at a shear rate of 100 to 500 Pa·s, preferably 10 to 250 Pa·s, and particularly preferably 20 to 150 Pa·s, is preferably 5 to 500 Pa·s.

[0067] The adducts of the present invention are particularly suitable for curing epoxy resins.

[0068] The present invention further provides a curing agent for epoxy resins comprising the adduct of the present invention and at least one further component selected from the group consisting of a further amine, a cure accelerator, and a reducer.

[0069] The curing agent preferably contains 1% to 80% by weight, preferably 2% to 60% by weight, in particular 5% to 50% by weight of the adduct of the present invention.

[0070] The curing agent for epoxy resins is preferably not water-based. It contains, in particular, less than 15% by weight, preferably less than 10% by weight, of water. Such a curing agent is suitable for non-aqueous epoxy resin products, especially floor coatings.

[0071] The curing agent preferably includes at least one additional amine having an aliphatic amino group and at least three amine hydrogens. This additional amine is preferably incorporated into the adduct only after the reaction of the amine mixture with the diepoxide has taken place. This additional amine may be the same amine as that used in the reaction to form the adduct, such as the diamine of formula (I), or it may be a different amine.

[0072] Suitable further amines are, inter alia, N-benzylethane-1,2-diamine, N-benzylpropane-1,2-diamine, N-benzyl-1,3-bis(aminomethyl)benzene, N-(2-ethylhexyl)-1,3-bis(aminomethyl)benzene or N-(2-phenylethyl)-1,3-bis(aminomethyl)benzene, and also 2,2-dimethylpropane-1,3-diamine, pentane-1,3-diamine (DAM). P), pentane-1,5-diamine, 1,5-diamino-2-methylpentane (MPMD), 2-butyl-2-ethylpentane-1,5-diamine (C11-neodiamine), hexane-1,6-diamine, 2,5-dimethylhexane-1,6-diamine, 2,2(4),4-trimethylhexane-1,6-diamine (TMD), heptane-1,7-diamine, octane-1,8-diamine, nonane-1,9-diamine, decane- 1,10-diamine, undecane-1,11-diamine, dodecane-1,12-diamine, 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 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]heptane (NBDA), 2.6]decane, 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-1,1 2-diamines, 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 Jeffamine® D-230, Jeffamine® D-400 or Jeffamine® D-100. (Trademark) T-403 (all manufactured by Huntsman), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentethylenehexamine (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-methylpentane-1,5-diamine amines, N3-(3-aminopentyl)pentane-1,3-diamine, N5-(3-amino-1-ethylpropyl)-2-methylpentane-1,5-diamine, N,N'-bis(3-amino-1-ethylpropyl)-2-methylpentane-1,5-diamine, 3-(2-aminoethyl)aminopropylamine, bis(hexamethylene)triamine (BHMT), N-aminoethylpiperazine, 3-dimethylaminopropylamine (DMAPA) or 3-(3-(dimethylamino)propylamino)propylamine (DMAPAPA).

[0073] It may be advantageous if the curing agent of the present invention comprises a combination of two or more additional amines.

[0074] N-benzylethane-1,2-diamine, N-benzylpropane-1,2-diamine, N-benzyl-1,3-bis(aminomethyl)benzene, N-(2-ethylhexyl)-1,3-bis(aminomethyl)benzene, N-(2-phenylethyl)-1,3-bis(aminomethyl)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, average molecular weight M in the range of 200-500 g / mol n Polyoxypropylenediamine having an average molecular weight M in the range of 300 to 500 g / mol n Preferred are further amines selected from the group consisting of polyoxypropylene triamines having the formula: DMAPAPA, BHMT, DETA, TETA, TEPA, PEHA, DPTA, N3-amines and N4-amines.

[0075] The curing agent is particularly preferably N-benzylethane-1,2-diamine, TMD, 1,2-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, IPDA, 2(4)-methyl-1,3-diaminocyclohexane, MXDA, an average molecular weight M in the range of 200 to 500 g / mol n and an average molecular weight M in the range of 300 to 500 g / mol. n and at least one further amine selected from the group consisting of polyoxypropylene triamines having the formula:

[0076] A particularly preferred further amine is N-benzylethane-1,2-diamine, which allows for a hardener with particularly good processability, fast curing and a low tendency to blushing effects.

[0077] Another particularly preferred further amine is MXDA, optionally in the form of an amine-functional adduct with the epoxy resin, which allows for particularly fast curing.

[0078] Another particularly preferred further amine is IPDA, optionally in the form of an amine-functional adduct with an epoxy resin, which allows for particularly high glass transition temperatures and final hardness.

[0079] Suitable hardening accelerators are, inter alia, acids or compounds hydrolyzable to acids, especially organic carboxylic acids such as, for example, acetic acid, benzoic acid, salicylic acid, 2-nitrobenzoic acid, lactic acid, etc., organic sulfonic acids such as, for example, methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, sulfonic acid esters, other organic or inorganic acids, such as, in particular, phosphoric acid, or mixtures of the aforementioned acids and acid esters, nitrates, in particular calcium nitrate, etc.; 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, phenolic resins or Mannich bases, such as, in particular, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol or phenol, polymers prepared from formaldehyde and N,N-dimethylpropane-1,3-diamine, phosphites, such as, in particular, di- or triphenylphosphite, or compounds containing a mercapto group.

[0080] Acids, nitrates, tertiary amines or Mannich bases, especially salicylic acid, calcium nitrate or 2,4,6-tris(dimethylaminomethyl)phenol, or combinations of these accelerators are preferred.

