Amine-epoxy resin adduct

Abstract

The subject of the present invention is an amine-functional adduct resulting from the reaction of at least one diamine of formula (I) and at least one aromatic diepoxide in a stoichiometric ratio of 1.3 - 1.7 moles of diamine per 1 molar equivalent of epoxy groups. The adduct is liquid at room temperature without a diluent and surprisingly has a low viscosity. It enables epoxy resin coatings with low or no emissions, having good processing properties, rapid curing, and high surface quality, even under wet and cold conditions, and there is great flexibility when combined with other amines and diluents.

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 then 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, specks, 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, specks, roughness or a tendency to be tacky, which is also referred to as "blushing". Blushing is caused by the formation of salts from amines present in the curing agent component and 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 stoichiometric amount or the level of excess diamine in the production of the adduct. Adducts prepared with 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 advantageous per se. 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 bind to 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] In the prior art, adducts of diamines without diluents and aromatic epoxy resins are typically prepared in a stoichiometric ratio of at least 2.5 moles of diamine to 1 mole equivalent of epoxy groups, for example in Comparative Example 2 of EP0722965 or in Synthesis Examples 1 and 3 of US7598325. Adducts prepared with a lesser excess of diamine contain a diluent, typically benzyl alcohol, as in the case of WO2019 / 134824, where adducts of methylcyclohexyl diamine or isophorone diamine or m-xylene diamine with 1.25 moles of diamine per 1 mole equivalent of epoxy groups were prepared and benzyl alcohol was added thereto to allow a workable viscosity.

[0005] Example 3 of US3625918 describes an adduct of isophorone diamine and bisphenol A diglycidyl ether in a ratio of 1.2 moles of diamine to 1 mole equivalent of epoxy groups. The adduct is a solid at room temperature.

[0006] WO 2017 / 046293 discloses adducts of N-benzylpropane-1,2-diamine and N-benzylethane-1,2-diamine with bisphenol A-diglycidyl ether in a ratio of 2.5 moles of diamine to 1 mole equivalent of epoxy groups (Adduct 1 or Adduct 8).

[0007] Adducts of alkylated diamines and epoxides are also known as components of curing agents for aqueous epoxy resin products. Such adducts typically contain polyether units and are diluted with water and usually also a large amount of unreacted diamine after the reaction.

[0008] Adducts of diamines and aromatic epoxy resins that are produced with a low excess of diamine and remain liquid and easy to handle at room temperature without the use of diluents are unknown in the prior art. Summary of the Invention

[0010] Accordingly, it is an object of the present invention to provide a diamine-epoxy resin adduct which is prepared using a low excess of diamine, does not require the addition of diluents, remains liquid for a relatively long time at room temperature, is easy to handle, and when used as a curing agent for epoxy resin coatings, allows good processability, rapid curing, and a defect-free glossy surface even under wet and cold conditions.

[0011] This object is achieved by an adduct as described hereinafter. It is prepared from a diamine of formula (I), which is a monoalkylated primary diamine, and an aromatic diepoxide in a stoichiometric ratio of 1.3 to 1.7 moles of diamine to 1 mole equivalent of epoxy groups. Surprisingly, the adduct is liquid at room temperature without the addition of diluents and has a low viscosity, and remains liquid and transparent even after standing for a relatively long time. Thus, it does not need to be heated or diluted to be used as a component of a curing agent for epoxy resins.

[0012] It contains a relatively high concentration of adduct molecules and only a very low content of unreacted diamine of formula (I). Thus, it has a particularly low odor and can be used in various ways as a curing agent for epoxy resins. It enables a curing agent that is free of diluents or contains low diluents and has a particularly high concentration of adduct molecules, and thus cures faster. In addition, it can be combined with a large number of other amines, especially also with non-alkylated primary diamines, which allows for fast curing and a high glass transition temperature and is particularly economical.

[0013] Despite the high content of higher adduct molecules, the adducts of the present invention surprisingly dilute the epoxy resin composition very well. It enables epoxy resin coatings with low or no emissions, which have good processing properties and fast curing, and hardly tend to have defects related to clouding even under wet and cold conditions, and have high hardness and a low tendency to yellowing after curing. Detailed Description of the Invention

[0015] The present invention provides an amine-functional adduct resulting from the reaction of the following substances in a stoichiometric ratio of 1.3 - 1.7 moles of diamine to 1 mole equivalent of epoxy groups:

[0016] (i) at least one diamine of formula (I)

[0017]

[0018] wherein

[0019] A is an alkylene, cycloalkylene or aralkylene group having 2 - 12 carbon atoms, and

[0020] R is an alkyl, cycloalkyl or aralkyl group having 1 - 12 carbon atoms,

[0021] wherein the two nitrogen atoms 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

[0022] (ii) at least one aromatic diepoxide.

[0023] If the diepoxide contains at least one aromatic ring, it is referred to as "aromatic".

[0024] "Primary amino group" refers to an amino group that is connected to a single organic group and carries two hydrogen atoms; "secondary amino group" refers to an amino group that is connected to two organic groups and carries one hydrogen atom, and the organic groups can also together be part of a ring; and "tertiary amino group" refers to an amino group that is connected to three organic groups and does not carry any hydrogen atoms, where two or three of them can also be part of one or more rings.

[0025] "Amine hydrogen" refers to the hydrogen atoms of primary and secondary amino groups.

