Epoxy resin hardener

Abstract

The present invention provides a curing agent for epoxy resins, comprising at least one amine A1 of formula (I) and at least one amine A2, which is a polyalkyleneamine or polyethyleneimine, wherein the weight ratio of amine A1 / amine A2 is in the range of 20 / 1 to 1 / 2. The curing agent of the present invention provides inexpensive, low-discharge epoxy resin products that have good processability, a long pot life, unexpectedly fast curing, especially under low-temperature conditions, high strength, high bond strength, high glass transition temperature, and low tendency to yellowing, and that form unexpectedly good surfaces in two-dimensional applications and under wet and low-temperature conditions, with almost no blush-related defects. Such epoxy resin products can be advantageously used, in particular, as floor coatings or adhesives.

Description

[Technical field]

[0001] Epoxy resins, hardeners for epoxy resin compositions and their use, especially as coatings or adhesives. [Background technology]

[0002] Epoxy resin-based coatings and adhesives are widely used in the building industry. They consist of liquid or paste-like resin and hardener components that are mixed prior to application and then cured at ambient temperatures in the range of about 5-35°C to form a strong and stable material. Especially in two-dimensional applications, such epoxy resin compositions have a tendency to surface defects such as haze, mottling, roughness or tackiness, also known as "blushing". Blushing is caused by amines present in the hardener components that form salts with carbon dioxide (CO2) in the air, and occurs especially at high humidity and low temperatures. Particularly in aesthetically demanding coating applications such as floor coatings, the occurrence of blushing-related surface defects is highly detrimental and usually requires tedious repair or overcoating of the defective areas or often the entire coating.

[0003] Thinners are used to reduce the viscosity of epoxy resin compositions so that they can be easily applied and have good wetting on the substrate surface. At the same time, thinners also reduce susceptibility to blushing. Commonly used thinners, such as benzyl alcohol, are volatile compounds (VOCs or SVOCs) that are not incorporated into the polymer matrix upon curing and therefore may result in emissions. For low emission products, which are increasingly demanded by consumers, this means that thinners can be used in small amounts or not at all.

[0004] To reduce blushing, it is possible to use alkylated amines as reactive diluents in the hardener component, as described in EP 2,943,464, WO 2016 / 023839, EP 3,138,863 or EP 3,144,335. However, alkylated amines slow down the cure and reduce the glass transition temperature obtained after cure, making them particularly unattractive for adhesive applications.

[0005] Polyalkyleneamines such as TETA, TEPA or N4 amines are commonly used curing agents for epoxy resins. They provide fast cure but can be prone to blushing-related defects and can be more brittle after curing, which can manifest as reduced elongation and reduced strength and bond strength. To achieve high bond strength, the adhesive must not be too brittle, as it may break under low stress even if the adhesion is good. Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention aims to provide a hardener for epoxy resins which overcomes the drawbacks of the prior art relating to viscosity, blushing, cure speed, glass transition temperature and brittleness. [Means for solving the problem]

[0007] This object is achieved by the curing agent as claimed in claim 1. The curing agent according to the invention is in particular based on the combination of at least one alkylated amine A1 with at least one amine A2 which is a polyalkyleneamine or a polyethyleneimine.

[0008] The hardener of the present invention has a low viscosity and provides very good thinning of the resin components. Despite the presence of amine A2, which is prone to blushing, it surprisingly shows a very low tendency to blushing-related defects. At the same time, it achieves high curing speeds without any excessive negative effect on the pot life, even when the proportion of amine A2 is surprisingly low. Curing results in hard, less brittle materials with high bond strength and sufficiently high glass transition temperatures. For production reasons, the alkylated amines are somewhat more expensive than the amines typically used as curing agents for epoxy resins. The additional use of amine A2, which is cheap and widely available, also means that the hardener of the present invention is particularly attractive economically.

[0009] The curing agent of the present invention achieves low-emission epoxy resin products with good processability and fast curing, especially under low temperature conditions. In the case of two-dimensional applications, good surfaces are formed, especially with few blush-related defects, even under high humidity and low temperature conditions. After curing, the products show high strength, high bond strength and high glass transition temperature; and they have almost no tendency to yellowing. Such epoxy resin products can be advantageously used as coatings, especially floor coatings, where low-emission or no-emission products are desired and where low viscosity and good processability, even with little or no thinner, and high aesthetic requirements must be met, and as adhesives where fast-curing products with long pot life and open time, high strength, high bond strength and high glass transition temperature are required.

[0010] Further aspects of the invention are the subject matter of further independent claims. Particularly preferred embodiments of the invention are the subject matter of the dependent claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention relates to a process for the preparation of a compound comprising at least one amine A1 of formula (I) and at least one amine A2 which is a polyalkyleneamine or a polyethyleneimine, [ka] (In the formula, m is 0 or 1, n is 1 or 2, and (m+n) is 2; A is 1,2-ethylene or 1,2-propylene; R is H or an alkyl group having 1 to 12 carbon atoms; and Y is an optionally substituted aromatic or alicyclic group having 6 to 20 carbon atoms; The weight ratio of amine A1 / amine A2 is within the range of 20 / 1 to 1 / 2; The present invention provides a hardener for epoxy resins.

[0012] "Polyalkyleneamine" refers to a linear polyamine containing at least three amino groups separated from each other by alkylene groups.

[0013] "Polyethyleneimine" refers to the product of the polymerization of ethyleneimine, which consists primarily of primary, secondary, and tertiary amino groups linked through 1,2-ethylene groups.

[0014] A "primary amino group" refers to an amino group that is bonded to one organic group and has two hydrogen atoms; a "secondary amino group" refers to an amino group that is bonded to two organic groups which together may 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 be part of one or more rings, and has no hydrogen atoms.

[0015] "Amine hydrogen" refers to the hydrogen atoms of primary and secondary amino groups.

[0016] "Amine hydrogen equivalent weight" refers to the mass of an amine or amine-containing composition that contains one molar equivalent of an amine hydrogen.

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

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

[0019] "Molecular weight" refers to the molar mass of a molecule (g / mol). "Average molecular weight" refers to the number average M n which is typically measured by gel permeation chromatography (GPC) against polystyrene as a standard.

[0020] "Pot life" refers to the period during which an epoxy resin composition is processable, i.e., the longest possible time between mixing the components and application of the mixed composition that is sufficiently free-flowing to wet the surface of a substrate.

[0021] The "open time" of an adhesive refers to the maximum period of time during which a cohesive bond is possible between the application of the adhesive and the connection of the parts to be joined.