[0081] Suitable thinners include, inter alia, 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 mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, propylene glycol butyl ether, propylene glycol phenyl ether, dipropylene glycol dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol di-n-butyl ether, diphenylmethane, diisopropyl naphthalene, mineral oil fractions such as Solvesso® grades (manufactured by Exxon), alkylphenols such as tert-butylphenol, nonylphenol, dodecylphenol, cardanol (obtained from cashew nut shell oil and containing 3-(8,11-pentadecadienyl)phenol as its main constituent), styrenated phenol, bisphenols, aromatic hydrocarbon resins, especially those containing phenolic groups, alkoxylated phenols, especially ethoxylated or propoxylated phenols, especially 2-phenoxyethanol, adipates, sebacates, phthalates, benzoates, organic phosphates or sulfonates or sulfonamides.

[0082] Preferred thinners have a boiling point above 200°C.

[0083] The thinner is preferably selected from the group consisting of benzyl alcohol, styrenated phenol, ethoxylated phenol, aromatic hydrocarbon resins containing phenolic groups, especially Novares® LS 500, LX 200, LA 300 or LA 700 products (manufactured by Ruetgers), diisopropyl naphthalene and cardanol.

[0084] Benzyl alcohol is particularly preferred.

[0085] Phenol-containing thinners are also effective as curing accelerators.

[0086] The hardener may comprise further components, in particular: further adducts, in particular adducts of IPDA, MXDA, DETA, TETA or TEPA with bisphenol A, F or A / F diglycidyl ether, or adducts of MPMD or ethane-1,2-diamine or propane-1,2-diamine with cresyl glycidyl ether, where unreacted MPMD, ethane-1,2-diamine or propane-1,2-diamine has been removed by distillation after the reaction; monoamines, such as, in particular, benzylamine or furfurylamine; - polyamidoamines, in particular reaction products of monobasic or polybasic carboxylic acids or their esters or anhydrides, in particular dimer fatty acids, with polyamines, in particular DETA or TETA, used in stoichiometric excess; Mannich bases, especially phenalkamines, ie reaction products of phenols, especially cardanol, with aldehydes, especially formaldehyde, and polyamines. aromatic polyamines, such as in particular 4,4'-, 2,4'- and / or 2,2'-diaminodiphenylmethane, 2,4- and / or 2,6-tolylenediamine, 3,5-dimethylthio-2,4-tolylenediamine and / or 3,5-dimethylthio-2,6-tolylenediamine, 3,5-diethyl-2,4-tolylenediamine and / or 3,5-diethyl-2,6-tolylenediamine; - 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 may include:

[0087] The present invention further provides an epoxy resin composition comprising: a resin component comprising at least one epoxy resin, and a hardener component comprising the adduct of the present invention.

[0088] The hardener component preferably includes the hardeners described above.

[0089] Suitable epoxy resins are obtainable in known manner, inter alia, from the reaction of epichlorohydrin with polyols, polyphenols or amines.

[0090] Suitable epoxy resins are especially aromatic epoxy resins, especially bisphenol A, bisphenol F or bisphenol A / F (where A represents acetone, used as a reactant in the preparation of these bisphenols, and F represents formaldehyde). In the case of bisphenol F, positional isomers may also be present, more particularly those derived from 2,4'- or 2,2'-hydroxyphenylmethane. dihydroxybenzene derivatives, such as resorcinol, hydroquinone or catechol; further bisphenols or polyphenols, such as bis(4-hydroxy-3-methylphenyl)methane, 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C), bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-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( ... 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-hydroxy-1-naphthyl)methane, bis(4-hydroxy-1-naphthyl)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; novolaks, which are in particular condensation products of phenol or cresol with formaldehyde or paraformaldehyde or acetaldehyde or crotonaldehyde or isobutyroaldehyde or 2-ethylhexanal or 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); It is a glycidyl ether of

[0091] Further suitable epoxy resins are aliphatic or cycloaliphatic polyepoxides, especially - saturated or unsaturated, branched or unbranched, cyclic or open-chain di-, tri- or tetrafunctional C2-C 30 glycidyl ethers of alcohols, especially ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, polypropylene glycol, dimethylolcyclohexane, neopentyl glycol, dibromoneopentyl glycol, castor oil, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol or glycerol, or alkoxylated glycerol or alkoxylated trimethylolpropane; - hydrogenated bisphenol A, F or A / F liquid resins or glycidylation products of hydrogenated bisphenol A, F or A / F; N-glycidyl derivatives of amide or heterocyclic nitrogen bases, such as triglycidyl cyanurate or triglycidyl isocyanurate, or reaction products of epichlorohydrin with hydantoin is.

[0092] The epoxy resin is preferably a liquid resin or a mixture comprising two or more liquid epoxy resins.

[0093] "Liquid epoxy resin" refers to a commercial polyepoxide having a glass transition temperature below 25°C.

[0094] The resin component optionally contains a small proportion of solid epoxy resin as well.

[0095] The epoxy resins are liquid bisphenol-based resins, 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 low viscosity for epoxy resins, allowing for fast cure and high hardness. They may contain a small percentage of solid bisphenol A resin or novolac glycidyl ether.

[0096] The resin component may include a reactive diluent.

[0097] Preferred reactive diluents are reactive diluents containing epoxy groups, especially butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane di- or triglycidyl ether, phenyl glycidyl ether, cresyl 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, in particular, C8-C6 10 Or C 12 ~C 14 Or C 13 ~C 15 It is an alkyl glycidyl ether.