[0026] "Amine hydrogen equivalent" refers to the mass of an amine or amine-containing composition containing one mole equivalent of amine hydrogen. It is expressed in the mass unit "g / Eq".

[0027] "Epoxy equivalent" refers to the mass of an epoxy group-containing compound or composition containing one mole equivalent of epoxy groups. It is expressed in the mass unit "g / Eq".

[0028] A substance name starting with "poly", such as polyamine or polyepoxide, refers to a substance that formally contains two or more functional groups appearing in its name per molecule.

[0029] "Diluent" refers to a substance that is soluble in epoxy resin and reduces its viscosity, and does not chemically bond to the epoxy resin polymer during the curing process.

[0030] "Molecular weight" refers to the molar mass of a molecule (grams / mole). "Average molecular weight" refers to the number-average molecular weight M n n of a polydisperse mixture of oligomer or polymer molecules, which is usually determined by gel permeation chromatography (GPC) using polystyrene as a standard.

[0031] "Gel time" is the time period from mixing the components of an epoxy resin composition until it gels.

[0032] "Room temperature" refers to a temperature of 23 °C.

[0033] 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 formula (I) are derived from commercially available primary diamines.

[0034] A is particularly 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).

[0035] A is most preferably 1,2-ethylene. These diamines of formula (I) allow adducts with particularly low viscosities and particularly high reactivities and allow a particularly low tendency to yellowing.

[0036] R is preferably selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, 3-methylbut-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.

[0037] Preferred are groups R having 6-12 carbon atoms, especially 6-8 carbon atoms.

[0038] R is particularly preferably selected from 2-ethylhexyl, 2-phenylethyl, benzyl, 1-naphthylmethyl and cyclohexylmethyl.

[0039] Most preferably, R is benzyl. These diamines of formula (I) allow adducts with particularly low viscosities, particularly high reactivities, a particularly low tendency to turbidity effects, and a low tendency to yellowing, especially when combined with group A which does not contain an aromatic group.

[0040] The diamines of formula (I) are particularly preferably selected from N-benzyl-1,2-ethylenediamine, N-(1-naphthylmethyl)-1,2-ethylenediamine, N-cyclohexylmethyl-1,2-ethylenediamine, N-benzyl-1,2-propylenediamine and N-(2-ethylhexyl)-bis(aminomethyl)-1,3-benzene.

[0041] The most preferred diamine of formula (I) is N-benzyl-1,2-ethylenediamine. This diamine allows adducts with particularly low viscosities and reactivities.

[0042] The diamines of formula (I) are preferably prepared by partially alkylating at least one amine of formula H2N-A-NH2 with at least one alkylating agent.

[0043] The alkylation is preferably reductive alkylation using an aldehyde or a ketone as the alkylating agent and hydrogen.

[0044] 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.

[0045] When using molecular hydrogen, the reductive alkylation is preferably carried out in a pressure apparatus 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.

[0046] The reductive alkylation is preferably carried out at a temperature of 40 - 120 °C, especially 60 - 100 °C.

[0047] 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 stripping. If desired, the reaction mixture can be further purified, especially by distilling off part or all of the dialkylated amine from the resulting diamine of formula (I).

[0048] The diamine of formula (I) for preparing the adduct preferably has a purity of at least 80% by weight. Thereby, a highly reactive adduct is obtained. The purity is preferably at least 85% by weight, more preferably at least 90% by weight, especially at least 95% by weight.

[0049] The aromatic diepoxides are 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.

[0050] The aromatic diepoxide is particularly preferably bisphenol A - diglycidyl ether, bisphenol F - diglycidyl ether or bisphenol A / F - diglycidyl ether, especially bisphenol A - diglycidyl ether.

[0051] The aromatic diepoxides are preferably used in industrial grade quality.

[0052] Particularly preferred are commercially available liquid resins such as especially GY 240, GY250, GY 281, GY 282, GY 285, PY 304 or PY 720 (both from Huntsman), or 330, 331, 332, 336, 351, 352, 354 or 356 (both from Dow).

[0053] The aromatic diepoxides preferably have an epoxy equivalent in the range of 110 to 260 g / Eq, preferably 156 to 200 g / Eq.

[0054] In the preparation of the adduct, the diamine of formula (I) is used in a stoichiometric ratio of 1.3 - 1.7 moles of diamine to 1 mole equivalent of epoxy groups.

[0055] The stoichiometric ratio is preferably in the range of 1.4 - 1.6 moles of diamine to 1 mole equivalent of epoxy groups.

[0056] Preferably, the temperature during the reaction is in the range of 40 to 120 °C, especially 60 to 100 °C.

[0057] After the reaction, the unreacted diamine of formula (I) is preferably not removed from the reaction product but retained therein and is a component of the adduct.

[0058] The adduct contains a so-called 2:1 adduct formed by the addition of 2 moles of the diamine of formula (I) and 1 mole of diepoxide. In the case of N-benzyl-1,2-ethanediamine and bisphenol A-diglycidyl ether, the adduct mainly contains the following 2:1 adducts, in decreasing order of content:

[0059]

[0060]

[0061] The adduct also contains higher adducts, especially the so-called 3:2 adduct formed by the addition of 3 moles of the diamine of formula (I) and 2 moles of diepoxide. In the case of N-benzyl-1,2-ethanediamine and bisphenol A-diglycidyl ether, mainly the following:

[0062]

[0063] Among them, there are also 3:2 adducts resulting from the reaction with secondary amines.