[0022] "Room temperature" refers to a temperature of 23°C.

[0023] Preferably, the curing agent is not aqueous, in particular it contains less than 10% by weight of water, preferably less than 5% by weight, more preferably less than 2.5% by weight of water, such a curing agent is particularly suitable for curing non-emulsified epoxy resins, resulting in a very hydrophobic and stable material.

[0024] Preferably, A is 1,2-ethylene. Such amines A1 provide a particularly fast cure.

[0025] R is preferably H or methyl or phenyl, more preferably H or methyl, in particular H. Such amines A1 are accessible in a particularly simple manner.

[0026] Preferably, Y is an optionally substituted phenyl, 1-naphthyl or cyclohexyl group.

[0027] Y is more preferably a phenyl group. Such amines A1 provide a particularly good surface.

[0028] The amine A1 of formula (I) is preferably selected from the group consisting of N-benzylethane-1,2-diamine, N,N'-dibenzylethane-1,2-diamine, N-(1-naphthylmethyl)ethane-1,2-diamine, N-cyclohexylmethylethane-1,2-diamine, N-benzylpropane-1,2-diamine and N,N'-dibenzylpropane-1,2-diamine.

[0029] Preference is given to amines A1 of formula (I) in which m and n are each 1. These allow a particularly rapid curing.

[0030] Such amines A1 of formula (I) optionally additionally contain a proportion of dialkylated amines A1 of formula (I) where m is 0 and n is 2, where the weight ratio of monoalkylated amines (n and m are both 1) to dialkylated amines (n is 2) is preferably at least 50 / 50, more preferably at least 65 / 35 and in particular at least 70 / 30.

[0031] N-benzylethane-1,2-diamine or N-benzylpropane-1,2-diamine are particularly preferred.

[0032] N-benzylethane-1,2-diamine may contain a certain proportion of N,N'-dibenzylethane-1,2-diamine.N-benzylpropane-1,2-diamine may contain a certain proportion of N,N'-dibenzylpropane-1,2-diamine.

[0033] The most preferred amine A1 of formula (I) is N-benzylethane-1,2-diamine, which optionally contains up to 35% by weight of N,N'-dibenzylethane-1,2-diamine, based on the sum of the two amines, which gives a particularly rapid cure.

[0034] It is preferred to use amines A1 of formula (I) as constituents of a reaction mixture resulting from the partial alkylation of ethane-1,2-diamine or propane-1,2-diamine with at least one alkylating agent.

[0035] Preferably, the alkylation is a reductive alkylation, where the alkylating agent used is an aldehyde or ketone and hydrogen.

[0036] The reductive alkylation is preferably carried out in the presence of a suitable catalyst, preferred catalysts being palladium on carbon (Pd / C), platinum on carbon (Pt / C), Adams' catalyst or Raney nickel, in particular palladium on carbon or Raney nickel.

[0037] When molecular hydrogen is used, the reductive alkylation is carried out in a pressure device at a hydrogen pressure of 5 to 150 bar, in particular 10 to 100 bar. It can be carried out in a batchwise process or, preferably, in a continuous process.

[0038] The reductive alkylation is preferably carried out at a temperature within the range of 40 to 120°C, particularly 60 to 100°C.

[0039] Ethane-1,2-diamine or propane-1,2-diamine is preferably used in a stoichiometric excess relative to the aldehyde or ketone, and the excess is at least partially removed from the reaction mixture after alkylation, in particular by stripping. If desired, the reaction mixture can then be further purified by liberating the mono- and at least partially di-alkylated amines, in particular by distillation.

[0040] The curing agent for epoxy resins according to the invention also contains at least one amine A2 which is a polyalkyleneamine or a polyethyleneimine.

[0041] Suitable polyethyleneimines are the products of the polymerization of ethyleneimine. They are mixtures of various molecules having a distribution of molecular weights that typically occurs in polymerizations.

[0042] The polyethyleneimine preferably has an average molecular weight M in the range of 200 to 1500 g / mol, in particular in the range of 200 to 1000 g / mol. n has.

[0043] Suitable polyethyleneimines can be prepared by known processes or they are commercially available, in particular as Lupasol® FG or Lupasol® G 20 Anhydrous (from BASF) or as Epomin® SP-003, Epomin® SP-006, Epomin® SP-012 or Epomin® SP-018 (from Nippon Shokubai Co., Ltd.).

[0044] Preferred amines A2 are polyalkyleneamines, especially those of formula (II) shown below, which give epoxy resin products with particularly good processability.

[0045] The amine A2 is a polyalkyleneamine of formula (II) [ka] (In the formula, x is an integer from 1 to 6, and B is independently an alkylene group having 2 to 6 carbon atoms. It is preferable that:

[0046] The amines A2 of formula (II) are particularly used in technical grade quality, which typically result from a preparation process of the amines of formula (II) in which the content of polyalkyleneamines of formula (II) can vary depending on the preparation and purification process form.

[0047] Suitable polyalkyleneamines of formula (II) are in particular diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), the higher homologues of linear polyethyleneamines, 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, 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 or bis(6-aminohexyl)amine (BHMT).

[0048] Preferably, x is 1 or 2 or 3 or 4.

[0049] Preferably, B is 1,2-ethylene or 1,3-propylene or 1,6-hexylene.

[0050] Preferred polyalkyleneamines of formula (II) are TETA, TEPA, PEHA or N4 amines. These amines A2 give epoxy resin products with particularly rapid curing and high glass transition temperatures.

[0051] A further preferred polyalkyleneamine of formula (II) is BHMT. With this amine A2, adhesives having particularly low brittleness and particularly high bond strength are obtained. In particular, BHMT is used here in technical grade quality, which is obtained in the preparation of hexane-1,6-diamine. Such technical grade quality BHMT is commercially available, for example as Dytek® BHMT amine (50-78%) (Invista).

[0052] It may be advantageous to use mixtures of two or more amines A2, in particular mixtures of BHMT and TETA, TEPA, PEHA or N4 amines, which result in less brittle materials with particularly high bond strengths at high glass transition temperatures.

[0053] The weight ratio of amine A1 and amine A2 (A1 / A2) is preferably in the range of 15 / 1 to 1 / 2, which provides an epoxy resin product with a long pot life, fast curing, high resistance to blushing-related defects and a high glass transition temperature.

[0054] In one embodiment of the present invention, the weight ratio of amine A1 to amine A2 (A1 / A2) is preferably in the range of 15 / 1 to 1 / 1, in particular 10 / 1 to 2 / 1. Such hardeners are particularly suitable for epoxy resin coatings which must be particularly resistant to blushing-related defects.