[0098] The epoxy resin composition preferably comprises at least one further component selected from the group consisting of a thinner, a curing accelerator, and a filler.

[0099] Suitable accelerators are those already mentioned, especially salicylic acid, calcium nitrate or 2,4,6-tris(dimethylaminomethyl)phenol or combinations thereof.

[0100] Suitable thinners are those already mentioned, especially those with a boiling point above 200°C.

[0101] The thinner is preferably selected from the group consisting of benzyl alcohol, styrenated phenol, ethoxylated phenol, aromatic hydrocarbon resins containing phenolic groups, especially Novares® LS 500, LX 200, LA 300 or LA 700 products (manufactured by Ruetgers), diisopropyl naphthalene and cardanol.

[0102] Benzyl alcohol is particularly preferred.

[0103] Suitable fillers are in particular ground or precipitated calcium carbonate, barite, talc, quartz flour, silica sand, silicon carbide, biotite, dolomite, wollastonite, kaolin, mica (potassium aluminum silicate), molecular sieves, aluminum 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 beads, optionally coated with fatty acids, especially stearates.

[0104] Calcium carbonate, quartz flour, silica sand or combinations thereof are preferred.

[0105] The epoxy resin composition may optionally contain auxiliaries and additives, in particular: reactive diluents, especially those already mentioned, or epoxidized soybean or linseed oil, compounds containing acetoacetate groups, especially acetoacetylated polyols, butyrolactone, carbonates, aldehydes, isocyanates or silicones with reactive groups; - polymers, in particular polyamides, polysulfides, polyvinyl formal (PVF), polyvinyl butyral (PVB), polyurethanes (PUR), polymers containing carboxyl groups, polyamides, butadiene-acrylonitrile copolymers, styrene-acrylonitrile copolymers, butadiene-styrene copolymers, in particular homopolymers or copolymers of unsaturated monomers from the group consisting of ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth)acrylates, in particular chlorosulfonated polyethylene or fluorine-containing polymers or sulfonamide-modified melamine; - fibres, in particular glass, carbon, metal, ceramic or polymer fibres, such as polyamide or polyethylene fibres; pigments, in particular titanium dioxide, iron oxide or chromium(III) oxide; - rheology modifiers, in particular thickeners or anti-settling agents; - adhesion promoters, especially organoalkoxysilanes; - flame retardant substances, in particular the aluminium hydroxide or magnesium hydroxide fillers 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, i.e. diphenyl ethers, phosphates, such as in particular diphenyl cresyl phosphate, resorcinol bis(diphenyl phosphate), resorcinol diphosphate oligomer, tetraphenylresorcinol diphosphite, ethylenediamine diphosphate, bisphenol A bis(diphenyl phosphate), tris(chloroethyl) 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 resin, ethylene bis(tetrabromophthalimide), ethylene bis(dibromonolbornanedicarboxamide), 1,2-bis(tribromophenoxy)ethane, tris(2,3-dibromopropyl)isocyanurate, tribromophenol, hexabromocyclododecane, bis(hexachlorocyclopentadieno)cyclooctane, or chloroparaffins; or - additives, in particular dispersing paraffin waxes, film-forming aids, wetting agents, levelling agents, defoamers, degassing agents, stabilizers against oxidation, heat, light or UV radiation, or biocides It may further include:

[0106] The epoxy resin composition preferably comprises further auxiliaries and additives, especially pigments, wetting agents, leveling agents and / or defoamers.

[0107] The epoxy resin composition preferably has only a low content of thinner, preferably less than 20% by weight, more preferably less than 15% by weight, especially less than 10% by weight, which allows for low or no-emission epoxy resin products.

[0108] 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.

[0109] In the epoxy resin composition, the ratio of the number of groups highly reactive with epoxy groups to the number of epoxy groups is preferably within the range of 0.5 to 1.5, particularly 0.7 to 1.2.

[0110] The primary and secondary amino groups present in the epoxy resin composition, as well as any further groups present that are highly reactive towards epoxy groups, react with the epoxy group, resulting in its ring opening (addition reaction). As a result of this reaction, the composition first polymerizes and thereby cures.

[0111] The resin component and the hardener component of the epoxy resin composition are stored in separate containers. The further components of the epoxy resin composition can be present as components of the resin component or of the hardener component; the further component that is highly reactive with epoxy groups is preferably a component of the hardener component. It is also possible for the further component to be present as a further dedicated component.

[0112] Suitable containers for storing the resin or hardener components are, inter alia, vats, hobboxes, bags, buckets, cans, cartridges, or tubes. The components are storable, meaning that they can be stored for several months to over a year before use without any change in their respective properties to an extent relevant to their use. For use of the epoxy resin composition, the components are mixed together immediately before or during application. The mixing ratio between the resin and hardener components is preferably selected so that the groups of the hardener component that are highly reactive with epoxy groups are in a suitable ratio to the epoxy groups of the resin component, as described above. In parts by weight, the mixing ratio between the resin and hardener components is usually in the range of 1:10 to 10:1.

[0113] The components are mixed by any suitable method; this mixing can be done continuously or batchwise. If the mixing is not done immediately before application, it must be ensured that too much time does not pass between mixing the components and their application, and that the application occurs within the pot life. Mixing is typically done at ambient temperature, typically within the range of about 5 to 40°C, preferably about 10 to 35°C.

[0114] Curing by chemical reaction begins with mixing the two components as described above. Curing is typically carried out at temperatures ranging from 0 to 150°C. It is preferably carried out at ambient temperature and typically extends over a period of a few days to several weeks. The duration depends on factors such as temperature, the reactivity of the components and their stoichiometry, as well as the presence of curing accelerators.