[0064] This adduct also contains other higher adducts, so-called >3:2 adducts, especially those obtained by the addition of 4 moles of the diamine of formula (I) and 3 moles of the diepoxide or 5 moles of the diamine of formula (I) and 4 moles of the diepoxide.

[0065] The adducts of the present invention preferably contain 2:1 adducts and higher adducts in a weight ratio of 30 / 70 - 49.9 / 50.1, especially 35 / 65 - 49 / 51. Such adducts enable a favorable combination of low viscosity and rapid curing.

[0066] The adducts of the present invention surprisingly remain liquid at room temperature for a long time and are easy to handle, even when they are substantially free of diluent or water.

[0067] The adduct preferably contains less than 1% by weight of diluent or water.

[0068] The adduct preferably has a viscosity of 50 - 500 Pa·s, especially 100 - 400 Pa·s at 20 °C, which is measured using a cone-plate viscometer at a shear rate of 10 s -1 of shear rate.

[0069] The adducts of the present invention are particularly suitable for curing epoxy resins.

[0070] 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.

[0071] The curing agent preferably contains 1 - 70% by weight, preferably 2 - 60% by weight, more preferably 3 - 50% by weight, especially 4 - 40% by weight, and most preferably 5 - 30% by weight of the adduct of the present invention.

[0072] The curing agent is preferably not water-based. It especially contains 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.

[0073] The curing agent preferably comprises at least one other amine having an aliphatic amino group and at least three amine hydrogens. This other amine is not added during the preparation of the adduct, but is only mixed with the adduct later. This other amine can be the same amine as the amine used as the diamine of formula (I) to prepare the adduct, or it can be a different amine.

[0074] 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 2.6 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-1,12-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, for example 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).

[0075] It may be advantageous when the curing agent of the present invention comprises a combination of two or more other amines.

[0076] Preferably selected from N-benzyl-1,2-ethylenediamine, N-benzyl-1,2-propylenediamine, 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.

[0077] Among them, preferred are 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 or polyoxypropylenetriamine.

[0078] A 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 to have almost no clouding effect.

[0079] Another particularly preferred amine is MXDA, optionally in the form of an amine-functional adduct with an epoxy resin. This amine allows for particularly rapid curing.

[0080] Another particularly preferred amine is IPDA, optionally in the form of an amine-functional adduct with an epoxy resin. This amine enables a particularly high glass transition temperature and final hardness.

[0081] Preferably, the amount of IPDA and / or the adduct of IPDA with an epoxy resin present in the curing agent is such that the ratio of the number of amine hydrogens derived from IPDA and the diamine of formula (I) is from 90 / 10 to 20 / 80, more preferably from 85 / 15 to 25 / 75, especially from 80 / 20 to 30 / 70. The amine hydrogens of free IPDA, adducted IPDA, free diamine of formula (I), and adducted diamine of formula (I) are also counted here. This curing agent allows for a particularly attractive combination of rapid curing, high final hardness, high glass transition temperature, and little tendency to a clouding effect.

[0082] Suitable accelerators are especially acids or compounds that can be hydrolyzed to acids, especially organic carboxylic acids such as acetic acid, benzoic acid, salicylic acid, 2-nitrobenzoic acid, lactic acid, organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid, or 4-dodecylbenzenesulfonic acid, sulfonic esters, other organic or inorganic acids, especially such as phosphoric acid, or mixtures of the above acids and acid esters; nitrates, especially such as 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, for example especially benzyltrimethylammonium chloride, amidines, for example especially 1,8-diazabicyclo[5.4.0]undec-7-ene, guanidines such as especially 1,1,3,3-tetramethylguanidine, phenols especially bisphenols, phenolic resins or Mannich bases, for example especially 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, or polymers prepared from phenol, formaldehyde, and N,N-dimethyl-1,3-propanediamine, phosphites, for example especially diphenyl or triphenyl phosphite, or compounds having a mercapto group.

[0083] 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.

[0084] Suitable diluents are in particular 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 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, diisopropylnaphthalene, mineral oil fractions such as grades (from Exxon), alkylphenols such as tert-butylphenol, nonylphenol, dodecylphenol, cardanol (from cashew nut shell liquid, containing mainly 3-(8,11-pentadecadienyl)phenol), styrenated phenol, bisphenols, aromatic hydrocarbon resins, especially those of the type containing phenolic groups, alkoxylated phenols, especially ethoxylated or propoxylated phenols, especially 2-phenoxyethanol, adipates, sebacates, phthalates, benzoates, organic phosphates or sulfonates or sulfonamides.

[0085] Preferred diluents have a boiling point above 200 °C.

[0086] The diluent is preferably selected from benzyl alcohol, styrenated phenol, ethoxylated phenol, aromatic hydrocarbon resins containing phenolic groups, especially products LS 500, LX 200, LA 300 or LA 700 (from Rütgers), diisopropylnaphthalene and cardanol.

[0087] Particularly preferred is benzyl alcohol.

[0088] Diluents containing phenolic groups can also function effectively as accelerators.