[0055] In a further embodiment of the present invention, the weight ratio of amine A1 to amine A2 (A1 / A2) is preferably in the range of 10 / 1 to 1 / 2, in particular 5 / 1 to 1 / 2. Such hardeners are particularly suitable for epoxy resin adhesives in which the bond strength and glass transition temperature should be particularly high.

[0056] The curing agent optionally contains at least one additional amine, which can affect the properties of the curing agent as desired, such as lowering the viscosity, increasing the reactivity, adjusting the amine hydrogen weight or improving compatibility with the epoxy resin, or can have economic benefits.

[0057] Preferred further amines are aliphatic, cycloaliphatic or araliphatic polyamines having at least two, in particular at least three, amine hydrogens, in particular 2,2-dimethylpropane-1,3-diamine, pentane-1,3-diamine (DAMP), 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, Diamines, 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 (isophoronediamine or 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-tetraoxospiro[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 the higher oligomers of these diamines, bis(3-aminopropyl)polytetrahydrofuran or other polytetrahydrofuran diamines, alicyclic diamines containing ether groups derived from the propoxylation and subsequent amination of 1,4-dimethylolcyclohexane (especially that available as Jeffamine® RFD-270 (Huntsman)), or polyoxyalkylene di- or -triamines (especially Jeffamine® RFD-270 (Huntsman)). Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-2000, Jeffamine® EDR-104, Jeffamine® EDR-148, Jeffamine® EDR-176, Jeffamine® T-403, Jeffamine® T-3000, Jeffamine® T-5000 (all from Huntsman), or the corresponding amines from BASF or Nitroil, -aminoethylpiperazine, 3-dimethylaminopropylamine (DMAPA), 3-(3-(dimethylamino)propylamino)propylamine (DMAPAPA), N-benzyldiethylenetriamine, N-benzyltriethylenetetramine, N,N'-dibenzyltriethylenetetramine, N''-benzyl-N,N'-bis(3-aminopropyl)ethylenediamine, N'',N'''-dibenzyl-N,N'-bis(3-aminopropyl)ethylenediamine, N-benzyl-1,3-bis(aminomethyl)benzene, N,N'-dibenzyl-1,3-bis(aminomethyl)benzene, N-(2-ethylhexyl)-1,3-bis(aminomethyl)benzene, N,N'-bis(2-ethylhexyl)-1,3-bis(aminomethyl)benzene, styrenated MXDA (available as Gaskamine® 240, Mitsubishi Gas Chemical Company, Inc.), adducts of the above or further polyamines with epoxides or epoxy resins, in particular with diepoxides or monoepoxides or with polyamidoamines, in particular reaction products of mono- or polybasic carboxylic acids or their esters or anhydrides, in particular dimeric fatty acids, with aliphatic, cycloaliphatic or aromatic polyamines, in particular polyalkyleneamines, such as DETA or TETA, used in stoichiometric excess, or Mannich bases, in particular phenalkamines, i.e. reaction products of phenols, in particular cardanol, with aldehydes, in particular formaldehyde, and polyamines.

[0058] Preferably, the curing agent of the present invention is TMD, 1,2-, 1,3- or 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, an average molecular weight M in the range of 200 to 500 g / mol. n The polyoxypropylene diamines having the formula:

[0059] Of these, TMD, 1,3-bis(aminomethyl)cyclohexane, IPDA, MXDA, or DMAPAPA is preferred.

[0060] Among these, adducts of MXDA and / or IPDA and / or TETA with bisphenol A or bisphenol F diglycidyl ether, particularly with a molar ratio of amine molecules to epoxy groups in the range of 3:1 to 50:1, are more preferred.

[0061] Among these, an adduct of MPMD or propane-1,2-diamine with cresyl glycidyl ether, particularly ortho-cresyl glycidyl ether, is more preferred. The formation of the adduct is preferably carried out with an excess of MPMD or propane-1,2-diamine relative to the cresyl glycidyl ether, and the amine that has not formed the adduct is preferably removed by distillation after the reaction.

[0062] Preferably, the curing agent may comprise a combination of two or more of the above additional amines.

[0063] A particularly preferred further amine is IPDA. Such curing agents are widely available, inexpensive, and result in epoxy resin products having particularly high hardness and glass transition temperatures.

[0064] A particularly preferred further amine is also DMAPAPA. Such hardeners are particularly suitable for epoxy resin adhesives. This leads to particularly high compressive strength and particularly high bond strength, especially on steel.

[0065] The hardener optionally includes at least one thinner.

[0066] Xylene, 2-methoxyethanol, dimethoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyoxyethanol, 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, Particularly suitable are dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol di-n-butyl ether, diphenylmethane, diisopropyl naphthalene, mineral oil fractions such as, for example, Solvesso® grades (from Exxon), t-butylphenol, nonylphenol, dodecylphenol, cardanol (from cashew nut shell oil which contains 3-(8,11,14-pentadecatrienyl)phenol as its main constituent), styrenated phenols, bisphenols, aromatic hydrocarbon resins (especially the types containing phenolic groups), alkoxylated phenols, especially ethoxylated or propoxylated phenols, especially alkylphenols such as 2-phenoxyethanol, adipates, sebacates, phthalates, benzoates, organophosphates or sulfonates or sulfonamides.

[0067] Preferred thinners have a boiling point above 200°C.

[0068] The thinner is preferably selected from the group consisting of benzyl alcohol, styrenated phenol, ethoxylated phenol, aromatic hydrocarbon resins containing phenolic groups, in particular Novares® LS 500, LX 200, LA 300 or LA 700 grades (manufactured by Ruetgers), diisopropyl naphthalene and cardanol.

[0069] Benzyl alcohol is particularly preferred.

[0070] Thinners containing phenolic groups are also effective as accelerators.

[0071] The curing agent optionally includes at least one accelerator.

[0072] Suitable accelerators are substances which accelerate the reaction of amino groups with epoxy groups, in particular: acids or compounds hydrolyzable to acids, in particular organic carboxylic acids such as acetic acid, benzoic acid, salicylic acid, 2-nitrobenzoic acid, lactic acid, organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, sulfonic acid esters, in particular phosphoric acid, or other organic or inorganic acids, or mixtures of the aforementioned acids and acid esters; nitrates, in particular calcium nitrate; tertiary amines, in particular 1,4-diazabicyclo[2.2.2]octane, benzyldimethylamine, α-methylbenzyldimethylamine, triethanolamine, dimethylaminopropylamine, in particular N-methylimidazole, N-vinyl amine, etc. imidazoles, such as imidazole or 1,2-dimethylimidazole, salts of such tertiary amines, in particular quaternary ammonium salts, such as benzyltrimethylammonium chloride, amidines, in particular 1,8-diazabicyclo[5.4.0]undec-7-ene, guanidines, in particular 1,1,3,3-tetramethylguanidine, phenols, in particular bisphenols, phenolic resins or Mannich bases, in particular 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, or polymers of phenols, formaldehyde and N,N-dimethylpropane-1,3-diamine, phosphites, in particular di- or triphenyl phosphite, or compounds containing a mercapto group.