[0115] When freshly mixed, the epoxy resin composition has a low viscosity. The viscosity at 20°C 10 minutes after mixing the resin and hardener components is preferably less than 10 s -1 The viscosity of the polymer is in the range of 300 to 4000 mPa·s, preferably 300 to 3000 mPa·s, and particularly 300 to 2000 mPa·s, as measured using a cone-plate viscometer at a shear rate of 1000 mPa·s.

[0116] The epoxy resin composition is applied to at least one substrate, the following substrates being particularly suitable: glass, glass ceramics, concrete, mortar, cement screed, fibre cement, brick, tile, plaster or natural stone, such as granite or marble; - Repair or leveling compounds based on PCC (polymer modified cement mortar) or RCC (epoxy resin modified cement mortar); - metals or alloys, such as aluminium, iron, steel, copper, surface-upgraded metals or alloys, such as galvanised or chrome-plated metals, and other non-ferrous metals; - Asphalt or bitumen; leather, textiles, paper, wood, wood materials glued with resins, for example phenolic, melamine or epoxy resins, resin-textile composites or further 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 (in each case untreated or surface-treated, for example by plasma, corona or flame); - Fiber reinforced plastics, such as carbon fiber reinforced plastics (CFP), glass fiber reinforced plastics (GFP) and sheet molding compounds (SMC); - insulating foams, especially made of EPS, XPS, PUR, PIR, rock wool, glass wool or foam glass; - coated or painted substrates, in particular painted tiles, coated concrete, powder-coated metals or alloys or painted metal sheets; - coated floors which have been overcoated with a coating, paint or varnish, in particular a further floor covering layer.

[0117] If necessary, the substrate can be pretreated before application by, inter alia, physical and / or chemical cleaning methods or the application of an activator or primer.

[0118] Curing the epoxy resin composition provides a cured composition.

[0119] 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 composite materials, such as in particular CFRP or GFRP.

[0120] The epoxy resin compositions are particularly preferably used as coatings, which is understood here to mean all kinds of coverings that are applied over an area, especially floor coverings, paints, varnishes, sealants, base coats, primers or protective coatings, especially also those for strong corrosion protection.

[0121] The epoxy resin compositions are particularly suitable as floor coverings or floor coatings indoors, such as in offices, industrial halls, sports halls or cold rooms, or outdoors for balconies, terraces, multi-storey car parks, bridges or roofs, as protective coatings for concrete, cement, metal, plastic or wood, for example for surface sealing of wooden constructions, vehicles, loading docks, tanks, silos, shafts, pipelines, machinery or steel constructions, such as ships, quays, offshore platforms, lock gates, hydroelectric power plants, river constructions, swimming pools, wind turbines, bridges, chimneys, cranes or sheet pile walls, or as undercoats, tie coats or anticorrosive primers or for hydrophobizing surfaces.

[0122] The epoxy resin compositions are particularly advantageously used for low-emission coatings with environmental quality certification, for example according to Emicode (EC1 Plus), AgBB, DIBt, Der Blaue Engel, AFSSET, RTS (M1) and the US Green Building Council (LEED).

[0123] For use as a coating, the epoxy resin composition advantageously has a fluid consistency with low viscosity and good leveling properties. The mixed composition is typically applied to the surface of a substrate within its working life as a thin film having a layer thickness of about 50 μm to about 5 mm, typically at ambient temperature. It is typically applied by pouring onto the substrate to be coated and then spreading it evenly, for example, with a doctor blade or a notched trowel. It can also be applied with a brush or roller, or in the form of a spray application, such as for anti-corrosion coatings on steel. Curing typically produces a high-hardness, substantially uniform, glossy, and non-tacky film with good adhesion to a wide variety of different substrates.

[0124] In this case, the epoxy resin composition is used in particular in a coating method comprising the following steps: (i) mixing the components of the epoxy resin composition; (ii) applying the mixed composition to a substrate within the pot life, followed by curing the mixed composition;

[0125] It is possible to apply a further coating to the fully or partially cured composition, in which case the further layer may also be an epoxy resin composition or another material, especially a polyurethane or polyurea coating.

[0126] It is also particularly preferred to use the epoxy resin composition as an adhesive. When used as an adhesive, the epoxy resin composition typically has a paste-like consistency with structurally viscous properties after the components are mixed. 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 to form an adhesive bond within the open time of the adhesive.

[0127] The mixed adhesive is applied by means of a brush, roll, spatula, doctor blade or trowel, among others, or from a tube, cartridge or metering device.

[0128] The adhesive is suitable for use in the construction industry, in particular for the strengthening of buildings with steel sheets or sheets made of carbon fiber reinforced composite plastics (CFRP), for buildings containing bonded precast concrete components, in particular bridges or concrete towers, shafts, pipelines or tunnels, for example for wind turbines, or for buildings containing bonded natural stone, ceramic elements or parts made of fiber cement, steel, cast iron, aluminum, wood or polyester, for fixing dowels or steel rods in boreholes, for example for fixing handrails, balustrades or door frames, for repairs in concrete maintenance, especially filling of edges, holes or joints, or for bonding polyvinyl chloride (PVC) films, softened polyolefins (Combiflex®) or adhesive-modified chlorosulfonated polyethylene (Hypalon®) to concrete or steel.