[0089] The curing agent can contain other components, especially the following:

[0090] - other adducts, in particular adducts of MXDA, DETA, TETA or TEPA with bisphenol A, F or A / F diglycidyl ether, or adducts of MPMD or 1,2-ethylenediamine or 1,2-propylenediamine with tolyl glycidyl ether, where the unreacted MPMD or 1,2-ethylenediamine or 1,2-propylenediamine is removed by distillation after the reaction;

[0091] - diamines having two secondary amino groups, especially those derived from diamines of formula (I) alkylated on both nitrogen atoms, especially N,N'-dibenzyl-1,2-ethylenediamine, or other diamines having two secondary amino groups;

[0092] - monoamines, such as in particular benzylamine or furfurylamine;

[0093] - Polyamidoamines, in particular reaction products of mono- or polycarboxylic acids or their esters or anhydrides, in particular dimer fatty acids, with polyamines used in stoichiometric excess, in particular DETA or TETA;

[0094] - Mannich bases, in particular phenolic alkylamines, i.e. reaction products of phenols (in particular cardanol) with aldehydes (in particular formaldehyde) and polyamines.

[0095] - Aromatic polyamines, such as in particular 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;

[0096] - Compounds having a mercapto group, in particular liquid thiol-terminated polysulfide polymers, thiol-terminated polyalkylene oxides, thiol-terminated polyalkylene derivatives, polyesters of thioacids, 2,4,6-trimercapto-1,3,5-triazine, triethylene glycol dithiol or ethanedithiol.

[0097] In addition to the adducts according to the invention, optionally other diamines of formula (I) and optionally IPDA, the curing agent preferably has only a low content of other amines.

[0098] Preferably, at least 30%, more preferably at least 40%, in particular at least 50% of all amine hydrogens present in the curing agent are derived from the diamines of formula (I) and IPDA. The amine hydrogens of the adduct diamines of formula (I), adduct IPDA, free diamines of formula (I) and free IPDA are also counted here. Such a curing agent enables an attractive combination of rapid curing, a very low tendency to turbidity effects, high hardness and a high glass transition temperature.

[0099] The curing agent preferably has only a small amount of diluent, more particularly 0 - 50% by weight, preferably 0 - 30% by weight of diluent, in particular benzyl alcohol.

[0100] The present invention further provides an epoxy resin composition comprising

[0101] - A resin component comprising at least one epoxy resin, and

[0102] - A curing agent component comprising the adduct according to the invention.

[0103] The curing agent component preferably comprises the above-mentioned curing agent.

[0104] Suitable epoxy resins can be obtained in a known manner, in particular by reaction of epichlorohydrin with polyols, polyphenols or amines.

[0105] Suitable epoxy resins are especially aromatic epoxy resins, in particular glycidyl ethers of the following substances:

[0106] - 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.

[0107] - Dihydroxybenzene derivatives such as resorcinol, hydroquinone or catechol;

[0108] - 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), 1,3-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;

[0109] - Novolacs, which are especially condensation products of phenol or cresol with formaldehyde or paraformaldehyde or acetaldehyde or crotonaldehyde or isobutyraldehyde or 2-ethylhexanal or benzaldehyde or furfural;

[0110] - Aromatic amines such as aniline, toluidine, 4-aminophenol, 4,4'-methylenediphenyldiamine, 4,4'-methylenediphenyldi(N-methyl)amine, 4,4'-[1,4-phenylenebis(1-methylethylidene)]diphenylamine (diphenylamine-P) or 4,4'-[1,3-phenylenebis(1-methylethylidene)]diphenylamine (diphenylamine-M).

[0111] Other suitable epoxy resins are aliphatic or cycloaliphatic polyepoxides, especially

[0112] - 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;

[0113] - hydrogenated bisphenol A, F or A / F liquid resins or glycidylated products of hydrogenated bisphenol A, F or A / F;

[0114] - N-glycidyl derivatives of amides or heterocyclic nitrogen bases, such as triglycidyl cyanurate or triglycidyl isocyanurate, or reaction products of epichlorohydrin and hydantoin.

[0115] The epoxy resin is preferably a liquid resin or a mixture comprising two or more liquid epoxy resins.

[0116] "Liquid epoxy resin" means an industrial polyepoxide having a glass transition temperature below 25 °C.

[0117] The resin component may optionally additionally comprise a certain proportion of solid epoxy resin.

[0118] 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 comprise a certain proportion of solid bisphenol A resin or novolac glycidyl ether.

[0119] The resin component may comprise a reactive diluent.

[0120] 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-C10 or C 12 -C 14 or C 13 -C 15 Alkyl glycidyl ether.

[0121] The epoxy resin composition preferably contains at least one other component selected from diluents, accelerators, and fillers.

[0122] Suitable accelerators are those already mentioned, especially salicylic acid, calcium nitrate, or 2,4,6-tris(dimethylaminomethyl)phenol or combinations thereof.

[0123] Suitable diluents are those already mentioned, especially those with a boiling point greater than 200 °C.

[0124] 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.

[0125] Particularly preferred is benzyl alcohol.

[0126] 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.

[0127] Preferred are calcium carbonate, quartz powder, quartz sand, or combinations thereof.