[0073] Preferred accelerators are acids, nitrates, tertiary amines or Mannich bases.

[0074] Particularly preferred is salicylic acid or calcium nitrate or 2,4,6-tris(dimethylaminomethyl)phenol or a combination thereof.

[0075] The combination of calcium nitrate and 2,4,6-tris(dimethylaminomethyl)phenol is most preferred, as this achieves particularly rapid curing even at low temperatures and particularly high hardness.

[0076] Calcium nitrate is used in particular in the form of an aqueous solution having between 20% and 70% by weight of calcium nitrate.

[0077] The present invention further comprises: - a resin component comprising at least one epoxy resin; and a hardener component comprising the above hardener containing at least one amine A1 of formula (I) and at least one amine A2 which is a polyalkyleneamine or a polyethyleneimine; The epoxy resin composition includes:

[0078] Suitable epoxy resins are obtained in known manner, in particular by oxidation of olefins or by reaction of epichlorohydrin with polyols, polyphenols or amines.

[0079] Suitable epoxy resins are in particular aromatic epoxy resins, in particular the glycidyl ethers of: bisphenol A, bisphenol F or bisphenol A / F, where A represents acetone and F represents formaldehyde, are reactants for preparing these bisphenols. In the case of bisphenol F, positional isomers may be present and may in particular be derived from 2,4'- or 2,2'-hydroxyphenylmethane. - dihydroxybenzene derivatives such as resorcinol, hydroquinone or catechol; -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-t-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 B) further bisphenols or polyphenols such as 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-hydroxynaphthal-1-yl)methane, bis(4-hydroxynaphthalene-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; novolaks, in particular condensation products of phenol or cresol with formaldehyde or paraformaldehyde or acetaldehyde or crotonaldehyde or isobutyraldehyde 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).

[0080] Further suitable epoxy resins are aliphatic or cycloaliphatic polyepoxides, in particular: - di-, tri- or tetrafunctional C2-C, which are saturated or unsaturated, branched or unbranched, cyclic or open-chain 30 glycidyl ethers of alcohols, in particular 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 amides or heterocyclic nitrogen bases, such as triglycidyl cyanurate or triglycidyl isocyanurate, or the reaction products of epichlorohydrin and hydantoin. - epoxy resins derived from the oxidation of olefins, such as in particular vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene, isoprene, 1,5-hexadiene, butadiene, polybutadiene or divinylbenzene.

[0081] Preferably, the epoxy resin is a liquid resin or a mixture containing two or more liquid epoxy resins.

[0082] "Liquid epoxy resin" refers to commercial polyepoxides having a glass transition temperature below 25°C.

[0083] The resin component optionally further comprises a percentage of a solid epoxy resin.

[0084] The epoxy resins are in particular liquid bisphenol-based resins, in particular bisphenol A diglycidyl ether and / or bisphenol F diglycidyl ether, such as those available from Olin, Huntsman or Momentive. These liquid resins have low viscosity for epoxy resins and provide fast curing and high hardness. They may also contain a proportion of solid bisphenol A resin or novolac glycidyl ether.

[0085] The resin component may contain a reactive diluent.

[0086] Preferred reactive diluents are in particular butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane di- or triglycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, guaiacol glycidyl ether, 4-methoxyphenyl glycidyl ether, pn-butylphenyl glycidyl ether, pt-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, in particular, C8- to C9-C10-C12-C14-C16-C18-C19-C22-C21-C32-C31-C22-C31-C22-C32-C31-C22-C31 ... 10 - or C 12 -~C 14 - or C 13 -~C 15 -Reactive diluents containing epoxy groups such as glycidyl ethers of natural alcohols, such as alkyl glycidyl ethers.

[0087] The epoxy resin composition preferably contains at least one further component selected from the group consisting of thinners, accelerators and fillers.

[0088] Suitable accelerators are those already mentioned, in particular salicylic acid, calcium nitrate or 2,4,6-tris(dimethylaminomethyl)phenol or combinations thereof. The combination of calcium nitrate and 2,4,6-tris(dimethylaminomethyl)phenol is most preferred, which allows particularly rapid curing even at low temperatures and particularly high hardness to be achieved.

[0089] Suitable thinners are those already mentioned, particularly those having a boiling point above 200°C.

[0090] The thinner is preferably selected from the group consisting of benzyl alcohol, styrenated phenol, ethoxylated phenol, aromatic hydrocarbon resins containing phenolic groups, in particular Novares® LS 500, LX 200, LA 300 or LA 700 grades (manufactured by Ruetgers), diisopropyl naphthalene and cardanol.

[0091] Benzyl alcohol is particularly preferred.

[0092] The epoxy resin composition preferably contains only a small amount of thinner, preferably less than 25% by weight, more preferably less than 15% by weight, especially less than 10% by weight, which results in a low or no emission epoxy resin product.

[0093] Suitable fillers are in particular ground or precipitated calcium carbonate, optionally coated with fatty acids, in particular stearates, barite (baryte), talc, quartz flour, silica sand, silicon carbide, biotite, dolomite, wollastonite, kaolin, mica (potassium aluminium silicate), molecular sieves, aluminium oxide, aluminium hydroxide, magnesium hydroxide, silica, cement, gypsum, fly ash, carbon black, graphite, metal powders such as aluminium, copper, iron, zinc, silver or steel, PVC powder or hollow beads.

[0094] Calcium carbonate, ground quartz and silica sand are preferred.