[0129] Further fields of use relate to structural bonding in the construction or manufacturing industry, inter alia as adhesive mortars, assembly adhesives, reinforced adhesives, in particular as reinforced adhesives, such as for bonding thin sheets made of CFRP or steel to concrete, brickwork or wood, e.g. as element adhesives for bridge elements, sandwich element adhesives, facade element adhesives, reinforced adhesives, car body adhesives or half-shell adhesives for wind turbine rotor blades.

[0130] Such epoxy resin adhesives are also suitable for filling cavities, such as gaps, cracks or drilled holes, where the adhesive is filled or injected into the cavity and, after hardening, fills it and joins or sticks the sides of the cavity together with a force fit.

[0131] In this case, the epoxy resin composition is used in particular in a bonding method comprising the following steps: (i) mixing the components of the epoxy resin composition; (ii) The mixed composition is mixed within the pot life. - applied to at least one of the substrates to be bonded and joining the substrates to form a bond within the open time; or - applying into cavities or gaps between two or more substrates, and optionally inserting anchors into the cavities or gaps within the open time; The mixed composition is then cured.

[0132] "Anchor" here more specifically refers to a rebar, a threaded rod or a bolt. The anchor is in particular thus adhesively bonded to a wall, ceiling or foundation so that a part of it is adhered in a force-compatible manner and a part of it protrudes and can bear the construction load.

[0133] The same or different substrates may be bonded.

[0134] Application and curing of the epoxy resin composition provides the article.

[0135] The present invention therefore further provides articles resulting from the use of the epoxy resin composition.

[0136] The article is preferably a building or part thereof, in particular an above-ground or underground building, an office, an industrial hall, a sports hall, a cold room, a silo, a bridge, a roof, a staircase, a floor, a balcony, a terrace or a multi-storey car park, or an industrial or consumer good, in particular a quay, an offshore platform, a lock 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 component thereof.

[0137] The epoxy resin composition is characterized by advantageous properties. It can also be formulated with little or no thinner, and such formulations have surprisingly low viscosity and very good processability, and cure reproducibly and surprisingly quickly, even under humid and low-temperature conditions. This results in coatings with high mechanical and surface qualities. Such epoxy resin products are particularly suitable as coatings, especially for floors. [Example]

[0138] Examples are presented herein below that are intended to further clarify the invention as described, but the invention is not, of course, limited to these described examples.

[0139] "AHEW" stands for amine hydrogen equivalent weight.

[0140] "EEW" stands for epoxy equivalent weight.

[0141] "Standard Climatic Conditions" ("SCC") refers to a temperature of 23±1°C and a relative air humidity of 50±5%.

[0142] Chemicals used were from Sigma-Aldrich Chemie GmbH unless otherwise stated.

[0143] Measurement method description: Viscosity was measured using a thermostatic Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1°, cone tip-plate diameter 0.05 mm, shear rate 10 s -1 ) was measured.

[0144] Amine value was determined by titration (with 0.1 N HClO4 in acetic acid against crystal violet).

[0145] Liquid chromatography (UHPLC) was performed against external calibration for the quantitative determination of N-benzylethane-1,2-diamine after derivatization with phenyl isocyanate.

[0146] Gel permeation chromatography (GPC) was performed against polystyrene as a standard to determine the weight ratios of the 2:1 adduct, 3:2 adduct, and 3:2 hyperadduct.

[0147] Substances and abbreviations used: Araldite® GY 250: Bisphenol A diglycidyl ether, EEW 187 g / eq (Huntsman) Araldite® DY-E:C 12 ~C 14 Monoglycidyl ether of alcohol, EEW, approximately 290g / equivalent (Huntsman) B-EDA Mix: An amine mixture containing approximately 85% by weight of N-benzylethane-1,2-diamine and approximately 14% by weight of N,N'-dibenzylethane-1,2-diamine, prepared as follows: AHEW 55 g / equivalent B-EDA Pure Purified N-benzylethane-1,2-diamine, 150.2 g / mol, AHEW 50 g / eq, prepared as follows: DB-EDA N,N'-dibenzylethane-1,2-diamine, 240.4 g / mol, AHEW 120.2 g / eq (Sigma Aldrich) IPDA 3-aminomethyl-3,5,5-trimethylcyclohexylamine, AHEW 42.6 g / eq (Vestamin® IPD from Evonik)

[0148] Preparation of diamines of formula (I) and (II): Amine mixture containing N-benzylethane-1,2-diamine and N,N'-dibenzylethane-1,2-diamine (B-EDA mix): A round-bottom flask was charged with 180.3 g (3 mol) of ethane-1,2-diamine at room temperature under a nitrogen atmosphere. A solution of 106.1 g (1 mol) of benzaldehyde in 1200 ml of isopropanol was slowly added dropwise with thorough stirring, and stirring was continued for an additional 2 hours. The reaction mixture was then hydrogenated in a continuous hydrogenation apparatus using a Pd / C fixed-bed catalyst at 80 bar hydrogen pressure, a temperature of 80°C, and a flow rate of 5 ml / min. IR spectroscopy was used to monitor the reaction, with an IR peak at approximately 1665 cm -1 The hydrogenation solution was checked for the disappearance of the imine band at 65°C. The hydrogenation solution was then concentrated on a rotary evaporator at 65°C to remove unreacted ethane-1,2-diamine, water, and isopropanol. The reaction mixture thus obtained was a clear, pale yellow liquid with an amine value of 678 mg KOH / g and containing approximately 85 wt% N-benzylethane-1,2-diamine (retention time 8.47-8.57 min) and approximately 14 wt% N,N'-dibenzylethane-1,2-diamine (retention time 14.27 min), as determined by GC. This corresponds to a weight ratio of N-benzylethane-1,2-diamine to N,N'-dibenzylethane-1,2-diamine of 86 / 14.