[0128] The epoxy resin composition may optionally contain other auxiliaries and additives, especially the following:

[0129] -Reactive diluents, especially those already mentioned, or epoxidized soybean oil or linseed oil, compounds containing acetoacetate groups, especially acetylated polyols, butyrolactone, carbonates, aldehydes, isocyanates, or organosilicons with reactive groups;

[0130] - 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, said monomers especially selected from ethylene, propylene, butene, isobutene, isoprene, vinyl acetate or alkyl (meth)acrylates, especially chlorosulfonated polyethylene or fluoropolymers or sulfonamide-modified melamine;

[0131] - Fibers, especially glass fibers, carbon fibers, metal fibers, ceramic fibers or polymer fibers, such as polyamide fibers or polyethylene fibers;

[0132] - Pigments, especially titanium dioxide, iron oxide or chromium(III) oxide;

[0133] - Rheological modifiers, especially thickeners or anti-settling agents;

[0134] - Adhesion improvers, especially organoalkoxysilanes;

[0135] - Flame retardant substances, 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 oligomer, tetraphenyl resorcinol bisphosphite, ethylenediamine bisphosphate, bisphenol A-bis(diphenyl phosphate), tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, tris(2,3-dichloroisopropyl) phosphate, tris[3-bromo-2,2-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

[0136] - Additives, especially dispersion paraffin, film-forming aids, wetting agents, leveling agents, defoamers, degassing agents, stabilizers against oxidation, heat, light or UV radiation, or biocides.

[0137] The epoxy resin composition preferably contains other auxiliaries and additives, especially pigments, wetting agents, leveling agents and / or defoamers.

[0138] 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, and particularly less than 10% by weight of diluent. This enables an epoxy resin product with low emissions or no emissions.

[0139] The epoxy resin composition preferably has only a low content of water, preferably less than 5% by weight, and particularly less than 1% by weight of water.

[0140] In the epoxy resin composition, the ratio of the number of groups reactive with epoxy groups to the number of epoxy groups is preferably in the range of 0.5 to 1.5, particularly 0.7 to 1.2.

[0141] The primary and secondary amino groups present in the epoxy resin composition and optionally other groups reactive with epoxy groups react with the epoxy groups, causing ring opening (addition reaction). Mainly due to this reaction, the composition polymerizes and thus cures.

[0142] 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, and among them, other components reactive with epoxy groups are preferably components of the curing agent component. Similarly, other components can be present as separate other components.

[0143] Suitable containers for storing the resin component or the curing agent component are especially drums, barrels, bags, sachets, cans, cartridges or tubes. The components are storable, which means 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 with 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 generally in the range of 1:10 to 10:1.

[0144] The components are mixed by a suitable method; this mixing can be carried out continuously or intermittently. If the mixing is not carried out immediately before application, it must be ensured that not too much time elapses between mixing the components and applying the components, and the application is carried out within the pot life. The mixing is particularly carried out at ambient temperature, which is generally in the range of about 5 - 40 °C, preferably about 10 - 35 °C.

[0145] As described above, curing by chemical reaction begins with the mixing of two components. The curing is usually carried out at a temperature in the range of 0 to 150 °C. It is preferably carried out at ambient temperature and usually lasts for several days to several weeks. The duration depends in particular on the temperature, the reactivity of the components, their stoichiometric ratio, and on the presence of a promoter.

[0146] 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 to 4000 mPa·s, more preferably 300 to 3000 mPa·s, and particularly preferably 300 to 2500 mPa·s, measured using a cone and plate viscometer at a shear rate of 10 s -1 .

[0147] The epoxy resin composition is applied to at least one substrate, and the following substrates are particularly suitable:

[0148] - Glass, glass ceramics, concrete, mortar, cement screed, fiber cement, bricks, tiles, gypsum or natural stone, such as granite or marble;

[0149] - Repair or leveling materials based on PCC (polymer modified cement mortar) or ECC (epoxy resin modified cement mortar);

[0150] - Metals or alloys, such as aluminum, iron, steel, copper, other non-ferrous metals, including surface-refined metals or alloys, such as galvanized or chrome-plated metals;

[0151] - Tar or asphalt;

[0152] - Leather, fabric, paper, wood, wood materials bonded with resins (such as phenolic resins, melamine resins or epoxy resins), resin-fabric composites or other so-called polymer composites;

[0153] - 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;

[0154] - Fiber-reinforced plastics, such as carbon fiber-reinforced plastics (CFK), glass fiber-reinforced plastics (GFK) and sheet molding compounds (SMC);

[0155] - Insulating foams, especially insulating foams made of EPS, XPS, PUR, PIR, rock wool, glass wool or foam glass (foamed glass);

[0156] - Coated or painted substrates, especially painted tiles, coated concrete, powder-coated metals or alloys, or painted metal sheets;

[0157] - Coatings, paints or varnishes, especially coated floors that have been overcoated with another floor covering.

[0158] If required, the substrate can be pretreated before application, especially by physical and / or chemical cleaning methods or by applying an activator or primer.

[0159] A cured composition is obtained by curing an epoxy resin composition.

[0160] After curing, the epoxy resin composition especially has a high glass transition temperature, especially when it contains IPDA in addition to the adduct of the present invention in the curing agent.

[0161] After curing at room temperature for 14 days, the glass transition temperature is preferably at least 47 °C, preferably at least 49 °C during the first heating (first run), and at least 60 °C, preferably at least 63 °C during the second heating (second run), which is determined by DSC using the following measurement procedure: (1) measure at -10 °C for 2 minutes, (2) from -10 to 200 °C, heating rate of 10 K / min (= first run), (3) from 200 to -10 °C, cooling rate of -50 K / min, (4) measure at -10 °C for 2 minutes, (5) from -10 to 180 °C, heating rate of 10 K / min (= second run).