[0095] The epoxy resin composition optionally comprises further auxiliaries and additives, in particular: reactive diluents, in particular those already mentioned above, or epoxidized soybean oil or linseed oil, compounds containing acetoacetate groups, in particular acetoacetylated polyols, butyrolactones, carbonates, aldehydes, isocyanates or silicones with reactive groups; -solvent; further amines, in particular monoamines, such as in particular benzylamine or furfurylamine, or 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; - 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, homo- or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth)acrylates, in particular chlorosulfonated polyethylene or fluorine-containing polymers or sulfonamide-modified melamines; 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, in particular organoalkoxysilanes; flame retardant substances, in particular the above-mentioned aluminium hydroxide or magnesium hydroxide fillers, 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, in particular diphenyl cresyl phosphate, resorcinol bis(diphenyl phosphate), resorcinol diphosphate oligomers, tetraphenyl resorcinol diphosphite, ethylenediamine diphosphate, bisphenol A bis(diphenyl phosphate), tris(chloroethyl) phosphate, tris(chloroethyl) phosphate, phosphates such as tris(chloropropyl)phosphate, tris(dichloroisopropyl)phosphate, tris[3-bromo-2,2-bis(bromomethyl)propyl]phosphate, tetrabromobisphenol A, bis(2,3-dibromopropyl ether) of bisphenol A, brominated epoxy resins, ethylene bis(tetrabromophthalimide), ethylene bis(dibromonorbornanedicarboximide), 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, deaerators, stabilizers against oxidation, heat, light or UV radiation, or biocides.

[0096] The epoxy resin composition preferably comprises further auxiliaries and additives, in particular pigments, wetting agents, levelling agents and / or defoamers.

[0097] In the epoxy resin composition, the ratio of the number of groups 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.

[0098] The primary and secondary amino groups present in the epoxy resin composition, as well as any other groups present that are reactive towards epoxy groups, react with the epoxy groups resulting in their ring opening (addition reaction), and as a result of this reaction primarily the composition polymerizes and thereby cures.

[0099] The resin component and the hardener component of the epoxy resin composition are stored in separate containers. Further components of the epoxy resin composition may be present as components of the resin component or the hardener component; the further component reactive towards epoxy groups is preferably a component of the hardener component. It is also possible for the further component to be present as a dedicated further component.

[0100] Suitable containers for storing the resin component or the hardener component are in particular vats, pails, bags, buckets, cans, cartridges or tubes. The components are storable, meaning that they can be stored before use for several months to a year or more without their respective properties changing to a degree relevant for use. For use of the epoxy resin composition, the components are mixed together just before or during application. The mixing ratio of the resin component and the hardener component is preferably selected so that the groups of the hardener component that are reactive towards 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 of the resin component and the hardener component is typically in the range of 1:10 to 10:1.

[0101] The components are mixed by any suitable method; this mixing can be done continuously or batchwise. If the mixing is not done immediately before coating, care must be taken that the time between mixing the components and coating is not too long and that coating is done during the pot life period. Mixing is typically done at ambient temperature, typically within the range of about 5 to 40°C, preferably about 10 to 35°C.

[0102] Curing by chemical reaction is initiated by mixing the two components as described above. Curing typically proceeds at temperatures in the range of 0-150° C. Curing preferably proceeds at ambient temperature and typically lasts for a period of several days to several weeks. This period depends on factors including temperature, the reactivity and stoichiometry of the components, and on the presence of accelerators.

[0103] The epoxy resin composition is applied to at least one substrate, the following substrates being particularly preferred: - glass, glass ceramics, concrete, mortar, cement screed, fibre cement, brick, tile, plaster or natural stone such as granite or marble; - PCC (polymer-modified cement mortar) or ECC (epoxy resin-modified cement mortar) based repair or levelling compounds; - metals or alloys such as aluminium, iron, steel, copper and other non-ferrous metals, including surface-enhancing metals or alloys such as zinc-plated or chrome-plated metals; -Asphalt or bitumen; leather, textiles, paper, wood, wood-based materials bonded with resins, e.g. 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 (CFRP), glass fiber reinforced plastics (GFRP) and sheet molding compounds (SMC); - shielding foams, especially made of EPS, XPS, PUR, PIR, rock wool, glass wool or cellular glass; - coated or painted substrates, in particular painted tiles, coated concrete, powder-coated metals or alloys or painted metal sheets; - Coatings, paints or varnishes, in particular coated floors which have been overcoated with a further floor covering layer.

[0104] If necessary, the substrate can be pretreated prior to application, in particular by physical and / or chemical cleaning methods or by application of an activator or primer.

[0105] The above epoxy resin composition is cured to obtain a cured composition.

[0106] The above epoxy resin compositions are advantageously used as coatings, primers, adhesives, sealants, encapsulating compounds, casting resins or as matrices for fibre composites, especially CFRP or GFRP, the term "coating" also encompassing primers, paints, varnishes and sealants.

[0107] The epoxy resin composition is preferably used as a coating or adhesive.

[0108] The above epoxy resin compositions are more preferably used as coatings, where coating is understood to mean any kind of covering applied to an area, in particular floor coverings, paints, varnishes, sealants, primers or protective coatings, in particular those for heavy duty corrosion protection.

[0109] The epoxy resin composition is particularly suitable as a floor covering or floor coating for indoor use, such as in offices, industrial halls, gymnasiums or cooling spaces, or for outdoor use, such as balconies, terraces, parking decks, bridges or roofs, as a protective coating for concrete, cement, metal, plastic or wood, for example for surface sealing of wooden structures, vehicles, loading docks, tanks, silos, shafts, pipelines, machines or steel structures, such as ships, piers, marine platforms, lock gates, hydroelectric power plants, river structures, swimming pools, wind turbines, bridges, chimneys, cranes or sheet pile walls, or as an undercoat, tie coat or anti-corrosion primer, or for hydrophobizing surfaces.

[0110] In particular, the above epoxy resin compositions are advantageously used in low-emission coatings having an environmental quality seal, for example according to Emicode (EC1 Plus), AgBB, DIBt, Der Blaue Engel, AFSSET, RTS (M1) and the US Green Building Council (LEED).

[0111] For use as a coating, the epoxy resin composition advantageously has a fluid consistency with low viscosity and good leveling. The mixed composition is typically applied to the surface of a substrate at ambient temperature as a thin film having a layer of about 50 μm to about 5 mm during the pot life. Application is in particular carried out by pouring onto the substrate to be coated and then smoothing homogeneously, for example with a coating bar or a comb trowel. Application can also be carried out with a brush or roller, or in the form of a spray application, for example as an anti-corrosion coating on steel. Typically, curing results in a substantially homogeneous, glossy, non-tacky, high-hardness film with good adhesion to a wide variety of different substrates.

[0112] The present invention further comprises: (i) mixing the components of the epoxy resin composition described above; (ii) applying the mixed composition to a substrate during the pot life; A coating method is then provided which includes curing the mixed composition.