[0149] N-benzylethane-1,2-diamine (purified, B-EDA pure): 50 g of an amine mixture containing N-benzylethane-1,2-diamine and N,N'-dibenzylethane-1,2-diamine (B-EDA mix), prepared as described, was distilled under reduced pressure at 80 °C, resulting in 31.3 g of distillate (N-benzylethane-1,2-diamine), collected at a vapor temperature of 60–65 °C and 0.06 mbar. A colorless liquid was obtained with a viscosity of 8 mPa·s at 20 °C, an amine number of 750 mg KOH / g, and a purity, as measured by GC, of ​​greater than 97%.

[0150] Preparation of the adduct: Adduct A1: (Inventive Example) 53.0 g of the amine mixture B-EDAN mix (containing 0.3 mol of N-benzylethane-1,2-diamine and 0.03 mol of N,N'-dibenzylethane-1,2-diamine) prepared as described above was initially charged under a nitrogen atmosphere and heated to 80°C. To this, 36.8 g (0.2 mol of epoxy groups) of Araldite® GY 250 was slowly added with thorough stirring, while the temperature of the reaction mixture was maintained between 70 and 90°C by cooling. The reaction mixture was held within this temperature range for 1 hour and then cooled. A clear, slightly yellowish liquid was obtained with a viscosity at 20°C of 74 Pa·s and a calculated AHEW of 117 g / eq.

[0151] Adduct A1 contained 27.8 wt% N-benzylethane-1,2-diamine according to UHPLC, and the adduct molecules were in a weight ratio of 2:1 adduct / 3:2 adduct / 3:2 hyperadduct=46.5 / 27.2 / 26.3 according to GPC.

[0152] Adduct A2: (Inventive Example) 45.0 g (0.3 mol) of purified N-benzylethane-1,2-diamine (B-EDA pure) prepared as described above and 11.3 g (0.05 mol) of N,N'-dibenzylethane-1,2-diamine (DB-EDA) were initially charged under a nitrogen atmosphere, mixed, and heated to 80°C. To this, 36.8 g (0.2 mol of epoxy groups) of Araldite® GY 250 was slowly added with thorough stirring, while the temperature of the reaction mixture was maintained between 70 and 90°C by cooling. The reaction mixture was held within this temperature range for 1 hour and then cooled. A clear, slightly yellowish liquid was obtained with a viscosity at 20°C of 47 Pa·s and a calculated average energy equivalent weight (AHEW) of 117.3 g / eq.

[0153] Adduct A3: (Inventive Example) 45.0 g (0.3 mol) of purified N-benzylethane-1,2-diamine (B-EDA pure) prepared as described above and 19.3 g (0.08 mol) of N,N'-dibenzylethane-1,2-diamine (DB-EDA) were initially charged under a nitrogen atmosphere, mixed, and heated to 80°C. To this, 36.8 g (0.2 mol of epoxy groups) of Araldite® GY 250 was slowly added with thorough stirring, while the temperature of the reaction mixture was maintained between 70 and 90°C by cooling. The reaction mixture was held within this temperature range for 1 hour and then cooled. A clear, slightly yellowish liquid was obtained with a viscosity at 20°C of 19 Pa·s and a calculated average energy weight (AHEW) of 117.5 g / eq.

[0154] Adduct A4: (Comparative Example) 45.0 g (0.3 mol) of purified N-benzylethane-1,2-diamine (B-EDA pure) prepared as described above was initially charged under a nitrogen atmosphere and heated to 80°C. To this, 36.8 g (0.2 mol of epoxy groups) of Araldite® GY 250 was slowly added with thorough stirring, while the temperature of the reaction mixture was maintained between 70 and 90°C by cooling. The reaction mixture was held within this temperature range for 1 hour and then cooled. A clear, slightly yellowish liquid was obtained with a viscosity at 20°C of 262 Pa·s and a calculated AHEW of 116.3 g / eq.

[0155] Adduct A4 contained 24.2 wt% N-benzylethane-1,2-diamine according to UHPLC, and the adduct molecules were in a weight ratio of 2:1 adduct / 3:2 adduct / 3:2 hyperadduct=42.5 / 27.0 / 30.5 according to GPC.

[0156] Preparation of hardener and epoxy resin composition: Examples 1 to 12: For each example, the components of the resin components specified in Tables 1-3 were mixed in the amounts specified (in parts by weight) using a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.), and stored with the exclusion of moisture.

[0157] The components of the hardener composition specified in Tables 1-3 were treated and stored similarly.

[0158] The two components of each composition were then processed using a centrifugal mixer to form a homogeneous liquid, which was immediately tested as follows: After 10 minutes of mixing, the viscosity was measured at 20° C. (“Viscosity (10 min)”).

[0159] Gel time was measured under standard climatic conditions by occasionally stirring the mixed composition (25 g) with a spatula until it began to gel.

[0160] For the determination of the Shore D hardness in accordance with DIN 53505, two cylindrical test 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 and 2 days (1d SCC and 2d SCC); the other was stored at 8°C and 80% relative humidity and the hardness was measured after 1 and 2 days at low temperature (1d 8°C / 80% and 2d 8°C / 80%).