[0162] The epoxy resin composition is preferably used as a coating, primer, adhesive, sealant, casting compound, casting resin, impregnating resin or as a matrix for fiber composites, especially for example CFK or GFK.

[0163] 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.

[0164] The epoxy resin composition is particularly suitable as an indoor floor covering or floor coating, for example 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, for example for surface sealing of wooden structures, vehicles, loading areas, tanks, silos, shafts, pipes, machines or steel structures, such as 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 anti-corrosion primer or for surface hydrophobization.

[0165] This epoxy resin composition is particularly advantageously used in low-emission coatings with environmentally friendly quality seals, such as those meeting the requirements of Emicode (EC1Plus), AgBB, DIBt, the Blue Angel (Der Blaue Engel), AFSSET, RTS (M1), and the US Green Building Council (LEED).

[0166] For use as a coating, the epoxy resin composition advantageously has a liquid consistency with low viscosity and good levelling properties. Usually at ambient temperature, within its pot life, the mixed composition is applied planar to a substrate in the form of a film with a layer thickness of from about 50 μm to about 5 mm. In particular, it is applied by pouring onto the substrate to be coated and then spreading it evenly, for example using a spatula 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 with good adhesion to a variety of different substrates.

[0167] Here, the epoxy resin composition is particularly used in a coating method comprising the following steps:

[0168] (i) Mixing the components of the epoxy resin composition,

[0169] (ii) Applying the mixed composition to a substrate within its pot life,

[0170] Subsequently curing the mixed composition.

[0171] 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.

[0172] 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 an adhesive joint.

[0173] The mixed adhesive is applied or coated in particular by brush, roller, spatula or trowel, or from a tube, cartridge or metering device.

[0174] This adhesive is particularly suitable for the construction industry, especially for strengthening building structures by means of 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 those for wind turbines, shafts, pipes 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, railings 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.

[0175] Other application areas relate to structural bonding in the construction or manufacturing industry, especially as bonding mortars, assembly adhesives, reinforcement adhesives, for example, especially 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, reinforcement adhesives, body adhesives or semi-shell adhesives for wind turbine rotor blades.

[0176] 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.

[0177] Here, the epoxy resin composition is particularly used in an adhesive method comprising the following steps:

[0178] (i) mixing the components of the epoxy resin composition,

[0179] (ii) applying the mixed composition

[0180] - to at least one substrate to be bonded and connecting the substrates during the open time to form a bonded body,

[0181] - or into a cavity or gap between multiple substrates, and optionally inserting an anchor into the cavity or gap during the open time,

[0182] and subsequently curing the mixed composition.

[0183] "Anchor" more specifically refers to a steel bar, screw or bolt here. Thus, such an anchor is especially adhesively bonded or anchored in a wall, wall, ceiling or foundation such that a part of it is adhesively bonded in a force-locking manner and a part of it protrudes and can withstand structural loads.

[0184] The same or different substrates can be bonded.

[0185] An article is obtained by applying and curing an epoxy resin composition.

[0186] Accordingly, the present invention also provides an article obtained by applying the epoxy resin composition.

[0187] The article is preferably a building or a part thereof, in particular a building above or below ground, office, industrial workshop, gymnasium, cold storage, silo, bridge, roof, staircase, floor, balcony, terrace or parking lot floor, or an industrial or consumer product, especially a dock, offshore platform, gate, crane, bulkhead, pipeline or rotor blade of a wind turbine, or a means of transportation, such as in particular an automobile, truck, rail vehicle, ship, aircraft or helicopter, or a mountable part thereof.

[0188] The epoxy resin composition is characterized by advantageous properties. It can also be formulated with little or no diluent, and this formulation has a surprisingly low viscosity and very good processability, and cures reliably and surprisingly quickly, 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. Examples

[0189] Specific examples will be described below, which are intended to further illustrate the present invention described. The present invention is of course not limited to these specific examples described.

[0190] "AHEW" stands for amine hydrogen equivalent.

[0191] "EEW" stands for epoxy equivalent.

[0192] "Standard climatic conditions" ("NK") means a temperature of 23 ± 1 °C and a relative air humidity of 50 ± 5%.

[0193] Unless otherwise stated, the chemicals used are products of Sigma-Aldrich Chemie GmbH.

[0194] Description of the measurement method:

[0195] 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 )

[0196] The amine value was determined by titration (with a solution of 0.1 N HClO4 in acetic acid against crystal violet).

[0197] Perform liquid chromatography (UHPLC) for the quantitative determination of N-benzyl 1,2-ethylenediamine after derivatization with phenyl isocyanate under external calibration.

[0198] Perform gel permeation chromatography (GPC) to determine the weight ratios of the 2:1 adduct, 3:2 adduct, and >3:2 adduct relative to a polystyrene standard.