[0113] It is possible to apply a further coating to the fully or partially cured composition, in which case said further layer may likewise be an epoxy resin composition or another material, in particular a polyurethane or polyurea coating.

[0114] It is also particularly preferred to use the epoxy resin composition described above as an adhesive. When used as an adhesive, after mixing the components, the epoxy resin composition typically has a paste-like consistency with viscous properties in structure. In application, the mixed adhesive is applied to at least one of the substrates to be bonded together during the pot life, connecting the substrates and forming an adhesive bond within the open time of the adhesive.

[0115] 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.

[0116] The adhesive is particularly suitable for use in the building industry, in particular for the reinforcement of building structures with steel sheets or sheets made of carbon fibre reinforced composite plastics (CFRP), in particular for structures comprising bonded precast concrete components such as bridges or concrete towers (e.g. wind turbines, shafts, pipelines or tunnels) or for structures comprising bonded natural stone, ceramic components or parts made of fibre cement, steel, cast iron, aluminium, wood or polyester, for anchors in drilled holes or for anchoring steel bars, e.g. for fixing handrails, balustrades or door frames, in particular for repairs such as filling edges, holes or joints in concrete maintenance or for bonding films of polyvinyl chloride (PVC), plasticised polyolefins (Combiflex®) or adhesive modified chlorosulfonated polyethylene (Hypalon®) to concrete or steel.

[0117] Further areas of use relate to structural bonding in the building or manufacturing industry, in particular as adhesive mortars, assembly adhesives, in particular as reinforcement adhesives, such as for bonding CFRP or steel sheets to concrete, brickwork or wood, e.g. as component adhesives for bridge components, sandwich component adhesives, facade component adhesives, reinforcing adhesives, car body construction adhesives or half-shell adhesives for rotor blades of wind turbines.

[0118] Such epoxy resin adhesives are likewise suitable for filling cavities such as fissures, cracks or drill holes, where the adhesive is filled or injected into the cavity and fills the cavity after hardening and bonds or adheres to the flanks of the cavity and to each other in a mating manner.

[0119] The present invention relates to (i) mixing the components of the epoxy resin composition described above; (ii) During the pot life, the mixed composition is - applied to at least one of the substrates to be bonded together and joining the substrates to form a bond within the open time; or - applying into a cavity or gap between two or more substrates and, optionally within an open time, inserting an anchor into said cavity or gap; There is further provided a bonding method which comprises subsequently curing the mixed composition.

[0120] Here, the term "anchor" more specifically refers to a reinforcing bar, a cut bolt, or a bolt. The anchor is particularly connected or anchored to a wall, ceiling, or foundation with an adhesive so that a part of the anchor is connected to the wall, ceiling, or foundation so that a part of the anchor is protruding and capable of supporting a construction load.

[0121] Similar or dissimilar substrates may be bonded.

[0122] The application and curing of the epoxy resin composition or coating or bonding method described above results in an article coated or bonded with the composition, which may be an architectural structure or part thereof, in particular an above-ground or underground architectural structure, an office, an industrial hall, a sports hall, a freezer, a silo, a bridge, a roof, a staircase, a balcony, a terrace or a parking deck, or may be an industrial or consumer product, in particular a pier, 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, in particular a car, truck, rail car, ship, aircraft or helicopter, or an installable component thereof.

[0123] The present invention therefore further provides an article resulting from the coating method described above or from the bonding method described above.

[0124] The epoxy resin composition described above is characterized by advantageous properties. It is inexpensive and has good processability, especially with little or no thinner, which allows low or no emission products to be obtained. It has a long pot life, fast curing even under low temperature conditions, high resistance to blush-related defects, especially under high humidity and low temperature conditions, as well as a high glass transition temperature and low brittleness; and it hardly shows any tendency to yellowing. It is particularly suitable as a coating, especially for floors, or as an adhesive, which is applied at ambient temperature. EXAMPLES

[0125] In the following, examples are given which are intended to clarify the invention as described. Naturally, the invention is not limited to these described examples.

[0126] "AHEW" stands for amine hydrogen equivalent weight.

[0127] "EEW" stands for epoxy equivalent weight.

[0128] "Standard weather conditions" refers to a temperature of 23±1°C and a relative air humidity of 50±5%.

[0129] Measurement method description: The viscosity was measured using a thermostatic Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1°, cone-tip-plate distance 0.05 mm, shear rate 10 s -1 ) was measured.

[0130] Amine values ​​were determined by titration (0.1N HClO4 in acetic acid vs. crystal violet).

[0131] Substances and abbreviations used: Sikafloor®-264N(A) Sikafloor®-264N component A (RAL 5005), filled pigment resin component of epoxy resin floor coating, EEW 450g / eq (from Sika) Sikadur®-30(A) Sikadur®-30 component A, a quartz-filled resin component of a structural epoxy resin adhesive containing bisphenol A diglycidyl ether and butane-1,4-diol diglycidyl ether, EEW approx. 700 g / eq (manufactured by Sika) B-EDA N-benzylethane-1,2-diamine, prepared as described below, 50.1 g / eq AHEW B-PDA N-benzylpropane-1,2-diamine, prepared as described below, AHEW 54.8g / eq. TEPA Tetraethylenepentamine, approx. 30g / equivalent of AHEW (technical grade, manufactured by Huntsman) BHMT bis(6-aminohexyl)amine, approximately 43 g / eq AHEW (Dytek® BHMT-HP, from Invista) BHMT-50 Technical grade quality bis(6-aminohexyl)amine with a purity in the range of 50-78% by weight, approximately 48 g / eq AHEW (Dytek® BHMT Amine (50-78%), manufactured by Invista) PEI Polyethyleneimine, average molecular weight about 800 g / mol, AHEW about 38 g / eq (Lupasol® FG, manufactured by BASF) IPDA 3-aminomethyl-3,5,5-trimethylcyclohexylamine, AHEW 42.6 g / eq (Vestamin® IPD, manufactured by Evonik) BAC 1,3-bis(aminomethyl)cyclohexane, AHEW 35.5g / eq (Mitsubishi Gas Chemical Co., Ltd.) TMD 2,2(4),4-trimethylhexamethylenediamine, AHEW 39.6 g / eq (Vestamin® TMD, manufactured by Evonik) MPMD 1,5-diamino-2-methylpentane, AHEW 29.0 g / eq (Dytek® A, from Invista) Adduct-1 Adduct of propylene-1,2-diamine with technical grade o-cresyl glycidyl ether (prepared as described below), AHEW 90g / eq. DMAPAPA 3-(3-(dimethylamino)propylamino)propylamine, AHEW 53g / eq (DMAPAPA, from Arkema). Ca Nitrate Solution 50% by weight calcium nitrate tetrahydrate in water Ancamine® K54 2,4,6-tris(dimethylaminomethyl)phenol (Air Products) Quartz powder particle size 0~75μm Quartz sand grain size 0.1~0.3mm Precipitated lime carbonate Stearate-coated precipitated lime carbonate (Socal® U1S2, Solvay)

[0132] B-EDA and B-PDA are amines A1. TEPA, BHMT, BHMT-50 and PEI are amines A2.