[0161] The first film was applied to a glass plate with a layer thickness of 500 μm, which was stored / cured under standard conditions. The Koenig hardness (Koenig pendulum hardness, measured according to DIN EN ISO 1522) of this film was measured after 1 day ("Koenig hardness (1d SCC)"), 2 days ("Koenig hardness (2d SCC)"), 4 days ("Koenig hardness (4d SCC)"), 7 days ("Koenig strength (7d SCC)"), and 14 days ("Koenig hardness (14d SCC)"). Once a value of more than 200 s was achieved, the Koenig hardness was not measured again. After 14 days, the appearance of the film was evaluated (designated "Appearance (SCC)" in the table). A film was described as "good" if it had a glossy, non-sticky surface without any structure. "Structure" refers to any kind of marking or pattern on a surface.

[0162] The second film was applied to a glass plate with a layer thickness of 500 μm, which was immediately stored / cured at 8 °C and 80% relative humidity for 7 days after application, and then for 2 weeks under standard climatic conditions. 24 hours after application, a polypropylene bottle cap, underneath which a small moistened sponge had been placed, was placed on the film. After another 24 hours, the sponge and bottle cap were removed and placed on a new spot on the film, from which they were in turn removed and replaced after 24 hours, a total of four times. The appearance of the film was then evaluated in the same way as described for appearance (SCC) (designated "Appearance (8 °C / 80%)" in the table). The number and nature of visible marks formed on the film as a result of the moistened sponge and / or bottle cap on top were also reported in each case. The number of white-colored spots was reported as "blush." ​​Faint white discolored spots were designated "(1)." The designation "Ring" was reported if a ring-shaped mark was present due to the subsidence of the lid of the first bottle applied 24 hours after application. Such a ring-shaped mark indicates that the coating did not harden and could not be walked on immediately. The Koenig hardness of the thus cured films was measured again in each case after 7 days at 8°C and 80% relative humidity ("Koenig Hardness (7d 8°C / 80%)"), then after another 2 days under SCC ("Koenig Hardness (+2d SCC)"), after 7 days under SCC ("Koenig Hardness (+7d SCC)"), and after 14 days under SCC ("Koenig Hardness (+14d SCC)"). Once a value of more than 190s was achieved, the Koenig hardness was not measured again.

[0163] As a measure of yellowing, the change in color after stressing in a weathering tester was also measured. For this purpose, a further film was applied to a glass plate in a layer thickness of 500 μm, which was stored / cured under standard climatic conditions for 2 weeks and then exposed to a Q-SUN Daylight-Q optical filter and 0.51 W / m at 340 nm. 2The films were stressed for 72 hours at a temperature of 65°C in a Model Q-Sun Xenon Xe-1 weathering tester equipped with a xenon lamp having a light intensity of 1000 Hz and 1000 Hz (Q-Sun (72h)). The color difference ΔE between the stressed film and the corresponding unstressed film was then measured using a Shenzen 3NH Technology Co., Ltd. NH310 colorimeter equipped with a silicon photoelectric diode detector, Illuminant A, and a color space measurement interface CIE L*a*b*C*H*. A ΔE value of 5 or less indicates slight yellowing.

[0164] The results are reported in Tables 1-3.

[0165] Examples designated with "(Ref.)" are comparative examples.

[0166] [Table 1]

[0167] [Table 2]

[0168] [Table 3] The present disclosure includes the following inventive aspects: <Aspect 1> in a stoichiometric ratio of at least 1.2 moles of diamine of formula (I) per mole equivalent of epoxy groups, (i) an amine mixture containing at least one diamine of formula (I) and at least one diamine of formula (II) in a weight ratio ranging from 65 / 35 to 95 / 5; [ka] (In the formula, A is an alkylene group, a cycloalkylene group, or an arylalkylene group having 2 to 12 carbon atoms; R is an alkyl group, a cycloalkyl group, or an arylalkyl group having 1 to 12 carbon atoms; wherein the two nitrogen atoms in the diamines of formula (I) and (II) are each separated from each other by at least two carbon atoms, and the diamines of formula (I) have a total of 8 to 15 carbon atoms. and, (ii) at least one diepoxide Amine functional adduct from reaction with <Aspect 2> The amine mixture used for preparing the adduct contains at most 5% by weight, preferably at most 3% by weight, more preferably at most 2% by weight, in particular at most 1% by weight of amines of formula H 2 NA-NH 2 2. The adduct according to aspect 1, characterized in that it has a diamine content of <Aspect 3> 3. The adduct according to aspect 1 or 2, characterized in that the groups A and R in the diamines of formulae (I) and (II) are identical groups. <Aspect 4> 4. The adduct of any one of aspects 1 to 3, wherein the diamine of formula (I) is N-benzylethane-1,2-diamine and the diamine of formula (II) is N,N'-dibenzylethane-1,2-diamine. <Aspect 5> 5. The adduct according to any one of aspects 1 to 4, wherein the weight ratio of the diamine of formula (I) to the diamine of formula (II) is in the range of 70 / 30 to 95 / 5, preferably 80 / 20 to 90 / 10. <Aspect 6> The amine mixture comprises at least one aldehyde or ketone and a carboxylic acid having the formula: H 2 NA-NH 2 6. The adduct according to any one of aspects 1 to 5, characterized in that it is the reaction product from the reductive alkylation of at least one amine of <Aspect 7> 7. The adduct according to any one of aspects 1 to 6, wherein the diepoxide is an aromatic diepoxide. <Aspect 8> 8. The adduct according to any one of aspects 1 to 7, characterized in that the stoichiometric ratio is in the range of 1.3 to 2, in particular 1.4 to 1.7 moles of diamine of formula (I) per 1 molar equivalent of epoxy groups of the diepoxide. <Aspect 9> 9. The adduct according to embodiment 8, comprising the 2:1 adduct and higher adducts in a weight ratio ranging from 30 / 70 to 80 / 20. <Aspect 10> 10. The adduct according to any one of aspects 1 to 9, characterized in that it contains less than 1% by weight of thinner or water. <Aspect 11> A curing agent for epoxy resins, comprising the adduct according to any one of Aspects 1 to 10 and at least one additional component selected from the group consisting of an additional amine, a curing accelerator, and a reducer. <Aspect 12> 12. A curing agent for epoxy resins according to claim 11, characterized in the presence of at least one additional amine having an aliphatic amino group and at least three amine hydrogens that was not present during the preparation of the adduct. <Aspect 13> The further amines include N-benzylethane-1,2-diamine, 2,2(4),4-trimethylhexane-1,6-diamine, 1,2-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 2(4)-methyl-1,3-diaminocyclohexane, 1,3-bis(aminomethyl)benzene, and an average molecular weight M in the range of 200 to 500 g / mol. n and an average molecular weight M in the range of 300 to 500 g / mol. n 13. The curing agent for epoxy resins according to claim 11 or 12, characterized in that it is selected from the group consisting of polyoxypropylene triamines having the formula: <Aspect 14> An epoxy resin composition comprising: a resin component comprising at least one epoxy resin, and a curing agent component comprising the adduct according to any one of aspects 1 to 9 or the curing agent according to any one of aspects 11 to 13. <Aspect 15> 15. Use of the epoxy resin composition according to embodiment 14 as a coating, a primer, an adhesive, a sealant, a potting compound, a casting resin, an impregnating resin, or as a matrix for a fiber composite material. <Aspect 16> 16. An article obtained from the use according to embodiment 15.