[0199] Substances and abbreviations used:

[0200] GY 250: Bisphenol A - diglycidyl ether, EEW 187 g / Eq (from Huntsman)

[0201] DY-E: C 12 to C 14 Mono glycidyl ether of alcohol, EEW approximately 290 g / Eq (from Huntsman)

[0202] B-EDA N-benzyl-1,2-ethylenediamine, prepared as described below, 150.2 g / mol, AHEW 50 g / Eq

[0203] IPDA 3-aminoethyl-3,5,5-trimethylcyclohexylamine, AHEW 42.6 g / Eq ( IPD, obtained from Evonik)

[0204] K54 2,4,6-tris(dimethylaminomethyl)phenol (from Air Products)

[0205] Preparation of the diamine of formula (I):

[0206] N-benzyl-1,2-ethylenediamine (B-EDA):

[0207] At room temperature and under a nitrogen atmosphere, add 180.3 g (3 mol) of 1,2-ethylenediamine to a round-bottom flask. While stirring well, slowly add a solution of 106.0 g (1 mol) of benzaldehyde in 1200 ml of isopropanol and continue stirring for 2 hours. Then, in a continuous hydrogenation apparatus, hydrogenate the reaction mixture 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, use IR spectroscopy to check if the imine band is at approximately 1665 cm -1Disappeared. Then the hydrogenated solution was concentrated on a rotary evaporator at 65 °C to remove unreacted 1,2-ethylenediamine, water, and isopropanol. The resulting reaction mixture 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) as determined by GC.

[0208] 120 g of this reaction mixture was purified by vacuum distillation at 80 °C, and 75.1 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 > 97% as determined by GC, and was used in the following examples. It was used in further examples.

[0209] Preparation of the adduct:

[0210] Adduct A1: (The adduct of the present invention, which contains 1.5 moles of diamine (I) relative to 1 molar equivalent of epoxy groups)

[0211] Under a nitrogen atmosphere, 45.0 g (0.3 mol) of N-benzyl-1,2-ethylenediamine (B-EDA) was precharged and heated to 80 °C. While stirring well, 36.8 g (0.2 mol epoxy groups) of GY 250 was slowly added thereto, and the temperature of the reaction mixture was maintained between 70 and 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 262 Pa·s at 20 °C (viscosity at 25 °C was 132 Pa·s), an amine value of 408 mg KOH / g, and a calculated AHEW of 116.3 g / Eq.

[0212] After storing in a sealed container at room temperature for 3 months, the adduct remained clear and liquid.

[0213] Adduct A1 contains 24.2 wt% of N-benzyl-1,2-ethylenediamine as measured by UHPLC, and the weight ratio of the adduct molecules as measured by GPC is 2:1 adduct / 3:2 adduct / >3:2 adduct = 42.5 / 27.0 / 30.5.

[0214] Adduct A2: (Comparative example containing 2.5 moles of diamine (I) relative to 1 molar equivalent of epoxy groups)

[0215] Under a nitrogen atmosphere, 45.0 g (0.3 mol) of N-benzyl-1,2-ethylenediamine (B-EDA) was pre-placed and heated to 80 °C. While stirring thoroughly, 22.5 g (0.12 mol of epoxy groups) GY 250 was slowly added thereto, and the temperature of the reaction mixture was maintained between 70 and 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 2.8 Pa·s at 20 °C, an amine value of 493 mg KOH / g, and a calculated AHEW of 86.5 g / Eq.

[0216] Adduct A2 contained 45.1 wt% of N-benzyl 1,2-ethylenediamine as measured by UHPLC, and the weight ratio of the adduct molecules as measured by GPC was 2:1 adduct / 3:2 adduct / >3:2 adduct = 63 / 27 / 10.

[0217] Adduct A3: (IPDA adduct)

[0218] Under a nitrogen atmosphere, 51.1 g (0.3 mol) of IPDA and 147.3 g of benzyl alcohol were pre-placed and heated to 80 °C. While stirring thoroughly, 37.6 g (0.2 mol of epoxy groups) GY 250 was slowly added thereto, and the temperature of the reaction mixture was maintained between 70 and 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, and its calculated AHEW was 236.4 g / Eq.

[0219] Preparation of the curing agent and the epoxy resin composition:

[0220] Examples 1-9:

[0221] For each example, the components of the resin compositions specified in Tables 1 and 2 were mixed in the specified amounts (parts by weight) using a centrifugal mixer (SpeedMixer TM DAC 150, FlackTek Inc.) and stored while excluding moisture.

[0222] The components of the curing agent compositions specified in Tables 1 and 2 were processed and stored in the same manner.

[0223] 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:

[0224] After mixing for 10 minutes, the viscosity was measured at 20 °C ("viscosity (10')").

[0225] The gelling time is determined by moving the mixed composition (25 g) from time to time with a spatula until it begins to gel under standard climatic conditions.

[0226] To determine the Shore D hardness in accordance with DIN 53505, two cylindrical specimens (diameter 20 mm, thickness 5 mm) are prepared in each case. One is stored under standard climatic conditions and the hardness is measured after 1 day and 2 days (1d NK and 2d NK), while the other sample is stored at 8 °C and 80 % relative humidity and the hardness is measured after 1 day and 2 days in the cold state (1d 8 ° / 80 % and 2d 8 ° / 80 %).

[0227] The first coating film is 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)”), after 2 days (“ hardness (2d NK)”), after 4 days (“ hardness (4d NK)”), after 7 days (“ hardness (7d NK)”) and after 14 days (“ hardness (14d NK)”) the hardness ( pendulum hardness, measured according to DIN EN ISO 1522) of the film is determined. Once a value greater than 200 s is obtained, the hardness is no longer determined. After 14 days, the appearance of the film is evaluated (referred to as “appearance (NK)” in the table). If the film has a shiny, non-sticky surface and no structure, it is called “good”. “Structure” means any kind of marking or pattern on the surface.