[0133] N-Benzylethane-1,2-diamine (B-EDA): First, 180.3 g (3 mol) of ethylene-1,2-diamine was charged in a round-bottom flask at room temperature under nitrogen atmosphere. With good stirring, a solution of 106.0 g (1 mol) of benzaldehyde in 1200 ml of isopropanol was slowly added dropwise and the mixture was stirred for 2 hours. The reaction mixture was then hydrogenated in a continuous hydrogenation apparatus with a Pd / C fixed bed catalyst at 80 bar hydrogen pressure, a temperature of 80° C. and a flow rate of 5 ml / min. Infrared spectroscopy was used to monitor the reaction, observing a peak at approximately 1665 cm -1 It was checked whether the imine band of 1,2-diamine disappeared. The hydrogenation solution was then concentrated in a rotary evaporator at 65 °C to remove unreacted ethylene-1,2-diamine, water and isopropanol. The reaction mixture thus obtained was a clear, pale yellowish liquid with an amine value of 678 mg KOH / g. 50 g of this liquid were distilled under reduced pressure at 80 °C and 31.3 g of distillate were collected at a vapor temperature of 60-65 °C and 0.06 mbar. A colorless liquid was obtained with a viscosity of 8.3 mPa·s at 20 °C, an amine value of 750 mg KOH / g and a purity of >97% as determined by GC.

[0134] N-Benzylpropane-1,2-diamine (B-PDA): First, a round-bottom flask was charged with 444.8 g (6 mol) of propane-1,2-diamine at room temperature under nitrogen atmosphere. With good stirring, a solution of 212.2 g (2 mol) of benzaldehyde in 1,500 ml of isopropanol was slowly added dropwise and the mixture was stirred for 2 hours. The reaction mixture was then hydrogenated in a continuous hydrogenation apparatus with a Pd / C fixed bed catalyst at 90 bar hydrogen pressure, a temperature of 85° C. and a flow rate of 5 ml / min. Infrared spectroscopy was used to monitor the reaction, and the peak peak at approximately 1665 cm -1It was checked whether the imine band of 1,2-diamine disappeared. The hydrogenation solution was then concentrated in a rotary evaporator at 65° C. to remove unreacted propane-1,2-diamine, isopropanol and water. A clear, pale yellowish liquid was obtained. 300 g of this liquid was distilled under reduced pressure at 80° C. and 237.5 g of distillate was collected at a vapor temperature of 60-65° C. and 0.08 mbar. A colorless liquid was obtained with an amine value of 682 mg KOH / g, which was 1 H NMR showed approximately 2 / 1 ratio and GC purity of >97%. 1 -benzylpropane-1,2-diamine and N 2 -benzylpropane-1,2-diamine.

[0135] Addendum-1: Under a nitrogen atmosphere, an initial charge of 4.15 kg propylene-1,2-diamine was heated to 70° C., then, with good stirring, 2.93 kg Araldite® DY-K (o-cresyl glycidyl ether, technical grade, from Huntsman) was added slowly, bringing the reaction mixture to a temperature of 70-80° C. After 1 h at 80° C., the reaction mixture was cooled and the volatile constituents were removed by distillation through a thin-film evaporator (0.5-1 mbar, jacket temperature 115° C.).

[0136] Preparation of the epoxy resin composition: Examples 1 to 13: (Coating) For each example, the components of the curing agent component shown in Tables 1 to 2 were mixed in the amounts (parts by weight) shown using a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) and stored while excluding moisture.

[0137] The resin component used was Sikafloor®-264N comp. A (blue) (manufactured by Sika) in the amounts (parts by weight) shown in Tables 1-2.

[0138] The two components of each composition were then processed in a centrifugal mixer to obtain a homogenous liquid, which was immediately tested as follows: Ten minutes after mixing, the viscosity was measured at 20° C. (“Viscosity (10′)”).

[0139] For the measurement of Shore D hardness ~ DIN 53505, two cylindrical specimens (diameter 20 mm, thickness 5 mm) were prepared in each case: one was stored under standard weather 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 in low temperature conditions (1d 8° / 80% and 2d 8° / 80%).

[0140] The first film was applied to a glass plate with a layer thickness of 500 μm and was stored / cured under standard weather conditions. The König hardness (König pendulum hardness, measured according to DIN EN ISO 1522) was measured on this film after 1 day ("König hardness (1d SCC)"), 2 days ("König hardness (2d SCC)"), 4 days ("König hardness (4d SCC)"), 7 days ("König hardness (7d SCC)") and 14 days ("König hardness (14d SCC)"). After 14 days, the appearance of the film was evaluated (in the table, indicated as "Appearance (SCC)"). A film was described as "good" if it had a shiny, non-sticky surface without structure. "Structure" refers to any kind of mark or pattern on the surface. Films that have a non-tacky surface without structure, but with reduced gloss, are described as "matte."

[0141] The second film was applied to a glass plate with a layer thickness of 500 μm, which was stored / cured immediately after application at 8° C. and 80% relative humidity for 7 days and then stored / cured for 2 weeks under standard weather conditions. 24 hours after application, a polypropylene bottle top with a wet sponge underneath was placed on the film. After another 24 hours, the sponge and bottle top were removed and placed in a new location on the film, from which the bottle top was then removed after 24 hours and placed again on the film, for a total of 4 times. The appearance of the film was then evaluated as described for appearance (SCC) (indicated in the table as "Appearance (8° / 80%)"). Here, the number and type of visible marks made on the film by the wet sponge and / or the bottle top thereon were also reported in each case. The number of white spots was reported as "brushing". The intensity of any ring-shaped impression made by the sinking of the first bottle top applied 24 hours after application was reported as "ring". Such a ring-shaped impression indicates that the coating is not capable of being walked on. On the thus cured films, the König hardness was measured in each case again at 8° C. and 80% relative humidity (“König Hardness after 7 days (7d 8° / 80%)”), then again after a further 2 days by SCC (“König Hardness (+2d SCC)”), after 7 days by SCC (“König Hardness (+7d SCC)”), and after 14 days by SCC (“König Hardness (+14d SCC)”).