Claims

1. in a stoichiometric ratio of at least 1.2 moles of diamine of formula (I) per mole equivalent of epoxy groups, (i) an amine mixture containing at least one diamine of formula (I) and at least one diamine of formula (II) in a weight ratio ranging from 65 / 35 to 95 / 5; 【Chemical 1】 (In the formula, A is an alkylene group, a cycloalkylene group, or an arylalkylene group having 2 to 12 carbon atoms; R is an alkyl, cycloalkyl, or arylalkyl group having 1 to 12 carbon atoms; wherein the two nitrogen atoms in said diamines of formula (I) and (II) are each separated from each other by at least two carbon atoms, and said diamines of formula (I) have a total of 8 to 15 carbon atoms. and, (ii) at least one diepoxide an amine-functional adduct from the reaction of The amine mixture used to prepare the adduct comprises 5% by weight or less of an amine compound of the formula: ２ N-A-NH ２ The adduct is characterized by having a diamine content of

2. 2. The adduct of claim 1, wherein the groups A and R in the diamines of formulae (I) and (II) are identical groups.

3. 3. The adduct according to claim 1 or 2, characterized in that the diamine of formula (I) is N-benzylethane-1,2-diamine and the diamine of formula (II) is N,N'-dibenzylethane-1,2-diamine.

4. 4. The adduct according to claim 1, wherein the weight ratio of said diamine of formula (I) to said diamine of formula (II) is in the range of 70 / 30 to 95 / 5.

5. The amine mixture comprises at least one aldehyde or ketone and a carboxylic acid having the formula: ２ N-A-NH ２ 5. The adduct according to claim 1, wherein the adduct is a reaction product from the reductive alkylation of at least one amine of

6. The adduct according to any one of claims 1 to 5, characterized in that the diepoxide is an aromatic diepoxide.

7. 7. The adduct according to any one of claims 1 to 6, characterized in that the stoichiometric ratio is in the range of 1.3 to 2 moles of diamine of formula (I) per 1 molar equivalent of epoxy groups of the diepoxide.

8. 8. The adduct according to claim 7, characterized in that it contains a 2:1 adduct and a higher adduct in a weight ratio ranging from 30 / 70 to 80 / 20, wherein the higher adduct means an adduct obtained from the addition of a diamine and a diepoxide in a molar ratio of 3:2, 4:3 or 5:

4.

9. The adduct according to any one of claims 1 to 8, characterized in that it contains less than 1% by weight of thinner or water.

10. 10. A curing agent for epoxy resins comprising the adduct of any one of claims 1 to 9 and at least one further component selected from the group consisting of a further amine, a curing accelerator, and a reducer.

11. 11. A curing agent for epoxy resins according to claim 10, characterized in that at least one additional amine having an aliphatic amino group and at least three amine hydrogens is present that was not present during the preparation of the adduct.

12. The further amines include N-benzylethane-1,2-diamine, 2,2(4),4-trimethylhexane-1,6-diamine, 1,2-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 2(4)-methyl-1,3-diaminocyclohexane, 1,3-bis(aminomethyl)benzene, and amines with average molecular weights M in the range of 200 to 500 g / mol. ｎ and an average molecular weight M in the range of 300 to 500 g / mol. ｎ 12. A curing agent for epoxy resins according to claim 10 or 11, characterized in that it is selected from the group consisting of polyoxypropylene triamines having the formula:

13. An epoxy resin composition comprising: a resin component comprising at least one epoxy resin, and - a hardener component comprising an adduct according to any one of claims 1 to 8 or a hardener according to any one of claims 10 to 12.

14. 14. Use of the epoxy resin composition according to claim 13 as a coating, primer, adhesive, sealant, potting compound, casting resin, impregnating resin or as a matrix for fibre composites.

15. 15. Articles obtained from the use according to claim 14.

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