[0228] The second coating film is applied to a glass plate with a layer thickness of 500 μm and immediately stored / cured at 8 °C and 80 % relative humidity for 7 days after application, and then stored / cured under standard climatic conditions for 2 weeks. After 24 hours of application, a polypropylene bottle cap is placed on the film and a wet sponge is placed under the cap. After another 24 hours, the sponge and the cap are removed and placed at a new position on the film, and after 24 hours they are removed from the new position in turn and repositioned, which is carried out a total of 4 times. Then the appearance of the film is evaluated in the same way 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 are also reported. As “cloudiness”, the number of white spots is reported. The faintly white discolored spots are noted as “(1)”. If there is an annular imprint due to sinking within the first 24 hours after placing the cap, it is reported as “ring”. Such an annular imprint indicates that the coating is not yet walkable on. The Hardness was measured after 7 days at 8 °C and 80% relative humidity (“ Hardness (7d 8 ° / 80%)”), then after 2 more days at NK (“ Hardness (+2d NK)”), after 7 days at NK (“ Hardness (+7d NK)”), or after 14 days at NK (“ Hardness (+14d NK)”). Once a value greater than 190 s was reached, hardness was no longer measured .

[0229] The Tg value (glass transition temperature) was determined by DSC on cured samples stored for 14 days under standard climatic conditions using a Mettler Toledo DSC 3+700 instrument and the following measurement procedure: (1) 2 minutes at -10 °C, (2) -10 to 200 °C at a heating rate of 10 K / min (= first run), (3) 200 to -10 °C at a cooling rate of -50 K / min, (4) 2 minutes at -10 °C, (5) -10 to 180 °C at a heating rate of 10 K / min (= second run).

[0230] As a measure of yellowing, the change in color after loading in a weathering tester was also determined. For this purpose, a coating film with a layer thickness of 500 μm was applied again on a glass plate, stored / cured for 2 weeks under standard climatic conditions, 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 thus loaded compared to the corresponding unloaded film was determined 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 maximum ΔE value of 5 indicates slight yellowing.

[0231] The results are reported in Tables 1 and 2.

[0232] The examples designated as “(Ref.)” are comparative examples.

[0233]

[0234]

[0235] Table 1: Composition and properties of Examples 1 - 5

[0236]

[0237] Table 2: Composition and properties of Examples 4 and 6-9

Claims

1. An amine-functional adduct obtained from the reaction of the following substances in a stoichiometric ratio of 1.3 - 1.7 moles of diamine per 1 mole equivalent of epoxy group (i) at least one diamine of formula (I) wherein A is an alkylene, cycloalkylene or aralkylene having 2 - 12 carbon atoms, and R is an alkyl, cycloalkyl or aralkyl having 1 - 12 carbon atoms, wherein the two nitrogen atoms 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 aromatic diepoxide; It is characterized in that The diamine of formula (I) used for preparing the adduct has a purity of at least 90 wt%.

2. The adduct of claim 1, characterized in that A is selected from 1,2-ethylene, 1,2-propylene, 2-methyl-1,2-propylene, 1,3-pentylene, 1,2-cyclohexylene, 1,4-cyclohexylene, 4-methyl-1,3-cyclohexylene, 2-methyl-1,3-cyclohexylene, 1,3-cyclohexylenebis(methylene), 1,4-cyclohexylenebis(methylene), 1,3-phenylenebis(methylene) and 1,4-phenylenebis(methylene).

3. The adduct according to claim 1, characterized in that R is selected from 2-ethylhexyl, 2-phenylethyl, benzyl, 1-naphthylmethyl and cyclohexylmethyl.

4. The adduct according to any one of claims 1 to 3, characterized in that The diamine of formula (I) is N-benzyl-1,2-ethanediamine.

5. The adduct according to any one of claims 1-3, characterized in that It contains 2:1 adduct and higher adducts in a weight ratio of 30 / 70 - 49.9 / 50.

1.

6. The adduct according to any one of claims 1 to 3, characterized in that It contains less than 1 wt% of diluent or water.

7. The adduct according to any one of claims 1-3, characterized in that, Measured using a cone and plate viscometer at a shear rate of 10 s -1 The viscosity at 20 °C is in the range of 50 - 500 Pa·s.

8. A curing agent for epoxy resin, which comprises the adduct according to any one of claims 1 to 7 and at least one other component selected from other amines, accelerators and diluents.

9. The curing agent for epoxy resin according to claim 8, characterized in that, Comprising 1 - 70 wt% of the adduct according to any one of claims 1 - 7.

10. The curing agent for epoxy resin according to claim 8 or 9, characterized in that, Optionally further comprises 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane in the form of an amine-functional adduct with epoxy resin as other component.

11. The epoxy resin curing agent according to claim 10, characterized in that, The ratio of the number of amine hydrogens derived from 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane to the amine hydrogens derived from the diamine of formula (I) is 90 / 10 - 20 / 80.

12. An epoxy resin composition, which comprises: - a resin component comprising at least one epoxy resin, and - a curing agent component, which comprises the adduct according to any one of claims 1 to 7 or the curing agent according to any one of claims 8 to 11.

13. Use of the epoxy resin composition according to claim 12 as a coating, adhesive, sealant, casting, casting resin, impregnating resin or as a matrix for fiber composites.

14. Use of the epoxy resin composition according to claim 12 as a primer.

15. An article obtained from the use according to claim 13 or 14.

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