[0142] The change in color after stressing in a weathering machine was further measured as the degree of yellowing. For this, a further film was applied to a glass plate in a layer thickness of 500 μm, which was stored / cured for 2 weeks under standard weather conditions and then exposed to a Q-SUN Daylight-Q optical filter and 0.51 W / m at 340 nm. 2The films were then stressed for 72 hours (Q-Sun(72h)) 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 nm. The color difference ΔE of the stressed films relative to the corresponding unstressed films was then measured using a silicon photodiode detector, a light source A, a color space measurement interface CIE L * a * b * C * H * The color was measured using a NH310 colorimeter manufactured by Shenzen 3NH Technology Co., Ltd. A ΔE value of 5 or less indicates slight yellowing.

[0143] The results are reported in Tables 1-2.

[0144] The examples marked with "(Ref.)" are comparative examples.

[0145] [Table 1]

[0146] [Table 2]

[0147] Examples 14 to 20: (Adhesive) For each example, the components of the hardener component shown in Table 3 were mixed in the amounts (parts by weight) shown using a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) and stored with the exclusion of moisture.

[0148] The resin component used was Sikadur®-30 Component A (Sika) in the amount (parts by weight) shown in Table 3.

[0149] For each example, the resin and hardener components were then processed in a centrifugal mixer to obtain a homogenous paste which was immediately tested as follows.

[0150] Pot life was measured under standard weather conditions by moving the mixed adhesive with a spatula every 5 minutes until the adhesive became so viscous that further processing was impossible.

[0151] Mechanical properties were measured by applying the mixed adhesive to a silicone mould and curing under standard weather conditions to form dumbbell shaped specimens 10mm thick and 150mm long with a gauge length of 80mm and a gauge width of 10mm. Tensile specimens were removed from the mould after curing for 7 days and used to measure tensile strength ("TS") and elongation at break ("EaB") at a strain rate of 1mm / min per EN ISO 527.

[0152] Surface characteristics were evaluated on dumbbell shaped samples to measure mechanical properties on the side exposed to air during curing. Non-tacky surfaces were termed "smooth".

[0153] The tensile shear strength on steel (LSS steel) was measured by applying the mixed adhesive in a layer thickness of 0.5 mm between two heptane-degreased steel sheets with an overlapping bond area of ​​10 x 25 mm to form a multiple adhesive bond. After a storage time of 7 days under standard climatic conditions, the tensile shear strength was measured at a strain rate of 10 mm / min to DIN EN 1465.

[0154] Carbon fiber composite (CRP) tensile shear strength (LSS CRP) was measured by applying the mixed adhesive in a 0.5 mm layer thickness between two heptane-degreased Sika® CarboDur® S512 laminae with an overlapping bond area of ​​10 x 50 mm to form a multiple adhesive bond. After a storage time of 7 days under standard weather conditions, the tensile shear strength was measured as described above.

[0155] Compressive strength ("CS") was measured under standard weather conditions by applying the mixed adhesive to a silicone mold to obtain cuboids with dimensions of 12.7 x 12.7 x 25.4 mm and allowing these to cure under standard weather conditions. After 7 days, several such cuboids were removed from the mold and compressed to failure according to ASTM D695 at a test speed of 1.3 mm / min, with the compressive strength value being read at the maximum force in each case.

[0156] The Tg (glass transition temperature) was determined by DSC on cured adhesive samples that had been stored for 14 days under standard climatic conditions with a Mettler Toledo DSC 3+700 instrument and the following measurement program: (1) -10°C for 2 min, (2) -10 to 200°C (=1st run) with a heating rate of 10 K / min, (3) 200 to -10°C with a cooling rate of -50 K / min, (4) -10°C for 2 min, (5) -10 to 180°C (=2nd run) with a heating rate of 10 K / min.

[0157] The results are reported in Table 3.

[0158] The examples marked with "(Ref.)" are comparative examples.

[0159] [Table 3]

Claims

1. A curing agent for epoxy resins comprising at least one amine A1 of formula (I) below and at least one amine A2 which is a polyalkyleneamine or a polyethyleneimine: 【Chemistry 1】 (In the formula, m is 0 or 1, n is 1 or 2, and (m+n) is 2; A is 1,2-ethylene or 1,2-propylene; R is H or an alkyl group having 1 to 12 carbon atoms; and Y is an optionally substituted aromatic or alicyclic group having 6 to 20 carbon atoms; the weight ratio of amine A1 / amine A2 is in the range of 15 / 1 to 1 / 1; Hardener for epoxy resin.

2. 2. The curing agent according to claim 1, wherein Y is a phenyl group.

3. 3. The curing agent according to claim 1, wherein m and n are each 1.

4. 4. The curing agent according to claim 1, wherein the amine A1 of formula (I) is N-benzylethane-1,2-diamine.

5. 5. The curing agent according to claim 1, wherein the amine A2 is a polyalkyleneamine of formula (II): 【Chemistry 2】 (In the formula, x is an integer from 1 to 6, and B is independently an alkylene group having 2 to 6 carbon atoms.

6. 2,2(4),4-trimethylhexane-1,6-diamine, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 2(4)-methyl-1,3-diaminocyclohexane, 1,3-bis(aminomethyl)benzene, average molecular weight M in the range of 200 to 500 g / mol ｎ 6. The curing agent according to claim 1, further comprising at least one further amine selected from the group consisting of polyoxypropylenediamines having the formula

7. 7. The hardener of claim 6, characterized in that the further amine present is 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane.

8. 7. The hardener of claim 6, wherein the further amine present is 3-(3-(dimethylamino)propylamino)propylamine.

9. An epoxy resin composition comprising: a resin component comprising at least one epoxy resin, and - a hardener component comprising a hardener according to any one of claims 1 to 8.

10. 10. The epoxy resin composition according to claim 9, characterized in that it comprises at least one further component selected from the group consisting of thinners, accelerators and fillers.

11. A coating method comprising the steps of: (i) mixing the components of the epoxy resin composition according to claim 9 or 10; (ii) applying the mixed composition during the pot life to a substrate; The mixed composition is then cured.

12. A method of bonding comprising the steps of: (i) mixing the components of the epoxy resin composition according to claim 9 or 10; (ii) during the pot life, the mixed composition - applied to at least one of the substrates to be bonded to one another and joining said substrates to form a bond within the open time, or - applying to a cavity or gap between two or more substrates and optionally inserting anchors into said cavities or gaps during said open time; The mixed composition is then cured.

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